USOO9447018B2

(12) United States Patent (10) Patent No.: US 9.447,018 B2

GadeWar et al. (45) Date of Patent: Sep. 20, 2016

(54) ETHYLACETATE PRODUCTION 7,700,811 B2 4/2010 Kourtakis et al.

7,700,812 B2 4/2010 Kourtakis et al.
(71) Applicant: Greenyug, LLC, Santa Barbara, CA 7,700,813 B2 4/2010 Kourtakis et al.
(US) 7,705,192 B2 4, 2010 Kourtakis et al.
(72) Inventors: Sagar B. Gadewar, Goleta, CA (US); ;3 R: 338E. Sakset al.
Peter K. Stoimenov, Goleta, CA (US) 8,080,684 B2 12/2011 Hassan et al.
8,080,695 B2 12/2011 Tsuchida et al.
(73) Assignee: sinus LLC, Santa Barbara, CA 8,304,587 B2 11/2012 Warner et al.
8,318,989 B2 11/2012 Kourtakis et al.
8,558,025 B2 10/2013 Gad
(*) Notice: Subject to any disclaimer, the term of this 8,562.921 B2 10/2013 E.
past
M YW-
iss,
y
6 ayS.
listed under 35 9,018,427 B2
2006/0178524 A1
4/2015 Gadewar et al.
8, 2006 Zuber et al.
(21) Appl. No.: 14/023,125 2013, O197266 A1 8/2013 Gadewar et al.
(22) Filed: Sep. 10, 2013 FOREIGN PATENT DOCUMENTS
(65) Prior Publication Data BR 9104652 A 4f1993
EP O101910 A1 3, 1984
US 2014/OO12037 A1 Jan. 9, 2014 EP O151886 A1 8, 1985
O O EP O2O1105 A1 11F1986
Related U.S. Application Data EP 0331021 A1 9, 1989
FR 2743.060 A1 7/1997
(63) Continuation-in-part of application No. 12/925,460, GB 287846 4f1929
filed on Oct. 20, 2010, now Pat. No. 8,558,025. GB 312345 8, 1930
GB 470773 8, 1937
(60) Provisional application No. 61/253,349, filed on Oct. (Continued)
20, 2009. O1
(51) Int. Cl. OTHER PUBLICATIONS
CD7C 67/40 (2006.01)
CD7C 67/48 (2006.01) Tsai et al., Industrial and Engineering Chemistry Research, Design
BOID 3/40 (2006.01) and Control of the Side Reactor Configuration for Production of
C07C 67/58 (2006.01) Ethyl Acetate, 2008, 47, pp. 9472-9484.*
BOID 3/00 (2006.01) Stevens et al. Kirk-Othmer Encyclopedia of Chemical Technology,
(52) U.S. Cl. Extraction, Liquid-Liquid, 2007, pp. 1-62.*
CPC ............... C07C 67/58 (2013.01); B0ID3/001 Foreign communication from a related counterpart application
(2013.01); B0ID3/009 (2013.01); C07C 67/40 International Preliminary Report on Patentability, PCT/US2013/
(2013.01); YO2P 20/12720/582
(2015.11); YO2P
(2015.11)
02404 Aug. 5, 2014.9 pages.
Foreign communication from a related counterpart application—
International Search Report and Written Opinion, PCT/US2014/
(58) Field of Classification Search 053894, Oct. 31, 2014, 9 pages.
CPC ....... C07C 67/58; C07C 67/40; So's Office Action dated Oct. 27, 2014 (17 pages), U.S. Appl. No.
14, 183,273, filed Feb. 18, 2014.
See application file for complete search history. (Continued)
(56) References Cited
U.S. PATENT DOCUMENTS Primary Examiner — Paul A Zucker
1992.480 A 2f1935 Fuchs et al.
(74) Attorney, Agent, or Firm — Andrew M. Metrailer;
2,525,829 A 10/1950 Royer et al. Conley Rose, P.C.
2,544,562 A * 3, 1951 Vesta ...................... CO7C 45,85
518/727
3,714.236 A 1/1973 Wright, Jr. et al. (57) ABSTRACT
4,052,424 A 10/1977 Vanderspurt
4,220,803 A 9/1980 Marcinkowsky et al. A method of purifying an ethyl acetate stream comprises
4,379,028 A * 4/1983 Berg ........................ BOD 3/40
2O3/51
contacting an inlet stream with a solvent, transferring at least
4,435,595 A 3/1984 Agreda et al.
a portion of the impurity compound from the inlet stream
4,440,946 A 4, 1984 Summerville et al. into the solvent to form an extract and a purified product,
4,523,027 A 6, 1985 Kummer et al. separating the extract from the purified product, separating
4,569,726 A 2/1986 Berg et al. the portion of the impurity compound from the extract,
4,645,570 A 2f1987 Sridhar et al. forming an impurities stream and a regenerated solvent, and
4,825,013 A 4/1989 Quarderer et al. recycling at least a portion of the regenerated solvent to
4,996,007 A 2f1991 Chao et al. contact the inlet stream. The inlet stream comprises ethyl
5,194,675 A 3/1993 Joerg et al. acetate and an impurity compound, and the extract com
5,334,751 A 8, 1994 Lemanski et al.
6,407.295 B1 6, 2002 Kaizik et al. prises the solvent and the portion of the impurity compound
6,632,330 B1 * 10/2003 Colley .................... CO7C 67/54 transferred from the inlet stream.
203/18
6,809,217 B1 10/2004 Colley et al.
7,700,810 B2 4/2010 Kourtakis et al. 26 Claims, 17 Drawing Sheets
 US 9.447,018 B2
Page 2

(56) References Cited Vogel, Arthur Israel, “Vogel's textbook of practical organic chem
istry,” 5th edition, revised by Brian S. Furniss, et al., 1989, 15 pages
FOREIGN PATENT DOCUMENTS of cover, publishing information, and contents, John Wiley & Sons,
Inc.
JP 59025334 A 2, 1984 Foreign communication from a related counterpart application—
JP 5186392 A 7, 1993 International Search Report and Written Opinion, PCT/US2014/
JP TO53676 B2 6, 1995 016957, Jun. 27, 2014, 9 pages.
SU 362814 A1 12, 1972 Notice of Allowance dated Mar. 11, 2015 (30 pages), U.S. Appl. No.
WO 2011131609 A2 10, 2011 13/363,858, filed Feb. 1, 2012.
WO 2013055334 A1 4/2013
WO 2013116492 A1 8, 2013 Notice of Allowance dated Jan. 6, 2015 (12 pages), U.S. Appl. No.
14, 183,273, filed Feb. 18, 2014.
OTHER PUBLICATIONS Filing receipt and specification for patent application entitled “Pro
duction of higher alcohols,” by Sagar B. Gadewar, et al., filed Feb.
Inui, Kanichiro, et al., “Effective formation of ethyl acetate from 18, 2014 as U.S. Appl. No. 14/183,273.
ethanol over Cu-Zn Zr—Al-O catalyst.” Journal of Molecular Filing receipt and specification for provisional patent application
Catalysis A: Chemical, 2004, pp. 147-156, vol. 216, Elsevier B.V. entitled “Production of butanols and ethyl acetate.” by Sagar B.
Inui, Kanichiro, et al., “Direct synthesis of ethyl acetate from Gadewar, et al., filed Feb. 19, 2013 as U.S. Appl. No. 61/766,484.
ethanol carried out under pressure,” Journal of Catalysis, 2002, pp. Filing receipt and specification for provisional patent application
207-215, vol. 212, Elsevier Science. entitled “Production of higher alcohols from ethanol.” by Brian
SantaceSaria, E., et al., “Ethanol dehydrogenation to ethyl acetate by
using copper and copper chromite catalysts,” Chemical Engineering Christopher Vicente, et al., filed Dec. 5, 2013 as U.S. Appl. No.
Journal, 2012, pp. 209-220, vol. 179, Elsevier B.V. 61/912,235.
Takeshita, Kenji, et al., “Reduced copper catalyzed conversion of Yang, Ke Wu, et al., “One-step Synthesis of n-Butanol from Ethanol
primary alcohols into esters and ketones.” Bulletin of the Chemical Condensation over Alumina-supported Metal Catalysts.” Chinese
Society of Japan, Sep. 1978, pp. 2622-2627, vol. 51, No. 9. Chemical Letters, 2004, pp. 1497-1500, vol. 15, No. 12.
Tsai, Reui-Chiang, et al., “Design and control of the side reactor Filing receipt and specification for provisional patent application
configuration for production of ethyl acetate.” Ind. Eng. Chem. entitled “Production of ethyl acetate and butyl acetates from etha
Res., 2008, pp. 9472-9484, vol. 47, No. 23, American Chemical nol.” by Sagar B. Gadewar, et al., filed Dec. 4, 2013 as U.S. Appl.
Society.
Filing receipt and specification for provisional patent application No. 61/911,832.
entitled “Ethyl acetate production.” by Sagar B. Gadewar, filed Oct. Filing receipt and specification for international application entitled
20, 2009 as U.S. Appl. No. 61/253,349. “Production of higher alcohols,” filed Feb. 18, 2014 as international
Foreign communication from a related counterpart application— application No. PCT/US2014/016957.
International Search Report and Written Opinion, PCT/US2011/ Filing receipt and specification for international application entitled
056015, May 24, 2012, 8 pages. “Ethyl acetate production.” filed Oct. 20, 2010 as international
Foreign communication from a related counterpart application— application No. PCT/US2010/002806.
International Search Report and Written Opinion, PCT/US2013/ Foreign communication from a related counterpart application—
024104, May 30, 2013, 12 pages. International Preliminary Report on Patentability, PCT/US2011/
Machine translation (9 pages) of French patent No. 2743.060 Al 056015, Apr. 15, 2014, 6 pages.
issued on Jul. 4, 1997. Foreign communication from a related counterpart application—
Smith, Michael B., “March's advanced organic chemistry: reac Search Report, European Application No. 11873809.5 filed on Apr.
tions, mechanisms, and structure,' 7th edition, 2013, 8 pages of 15, 2015.
cover, publishing information, and contents, John Wiley & Sons,
Inc. * cited by examiner
U.S. Patent Sep. 20, 2016 Sheet 1 of 17 US 9.447,018 B2

EEEEEEEEE ESSEE

ES

a . S8
EEE

ESL REEN

Azeotrope
i

.4

. ,
EAEE XEEEEE

Figure 1: Reactive residue curve maps at pressures of 1 atm and 5 atm.

U.S. Patent Sep. 20, 2016 Sheet 2 of 17 US 9.447,018 B2

ESHAE HREE

3.

3.

, sos. . . . . . . . . . . . .------------ X.
2 . , ,8
EASEE CEA.E.H.E.

E. YREN

..a

. -------TI-...--------------------------
O. E. S.E. 8
ESCEE EiEEE

Figure 2: Reactive residue curve maps at pressures of 10 atm and 20 atm.

U.S. Patent Sep. 20, 2016 Sheet 3 of 17 US 9.447,018 B2

14

Figure 3: Single feed reactive distillation column schematic.

U.S. Patent Sep. 20, 2016 Sheet 4 of 17 US 9.447,018 B2

Figure 4: Schematic for a reactive distillation system with subsequent product

hydrogenation.
U.S. Patent Sep. 20, 2016 Sheet 5 Of 17 US 9.447,018 B2

Figure 5: Double feed reactive distillation column schematic with an upper feed of
ethanol and lower feed of hydrogen.
U.S. Patent Sep. 20, 2016 Sheet 6 of 17 US 9.447,018 B2

80

82

Figure 6: Double feed reactive distillation column schematic using dual catalyst
beds with an upper feed of ethanol and lower feed of hydrogen.
U.S. Patent Sep. 20, 2016 Sheet 7 Of 17 US 9.447,018 B2

54

46

"- (W) 1" ()

48

58

(b)

Figure 7: Side reactor configuration (a) upward flow feed to side reactor (b)
downward flow feed to Side reactor.
U.S. Patent Sep. 20, 2016 Sheet 8 of 17 US 9.447,018 B2

84

86

70

82

-> 92

Figure 8: Double Side reactor configuration (a) upward flow feed to multiple side
reactors (b) downward flow feed to multiple side reactors.
U.S. Patent Sep. 20, 2016 Sheet 9 Of 17 US 9.447,018 B2
U.S. Patent Sep. 20, 2016 Sheet 10 of 17 US 9.447,018 B2

NOILVYH).XE
U.S. Patent Sep. 20, 2016 Sheet 11 of 17 US 9.447,018 B2

se?und]
U.S. Patent Sep. 20, 2016 Sheet 12 of 17 US 9.447,018 B2
U.S. Patent Sep. 20, 2016 Sheet 13 of 17 US 9.447,018 B2
U.S. Patent Sep. 20, 2016 Sheet 14 of 17 US 9.447,018 B2
U.S. Patent Sep. 20, 2016 Sheet 15 Of 17 US 9.447,018 B2

643
aan
94.
U.S. Patent US 9.447,018 B2
U.S. Patent Sep. 20, 2016 Sheet 17 Of 17 US 9.447,018 B2

8;
s:
8.
-8
x. 8
3.
:
8: E.
assera-exexed:sawy
 US 9,447,018 B2
1. 2
ETHYLACETATE PRODUCTION co-precipitate composition comprising silver-cadmium
zinc-zirconium which is substantially in the free metal form.
CROSS-REFERENCE TO RELATED Use of the Tischenko reaction for the production of mixed
APPLICATIONS esters from aldehydes is described in U.S. Pat. No. 3,714,
236.
This application is a continuation-in-part of and claims U.S. Pat. No. 5,334,751 describes production of ethyl
priority to U.S. patent application Ser. No. 12/925,460 filed acetate by reaction of ethanol and oxygen in the presence of
on Oct. 20, 2010, now U.S. Pat. No. 8,558,025, to Sagar B. a solid catalyst that contains crystalline TiPO, and has the
Gadewar and entitled “Ethyl Acetate Production,” which is formula PdMTiPO, where M is Cd, Au, Zn, T1, or an
a Non-Provisional application of and claims priority to U.S. 10
alkali metal or alkaline earth metal, a is 0.0005-0.2, b is 0.3a,
Provisional Application No. 61/253,349, filed Oct. 20, 2009 c is 0.5-2.5. X has a value to satisfy the valencies, and Tiand
to Sagar B. Gadewar and entitled “Ethyl Acetate Produc P of the crystalline TiPO, represent part of the crystalline
tion, both of which are incorporated herein by reference in
their entirety. TiP.O.
15 BR-A-91/04652 describes pre-treatment of a palladium
STATEMENT REGARDING FEDERALLY on a silica carrier catalyst for production of ethyl acetate by
SPONSORED RESEARCH OR DEVELOPMENT direct oxidation of ethanol with air.
Production of esters from primary alcohols by dehydro
Not applicable. genation using bromous acid or a salt thereof in acid medium
is described in JP-A-59/025334.
REFERENCE TO A MICROFICHEAPPENDIX In SU-A-362814 there is described a process for produc
tion of ethyl acetate by dehydrogenation of ethanol at 180°
Not applicable. C. to 300° C. in the presence of a copper catalyst containing
Zinc as an activator with an ethanol feed rate of 250 to 700
BACKGROUND 25 liters per liter of catalyst per hour.
The dehydrogenation of ethanol to form ethyl acetate is
The following discussion is provided solely to assist the described in GB-A-287846. This proposes use of a dehy
understanding of the reader, and does not constitute an drogenating agent, such as a copper catalyst, a temperature
admission that any of the information discussed or refer of from 250° C. to 500° C., and a pressure of more than 10
ences cited constitute prior art to the present invention. 30 atmospheres (1.013x10 Pa).
Ethyl acetate can be produced from acetaldehyde accord Vapor phase contact of ethanol at a temperature above its
ing to the Tischenko reaction: critical temperature with a catalyst comprising copper and a
2CHCHO-->CHCOOC-Hs difficultly reducible oxide, such as Zinc oxide or manganese
oxide, is proposed in GB-A-312345, use of a temperature of
When acetaldehyde is produced from ethanol, ethyl 35 375° C. and a pressure of 4000 psi (27.58 Mpa) being
acetate can be produced from ethanol according to the Suggested.
following reaction: GB-A-470773 teaches a process for conversion of ethanol
to ethyl acetate by dehydrogenating ethanol over a catalyst
consisting of a reduced metal, for example, copper on
Alternately, ethanol can react with acetaldehyde accord 40 infusorial earth with 10% uranium oxide as promoter, main
ing to the following reaction: tained at a temperature of 220° C. to 260° C. removing by
condensation some of the gas-vapor product rich in hydro
gen resulting from the reaction, and returning the gaseous
Conversion of primary alcohols into esters and ketones remainder rich in hydrogen to the catalyzing Zone.
using copper catalyst is described by K. Takeshita in the 45 EP-A-0151886 describes a process for the preparation of
Bulletin of the Chemical Society of Japan, (1978) vol. 51(9), C2+ esters of alkyl carboxylic acids from C2+ primary
pp. 2622-2627. alcohols which comprises contacting a vaporous mixture
U.S. Pat. No. 4,996,007 describes a process for the containing a primary C2+ alkanol and hydrogen in an
oxidation of primary alcohols to aldehydes, esters and acids. alkanol: hydrogen molar ratio of from 1:10 to about 1000:1
A primary alcohol is reacted with oxygen, with a catalyst 50 at a combined partial pressure of alkanol and hydrogen of
selected from ruthenium, rhodium, platinum, palladium, from about 0.1 bar (103 Pa) up to about 40 bar (4x10 Pa)
rhenium and mixtures thereof, with the option of quaternary and at a temperature in the range of from about 180° C. to
C1 to C20 alkyl ammonium co-catalyst, and dihydrodihy about 300° C. in a catalytic reaction Zone with a catalyst
droxynaphthalene, dihydroxyanthracene or a mixture consisting essentially of a reduced mixture of copper oxide
thereof as an oxygen activator. 55 and Zinc oxide, and recovering a reaction product mixture
In U.S. Pat. No. 4.220,803 catalytic dehydrogenation of containing a primary C2+ alkyl ester of an alkyl carboxylic
ethanol for the production of acetaldehyde and acetic acid acid which ester contains twice as many carbon atoms as the
using a Supported copper oxide essentially free of barium is primary C2+ alkanol.
proposed. In EP-A-0201105 there is described a method for con
U.S. Pat. No. 4,052,424 suggested a silver-cadmium alloy 60 verting primary alcohols, such as ethanol, to their corre
catalyst for use in production of alkyl alkanoate esters, by sponding alkanoate esters which involves the regulation of
contacting a primary alkanol in the vapor phase with the the mole feed ratio of hydrogen gas to alkanol in the reaction
catalyst at a temperature of between about 250° C. and 600° Zone of a copper-chromite containing catalyst.
C. One method of separating ethyl acetate from ethanol and
In U.S. Pat. No. 4,440,946 there is described a process for 65 water involves extractive distillation with an extractive
producing a carboxylate ester which comprises contacting a agent comprising polyethylene glycol and dipropylene gly
mixture of alcohol and aldehyde in the vapor phase with a col, diethylene glycol, or triethylene glycol as described in
 US 9,447,018 B2
3 4
U.S. Pat. No. 4,569,726 or with an extractive agent contain unit is configured to receive a liquid ethyl acetate product
ing dimethyl sulphoxide as described in U.S. Pat. No. stream from the reactive distillation column through the
4,379,028. bottoms product liquid ethyl acetate removal passage, con
Separation of ethyl acetate from a composition compris tact a liquid solvent feed stream with the liquid ethyl acetate
ing ethyl acetate, ethanol and water is described in JP-A- 5 product stream, provide an extract stream comprising a
05/1863.92 by feeding the composition to a distillation portion of any impurities in the liquid ethyl acetate product
column to obtain a quasi-azeotropic mixture comprising stream, and provide a purified product stream. The Stripping
ethyl acetate, ethanol and water, condensing it, separating unit is configured to receive the extract stream from the
the condensate into an organic layer and an aqueous layer, extraction unit, separate the portion of the impurities from
returning the organic layer to the column, and recovering 10 the extract stream, provide an outlet impurities stream, and
ethyl acetate as a bottom product from the column. provide a regenerated solvent stream back to the extraction
EP-A-0331021 describes how carbonylation of olefins to unit as at least a portion of the liquid solvent feed stream.
produce monocarboxylate esters causes formation of alde In an embodiment, a reactive distillation process produc
hydes and acetals as byproducts. Monocarboxylate esters ing high purity ethyl acetate from ethanol comprises feeding
produced in this way are subjected to a three step purifica- 15
tion process involving treatment with a strongly acidic a feed stream comprising ethanol to a reactive distillation
agent, followed by hydrogenation and distillation. The initial column, contacting the ethanol with a catalyst, dehydroge
treatment with a strongly acidic agent is intended to convert nating ethanol over the catalyst in the liquid phase during the
acetals to vinyl ethers and aldehydes and acetals to aldols. distillation process, removing ethyl acetate during the dis
The Subsequent hydrogenation step then converts these 20 tillation process as a bottoms product, and removing hydro
compounds to byproducts which are more easily separated gen during the distillation process as a top product.
from the desired monocarboxylate ester. These and other features will be more clearly understood
EP-A-0101910 contains a similar disclosure regarding from the following detailed description taken in conjunction
carbonylation of olefins to give monocarboxylate esters. It with the accompanying drawings and claims.
proposes treatment of the monocarboxylate ester with 25
hydrogen at elevated temperature in the presence of an BRIEF DESCRIPTION OF THE DRAWINGS
acidic ion exchanger or Zeolite doped with one or more
metals of Group VIII of the Periodic Table, followed by For a more complete understanding of the present disclo
hydrogenation. It is stated that acetals present as byproducts Sure and the advantages thereof, reference is now made to
are converted to vinyl ethers which are converted by hydro- 30 the following brief description, taken in connection with the
genation to low boiling esters or the aldehydes and acetals accompanying drawings and detailed description.
are converted to high boilers by an aldol reaction. Unsatu FIG. 1 shows reactive residue maps for conversion of
rated ketones are converted to Saturated ketones. ethanol to ethyl acetate at pressures of 1 and 5 atmospheres
U.S. Pat. No. 4,435,595 describes the use of reactive (atm) for an embodiment.
distillation to produce high-purity methyl acetate, by esteri- 35 FIG. 2 shows reactive residue maps for conversion of
fying methanol and acetic acid. The process provides for the ethanol to ethyl acetate at pressures of 10 and 20 atm for an
use of acetic acid and methanol which flow in counter embodiment.
current through a single reactive distillation column in the FIG. 3 shows a simplified schematic of a reactive distil
presence of an acid catalyst. The acetic acid, in addition to lation system according to an embodiment.
being a reagent, also acts as an extracting agent for the 40 FIG. 4 shows a simplified schematic of a reactive distil
non-reacted methanol and for the water which has been lation system according to another embodiment.
produced. Therefore, the methyl acetate is separated con FIG. 5 shows a simplified schematic of a reactive distil
tinuously from the acetic acid and removed from the top of lation system according to still another embodiment.
the column. FIG. 6 shows a simplified schematic of a reactive distil
45 lation system according to yet another embodiment.
SUMMARY FIGS. 7(a) and 7(b) shows a simplified schematic of a
reactive distillation system according to an embodiment.
In an embodiment, a method of purifying an ethyl acetate FIGS. 8(a) and 8(b) shows a simplified schematic of a
stream comprises contacting an inlet stream with a solvent, reactive distillation system according to another embodi
transferring at least a portion of the impurity compound 50 ment.
from the inlet stream into the solvent to form an extract and FIG. 9 illustrates a schematic flow diagram of a reactive
a purified product, separating the extract from the purified distillation system with a recycle according to an embodi
product, separating the portion of the impurity compound ment.
from the extract, forming an impurities stream and a regen FIG. 10 illustrates a schematic flow diagram of a product
erated solvent, and recycling at least a portion of the 55 separation system according to an embodiment.
regenerated solvent to contact the inlet stream. The inlet FIG. 11 illustrates a schematic flow diagram of a product
stream comprises ethyl acetate and an impurity compound, separation system according to another embodiment.
and the extract comprises the solvent and the portion of the FIG. 12 illustrates a schematic flow diagram of a stripping
impurity compound transferred from the inlet stream. section according to another embodiment.
In an embodiment, a reactive distillation system for 60 FIG. 13 illustrates a schematic co-current extraction flow
producing high purity ethyl acetate from ethanol comprises scheme according to an embodiment.
a reactive distillation column, an extraction unit, and a FIG. 14 illustrates a schematic counter-current extraction
stripping unit. The reactive distillation column comprises a flow Scheme according to an embodiment.
dehydrogenation catalyst, an ethanol inlet configured to pass FIG. 15 illustrates a schematic cross-current extraction
an ethanol feed over the dehydrogenation catalyst, a top 65 flow Scheme according to an embodiment.
product gaseous hydrogen removal passage, and a bottoms FIG. 16 illustrates a chart demonstrating the results of an
product liquid ethyl acetate removal passage. The extraction extraction of 2-butanone from ethyl acetate.
 US 9,447,018 B2
5 6
FIG. 17 illustrates another chart demonstrating the results reactor, etc.) in which a reaction is occurring. In general,
of an extraction of 2-butanone from ethyl acetate. Suitable separators may include any process equipment
FIG. 18 illustrates another chart demonstrating the results Suitable for separating at least one inlet stream into a
of an extraction of 2-butanone from ethyl acetate using plurality of effluent streams having different compositions,
several extracting Solution compositions. states, temperatures, and/or pressures. For example, the
separator may be a column having trays, packing, or some
DETAILED DESCRIPTION other type of complex internal structure. Examples of Such
columns include Scrubbers, strippers, absorbers, adsorbers,
A reactive distillation system and process are disclosed packed columns, and distillation columns having valve,
herein for producing high purity ethyl acetate from ethanol. 10 sieve, or other types of trays. Such columns may employ
This process is beneficial as it provides an improved com weirs, downspouts, internal baffles, temperature control ele
mercial method of upgrading ethanol to ethyl acetate, a more ments, and/or pressure control elements. Such columns may
valuable product. This improved commercial process may also employ some combination of reflux condensers and/or
be used where there is a Supply and/or a Surplus Supply of reboilers, including intermediate stage condensers and
ethanol. Further, this process reduces and/or eliminates the 15 reboilers. In an embodiment, the reactive distillation system
need for a separate acetaldehyde or acetic acid plant to described herein may comprise a distillation tower having at
provide the precursors for the ethyl acetate production least one catalyst disposed therein. The catalyst may take a
process. The raw material may comprise only ethanol, which variety of forms, and the separator may comprise any
may present an advantage relative to other processes requir combination of catalyst and separator structures. For
ing multiple feedstocks. In addition, bio-derived ethanol example, the separator may comprise sequential layers of
may be used to allow the process to be operated from catalysts and distillation packing and/or the packing may
renewable ethanol sources. Further, the present system and comprise catalytic elements such as pellets that act as a
method may utilize base-metal catalysts, which may be less structured packing. In some embodiments, the reactive dis
expensive than the precious metal based catalysts of other tillation system described herein may comprise a distillation
ethyl acetate production routes. Such catalysts can comprise 25 tower comprising one or more side reactors comprising at
copper, and may be composed of copper oxide mixed with least one catalyst disposed therein, where the one or more
one or more additional metals and/or metal oxides. The side reactors are coupled to and are in fluid communication
present systems and methods may allow for a one-step ethyl with the distillation tower
acetate production process, which may be advantageous As indicated above, the present systems and methods
relative to other processes that require further steps to purify 30 provide for the production of ethyl acetate from ethanol at a
the ethyl acetate product, including a selective removal of relatively low cost, along with a plant or distillation system
2-butanone, which forms a low boiling azeotrope with ethyl with significantly reduced complexity using reactive distil
acetate. Each of these advantages may be provided in a lation. The present disclosure further provides an improved
process that can also be less expensive than alternative process for the production of high purity ethyl acetate from
processes by ethyl acetate production from ethanol. 35 ethanol, or from a feedstock comprising a major proportion
In an embodiment, the present systems and methods can of ethanol and a minor proportion of impurities such as
provide a route to ethyl acetate by dehydrogenation and iso-propanol and iso-butanol. While not commonly present
dimerization of ethanol which is capable of yielding high in ethanol feed streams, impurities that can poison the
purity ethyl acetate from ethanol feed streams containing particular catalyst used should be limited, avoided and/or
significant amounts of byproducts or impurities. One issue 40 removed. For example, Sulfur or nitrogen heterocyclic com
in the production of ethyl acetate by dehydrogenation of pounds can frequently act as catalyst poisons and, if present,
ethanol is that the reaction product mixture is commonly a should be removed before introducing the ethanol feed
complex mixture including esters, alcohols, aldehydes and stream to the reactive distillation column. In an embodiment,
ketones. From a distillative separation point of view, the the ethanol feed may comprise water. The presence of water
mixture is further complicated due to the presence of azeo 45 in the ethanol feed does not severely reduce the performance
tropes. The reaction product mixtures commonly contain of the catalysts, which can tolerate up to 5% water by weight
components with boiling points close to ethyl acetate (Such in the ethanol. Ethanol conversion is reduced when using an
as n-butyraldehyde and/or butan-2-one), including compo ethanol source with significant water content, but the reac
nents which can form azeotropes with ethyl acetate, and/or tion selectivity increases. The use of an ethanol feed com
other components of the mixture. This may present a chal 50 prising a small amount of water may be advantageous by
lenge when high purity ethyl acetate is desired. allowing for the use a potentially less expensive ethanol
In chemical processing, chemical reaction and the puri source in the form of the ethanol/water azeotrope (about
fication of the desired products by distillation may be carried 4.4% water by weight). The effects of water are demon
out sequentially. The performance of this chemical process strated in the Examples described herein.
structure may be improved by the integration of reaction and 55 Ethyl acetate can be produced from ethanol according to
distillation in a single multifunctional process unit. This the following reactions:
integration concept is called “reactive distillation. As
advantages of this integration, chemical equilibrium limita
tions may be overcome, higher selectivities may be
achieved, the heat of reaction may be used in situ for 60
distillation, auxiliary solvents may be avoided, and/or azeo
tropic and/or closely boiling mixtures may be more easily The Tishchenko reaction may also provide a potential reac
separated. Increased process efficiency and reduction in tion route for the production of ethyl acetate from ethanol:
overall capital costs may result from the use of this
approach. 65
A reactive distillation system comprises at least one
separator and/or reactor (e.g., a distillation tower, side 2CHCHOesCHCOOC-Hs
 US 9,447,018 B2
7 8
In an embodiment, ethanol reacts in a single continuous to two separate chemical feed streams. For example, in some
reactive distillation column which provides sufficient resi of the present embodiments, dual feeds are an ethanol feed
dence time to achieve a relatively high conversion of etha and a separate hydrogen feed. The term “reactive distillation
nol. In an embodiment, the reactive distillation column may column” is used conventionally to refer to a distillation
be configured to provide a conversion of ethanol of at least 5
column in which both reaction and separation is performed.
about 10% and a selectivity of at least about 60%, as In this case, the primary and desired reaction is the conver
described in more detail herein. Table 1 shows the effect of
pressure on the boiling point of the pure components and sion of two ethanol molecules to one ethyl acetate molecule
azeotrope in the mixture. The azeotrope between ethanol and with release of two hydrogen molecules. Thus, the present
ethyl acetate is substantially avoided above a pressure of 13 10 invention provides systems and methods for the production
atm. of ethyl acetate from ethanol which includes reacting etha
TABLE 1.
Boiling point of reaction components.
Boiling Point, C.
P = 1 atm P = 5 atm P = 10 atm P = 20 atm P = 30 atm P = 40 atm

Hydrogen -161 -137.6 -123.7 -106.5 -94.3 -84.5

Acetaldehyde 20.4 71.9 101.1 1364 160.7 18O
Ethanol 78.3 125.2 150.2 179 198 212.7
Ethyl acetate 77 136 169.6 210.3 238.4 260.7
Ethanol/Ethyl 71.7 123.5 150.1 No Azeo No Azeo No Azeo
acetate azeotrope

25

Residue curve maps can be used to indicate feasible nol over a suitable dehydrogenation and/or dimerization
product compositions for distillation columns. In the pres catalyst, thereby producing ethyl acetate and hydrogen.
ence of reaction along with separation, reactive residue In an embodiment, a single reactive distillation column is
curve maps can be used to determine feasible products from 30
used. Hydrogen gas is removed (e.g., continuously) from the
a reactive distillation column. Reactive residue curve maps top of the reactive distillation column as an overhead stream.
at a pressure of 1 atm and 5 atm respectively are shown in Ethyl acetate is removed (e.g., continuously) from the bot
FIG.1. The stable nodes in the diagram are ethanol and ethyl tom of the column as a bottoms stream. Optionally, con
acetate, and, therefore, it is possible to design a reactive taminating byproducts present following reaction of the
distillation column where either ethanol or ethyl acetate can 35 ethanol over the dehydrogenation catalyst can be separated
be obtained as the bottoms product. Hydrogen is an unstable from the ethyl acetate product stream. Various byproduct
node in the diagram and can be obtained as the distillate. separation schemes are possible including, but not limited
Acetaldehyde and the ethanol/ethyl acetate azeotrope are to, reacting the byproducts in the product stream over a
saddle points in the diagram. suitable hydrogenation catalyst in the lower part of the
Reactive residue curve maps at pressures of 10 atm and 20 40 column or in a separate hydrogenation reactor. The hydro
atm respectively are shown in FIG. 2. The reactive residue genation can convert difficult to separate byproducts into
curve maps for any pressure above 20 atm are substantially species which are easier to separate from the ethyl acetate.
similar to the reactive residue curve map at 20 atm. Consequently, the process can also include purifying the
In view of the reactive residue maps discussed above, a ethyl acetate by distilling out resulting hydrogenated
set of reactive distillation systems effective to produce high 45 byproducts. In some embodiments, an extraction process
purity ethyl acetate from ethanol have been designed. The may be used selectively remove one or more byproducts
reactive distillation column can have single or multiple feed from the ethyl acetate products stream. Consequently, the
locations. process may also include purifying the ethyl acetate by
Reactive Distillation Column Configurations 50
contacting the product stream with an extractant, which can
be regenerated and recycled to the extraction system.
The present systems and methods provide a reactive In an embodiment, the reactive distillation column is
distillation system in which ethanol may be the sole or configured for the dehydrogenation of ethanol with the
primary component of the feed. In some embodiments, the formation of ethyl acetate. The reaction is accomplished by
ethanol feed is used in conjunction with a separate, second 55 passing the ethanol feed stream over a dehydrogenation
feed of hydrogen. Reference to a “single feed to a reactive catalyst under conditions where ethyl acetate is formed and
distillation column means that the column has only one hydrogen and ethyl acetate are withdrawn as top and bot
chemical feed stream Supplying intended reactant(s) to the toms products respectively. Such product draws drive the
column. Nonetheless, such a single feed distillation column thermodynamics of the process toward the desired products.
may have multiple entry points for the reactant, or recycling 60 In its simplest form, a reactive distillation system may
feed streams where a part of the reactant liquid or a partial comprise a reactor vessel operating with a liquid phase
distillate is drawn from the column and fed back into the reaction in which hydrogen and/or other light gases are
column at a different point, e.g., to achieve improved sepa removed as the overhead product and a reaction product is
ration and/or more complete reaction. A 'single ethanol removed as the bottoms product. Such a system may com
feed thus refers to a single feed stream, in which ethanol is 65 prise a batch reactor in which hydrogen is removed during
the sole or at least the primary constituent. In contrast, the the reaction and the liquid product is removed after comple
term “dual feed” in the context of a distillation column refers tion of the reaction to a desired degree of conversion.
 US 9,447,018 B2
10
An embodiment of a reactive distillation column with a acetate is formed from the reactants, an azeotrope between
single feed of ethanol is shown schematically in FIG. 3 can ethyl acetate and ethanol occurs. This azeotrope may result
produce hydrogen as a distillate and ethyl acetate as a in the overhead product 19 that leaves the top of the reactive
bottoms product. Column 10 contains a generally central distillation column 10 containing ethanol/ethyl acetate and/
catalyst Zone 12, and usually will include a top stage or or acetaldehyde in addition to hydrogen. A partial condenser
non-reactive rectifying section 13 and a bottom stage or 16 allows hydrogen to be removed as a distillate, while
non-reactive stripping section 15. Ethanol feed 14 is com acetaldehyde and ethanol are recycled back to the top of the
monly fed to the middle part of the reactive distillation reactive distillation column. At a pressure above about 13
column. Distillate removed at the top of the column is atm, the ethyl acetate and ethanol azeotrope disappears,
passed through a partial condenser 16, and hydrogen is 10 which improves the operation of the reactive distillation
separated from lower boiling constituents in reflux tank 18. column.
The hydrogen may leave the system as an overhead product The column 10 can be operated at any suitable pressure
stream 19, which in an embodiment may comprise trace between about 1 atm and about 80 atm. In an embodiment,
amounts of additional components including ethanol, ethyl the column 10 may be operated at a pressure ranging from
acetate, and/or one or more reaction byproducts. The con 15 about 1 atm to about 5 atm, about 5 atm to about 10 atm,
densed lower boiling constituents (i.e., reflux), or at least about 7 atm to about 12 atm, about 13 atm to about 15 atm,
some portion thereof, can be cycled back to the column for about 13 atm to about 20 atm, about 15 atm to about 20 atm,
further reaction and/or separation. The bottoms product can about 15 atm to about 30 atm, about 20 atm to about 30 atm,
be passed through reboiler 20, where a portion of the about 20 atm to about 50 atm, about 30 atm to about 40 atm,
bottoms product is evaporated and added back to the bottom about 40 atm to about 50 atm, or about 50 atm to about 60
of the column. The remaining bottoms product may pass out atm, about 60 atm to about 70 atm, about 60 atm to about 80
of the system as product stream 22. Alternatively, only a atm, or about 70 atm to about 80 atm. In an embodiment, the
portion of the bottoms product may be passed through reactive distillation is performed at a pressure where etha
reboiler 20, with the vapor portion passing back to the nol-ethyl acetate azeotrope is not present. The temperature
bottom of the column and the remainder of the bottoms 25 profile in the column is dictated by the mixture boiling point
product being combined with any bottoms product bypass along the height of the column. In an embodiment the
ing the reboiler 20 and passing out of the system as product temperature within the column may range from about 100°
stream 22 for further processes and/or use as a final product. C. to about 350° C., alternatively about 150° C. to about
The product stream 22 may comprise the ethyl acetate 250° C. The column 10 may comprise any number of stages
produced in the column along with unreacted ethanol and 30 equivalent to a number of theoretical stages sufficient to
potentially any side products produced by the reaction. The effect the reaction and separation of ethyl acetate to a desired
column reflux and reboil ratios are maintained such that purity. In an embodiment, the number of stages or the
essentially pure ethyl acetate is obtained as the bottoms number of height equivalents of a theoretical plate (HETP)
product. In an embodiment, the bottoms product stream 22 may range from about 1 to about 100, including for example
may comprise greater than about 90%, greater than about 35 from about 1 to about 10, about 10 to about 20, about 10 to
95%, greater than about 96%, greater than about 97%, about 50, about 20 to about 30, about 20 to about 70, about
greater than about 98%, greater than about 99%, or greater 30 to about 40, about 30 to about 50, about 30 to about 100,
than about 99.5% ethyl acetate by weight. about 50 to about 70, about 50 to about 100, or about 70 to
During operation, the reactants and products flow through about 100. As described in more detail below, a relatively
the reactor/column reacting and flashing along the length of 40 high conversion of ethanol to products can be achieved by
the reactor/column. In an embodiment, the reaction of the the counter-current flow of reactants and products in addi
reactants and/or products may occur in the catalyst Zone 12, tion to overcoming the reaction equilibrium by removal of
and the reactions may occur in the vapor and/or liquid phase. products through the concurrent distillation within the col
While not intending to be limited by theory, it is believed umn 10.
that the dehydrogenative dimerization of ethanol to ethyl 45 In an embodiment, the systems and methods may also
acetate may occur over the dehydrogenation and dimeriza include hydrogenating contaminants or reaction byproducts
tion catalysts described herein in the liquid phase. It has not in the bottoms stream or in the reacted fluid after it has
been previously recognized that the dehydrogenation and passed over the dehydrogenation catalyst and separating the
dimerization conversion of ethanol to ethyl acetate would hydrogenated contaminants or byproducts from the ethyl
occur in the liquid phase. The use of a liquid phase reaction 50 acetate. As noted above, aldehydes and/or ketones such as
may allow for reactive distillation to be effectively used for n-butyraldehyde and butan-2-one may be produced as
converting ethanol into ethyl acetate and hydrogen. Specific byproducts in the reaction. These byproducts boil at tem
catalysts useful in the reactive distillation systems and peratures close to the boiling point of ethyl acetate and may
methods disclosed herein are discussed in more detail below. be difficult to separate from ethyl acetate. FIG. 4 shows a
Ethyl acetate and hydrogen are produced due to the reaction 55 process schematic where the bottoms product 22 from the
over the dehydrogenation and dimerization catalyst. reactive distillation column 10 illustrated in FIG. 3 is sent to
Byproducts including, but not limited to, aldehydes, such as a hydrogenation reactor 24 comprising a hydrogenation
acetaldehyde, n-butyraldehyde, and/or crotonaldehyde: catalyst 26 with a hydrogen co-feed 28. Suitable hydroge
ethers, such as ethyl ether and n-butyl ether; ethyl acetate; nation catalyst(s) may comprise various components and are
ketones such as 2-butanone, acetone; and other alcohols, 60 described in more detail herein. At least a portion of the
Such as isobutanol, 2-butanol, 2-ethylbutanol, n-hexanol, n-butyraldehyde and/or butan-2-one impurities and/or
and/or 2-ethylhexanol may also be produced during the byproducts can be hydrogenated and can then be separated
reaction. The removal of the overhead stream 19 comprising using a separator 32. The separator 32 may comprise any of
hydrogen, which may occur by flashing, increases the extent the types of separators described herein with respect to the
of reaction. In general, the hydrogen concentration increases 65 reactive distillation system. Alternatively or in addition to
from the middle part of the column towards the top of the the separators already described, the separator 32 may be a
column. At pressures of about 13 bar or lower, as ethyl phase separator, which is a vessel that separates an inlet
 US 9,447,018 B2
11 12
stream into a Substantially vapor stream and a Substantially embodiment, the ethanol feed 46 and the hydrogen feed 48
liquid stream, Such as a knock-out drum, flash drum, are separated Sufficiently to allow byproduct hydrogenation
reboiler, condenser, or other heat exchanger. Such vessels to be substantially completed before hydrogen from the feed
also may have some internal baffles, temperature control reaches Substantial concentrations of ethanol being dehy
elements, and/or pressure control elements, but generally drogenated. Ethanol reacts over the catalyst producing ethyl
lack any trays or other type of complex internal structure acetate and hydrogen. Examples of Suitable dehydrogena
commonly found in columns. The separator also may be any tion and dimerization catalysts are described in more detail
other type of separator, such as a membrane separator. In a herein.
specific embodiment, the separator is a knockout drum. Due to boiling point differences, hydrogen moves towards
Finally, the separator may be any combination of the afore 10 the top of the column 40 and ethyl acetate moves towards the
mentioned separators arranged in series, in parallel, or bottom of the column 40. Acetaldehyde may be produced
combinations thereof. In an embodiment, separator 32 com during the reaction and may move up in the column 40. At
prises a distillation column. The outlet of the hydrogenation least a portion of the acetaldehyde, if present, can be
reactor 24 may be passed through a heat exchanger 30 (e.g., condensed in condenser 54 (e.g., a partial condenser, or a
a condenser) and cooled before entering the separator 32. 15 total condenser), passed through reflux tank 56, and recycled
The heat exchanger 30 may be any equipment suitable for back to column 40 as reflux. A product stream 59 comprising
heating or cooling one stream using another stream. Gen hydrogen is taken out as distillate from the reflux tank 56. A
erally, the heat exchanger 30 is a relatively simple device part of the bottom draw is taken out as the ethyl acetate
that allows heat to be exchanged between two fluids without product stream 58, while the remaining part is passed
the fluids directly contacting each other. Examples of Suit through reboiler 60 to be recycled to the column 40. In an
able heat exchangers 30 include, but are not limited to, shell embodiment, the bottom draw may be passed through a
and tube heat exchangers, double pipe heat exchangers, plate reboiler (e.g., similar to reboiler 60) and optionally passed to
fin heat exchangers, bayonet heat exchangers, reboilers, a separator where the vapor portion may pass to the column
condensers, evaporators, and air coolers. In the case of air 40 while at least a portion of the remainder is taken out as
coolers, one of the fluids comprises atmospheric air, which 25 the ethyl acetate product stream 58. The stream passing
may be forced over tubes or coils using one or more fans. through the reboiler 60 provides the evaporation effect and
The bottoms product stream 36 from the separator 32 may vapor flow for operating the column 40. The product stream
comprise ethyl acetate and may have a purity of greater than 58 may comprise the ethyl acetate produced in the column
about 90%, greater than about 95%, greater than about 96%, along with unreacted ethanol and potentially any side prod
greater than about 97%, greater than about 98%, greater than 30 ucts produced by the reaction.
about 99%, or greater than about 99.5% ethyl acetate by Byproducts Such as n-butyraldehyde and butan-2-one
weight. Unconverted hydrogen and the hydrogenated produced in the reaction may have boiling points close to the
byproducts may be removed as an overhead product 34, and boiling point of ethyl acetate. The lower hydrogen feed 48
may be used, for example, as fuel or a feed to one or more is useful in hydrogenating the by-products to produce com
processes. In an embodiment, the separator 32 may be 35 ponents that can be separated easily from ethyl acetate. The
operated between a pressure of 1 atm and 80 atm. ratio of the hydrogen feed to the ethanol feed can benefi
In an embodiment, the bottoms product stream 36 may cially be adjusted to minimize the amount of close boiling
pass to another separator. The separator may then separate byproducts, while not excessively reducing ethyl acetate to
the bottoms product stream into an ethyl acetate stream and ethanol. In an embodiment, the molar ratio of ethanol to
a byproduct stream comprising one or more heavier hydro 40 hydrogen ranges from about 1:10 to about 1000:1, e.g., from
genation products produced in the hydrogenation reactor 26. about 1:10 to about 1:1, from about 1:1 to about 5:1, from
This separation scheme may allow the resulting ethyl acetate about 1:1 to about 10:1, from about 5:1 to about 25:1, from
stream to have a purity of greater than about 90%, greater about 5:1 to about 50:1, from about 10:1 to about 50:1, from
than about 95%, greater than about 96%, greater than about about 10:1 to about 100:1, from about 50:1 to about 200:1,
97%, greater than about 98%, greater than about 99%, or 45 from about 50:1 to about 400:1, from about 100:1 to about
greater than about 99.5% ethyl acetate by weight. 500:1, from about 100:1 to about 1000:1, from about 200:1
In another embodiment of the invention, the reactive to about 1000:1, or from about 500:1 to about 1000:1.
distillation column has two feeds. Ethanol may be fed to the Hydrogen product from the reaction leaves at the top of the
upper part of the column (upper feed), and hydrogen may be column. In an embodiment, the column 40 may operate at
fed to the lower part of the column (lower feed). A schematic 50 any of the conditions (e.g., operating pressure, operating
for the double feed reactive distillation column is schemati temperature, etc.) discussed herein with respect to column
cally illustrated in FIG. 5. This system includes column 40 10 in FIG. 3. In addition, the column 40 may have any
containing catalyst 42 in catalyst Zone 44, and commonly number of stages, and in an embodiment, the column 40 may
may include a top stage or non-reactive rectifying section 50 have a number of stages as described with respect to column
and a bottom stage or non-reactive stripping section 52. In 55 10 in FIG. 3.
the illustrated system, ethanol feed 46 is delivered at or near As schematically illustrated in FIG. 6, the reactive distil
the top of the catalyst Zone 44, and the hydrogen feed 48 is lation column 70 has two feeds 80, 82 and uses two catalyst
delivered at or near the bottom of catalyst Zone 44. It should Zones, identified as an upper Zone 72 containing Catalyst A
be recognized columns can be designed with the ethanol 74 and a lower catalyst Zone 76 containing Catalyst B 78.
feed 46 location in other locations, e.g., within the catalyst 60 Ethanol feed 80 is fed to the upper part of the column 70
Zone 44 but above the hydrogen feed 48, such as from the (upper feed). Hydrogen feed 82 is fed to the lower part of the
approximate middle of the catalyst Zone 44 to the top of the column 70 (lower feed). The molar ratio of ethanol to
column 40. Similarly, columns with the hydrogen feed 48 in hydrogen may fall within any of the ranges described above
other locations can also be designed, e.g., with the hydrogen with respect to FIG. 5 (e.g., from about 1:10 to about 1000:1,
feed 48 from the approximate middle of the catalyst Zone 44 65 and all Sub-ranges). Ethanol may react over the upper
to the bottom of the column 40 or even higher within the catalyst (Catalyst A 74) producing ethyl acetate and hydro
catalyst Zone 44 but below the ethanol feed 46. In an gen. Examples of Suitable upper catalysts are described in
 US 9,447,018 B2
13 14
more detail herein with respect to the dehydrogenation and of the side reactors. In this embodiment, the column may not
dimerization catalysts. As with previous schematic designs contain a dehydrogenation catalyst, or in Some embodi
shown, the column 70 will usually include a top stage or ments, any catalyst at all.
non-reactive rectifying section 71 and a bottom state or Schematics for a side reactor reactive distillation column
non-reactive stripping section 79. with a single catalyst are shown in FIG. 7. A single side
Due to boiling point differences, hydrogen moves towards reactor is shown, however, multiple side reactors along the
the top of the column 70 and ethyl acetate moves towards the length of the reactive distillation column can be used. FIG.
bottom of the column 70. Acetaldehyde may be produced 7(a) shows a configuration where the feed 93 to the side
during the reaction and may move up in the column 70. At reactor 94 is bottom up and vapor phase. The outlet from
least a portion of the acetaldehyde, if present, can be 10 side reactor 94 is stream 95 which is sent back to the
condensed in condenser 84 and recycled back to the reaction distillation column 40 at any location in the column 40
Zone through reflux tank 86. Byproducts such as n-butyral above the location of feed 93. FIG. 7(b) shows a configu
dehyde and butan-2-one produced in the reaction can have ration where the feed 96 to the side reactor 97 is top down
boiling points close to the boiling point of ethyl acetate. The and liquid phase. The outlet from side reactor 97 is stream
lower hydrogen feed is useful in hydrogenating the by 15 98 which is sent back to the distillation column 40 at any
products over the lower catalyst (Catalyst B) to produce location in the column 40 below the location offeed 96. The
components that can be separated easily from ethyl acetate. side reactors 94 and 97 each contain catalyst for converting
Examples of hydrogenation catalysts (Catalyst B) are ethanol into ethyl acetate. Examples of suitable catalysts are
described in more detail herein. A product stream 88 com described in more detail herein.
prising hydrogen from the reaction leaves at the top of the The use of a side reactor using a liquid feed may allow for
column 70. A portion of the bottom draw is taken out as the the reaction to occur in the liquid phase. While not intending
ethyl acetate product stream 92, while the remaining portion to be limited by theory, it is believed that the dehydrogena
is passed through reboiler 90 to be recycled to the column tive dimerization of ethanol to ethyl acetate may occur over
70. In an embodiment, the bottom draw may be passed the dehydrogenation and dimerization catalysts described
through a reboiler (e.g., similar to reboiler 90) and optionally 25 herein in the liquid phase. As noted above, it has not been
passed to a separator where the vapor portion may pass to previously recognized that the dehydrogenation and
the column 70 while at least a portion of the remainder is dimerization conversion of ethanol to ethyl acetate would
taken out as the ethyl acetate product stream 92. The stream occur in the liquid phase. The use of a liquid phase reaction
passing through the reboiler 90 provides the evaporation may allow for reactive distillation to be effectively used for
effect and vapor flow for operating the column 70. The 30 converting ethanol into ethyl acetate and hydrogen.
product stream 92 may comprise the ethyl acetate produced While illustrated as a bottom up vapor phase design and
in the column along with unreacted ethanol and potentially a top down liquid phase design in FIGS. 7(a) and 7(b), the
any side products produced by the reaction. Subsequent side reactors 94, 97 may also operate bottom up using a
purification of product stream 92 comprising ethyl acetate liquid phase draw from the column 40 and top down using
may be needed to remove the hydrogenated byproducts from 35 a vapor phase draw from the column with the appropriate
the ethyl acetate, e.g., using a separator Such as that as equipment such as pumps, compressors, Valves, piping, etc.
shown in FIG. 4 as separator 32, which in an embodiment In an embodiment, the side reactors 94, 97 may be imple
may comprise a distillation column. mented as a single reactor vessel, or as a plurality of reactor
In an embodiment, the column 70 may operate at any of vessels arranged in series and/or parallel. In an embodiment,
the conditions (e.g., operating pressure, operating tempera 40 a plurality of side reactors may be implemented as shown in
ture, etc.) discussed herein with respect to column 10 in FIG. FIGS. 7(a) and 7(b) along the length of the column as
3. In addition, the column 70 may have any number of needed. In addition, the catalyst in both the column 40 and
stages, and in an embodiment have any number of stages as the side reactor 94 may convert ethanol into ethyl acetate,
described with respect to column 10 in FIG. 3. though the specific catalysts (e.g., catalyst compositions,
In the dual feed systems described above with respect to 45 catalyst forms, and/or catalyst component loadings) in each
FIGS. 5 and 6, the hydrogen feed should be at a sufficiently of the column 40 and the side reactor 94.97 may be the same
low level that it does not significantly adversely affect the or different. Suitable catalysts for converting ethanol into
dehydrogenation of ethanol in the Zone above, while being ethyl acetate may be selected based on the expected oper
effective to hydrogenate the undesirable close boiling point ating conditions, which may vary between the column 40
byproducts. Feed rates of hydrogen can be adjusted empiri 50 and the side reactor 94, 97.
cally to optimize this balance. Commonly, the ratio of Schematics for a side reactor reactive distillation with two
ethanol: hydrogen will be in a range of about 500:1 to 1:1 feeds and using two distinct catalyst Zones are shown in FIG.
molar ratio, more commonly about 500:1 to 10:1 or 500:1 to 8. A single side reactor is shown for each catalyst Zone in the
100:1. reactive distillation column 70, however, multiple side reac
In an embodiment, side reactors can be connected to a 55 tors along the length of the reactive distillation column 70
reactive distillation column to increase the catalyst holdup can be used for each catalyst Zone. FIG. 8 (a) shows a
for improved reactant conversion. In the side reactor configuration where the top Zone feed 99 to the side reactor
embodiment, the side reactor feed is withdrawn from the 100 is bottom up and vapor phase. The bottom Zone feed 102
distillation column and the reactor effluent is returned back to another side reactor 103 is also bottom up and vapor
to the same column. An adequate amount of catalyst may be 60 phase. The outlet from side reactor 100 is stream 101 which
arranged in a side reactor system where traditional reactor is sent back to the distillation column at any location in the
types and catalyst structures can be used. Also, the reaction column above the location of feed 99. The outlet from side
conditions within the side reactor Such as temperature can be reactor 103 is stream 104 which is sent back to the distill
adjusted independently of those prevailing in the distillation lation column at any location in the column above the
column by appropriate heat exchange. In some embodi 65 location offeed 102. FIG. 8 (b) shows a configuration where
ments, only the side reactor may comprise one or more the top Zone feed 105 to the side reactor 106 is top down and
catalysts, and the column may operate to separate the outlet liquid phase. The bottom Zone feed 108 to another side
 US 9,447,018 B2
15 16
reactor 109 is also top down and liquid phase. The outlet comprising ethyl acetate, and a stream 218 predominantly
from side reactor 106 is stream 107 which is sent back to the comprising the impurities removed from the ethyl acetate. In
distillation column at any location in the column below the Some embodiments, the product stream 216 may undergo
location of feed 105. The outlet from side reactor 109 is further processing to remove one or more impurities. For
stream 110 which is sent back to the distillation column at example, an optional dehydration process may be carried out
any location in the column below the location of feed 108. to remove any water present in the product stream 216.
Examples of suitable catalysts for side reactors 100 and 106 As schematically illustrated in FIG. 9, a system 200 for
may include any of the dehydrogenation and dimerization producing ethyl acetate may comprise a feed stream 202
catalysts described in more detail herein. Examples of comprising ethanol that can be fed to the reactive distillation
hydrogenation catalysts for side reactors 103 and 109 10 system 206. In an embodiment, the reactive distillation
include any of the hydrogenation catalysts described in more system 206 may comprise any of the reactive distillation
detail herein. systems described with respect to FIG. 3-8 herein. The
While illustrated as a bottom up vapor phase design and reactive distillation system may produce an overhead prod
a top down liquid phase design in FIGS. 8(a) and 8(b), the uct stream 208 and a bottoms product stream 210. The
side reactors 100, 103, 106, 109 may also operate bottom up 15 overhead product stream 208 may comprise hydrogen along
using a liquid phase draw from the column 70 and top down with trace amounts of other light components (e.g., ethanol,
using a vapor phase draw from the column 70 with the etc.) and may generally correspond to any of the streams 19,
appropriate equipment such as pumps, compressors, valves, 59, and/or 88 as illustrated in FIGS. 3-8. Similarly, the
piping, etc. In an embodiment, the side reactors 100, 103. bottoms product stream 210 may comprise ethyl acetate, at
106, 109 may be implemented as a single reactor vessel, or least a portion of any unreacted ethanol, and/or additional
as a plurality of reactor vessels arranged in series and/or reaction products (e.g., byproducts, impurities, etc.), and the
parallel. In an embodiment, a plurality of side reactors may bottoms product stream 210 may generally correspond to
be implemented as shown in FIGS. 8(a) and 8(b) along the any of the streams 22, 36, 58, and/or 92 as illustrated in
length of the column as needed. In addition, the respective FIGS. 3-8.
catalysts in the column 70 and/or the side reactors 100, 106 25 A products separation section 212 may receive the bot
may convert ethanol into ethyl acetate, though the specific toms product stream 210 from the reactive distillation sys
catalysts (e.g., catalyst compositions, catalyst forms, and/or tem 206. The products separation section 212 may comprise
catalyst component loadings) in each of the column 40 and any number or type of separation units, which may employ
the side reactors 100, 106 may be the same or different. pressure- or temperature-swing distillation, pressure- or
Suitable catalysts for converting ethanol into ethyl acetate 30 temperature-swing adsorption, membrane-based separation,
may be selected based on the expected operating conditions, cryogenic distillation, extraction, and/or any other Suitable
which may vary between the column 40 and the side reactors separation technology, all of which may be used to generate
100, 106. Similarly, the respective catalysts in the column 70 a desired product distribution. The products separation sec
and/or the side reactors 103, 109 may comprise hydrogena tion 212 may generally produce an ethyl acetate product
tion catalysts, though the specific catalysts (e.g., catalyst 35 stream 216. The ethyl acetate product stream 216 may
compositions, catalyst forms, and/or catalyst component comprise ethyl acetate having a purity of greater than about
loadings) in each of the column 70 and the side reactors 103. 90%, greater than about 95%, greater than about 96%,
109 may be the same or different. Suitable hydrogenation greater than about 97%, greater than about 98%, greater than
catalysts may be selected based on the expected operating about 99%, or greater than about 99.5% ethyl acetate by
conditions, which may vary between the column 70 and the 40 weight. In addition to the ethyl acetate product stream 216,
side reactors 100, 106. one or more additional streams may be produced by the
As schematically illustrated in FIG. 9, an ethyl acetate products separation section 212. In an embodiment, an
production system 200 may comprise a products separation impurities stream 218 may be produced. The impurities
and/or purification section 212 for use in removing a portion stream 218 may comprise one or more reaction products
of any byproducts or impurities from the product stream. In 45 (e.g., butanol, one or more aldehydes and/or ketones, etc.).
Some embodiments, the ethyl acetate product stream pro Each of the potential product streams 216, 218 may exit the
duced in the processes and systems described herein may system as separate product streams and/or exit the system
comprise one or more impurities. In some embodiments, the 200 for use as fuel and/or as a feed to additional downstream
ethyl acetate product stream produced in the reactive distil processes. While illustrated as separate streams 216, 218 one
lation systems described with respect to FIG. 3-8 may 50 or more of these streams may exit the system 200 as a
comprise less than about 10 wt.%, less than about 8 wt.%. combined product stream.
less than about 6 wt.%, less than about 4 wt.%, less than In an embodiment as shown in FIG. 10, the separation
about 2 wt.%, or less than about 1.5 wt.% impurities, and section 212 may comprise an extraction process 300 for
in some embodiments, more than about 0.01 wt.%, more removing a portion of the impurities in the product stream
than about 0.1 wt.%, more than about 0.5 wt.%, or more 55 210. For example, an extraction process 300 may be used to
than about 1 wt.%. The products separation section 212 may separate at least a portion of one or more byproducts from
be configured to provide at least one product stream 216 the ethyl acetate in the product stream 210, thereby improv
comprising ethyl acetate having a purity of greater than ing the quality and value of the ethyl acetate product stream.
about 90%, greater than about 95%, greater than about 96%, In this embodiment, the separation section 212 used to carry
greater than about 97%, greater than about 98%, greater than 60 out the extraction process 300 may be the same or similar to
about 99%, or greater than about 99.5% ethyl acetate by the separation section described above with respect to FIG.
weight. At least one additional stream 218 may be produced 9. The extraction process 300 generally comprises an extrac
comprising the remaining components of the product stream tion section 250 in which the product stream 210 is con
210 from the ethyl acetate production process 206 (e.g., a tacted with a solvent in a solvent stream 254 to transfer or
reactive distillation column as described above). In an 65 remove at least a portion of the impurities from the product.
embodiment, a plurality of streams can be produced in the The extract stream 256 comprising the impurities transferred
separation section comprising a stream 216 predominantly from the product can then be regenerated in a stripping
 US 9,447,018 B2
17 18
section 252, which generally involves separating the impu impurities stream 218 and/or vapor impurities stream 262
rities from the solvent to allow the impurities to be removed may exit the system for various downstream uses. In an
from the system and the solvent to be recycled. embodiment, the impurities stream may comprise commer
The extraction process 300 may receive the bottoms cially valuable chemicals that can be transferred for sale. In
product stream 210 from a reactive distillation system, Some embodiments, the impurities may be further separated
which may comprise any of the reactive distillation systems before being sold, or alternatively, the impurities can be used
described with respect to FIG. 3-8 herein. The extraction as fuel or any other suitable use.
process 300 may comprise the extraction section 250 in When used with the ethyl acetate production systems and
which the bottoms product stream 210 is contacted with a processes describe herein, the solvent used in the extraction
solvent in a solvent stream 254. In an embodiment, the 10 process 300 may be selected to remove the expected impu
extraction section 250 comprises a liquid-liquid contact rities within the ethyl acetate product stream (e.g., bottoms
vessel suitable for contacting two liquid streams. Suitable product stream 210). As noted above, the synthesis of ethyl
vessels and extraction section 250 configurations are acetate by consecutive dehydrogenation and condensation of
described in more detail herein. The solvent may draw a ethanol to ethyl acetate is accompanied by the formation of
portion of one or more impurities from the bottoms product 15 relatively small amounts of byproducts. At least a portion of
stream 210 into the solvent phase. The bottoms product the byproducts comprising various aldehydes, ketones, and
stream 210 having the portion of the impurities removed the like can be removed to improve the quality and purity of
may then exit the extraction section 250 as a purified product the ethyl acetate. In an embodiment, the extraction process
stream 216. The extract comprising the solvent and the 300 can be used to selectively extract at least a portion of the
portion of the impurity compound transferred from the byproducts that may be present in the ethyl acetate. In an
bottoms product stream 210 may then exit the extraction embodiment, the solvent may be configured to selectively
section 250 as an extract stream 256. react with and extract the impurities in the ethyl acetate. For
An optional drying section 258 may serve to remove any example, the solvent may comprise one or compounds
remaining solvent or a component of a solvent (e.g., water configured to reversibly react with the impurities, thereby
from an aqueous solvent) from the purified product stream 25 allowing the reaction to remove the impurities from the ethyl
216. The resulting dried purified product stream 260 may acetate in the extraction section 250 and then be reversed to
then leave the system as the final product stream. Any release the impurities in the Stripping section 252.
Suitable drying units may be used to remove at least a In an embodiment, the solvent may comprise a fluid
portion of the solvent from the purified product stream 216. comprising one or more extracting agents. In an embodi
Suitable drying units may include, but are not limited to, 30 ment, the extracting agent may comprise a nucleophilic
industrial dehydration units comprising adsorbents such as compound that can react with aldehydes and/or ketones to
Zeolites, alumina, Silica, and other drying agents arranged in form a corresponding adduct. The resulting reaction prod
a pressure and/or temperature Swing configuration, and/or ucts may have an increased solubility in the aqueous fluid,
liquid absorption (e.g., liquid-liquid extraction, gas-liquid thereby allowing the adducts to leave the ethyl acetate
extraction, etc.) using a drying agent. The purified product 35 product stream 210 and enter the solvent stream 254 to form
stream 216 and/or the dried purified product stream 260 may the extract stream 256. Within the stripping section 252, the
comprise ethyl acetate having a purity of greater than about adduct equilibrium may be shifted to release the extracting
90%, greater than about 95%, greater than about 96%, agents from the impurities. The impurities may then be
greater than about 97%, greater than about 98%, greater than separated from the solvent comprising the extracting agents
about 99%, or greater than about 99.5% ethyl acetate by 40 using any suitable separation technique such as vaporization
weight. and/or liquid-liquid separation.
In order to separate the impurities from the solvent, the Various extracting agents can be used in the aqueous
extract stream 256 may be transferred to a stripping section Solvent. In an embodiment, the extracting agents can com
252. In an embodiment, the impurities may be removed prise Sulfur and/or nitrogen. Suitable extracting agents can
using vapor-liquid stripping, heating, liquid-liquid phase 45 include, but are not limited to, hydrazine (NH), hydrox
separation, flashing and/or distillation, and/or any other ylamine (NH-OH), semicarbazide (HNNH(C=O)NH),
Suitable technique. Suitable vessels and stripping section phenylhydrazine (CH-NH), phenylhydroxylamine
252 configurations are described in more detail herein. As (CHNHOH), sodium hydrogen sulfite (NaHSO/
shown in FIG. 10, the stripping section 252 may result in the NaSOs), sodium sulfite (NaSO), salts thereof, aqueous
separation of the impurities from the extract stream 256, 50 solutions thereof, and any combinations thereof. While any
thereby producing a liquid impurities stream 218 and/or a of these extracting agents can be used, reference will be
vapor impurities stream 262, and a regenerate solvent stream made to sodium hydrogen Sulfite in the following discussion
254. In some embodiments, different components of the as an example.
impurities may leave the separation section 212 as either a In an embodiment, an aqueous solution of sodium hydro
vapor or a liquid, including those generated by the solvent 55 gen sulfite (which can also be referred to as sodium bisulfite)
and/or any reactions within the separation section 212. The can be used as the solvent in the extraction process 300.
Solvent may be regenerated by removing at least a portion of Sodium hydrogen sulfite can be sourced as a Solid, which
the impurities in the stripping section 252. In some embodi usually comprises a mixture of NaHSO and NaSOs. An
ments, only a portion of any extracted impurities can be aqueous solution can be made from the salt, and the use of
removed in the stripping section 252, and the resulting 60 an aqueous solution of sodium hydrogen sulfite provides an
regenerated solvent stream 254 may comprise a minor inexpensive, low toxicity Solution that can serve as the
amount of impurities. The regenerated solvent stream 254 Solvent in the extraction process. Additional extracting
may be recycled to the extraction section 250 to serve as the agents can include sodium sulfite (NaSO). Sodium sulfite
Solvent. In some embodiments, a new solvent stream (e.g., can be used by directly dissolving Sodium Sulfite in a
a makeup solvent stream) may enter the extraction section 65 solvent, or sodium hydroxide (NaOH) can be added to
separately or with the regenerated solvent stream 254 to Sodium hydrogen Sulfite as a Solid or in Solution. Further a
serve as the solvent in the extraction section 250. The liquid mixture of Sodium hydrogen Sulfite and Sodium sulfite can
 US 9,447,018 B2
19 20
be used in an ratio. The reactive moiety in the aqueous is provided as Sodium sulfite heptahydrate. The concentra
solution of sodium hydrogen sulfite is the hydrosulfite ion tion of the extracting agent may vary based on the compo
(HSO/SOs) and reactive moiety in an aqueous solution sition of the extracting agent, the form in which it is
of sodium sulfite is the sulfite ion (SO). Thus any soluble provided, the temperature of the solution, the composition of
hydrosulfite and/or Sulfite compound can also be used in the solution, and the like.
similar manner regardless of the counter ion. For example With respect to the temperature at which the extraction
hydrosulfite compounds including K", NH.' salts can also process takes place, it has been discovered that the extrac
be used along with or in place of sodium hydrogen Sulfite. tion efficiency of the impurities in the ethyl acetate with the
The aqueous Solution comprising the hydrosulfite ion aqueous solvent generally increases at a lower temperature
reacts reversibly with aldehydes and ketones such as 2-bu 10 relative to a higher temperature extraction. Accordingly,
tanone, acetone, acetaldehyde, thereby rendering them more lowering the temperature of the extraction process may
water soluble as sodium salts of hydrosulfite adducts of the result in a greater amount of the impurities being transferred
corresponding compounds. For example, the following reac from the ethyl acetate product to the solvent stream. In
tion may take place when the aqueous solution comprising general, the extraction section 250 may operate within a
the hydrosulfite ion is contacted with a fluid comprising a 15 temperature of between about 10° C. to about 70° C., from
ketone (e.g., 2-butanone) as follows: about 15° C. to about 60° C., or from about 20° C. to about
500 C.
Once the aqueous solvent contacts the ethyl acetate prod
uct stream (e.g., bottoms product stream 210) in the extrac
The resulting sodium salt of the 2-butanone sulfonate adduct tion step 250, the aqueous fluid comprising the adducts can
has higher solubility in water compared to ethyl acetate thus be separated from the organic ethyl acetate phase using
leading to partial extraction of 2-butanone from the organic liquid-liquid separation. The separated extract stream 256
(ethyl acetate) phase, thereby increasing the ethyl acetate can then be used to perform an additional extraction of
phase purity. The resulting adduct may be formed by various impurities from an ethyl acetate product stream and/or the
aldehydes and/or ketones, thereby providing for the ability 25 extract can be transferred to the stripping section 252 for
to selectively improve the removal efficiency of the impu regeneration. In general, the extract stream 256 comprising
rities generated in the ethyl acetate production process the adducts can be treated in the stripping section 252 to
during the extraction section 250. separate the organic compounds (e.g., the impurities, any
Within the extraction process 300, various factors may dissolved ethyl acetate, etc.) from the aqueous solvent
affect the extraction efficiency of the solvent within the 30 comprising the extracting agent. For example, the extract
extraction section 250 including the concentration of the stream may be heated to reverse the adduct formation, and
extracting agent in the solvent, the ratio of the solvent to the the organic phase can then be separated from the aqueous
ethyl acetate product, and the temperature at which the Solution. In some embodiments, the adducts may be sepa
extraction takes place. With respect to the concentration of rated by crystallization followed by a subsequent treatment
the extracting agent in the solvent, there are several consid 35 of the precipitated solids.
erations that can have an affect on the concentration of the When the adducts remains dissolved in the aqueous fluid,
compound in the solvent. In general, a higher concentration the adducts can be decomposed by heating to reverse the
of the extracting agent (e.g., NaHSO) in the aqueous fluid equilibrium and release the impurities (e.g., the aldehydes/
can reduces the ethyl acetate solubility in the solution. ketones) while regenerating the aqueous solution compris
However, as the concentration of the extracting agent rises 40 ing the extracting agent for reuse. The impurities can then be
above a certain amount, the resulting adduct may precipitate separated using evaporation, distillation, and/or liquid-liquid
out of solution. Such precipitation may complicate a con phase separation. In an embodiment, the aqueous Solution
tinuous process in terms of Solids handling equipment. In (e.g., the extract stream 256) may comprise the excess of
general, the amount of the extracting agent in the aqueous Sodium hydrogen Sulfite, the dissolved sodium hydrogen
fluid should be sufficient to provide an excess of the ions in 45 Sulfite adducts, and some amount dissolved ethyl acetate.
Solution but less than an amount that would result in The Solution can be regenerated by heating the solution to a
precipitation of the resulting adduct in the extract, which temperature Suitable to reverse the adduct formation equi
indicates that the solubility limit of the adduct has been librium. In an embodiment in which the nucleophile com
reached. Thus, the concentration of the extracting agent in pound comprises Sodium hydrogen Sulfite, the regeneration
the solvent may vary based on the concentration of the 50 can be achieved by heating the Solution to a temperature
impurities in the ethyl acetate product stream. In an embodi between about 45° C. and about 100° C. At this temperature,
ment, the concentration of the extracting agent (e.g., sodium the sodium hydrogen sulfite adduct decomposes to release
hydrogen sulfite) in the aqueous solution can vary. In an the impurities and the NaHSO. The released impurities and
embodiment, the extracting agent can comprise sodium any dissolved ethyl acetate can be separated from the
hydrogen Sulfite, and the amount of sodium hydrogen Sulfite 55 aqueous solution and collected. In some embodiments, the
in the aqueous solution can vary and may generally range organic compounds can be vaporized (e.g., in a flash tank)
from about 50 grams to about 420 grams, from about 300 or distilled from the aqueous solution, and/or alternatively
grams to about 420 grams of Solid (e.g., a mixture of the organic compounds can be separated based on a liquid
NaHSO and NaSOs) per liter of water. When the extract liquid phase separation. The remaining aqueous solution
ing agent is sodium hydrogen sulfite, the concentration may 60 may comprise the regenerated solvent for use in the extrac
generally range from about 5 to about 42 grams per 100 tion process 300. In an embodiment, the separation process
milliliters of solution, or from about 30 to about 42 grams within the Stripping section 252 may result in Some minor
per 100 milliliters of solution at about 68° F (about 20° C.). amount of the organic compounds remaining in the aqueous
In an embodiment, the extracting agent may be provided in solvent.
the form of sodium sulfite and/or a hydrate thereof, and the 65 During the heating process Some amount of the extracting
concentration may generally range from about 5 to about 68 agent may decompose to form an additional impurity. For
grams per 100 milliliters of solution when the sodium sulfite example, when the extracting agent comprises sodium
 US 9,447,018 B2
21 22
hydrogen Sulfite, heating may result in some Sulfur dioxide between about 1 to about 50 stages. The contact device or
being lost due to decomposition. The decomposition prod contact devices may operate at any suitable pressure. In an
ucts can be captured using an aqueous NaHSO Solution or embodiment, the contact device may operate at a pressure
an aqueous caustic solution (e.g., NaOH), which may be ranging from about 1 atm to about 80 atm, and a temperature
advantageous in preventing the release of the decomposition 5 of between about 10° C. to about 70° C., from about 15° C.
products to the atmosphere. The regenerated solvent solu to about 60° C., or from about 20° C. to about 50° C.
tion in the stream 354 may have higher or lower extracting Within the extraction section 302, at least a portion of the
agent concentration than desired. The concentration may be impurities may be transferred to the solvent. In an embodi
adjusted through the addition of water, Solid extracting ment, the extracting agent may react with a portion of the
agent, or an extracting agent solution until the desired 10 impurities in the product stream 310 to form an adduct and
concentration is reached. improve the solubility of the impurity in the solvent phase.
In some embodiments, the adducts can be removed from Once the product stream 310 and the solvent stream 319
the extract stream 256 by crystallization. For example, the have been contacted and separated within the extraction
adducts can be separated from the extract stream 256 by section 302, a purified product stream 216 and an extract
forming a sodium ketone/aldehyde hydrosulfite adduct crys 15 stream 256 may exit the extraction section 302. The purified
tals. If the adducts are crystallized out of solution, the product stream 216 may have an increased purity of ethyl
resulting crystals can be separated physically. The crystals acetate relative to the entering product stream 310. As
can then be heated to reverse the adduct formation. In an described above, the purified product stream 216 may pass
embodiment, the crystals may be dissolved in an aqueous to a drying unit to further remove any solvent to further
solution prior to heating to reverse the adduct formation. The purify the purified product stream. In an embodiment, the
resulting organic impurities can then be separated from the purified product stream 216 and/or a dried, purified product
extracting agent and any aqueous Solution. stream may comprise ethyl acetate having a purity of greater
The extraction process can be carried out using various than about 90%, greater than about 95%, greater than about
configurations and designs. An embodiment of an extraction 96%, greater than about 97%, greater than about 98%,
process 350 is schematically illustrated in FIG. 11. In this 25 greater than about 99%, or greater than about 99.5% ethyl
embodiment, a product stream 310 is fed to the extraction acetate by weight.
section 302. The product stream may generally correspond The extract stream 256 may comprise the solvent and the
to any of the streams 22, 36, 58, and/or 92 as illustrated in impurities removed from the product stream 310. The
FIGS. 3-8. The product stream 310 may predominantly extract stream 256 may pass to the stripping section 304. In
comprise ethyl acetate, though various byproducts including 30 an embodiment, the extract stream 256 may comprise a
ketones and/or aldehydes such as 2-butanone, acetone, and/ solvent fluid, the adducts formed by the reaction between the
or acetaldehyde may also be present. extracting agent and the impurities, any excess extracting
The extraction section 302 may also receive a solvent agent, and potentially some amount of dissolved ethyl
stream 319. In an embodiment, the solvent stream 319 may acetate. The stripping section 304 may comprise one or more
comprise an aqueous fluid and an extracting agent as 35 separation devices configured to separate the impurities
described above. The solvent comprising the extracting from the Solvent and any extracting agent. Various separa
agent may comprise an aqueous solution of hydrazine tion devices can be used including phase separators and
(NH), hydroxylamine (NH-OH), semicarbazide (HNNH liquid-liquid separators. In an embodiment, the separation
(C=O)NH), phenylhydrazine (CH-NH), phenylhydrox device within the stripping section 304 may comprise a flash
ylamine (CHNHOH), sodium hydrogen sulfite (NaHSO/ 40 tank. In this embodiment, the extract stream 256 may enter
Na2SOs), sodium sulfite (Na2SOs), salts thereof, aqueous the flash tank, be heated to a temperature sufficient to
solutions thereof, and any combination thereof. Additional dissociate the adduct, and evaporate at least a portion of any
Solvents useful with the extraction process can include impurities and dissolved ethyl acetate. The flash tank may
dichloromethane-ethanol and methyl isobutyl ketone operate at a pressure ranging from about 1 atm to about 80
(MIBK). The extraction section 302 may comprise one or 45 atm, and a temperature of between about 70° C. to about
more liquid-liquid contact devices configured to contact the 120° C., or from about 85° C. to about 100° C. In some
two liquid streams 319, 310. Various liquid-liquid contact embodiments, the separation device may comprise a distil
devices can be used including an extraction column, which lation column. The extract stream 256 can be heated within
may comprise packing material (e.g., structured packing, the distillation column to dissociate the adducts into the
random packing, trays, etc.) configured to increase mixing 50 impurities and the extracting agent within the Solvent. The
and the available contact area for mass transfer between the impurities may then be separated by distillation. The distil
two liquids. Additional Suitable structures can include a lation column may comprise about 1 to about 100 stages, or
series of mixer settlers, sieve trays, a Kerr-McGee extractor, about 1 to about 50 stages. The distillation column may
a packed tower, a rotating disk contactor, a Scheibel extrac operate at a pressure ranging from about 1 atm to about 80
tor, a pulsed column, and a centrifugal extractor. The extrac 55 atm. The temperature and pressure may be selected based on
tion may be carried out in a co-current, counter-current, the equilibrium on each stage within the distillation column.
and/or cross-current flow scheme, each of which is described In an embodiment, the temperature within the column may
in more detail below with respect to FIGS. 13, 14, and 15, range from about 50° C. to about 200° C., or from about 70°
respectively. In an embodiment, the extraction section can C. to about 150° C.
comprises a counter-current flow arrangement between the 60 In an embodiment, the stripping section may operate at a
Solvent and product streams. vacuum pressure relative to atmospheric pressure. A lower
A contact device within the extraction section may com operating pressure is generally expected to reduce the tem
prise a number of stages configured to provide the degree of perature at which the solvent can be separated from the
impurity removal from the product stream 310 and/or a impurities when the adducts are dissociated. In an embodi
desired purity of the purified ethyl acetate product stream. In 65 ment, the stripping section may operate at a pressure ranging
an embodiment, the contact device, or a plurality of contact from about 0.001 atm to about 1 atm and at a temperature of
devices, can contain between about 1 to about 100 stages, or between about 45° C. and about 100° C. In general, the
 US 9,447,018 B2
23 24
Solvent and/or extracting agent may break down during the respect to FIG. 11. In the interest of clarity, similar compo
heating process in the Stripping section, potentially releasing nents will not be described. The stripping section 354 may
contaminants into the vapor stream. By operating at a comprise any of the separation devices operating at any of
reduced pressure, and resulting reduced temperature, the rate the operating conditions as described above with respect to
of Solvent and/or extracting agent loss may be reduced. For FIG. 11, and the stripping section 354 can be used with the
example, by lowering the temperature at which the stripping remaining components of the extraction process 350 illus
occurs, the rate at which any hydrosulfite/sulfite in solution trated in FIG. 11. The stripping section 354 differs from the
breaks down to form sulfur dioxide can be reduced or stripping section 304 of FIG. 11 in that a purge gas stream
limited. 364 can be introduced into the stripping section 354, which
When the stripping section 304 comprises a phase sepa 10 can aid in the extraction of the impurities from the solvent
rator, an overhead product stream 306 may exit the stripping Solution. In an embodiment, the purge gas can comprise a
section 304 and pass to a condenser 308. The overhead gas having a boiling point significantly below that of the
stream 306 may comprise the separated impurities, dis impurities, and the purge gas may have a low solubility in
Solved ethyl acetate, and potentially minor amount of water the solvent and/or impurities to aid in separation from the
and decomposition products resulting from a breakdown of 15 Solvent and impurities. The purge gas can include, but is not
the extracting agent. Within the condenser 308, the tempera limited to, nitrogen, oxygen, argon, helium, hydrogen, car
ture of the overhead stream 306 may be reduced to condense bon dioxide, and any combination thereof (e.g., air). The use
the impurities into a liquid, which may leave the condenser of the purge gas may aid in removing the impurities from the
308 as an impurities stream 312. The impurities stream 312 extract stream 256 while maintaining a relatively low strip
may exit the system for sale, for use as fuel, and/or as a feed ping temperature. The use of the low temperature may aid in
to one or more Suitable downstream processes. Any remain limiting or reducing the breakdown of the solvent and/or
ing gases may exit the condenser as an off-gas stream 310. extracting agent, which can potentially resulting the genera
The off-gas stream 310 may comprise a portion of the tion of pollutants.
vaporized impurities, ethyl acetate, and any decomposition The extract stream 256 can be introduced into the strip
products from the solvent. The off-gas stream 310 can be 25 ping section 354 and can include a solvent fluid, the adducts
vented to the atmosphere or a flare, or as shown in FIG. 11, formed by the reaction between the extracting agent and the
recycled to be combined with the regenerated solvent stream impurities, any excess extracting agent, and potentially some
307. The regenerated solvent stream 307 may leave the amount of dissolved ethyl acetate. As the liquid extract
stripping section 304 as a bottoms stream and pass to the stream 256 flows through the Stripping section, a purge gas
contactor 314. The off-gas stream 310 may then be re 30 stream 364 can be introduced into the lower portion of the
absorbed within the contactor 314. The combined regener stripping section 354. The ratio of the purge gas Volumetric
ated solvent stream 254 may pass to a heat exchanger 316, flow rate to the extract stream volumetric flowrate can range
which may comprise any of the types of heat exchangers from about 1,000:1 to about 1:100, and the ratio may be
described herein. The regenerated solvent stream 254 may based on the amount of impurities present in the extract
be cooled within the heat exchanger 316 to a temperature 35 stream, the conditions within the stripping section 354,
suitable to allow the extracting agent within the solvent to and/or the solubility of the impurities in the purge gas. The
form an adducts with any corresponding impurities in the extract stream 256 can be heated to a temperature in the
product stream 310. The cooled, regenerated solvent stream range of about 45° C. to about 100° C. before and/or within
254 may then be combined with an optional solvent make the stripping section 354, resulting in at least a partial
up stream 318 to form the solvent stream 319. The make-up 40 dissociation of the adducts. Vapor-liquid stripping can then
stream may include the solvent comprising the extracting take place between the impurities released from the adducts
agent in any suitable concentration. In an embodiment, the and the purge gas. Since the impurities would generally have
make-up stream may server to adjust the concentration of a lower boiling point than the solvent, the impurities could
the extracting agent within the solvent stream 319 to a expect to be stripped into the purge gas stream.
desired level. 45 The stripping section 354 can have an overhead product
In Some embodiments, the stripping section 304 may stream 356 that can pass to a cooler 358 and into a separator
comprise a liquid-liquid separator. The liquid-liquid sepa 360. The overhead stream 356 may comprise the purge gas,
rator may operate at a pressure ranging from about 1 atm to impurities stripped by the purge gas, and potentially minor
about 80 atm. The extract stream 256 may be heated to a amount of solvent, ethyl acetate, and decomposition prod
temperature in the range of between about 40° C. to about 50 ucts resulting from a breakdown of the extracting agent.
120° C., or from about 45° C. to about 100° C. within the Within the cooler 358, the temperature of the overhead
separator, which may be sufficient to dissociate the adduct. stream 356 may be reduced to condense the impurities into
The impurities may then form an organic liquid phase that a liquid, which may then pass to the separator 360 and leave
is at least partially insoluble in the aqueous solvent. The as an impurities stream 362. The impurities stream 362 may
resulting phases may be separated in a liquid-liquid phase 55 exit the system for sale, for use as fuel, and/or as a feed to
separation device. Such as a settling tank or settling tower. one or more Suitable downstream processes. The purge gas
Suitable draw points may be used to provide a regenerated may not condense and may pass out of the separator 360 as
solvent stream 307 and an organics stream 306. The organics the purge gas stream 364 for recycle to the stripping section
stream 306 may leave the system without any further 354. The purge gas stream 364 may comprise a minor
separation or processing. The liquid-liquid separator may 60 amount of the impurities, the solvent, and the decomposition
comprise a gas vent Suitable for passing any off-gases back products, that can reach an equilibrium in the process due to
to the contactor 314. The aqueous phase may leave the the recycling of the purge gas stream 364. The regenerated
liquid-liquid separator as the regenerated solvent stream 307 solvent stream 307 can be processed and/or recycled as
and pass back to the extractor through the contactor 314 and described with respect to the regenerated solvent stream in
heat exchanger 316 as described above. 65 FIG 11.
FIG. 12 illustrates an embodiment of a stripping section The extraction section may comprise a number of flow
354 that is similar to the stripping section 304 described with configurations. The extraction may be carried out in a
 US 9,447,018 B2
25 26
co-current, counter-current, and/or cross-current flow each stage. In an embodiment, the cross-current extraction
scheme, as schematically illustrated in FIGS. 13, 14, and 15, scheme may comprise separate vessels (e.g., contactors,
respectively. An embodiment of a co-current extraction settlers, etc.) for each stage. In some embodiments, the
scheme is illustrated in FIG. 13. In this embodiment, the stages may be present in a single physical vessel with
extraction section may comprise a plurality of stages 402. internal contactors and separators. Further, while three
404, 406. For each stage 402,404, 406, the product stream stages 408, 410, 412 are shown in FIG. 15, less than three
310 and the solvent stream 319 may enter the stage and flow stage or more than three stages may be used. In an embodi
together through the stage. The Solvent and product may be ment, the number of stages may be between about 1 and
separated within the stage, for example using a settler/phase about 50 stages.
separator. Each phase may then pass to the next stage as 10 While described separately, the extraction section 302
separate phases. Alternatively, the combined fluids may pass may comprise any combination of the extraction schemes
to the next stage as a single stream. In general, the co-current illustrated in FIGS. 13, 14, and 15. For example, each stage
flow of solvent and product may allow the two streams to of the cross-current flow scheme may comprise a co-current
reach an equilibrium, and therefore, the co-current flow may or counter-current individual flow scheme. Various other
only provide an extraction equivalent to a single theoretical 15 combinations may also be possible.
stage. However, additional stages may be useful in practice
to provide additional residence/contact time to approach the Dehydrogenation and Dimerization Catalysts
equilibrium concentrations and mass transfer of the impu
rities from the ethyl acetate product into the solvent phase. Suitable dehydrogenation and dimerization catalysts are
The solvent phase may be separated from the product phase capable of converting at least a portion of the alcohol (e.g.,
within the last stage or within a separator downstream of the ethanol) in a feed stream to a higher valued product such as
last stage to produce the extract stream 256 and the purified ethyl acetate. Any catalyst capable of carrying out a dehy
product stream 216. While illustrated as separate stages 402. drogenation and dimerization reaction may be used alone or
404, 406, the stages may be present in a single physical in combination with additional catalytic materials in the
vessel. Further, while three stages 402,404, 406 are shown 25 reactors. In an embodiment, Suitable dehydrogenation and
in FIG. 13, less than three stage or more than three stages dimerization catalysts can generally comprise metals and/or
may be used. In an embodiment, the number of stages may oxides of copper, barium, ruthenium, rhodium, platinum,
be between about 1 and about 50 stages. palladium, rhenium, silver, cadmium, zinc, Zirconium, gold,
An embodiment of a counter-current extraction scheme is thallium, magnesium, manganese, aluminum, chromium,
illustrated in FIG. 14. In this embodiment, the extraction 30 nickel, iron, molybdenum, Sodium, strontium, tin, and mix
section may comprise a plurality of stages 408, 410, 412. tures thereof. In many cases, the catalyst material will be
The product stream 310 may enter at a first of the stages and provided on a support material. The catalyst can be treated
the solvent stream 319 may enter the last stage and flow with a carbonate (e.g., sodium carbonate), reduced with
countercurrently through each stage. The phases may be hydrogen, and/or other suitable treatments prior to use.
arranged to allow the phases to flow countercurrently based 35 In certain embodiments, the dehydrogenation and
on density differences, with the organic product phase flow dimerization catalyst may include a catalyst Support. The
upwards and the aqueous solvent phase flow downwards. catalyst Support stabilizes and Supports the catalyst. The type
The countercurrent flow of the product and solvent may of catalyst Support used depends on the chosen catalyst and
result in the most efficient extraction and mass transfer of the the reaction conditions. Suitable Supports may include, but
three flow schemes. The solvent phase may be separated 40 are not limited to, carbon, silica, silica-alumina, alumina,
from the product phase within the first stage 408 to allow the Zirconia, titania, ceria, Vanadia, nitride, boron nitride, het
extract stream 256 to leave the extraction section 302. eropolyacids, hydroxyapatite, Zinc oxide, chromia, Zeolites,
Similarly, the product phase may be separated from the carbon nanotubes, carbon fullerenes, and any combination
solvent phase within the last stage 412 to allow the purified thereof.
product stream 216 to leave the extraction section 302. 45 The dehydrogenation and dimerization catalyst can be
While illustrated as separate stages 408, 410, 412, the stages employed in any of the conventional types or structures
may be present in a single physical vessel. Further, while known to the art. It may be employed in the form of
three stages 408, 410, 412 are shown in FIG. 14, less than extrudates, pills, pellets, granules, broken fragments, or
three stage or more than three stages may be used. In an various special shapes. In an embodiment, consideration of
embodiment, the number of stages may be between about 1 50 the use of the catalyst in the reactive distillation system
and about 50 stages. and/or as a mass transfer Surface within the distillation
An embodiment of a cross-current extraction scheme is column may be taken into account when determining a
illustrated in FIG. 15. In this embodiment, the extraction Suitable shape. For example, the catalyst may have a shape
section may comprise a plurality of stages 414, 416, 418. similar to structured packing material or Suitable for inser
The product stream 310 may enter at a first of the stages and 55 tion in a structured packing. When the hydrogenation cata
progress through each stage 414, 416, 418. The solvent lyst is used with one or more side reactors, the catalyst may
stream 319 can be divided into portions 420, 422, 424, be disposed within a reaction Zone, and the feed may be
which may have the same or different flow rate. The portions passed therethrough in the liquid, vapor, or mixed phase, and
420, 422, 424 may pass to each stage 414, 416, 418, in either upward or downward, or inward or outward flow.
respectively, to contact the product within each stage 414, 60 The dehydrogenation and dimerization catalyst may typi
416, 418. Within each stage 414, 416,418, the solvent phase cally have a range of metal loadings. In an embodiment, the
may be separated from the product phase, and the solvent catalyst may have a copper oxide weight loading (i.e.,
phase portions may be recombined to form extract stream weight percentage) of between about 0.5% and about 90%,
256. The solvent phase may pass out of the last stage 418 as between about 10% and about 70%, between about 20% and
the purified product stream 216. The use of the cross-current 65 about 65%, between about 30% and about 60%, or about
flow configuration may allow the concentration of the impu 40% and about 50%. In an embodiment, the catalyst may
rities in the ethyl acetate product stream to be decreased in have a zinc oxide weight loading of between about 20% and
 US 9,447,018 B2
27 28
about 60%, between about 30% and about 50%, or between cined again. This process may be repeated to provide a final
about 40% and about 50%. In an embodiment, the catalyst catalyst material with a desired loading of each component.
may have a chromium oxide weight loading of between In an embodiment, a single metal may be added with each
about 20% and about 60%, or between about 30% and about cycle. The order in which the metals are added in the
50%. sequential process can be varied. Various metal weight
In an embodiment, the catalyst may comprise CuO/ZnO/ loadings may be achieved through the wet-impregnation
Al-O. In this embodiment, the catalyst may have a copper technique. In an embodiment, the wet-impregnation tech
oxide weight loading of between about 0.5% and about 90%, nique may be used to provide a catalyst having a copper
between about 10% and about 70%, between about 20% and weight loading ranging from about 0.5% and about 50%,
about 65%, between about 30% and about 60%, or about 10 with one or more additional components having a weight
40% and about 50%, and the zinc oxide and alumina may loading between about 0.1% and about 10%.
comprise the balance of the weight. In an embodiment, the The dehydrogenation and dimerization catalysts may also
catalyst may comprise CuO/ZnO/ZrO/Al2O, and the cata be prepared via a co-precipitation technique. In this tech
lyst may have a copper oxide weight loading of between nique, a measured amount of one or more appropriate metal
about 40% to about 90%, with the remainder of the com 15 nitrates (or other appropriate metal salts) are dissolved in
ponents forming the balance of the catalyst weight. In an de-ionized water. The total metal concentration can vary and
embodiment, the catalyst may comprise CuO/ZnO/ZrO/ may generally be between about 1 M and about 3 M. The
Cr2O, and the catalyst may have a copper oxide weight metal-nitrate solution may then be precipitated through the
loading of between about 20% to about 90% and a chro drop-wise addition of the Solution to a stirred, equal volume
mium oxide weight loading between about 30% and about of a sodium hydroxide solution at room temperature. The
50%, with the remainder of the components forming the Sodium hydroxide solution may generally have a concen
balance of the catalyst weight. In an embodiment, the tration of about 4M, though other concentrations may also
catalyst may comprise CuO/ZrO/Al2O. In an embodiment, be used as would be known to one of skill in the art with the
the catalyst comprises an alkaline earth metal and/or alkaline benefit of this disclosure. After addition of the metal nitrate
earth metal oxide and copper and/or copper oxide on a 25 Solution, the resulting Suspension can be filtered and washed
Support. In this embodiment, the Support may comprise with de-ionized water. The filtered solids can be dried
silica. overnight, for example, at a temperature of about 110° C.
Any of the materials useful as hydrogenation and The resulting mixed metal oxide can then be processed to a
dimerization catalysts, may be synthesized using a variety of desired particle size. For example, the resulting mixed metal
methods. In an embodiment, the dehydrogenation and 30 oxide can be pressed to a desired form, ground, and then
dimerization catalyst may be prepared via wet impregnation sieved to recover a catalyst material with a particle size in a
of a catalyst support. Using the wet-impregnation technique, desired range. Catalysts prepared using the co-precipitation
a metal nitrate dissolved in a suitable solvent may be used technique may have higher metal loadings than the catalysts
to prepare the catalyst, however any soluble compound prepared using the wet-impregnation technique.
would be suitable. A sufficient amount of solvent should be 35 The catalyst prepared via the co-precipitation technique
used to fully dissolve the metal nitrate and appropriately wet may be used in the prepared form and/or a catalyst binder
the Support. In one embodiment, copper nitrate and ethanol can be added to impart additional mechanical strength. In an
and/or water may be mixed in an amount Sufficient Such that embodiment, the prepared catalyst may be ground to a fine
the copper nitrate dissolves. Additional metal nitrates may powder and then stirred into a colloidal suspension (e.g., a
also be added to provide a catalyst with additional compo 40 colloidal Suspension of silica and/or alumina) in an aqueous
nents. The solute may then be combined with a suitable Solution. The resulting Suspension may be stirred while
Support material of appropriate particle size. The mixture being heated and allowed to evaporate to dryness. The
may then be refluxed at a temperature of approximately 100° heating may take place at about 80°C. to about 130°C. The
C. for approximately several hours (e.g., three to five hours) resulting Solid can then be processed to a desired particle
and then allowed to dry at a temperature of about 110° C. 45 size. For example, the resulting solid can be pressed to a
The dried material may then be heated to 200° C. to remove desired form, ground, and then sieved to recover a catalyst
the NO, component, and then the materials may be calcined material with a particle size in a desired range. Alternatively,
at about 450° C. to about 550° C. at a heating rate of about the colloidal suspension may be added to the 4M sodium
one to ten C./min. The amount of metal nitrate used in the hydroxide precipitation solution prior to addition of the
wet-impregnation technique can be adjusted to achieve a 50 metal nitrate Solution in the co-precipitation technique.
desired final metal weight loading of the catalyst Support. Various metal weight loadings may be achieved through the
When multiple components are used to provide a catalyst co-precipitation technique. In an embodiment, the co-pre
disposed on a Support, each component can be added via the cipitation technique may be used to provide a catalyst
wet-impregnation technique. The appropriate salts can be having a copper weight loading ranging from about 2% and
dissolved and impregnated on a Support in a co-impregna 55 about 80%, with one or more additional components having
tion process or a sequential process. In a co-impregnation a weight loading between about 2% and about 40%.
process, measured amount of the appropriate plurality of The resulting catalyst from either the wet-impregnation
metal salts may be dissolved in a Suitable solvent and used technique and/or the co-precipitation technique may be
to wet the desired catalyst Support. The impregnated Support further treated prior to use in the reactive distillation system
can then be dried and calcined to provide a final catalyst with 60 disclosed herein. In an embodiment, the catalyst may be
a desired weight loading. In the sequential impregnation treated with a sodium carbonate solution for a period of time
process, one or more measured amounts of salts may be to improve the selectivity of the catalyst. In this process, the
dissolved in a suitable solvent and used to wet the desired catalyst may be soaked in an aqueous solution of Sodium
catalyst Support. The impregnated Support can then be dried carbonate for a period of time ranging from about 1 hour to
and calcined. The resulting material can then be wetted with 65 about 48 hours, or alternatively about 2 hours to about 24
one or more additional salts that are dissolved in a suitable hours. In an embodiment, the Sodium carbonate Solution
solvent. The resulting material can then be dried and cal may have a concentration of about 0.2 M. The catalyst may
 US 9,447,018 B2
29 30
then be filtered and allowed to dry at about room tempera Hydrogenation Catalysts
ture. In an embodiment, the Sodium carbonate may comprise
from about 0.2 to about 3.0 weight percent of the catalyst The hydrogenation catalyst generally can include a Group
after being contacted with the Sodium carbonate solution. VIII metal and/or a Group VI metal. Examples of such a
In another treatment process, the catalyst may be reduced 5 catalyst can include, but is not limited to, Cu, Re, Ni, Fe, Co.
with hydrogen prior to use. In this embodiment, the catalyst Ru, Pd, Rh, Pt, Os, Ir, and alloys or any combination thereof,
may be heated and contacted with hydrogen, which may be either alone or with promoters such as W. Mo, Au, Ag, Cr,
flowing over the catalyst, for a period of time sufficient to Zn, Mn, Sn, B. P. Bi, and alloys or any combination thereof.
reduce the catalyst to a desired degree. In an embodiment,
the catalyst may be contacted with hydrogen at a tempera- 10 Other either
effective hydrogenation catalyst materials include
supported nickel or ruthenium modified with rhenium.
ture of about 190° C. to about 240° C. The hydrogen In an embodiment, the hydrogenation catalyst also includes
treatment may be conducted in combination with the sodium any one of the Supports
carbonate treatment, and may be performed prior to and/or desired functionality ofdescribed the
below, depending on the
catalyst. The hydrogenation
after the sodium carbonate treatment.
Without intending to be limited by theory, it is believed 15 catalysts may be prepared by methods known to those of
that the production of hydrogen during the dehydrogenation ordinary skill in the art.
and dimerization reaction within the process may result in In an embodiment, the hydrogenation catalyst includes a
contact between the dehydrogenation and dimerization cata Supported Group VIII metal catalyst and a metal sponge
lyst and a hydrogen stream Sufficient to at least partially material (e.g., a sponge nickel catalyst). Raney nickel pro
reduce the catalyst. Thus, the process described herein may 20 vides an example of an activated sponge nickel catalyst
have the potential for the in-situ reduction of the catalyst suitable for use in this invention. In an embodiment, the
during use. This may result in an initial break-in period in hydrogenation reaction in the invention is performed using
which the catalyst conversion and selectivity may change a catalyst comprising a nickel-rhenium catalyst or a tung
before reaching a steady state conversion and selectivity. sten-modified nickel catalyst. One example of a suitable
This in-situ reduction may be taken into account when 25 catalyst for the hydrogenation reaction of the invention is a
considering the degree to which a catalyst should be pre carbon-supported nickel-rhenium catalyst.
reduced with hydrogen. In an embodiment, a suitable Raney nickel catalyst may
In an embodiment, the dehydrogenation and dimerization be prepared by treating an alloy of approximately equal
catalyst described herein may be capable of achieving a amounts by weight of nickel and aluminum with an aqueous
relatively high conversion and/or selectivity of ethanol to 30 alkali Solution, e.g., containing about 25 weight% of sodium
ethyl acetate. As used herein, the “conversion of ethanol to hydroxide. The aluminum is selectively dissolved by the
ethyl acetate refers to the amount of ethanol consumed in the aqueous alkali solution resulting in a sponge shaped material
conversion reaction as represented by the formula: comprising mostly nickel with minor amounts of aluminum.
The initial alloy includes promoter metals (e.g., molybde
35 num or chromium) in the amount Such that 1 to 2 weight 96
FEOH.0 - FEOH remains in the formed sponge nickel catalyst. In another
Xethanol = 100 (Ed.)FEOH.0 embodiment, the hydrogenation catalyst is prepared using a
solution of ruthenium(III) nitrosylnitrate, ruthenium (III)
chloride
where F represents the molar flow rates of ethanol in the 40 The solution in water to impregnate a suitable Support material.
reactor effluent (e.g., the product stream comprising the is then dried to form a solid having a water
ethyl acetate), and Florio represents the molar flow rate of at atmosphericthan
content of less 1% by weight. The solid is then reduced
pressure in a hydrogen stream at 300° C.
ethanol into the reactor inlet. As used herein, the “selectiv
ity’ of the conversion refers to the amount of ethanol that is 4(uncalcined) or 400° C. (calcined) in a rotary ball furnace for
hours. After cooling and rendering the catalyst inert with
consumed in the conversion reaction that is converted to
45 nitrogen, 5% by Volume of oxygen in nitrogen is passed over
ethyl acetate as represented by the formula:
the catalyst for 2 hours.
In certain embodiments, the hydrogenation catalyst may
2FEOAC + FAch include a catalyst Support, which may be the same or
FEOH.0 - FEtOH 50 different than a catalyst support used with the dehydroge
nation and dimerization catalyst. In an embodiment, any of
the catalyst Supports discussed herein may be used to
where F and F represent the molar flow rate of ethyl Support a hydrogenation catalyst. The hydrogenation cata
acetate and acetaldehyde in the reactor effluent (e.g., the lyst can be employed in any of the conventional types or
product stream comprising the ethyl acetate), respectively, structures known to the art. In an embodiment, any of the
and the remaining terms are the same as described above 55 catalyst shapes and/or types discussed herein with respect to
with respect to the conversion of ethanol. In an embodiment, the dehydrogenation and dimerization catalyst may be used
the dehydrogenation and dimerization catalyst described with the hydrogenation catalyst.
herein may be capable of achieving a conversion of ethanol
in the reactive distillation process described herein of at least Production of Methyl Formate from Methanol
about 10%, at least about 20%, at least about 30%, at least 60
about 40%, or at least about 50%. In an embodiment, the In addition to use of the systems and methods described
dehydrogenation and dimerization catalyst described herein herein for converting ethanol to ethyl acetate, those systems
may be capable of achieving a selectivity of ethyl acetate in can also be used in processes with methanol as a feed instead
the reactive distillation process described herein of at least of ethanol, with the production of methyl formate and H as
about 60%, at least about 70%, at least about 80%, at least 65 products according to the following formula:
about 85%, at least about 90%, at least about 95%, or at least
about 96%.
 US 9,447,018 B2
31 32
Such a system and method can utilize selections from the TABLE 2
catalysts indicated for use with the ethanol feed. Products
can be withdrawn in similar manner as described for the Hydrogenation Feed and Products
ethanol to ethyl acetate process. Temperature 250° C.
Pressure 20 atm
EXAMPLES Weight %
Component Feed Products
The disclosure having been generally described, the fol
lowing examples are given as particular embodiments of the Ethyl acetate
Ethanol
93
2
92.9
2.1
10
disclosure and to demonstrate the practice and advantages Iso-propanol 3 3
thereof. It is understood that the examples are given by way n-butyraldehyde 1.5 trace
of illustration and are not intended to limit the specification butan-2-one
2-butanol
O.S
O
trace
O48
or the claims in any manner. n-butanol O 1.52
15
Example 1
Production of Ethyl Acetate from Ethanol Example 3

A 10 cm diameter distillation column is used, which has Wet-Impregnation Catalyst Preparation

been rendered adiabatic by heating casings with tempera Various catalysts including CuO/SiO, CuO/SiO
tures controlled in Such a way that the temperature gradient Al-O, CuO/ZnO, CuO/ZrO, CuO/SiO, ZrO, CuO/ZnO/
in the column is reproduced. Over a height of 3.5 m, the Al-O, CuO/Cr2O/BaO, CuO/Cr2O and CuO/Al2O were
column is comprised of rectification Zone with 8 stages each prepared via impregnation of the corresponding oxide cata
with a catalytic cell consisting of a cylindrical container with 25 lyst Support. The preparation involved dissolving 4 grams
a flat bottom. The bottom of the container is equipped with (g) of Cu(NO), 2.5H2O in 30 mL of de-ionized water,
a grid for retaining the catalyst and also can act as a gas and which was then added to 30 g of the appropriate oxide
liquid distributor. The stripping Zone is comprised of 12 Support and stirred until well mixed. The impregnated
stages, also with catalyst-containing cells. The rectification support was then dried in air at 110° C., followed by
section is considered to be above the feed stage and the 30
calcination in air at 450° C. The amount of Cu(NO).
stripping section is considered to be below the feed stage. 2.5HO was adjusted to achieve a desired final Cu weight
Each catalyst cell contains CuO/ZnO/Al2O. 200 proof loading. Enough water was used to wet the entire oxide
ethanol is fed to the 13" stage of the column, starting from support. Copper loadings between 0.5% and 20% by weight
the bottom. were achieved.
35
The column is regulated by establishing a reflux ratio
which is equal to 0.8, reboil ratio which is equal to 4 and Example 4
controlling the base temperature to 211° C. and the absolute Co-Impregnation and Sequential Impregnation
pressure to 20 bar. The reflux stream is mostly ethanol with Catalyst Preparation
small amounts of acetaldehyde. Under stabilized conditions, 40
a bottoms stream and a distillate stream are collected with
respective throughputs of about 170 g/h and 4 g/h. The Various catalysts including CuO/ZnO/SiO, CuO/ZrO/
bottoms product gives ethyl acetate purity of 98.5% with SiO, CuO/MgO/SiO, CuO/CaO/SiO, CuO/SrO/SiO,
Small amounts of n-butyraldehyde and butan-2-one. CuO/BaO/SiO, and CuO/Na2O/SiO, were prepared via
co-impregnation and sequential impregnation of a silica
Example 2
45 catalyst Support. For the co-impregnation, measured
amounts of Cu(NO).2.5H2O and M(NO).YHO (M=Zn,
Selective Hydrogenation of n-butyraldehyde and Zr, Mg, Ca, Sr, Ca, or Na; X=1, 2, 4: Y=2-6) were dissolved
in de-ionized water. The solution was added to the silica
butan-2-one Support and stirred until well mixed. The impregnated silica
50 was dried in air at 110°C., followed by calcination in air at
Selective hydrogenation of n-butyraldehyde and butan-2- 450° C.
one in the presence of ethyl acetate was conducted over a For the sequential impregnation, a measured amount of
hydrogenation catalyst. The reactor was filled with 20 g of M(NO) YHO (M=Mg, Ca, Sr, Ca, or Na: X=1 or 2:
0.1 wt % Pd on silica catalyst. Before the selective hydro Y=2-6) was dissolved in de-ionized water. The solution was
genation reaction, the catalyst was reduced at a temperature 55 then added to the silica support and mixed well. The silica
of 250° C. for 30 minutes. The catalyst reduction was was dried at 110° C. and then calcined at 450° C. in air. This
conducted at atmospheric pressure by delivering hydrogen procedure was then repeated using Cu(NO).2.5H2O in
using a mass flow controller. At the end of this procedure, place of the first metal nitrate. Copper loadings between
the catalyst was fully reduced. 0.5% and 20% by weight and an addition metal loading
The bottoms product from the reactive distillation col 60 between 0.1% and 10% by weight were achieved.
umn, whose composition is given in Table 2, was introduced
to a heater at a rate of 30 g/h and mixed with hydrogen prior Example 5
to admission to the selective hydrogenation reactor. The
reaction product was cooled using a jacketed condenser and Co-Precipitation Catalyst Preparation
the liquid condensate was analyzed by gas chromatography. 65
The results are summarized in Table 2, showing n-butyral Mixed-metal oxide catalysts were prepared via co-pre
dehyde and butan-2-one reduced to trace levels. cipitation from nitrate Solutions. In the co-precipitation
 US 9,447,018 B2
33 34
synthesis, a measured amount of the appropriate metal where Flo, Flo, and F represent the molar flow rates
nitrate (Cu, Zn, Zr, Al, Cr, Fe, Ni, and/or Ba) were dissolved of ethanol, ethyl acetate, and acetaldehyde in the reactor
in de-ionized water (total metal concentration ranges from effluent, respectively, and Florio represents the molar flow
1-3 M). The metal-nitrate solution was then precipitated by rate of ethanol into the reactor inlet. Acetaldehyde is a
drop-wise addition to a stirred, equal Volume of 4 Maqueous 5 reaction intermediate and so was included in the selectivity
NaOH at room temperature. After addition of all the metal calculation.
nitrate Solution, the Suspension was stirred for an additional
hour to ensure complete precipitation of the metals. The TABLE 3
precipitated solid was then filtered and washed with excess 10 Conversion and Selectivity for selected catalysts
de-ionized water. The solids were then dried overnight at in a fixed bed reactor at 220° C. and 1 atm
110°C. The resulting mixed metal oxide was then pressed,
ground, and sieved to recover a catalyst with particle sizes As
prepared/received
Reduced
in H2
between 450 and 850 um. Catalysts prepared in this manner
had copper oxide loadings between 40% and 80% by weight. 15 Catalyst sample X S X S
The loadings of other metal oxides ranged from 2% to 40% Pellet catalysts
by weight. In particular, CuO/ZnO/ZrO/Al2O, and CuO/
ZnO/ZrO/Cr2O catalysts were found to be especially CuO/ZnO/Al2O. 18.9 92.4 3SO 89.7
active and selective for the dehydrogenative dimerization of CuO/Cr2O/BaO
Impregnated catalysts
43.5 89.4 36.O 74.6
ethanol, as illustrated below in Example 6.
In addition to the catalysts prepare above, various cata CuO/SiO, 19.6 96.2 22.S. 80.9
lysts were prepared via co-precipitation and then a binder CuOf SiO2 Al2O3 43.O. 17.0
was incorporated. The catalyst binder was added to the CuO/Al2O. SO-2 47.3
CuOZnO 19.7 65.5
mixed-metal oxide prepared as described above by first CuO/ZrO, 41.5 63.4
grinding the mixed-metal oxide to a fine powder and then 25 CuO/SiO2–ZrO2 40.0 S9.7
stirring it into a colloidal suspension of silica or alumina in CuO/MgO, SiO, 37.9 7O.O 32.1 65.7
water. The resulting Suspension was stirred while heating at CuO/CaO/SiO, 33.3 734 29.0 42.7
CuO/SrO/SiO, 25.1 77.2 31.5 69.6
80-130° C. to dryness. The resulting solid was then be CuO/BaO/SiO, 31.0 73.2 33.6 73.6
pressed, ground, and sieved to appropriate particle sizes. CuO/Na2O/SiO, 19.4 95.9
30 CuO/ZrO/SiO, 39.1 58.7 54.0 61.6
Example 6 Co-precipitation catalysts
CuO/ZnO/ZrO/Al2O. 8.7 83.6 214 72.6
Dehydrogenative Dimerization of Ethanol CuO/ZnO/ZrO/Al2O/Na2CO 26.1 40.1 39.O 86.1
CuO/ZnO/ZrO/Cr2O. 28.8 92.0 20.9 80.9
A portion of the catalysts prepared as described in 35 CuO/ZnO/ZrO/Cr2O/Na2CO
CuO/ZnO/ZrO2, Fe2O.
37.O
34.1
90.2
92.1
35.9
17.O.
87.5
94.2
Examples 3 to 5 were treated with a NaCO solution by CuO/ZnO/ZrO-Fe-O/Na2CO 30.7 72.6
soaking the catalyst in a 0.2 M aqueous solution of NaCO CuO/ZnO/ZrO/Al2O/Cr2O. 24.5 88.4 18.5 79.4
for 2-24 hrs. The catalyst was then filtered and allowed to CuO/ZnO/ZrO/Al2O/Cr2O/Na2CO 33.2 86.3
dry in air at room temperature. Another portion of the
catalysts prepared as described in Examples 3 to 5 were 40
reduced in a hydrogen environment at 175-240° C. for a Example 7
period of 4-12 hours. These catalysts were then tested in
ethanol dehydrogenation reactions. Conversion and selec Pressure Effects on the Conversion
tivity for gas phase reactions were determined from use in a
fixed bed reactor operating at 190-240° C. and 1-24 atm. 45
A fixed bed reactor operated under similar conditions to
Pure ethanol was fed to the reactor with a weight hourly
space velocity (WHSV) between 0.1-1.5 hr'. Conversion those described with respect to Example 6 was used to test
and selectivity for liquid phase and mixed liquid/vapor the reaction conversion and selectivity of a catalyst under
phase reactions were determined in a fixed bed reactor, varying reaction pressures. Table 4 shows a typical trend in
operating at 190-240° C. and at pressures above 25 atm. 50 the conversion and selectivity of these catalysts when oper
Liquid phase reactions were also conducted in a batch ated at elevated pressures. Similar trends were seen for all
reactor at 180-200° C. and 20-31 atm (the reactor pressure catalysts tested at elevated pressures.
was maintained above the vapor pressure of ethanol at the
operating temperature). TABLE 4
Table 3 shows the conversion and selectivity of the 55
Conversion and Selectivity for CuO/ZnO/ZrO/Al2O/Na2CO
catalysts in a dehydrogenative dimerization reaction con reduced at 240° C. in H-) in a fixed bed reactor at 220° C.
ducted in a fixed bed reactor. Conversion (X) and selectivity
(S) were calculated from the composition of the reactor Pressure (atm) X S
effluent as 1 39.0 86.1
60 9.4 43.6 96.1
14.5 43.3 96.4
FEOH.0 - FEtOH 21.4 39.3 97.4
Xethanol = 100 (EFI)
FEtOH.0
(E. + FAH As seen by the results in Table 4, operation of catalysts at
65 higher pressures increases the selectivity of the catalyst
significantly. Increasing the pressure had little effect on the
conversion achieved by the catalysts.
 US 9,447,018 B2
35 36
Example 8 co-impregnation, measured amounts of Cu(NO).2.5H2O
and ZrO(NO),.6HO were dissolved in an appropriate
Liquid Phase Reaction amount of de-ionized water to fill the pore volume of the
The dehydrogenative dimerization of ethanol was also alumina Support. The solution was added to the alumina
conducted in the liquid phase. Reaction temperatures ranged
5 support and agitated until the liquid was fully absorbed by
from 180 to 200° C. and pressures were kept above the vapor the alumina. The impregnated alumina was dried in air at
pressure of ethanol at the reaction temperature (25-36 atm). 110° C., followed by calcination in air at 400-600° C. for
Liquid phase reactions were conducted in both a fixed bed 2-10 hours. Typical catalyst loadings ranged from 1-50 wt %
reactor and batch reactor. Table 5 shows the results for a 10
CuO and 2-40 wt % ZrO, and some of the catalyst weight
CuO/ZnO/Al2O3 catalyst in a batch reactor operating in the loadings were about 13 wt % CuO and about 7 wt % ZrO.
liquid phase. During a typical batch reaction, the pressure The supported CuO/ZrO/Al2O, could be treated with a
initially reached the vapor pressure of ethanol and then base Such as sodium carbonate after the calcination to
slowly increased beyond that pressure as the reaction gen improve catalyst selectivity. For these catalysts, a Volume of
erated H2 gas. The batch reactor results demonstrated that 15 an aqueous sodium carbonate solution Sufficient to fully
the dehydrogenative dimerization reaction occurs in the submerge the supported catalyst was prepared (0.1-1.0 M).
liquid phase.
The catalyst was then added to the solution and allowed to
TABLE 5
cure for 2-12 hours at room temperature. The catalyst was
then filtered and washed to remove the excess base, then
Conversion and Selectivity for CuO/ZnO/Al2O (reduced dried prior to use in a reaction. Bases other than Sodium
at 240 C. in H2) after 2 hrs in a batch reactor. carbonate that could be used include KCOs, Li2CO,
Temperature (C.) X S
CsCO, NaOH, Ca(OH), KOH, CsCH, Ba(OH).
The results of the impregnated catalyst are shown below
18O 4.4 84.1 in Table 7, wherein X and S are based on the formulas
190
2OO
6.1
13.0
81.5
96.1
25 provided above in Example 6.
TABLE 7
Based on the results of Examples 3 through 8, it can be Conversion and Selectivity for selected supported
seen that a high selectivity to ethyl acetate using the dehy catalysts in a fixed bed reactor operating at
drogenation and dimerization catalysts described herein 30 200° C. and 33 atm with an LHSV = 0.5 hr.
(e.g., CuO/ZnO/ZrO/Al2O/Na2CO, and/or CuO/ZnO/
Al2O) should enable the use of the system embodiments as Catalyst sample As prepared
illustrated in FIGS. 3, 5 and 7 of the present disclosure. For Impregnated catalyst X S
catalysts where 2-butanone is produced above acceptable
levels, the use of the system embodiments as illustrated in 35 CuO/ZrO2 on Al2O. 13.8 95.1
FIGS. 4, 6 and 8 of the present disclosure may be used.
Example 9
Example 11
Effect of Water in the Ethanol Feed
40 Co-Precipitation Catalyst Preparation
In this example, the effect of water in the ethanol feed was
investigated. A 4 wt % water in ethanol solution was fed to Mixed-metal oxide catalysts comprising CuO/ZrO/
a CuO/ZnO/Al2O catalyst in a fixed bed reactor to demon Al-O and CuO/ZrO were prepared via co-precipitation
strate the water tolerance of the catalyst. The reactor was from nitrate Solutions. As in a typical co-precipitation syn
maintained at 21.4 atm and the catalyst was heated to 45 thesis, a measured amount of the appropriate metal nitrates
200-240°C. Table 6 compares the conversion and selectivity were dissolved in de-ionized water (total metal concentra
achieved for both the 4 wt % water in ethanol and a pure tion ranges from 0.5-3 M). The metal-nitrate solution was
ethanol feed. then precipitated by drop-wise addition into a stirred, equal
volume of 1-4 Maqueous NaOH. The NaOH solution could
TABLE 6 50 be at room temperature or heated up to near boiling. After
Conversion and selectivity for CuO/ZnO/Al2O, in a fixed bed reactor
addition of all the metal nitrate Solution, the Suspension was
Operating at 21.4 atm for ethanol feeds with and without water. stirred for 2-24 hours to ensure complete precipitation of the
metal oxides. The precipitated solid was then filtered and
Temperature Pure Ethanol Feed 4% Water in Ethanol Feed washed with excess de-ionized water. The solids were then
(° C.) Conversion Selectivity Conversion Selectivity
55 dried at 110° C., followed by calcination at 220-500° C.
Catalysts prepared in this manner had CuO loadings
200 23.2 98.1 14.2 99.2 between about 40 to about 80 wt %. The loadings of other
220
240
37.9
47.9
97.1
94.4
29.2
42.6
98.6
98.0
metal oxides range from about 2 to about 40 wt %. Other
metal salts, such as acetates and carbonates, could be used
60 in place of the nitrates.
A catalyst binder could be added to the mixed-metal oxide
Example 10 to impart additional mechanical strength. The metal oxide
catalyst would be ground to a fine powder and then stirred
Impregnated Catalysts into a Suspension of the binder. The resulting slurry could
65 then be extruded or pressed, ground, and sieved to appro
A catalyst comprising CuO/ZrO/Al2O was prepared via priate particle sizes. An alternative could include adding the
co-impregnation of an alumina Support. As in a typical binder material to the NaOH precipitation solution prior to
 US 9,447,018 B2
37 38
addition of the metal nitrate solution. Binders can include 25 milliliters of the solvent solution that was prepared by
SiO, Al-O, bentonite and other clays, hydrotalcite, and diluting 15 milliliters of the original solvent solution (30
Al(OH). grams of sodium hydrogen sulfite per 100 milliliters of
The results of the co-precipitation catalyst are shown water) with 10 milliliters of water. The concentration of the
below in Table 8, wherein X and S are based on the formulas 2-butanone was measured after each step and the results are
provided above in Example 6. shown in FIG. 17.
The results indicate that smaller volumes with the same
TABLE 8 concentration of NaHSO, (15 ml extraction volumes) is less
Conversion and Selectivity for selected supported 10
efficient than larger ones (25 ml as shown in FIG. 16).
catalysts in a fixed bed reactor operating at Furthermore, a dilution of the NaHSO solution yielded
200° C. and 33 atm with an LHSV = 0.5 hr'. improved removal efficiency and reduced tendency to form
Catalyst sample As prepared crystals (FIG. 17). This unexpected results is likely due to
the higher solubility of the sodium sulfite 2-butanone adduct
Co-Precipitation Catalyst X S in a less concentrated aqueous NaHSO salt solution. Thus
15
17.2 96.2 we discovered that optimal removal rates are not achieved
17.8 98.6 by excessively high concentrations of NaHSO or small
extraction volumes but with concentration that is high
enough to provide NaHSO excess but not suppress the
Example 12 removal of the sodium sulfite 2-butanone adduct which has
to dissolve in the aqueous phase.
In order to demonstrate the extraction of impurities from
ethyl acetate using an aqueous solution comprising an Example 14
extracting agent, a Solution of sodium hydrogen Sulfite
(NaHSOs) was prepare using 30 grams of sodium hydrogen 25 The effect of the extraction temperature explored in this
sulfite per 100 milliliters of water. A product stream was example. In this example, an identical amount of ethyl
simulated by preparing an ethyl acetate solution containing acetate was treated with the same amount and the same
1.6 wt.% 2-butanone. The extraction was first conducted by concentration of the aqueous NaHSO, (30 grams of sodium
sequentially contact 100 milliliters of the ethyl acetate with hydrogen sulfite per 100 milliliters of water). The first
25 milliliters of the aqueous solution at a time. For each 30 sample was kept cooled for 2 hours at approximately 4°C.
extraction, the ethyl acetate solution was mixed with the 25 The final concentration of the 2-butanone in the sample
milliliters of the aqueous NaHSO solution. The separation maintained at 4°C. was measured by a gas chromatograph
funnel was vigorously shaken several times at room tem analysis as 0.08 wt.%. The sample maintained at room
perature then allowed to rest and let the ethyl acetate-water temperature (approximately 25°C.) had a final concentra
phase separation take place. The heavier, aqueous phase was 35 tion of about 0.18%. Thus, a greater amount of the 2-bu
drained and replaced with same amount of fresh NaHSO tanone was transferred from the ethyl acetate sample into the
Solution, and the procedure was repeated as needed until the solvent solution in the sample maintained at 4°C. than the
2-butanone level drops below the desired level. The residual sample maintained at room temperature.
concentration of the 2-butanone was tracked with a GC
analysis after each extraction step. The results of the analysis 40 Example 15
are illustrated in FIG. 16.
The results demonstrate that 3 consecutive washes The effect of the use of mixtures of sodium sulfite and
resulted in a final 2-butanone concentration below 0.1 wt.%. Sodium hydrogen Sulfite was explored in this example. The
Similar behavior would be expected for other ketones and sodium sulfite solution (NaSO) was prepared in situ by the
aldehydes such as acetone and acetaldehyde. 45 addition of NaOH to a solution of NaHSOs. A stoichiometric
amount of NaOH can be used to completely convert an
Example 13 amount of NaHSO into NaSOs. A less than stoichiometric
amount of NaOH can be used to create a mixture of NaSO
The effect of the extraction efficiency with respect to the and NaHSO. Tests were performed with a solution of
Volume and concentration of the solvent was explored in this 50 NaHSO, that was neutralized with NaOH to a 50% solution
example. In this example, the effects on the 2-butanone (corresponding to a mixture of 50% NaHSO and 50%
concentration in the ethyl acetate solution were determined NaSO) as well as a solution of NaHSO that was neutral
using different volumes of solvent as well as different ized with NaOH to a 100% solution (corresponding to
concentrations of the extracting agent in the solvent. The Substantially pure aqueous NaSO). Several multi-step
same ethyl acetate solution comprising 1.6 wt.%2-butanone 55 extractions were performed on a solution comprising ethyl
was prepared as in Example 12. The starting solvent Solution acetate solution comprising 1.86 wt.% 2-butanone. The
included 30 grams of sodium hydrogen sulfite per 100 results are presented in FIG. 18.
milliliters of water. A volume of 75 milliliters of the ethyl As shown in FIG. 18, each point on the graph represents
acetate solution was first contacted with 25 milliliters of the an extraction, wherein the X-axis represents the cumulative
Solvent solution in multiple extraction steps that were car 60 amount of extractant Solution used. The starting Solution of
ried out as described above in Example 12. The concentra NaHSO contained approximately 30 grams of NaHSO/100
tion of the 2-butanone was measured after each step and the ml. The exact concentration was determined by iodometric
results are shown in FIG. 17. Another volume of 75 milli titration and the solution was adjusted with 4 MNaOH as
liters of the ethyl acetate solution was then contacted with 15 needed to achieve the desired neutralization level. Although
milliliters of the solvent solution in multiple extraction 65 the tests demonstrate that the performance of the NaSO
steps. A fresh volume of 75 milliliters of the ethyl acetate containing extraction was slightly lower, the regeneration of
Solution was then contacted in multiple extraction steps with NaSO solution is expected to be much more reproducible
 US 9,447,018 B2
39 40
and with lower potential release of SO gas. A similar distillation column. In a fifteenth embodiment, the catalyst
performance is expected from corresponding mixtures of of the fourteenth embodiment may be disposed in the
NaHSO and NaSO. reactive distillation column. In a sixteenth embodiment,
separating the portion of the impurity compound from the
Additional Embodiments extract in any of the first to fifteenth embodiments may
comprise contacting the extract with a purge gas, transfer
Having described the systems and methods, various ring at least a portion of the impurity compound from the
embodiments may include, but are not limited to: extract to the purge gas, and separating the purge gas from
In a first embodiment, a method of purifying an ethyl at least the portion of the impurity compound. In a seven
acetate stream comprises contacting an inlet stream with a 10 teenth embodiment, separating the portion of the impurity
Solvent, transferring at least a portion of the impurity com compound from the extract in any of the first to sixteenth
pound from the inlet stream into the solvent to form an embodiments may occur at a pressure of between about
extract and a purified product, separating the extract from 0.001 atm and about 1 atm.
the purified product, separating the portion of the impurity In an eighteenth embodiment, a reactive distillation sys
compound from the extract, forming an impurities stream 15 tem for producing high purity ethyl acetate from ethanol
and a regenerated Solvent, and recycling at least a portion of comprises a reactive distillation column, an extraction unit,
the regenerated solvent to contact the inlet stream. The inlet and a stripping unit. The reactive distillation column com
stream comprises ethyl acetate and an impurity compound, prises a dehydrogenation catalyst, an ethanol inlet config
and the extract comprises the solvent and the portion of the ured to pass an ethanol feed over the dehydrogenation
impurity compound transferred from the inlet stream. In a catalyst, a top product gaseous hydrogen removal passage,
second embodiment, the solvent of the first embodiment and a bottoms product liquid ethyl acetate removal passage.
may comprise an aqueous fluid. In a third embodiment, the The extraction unit is configured to receive a liquid ethyl
method of the first or second embodiment can also include acetate product stream from the reactive distillation column
heating the extract after separating the extract from the through the bottoms product liquid ethyl acetate removal
purified product. Heating the extract can include heating the 25 passage, contact a liquid solvent feed stream with the liquid
extract to a temperature between about 85 45° C. and about ethyl acetate product stream, provide an extract stream
100° C. In a fourth embodiment, the solvent of any of the comprising a portion of any impurities in the liquid ethyl
first to third embodiments can also include an extracting acetate product stream, and provide a purified product
agent, and the extracting agent may be configured to stream. The stripping unit is configured to receive the extract
increase the solubility of the impurity compound in the 30 stream from the extraction unit, separate the portion of the
Solvent. In a fifth embodiment, the extracting agent of the impurities from the extract stream, provide an outlet impu
fourth embodiment may comprise sodium hydrogen sulfite. rities stream, and provide a regenerated solvent stream back
In a sixth embodiment, the extracting agent of the fourth to the extraction unit as at least a portion of the liquid solvent
embodiment may comprise a compound selected from the feed stream. In a nineteenth embodiment, the system of the
group consisting of hydrosulfite ion, Sulfite ion, hydrazine, 35 eighteenth embodiment can also include a drying unit, and
hydroxylamine, semicarbazide, phenylhydrazine, phenylhy the drying unit can be configured to receive the purified
droxylamine, salts thereof, aqueous Solutions thereof, and product stream from the extraction unit, remove at least a
any combination thereof. In a seventh embodiment, the portion of any water in the purified product stream, and
method of any of the fourth to sixth embodiments can also provide a dried purified product stream. In a twentieth
include reacting the extracting agent and the impurity com 40 embodiment, the extraction unit of the eighteenth or nine
pound to form an adduct in response to contacting the inlet teenth embodiments may be configured to contact the liquid
stream with the solvent. In an eighth embodiment, separat solvent feed stream with the liquid ethyl acetate product
ing the portion of the impurity compound from the extract in stream using a counter-current flow. In a twenty first
the seventh embodiment may comprise dissociating the embodiment, the extraction unit of the eighteenth or nine
adduct. In a ninth embodiment, the impurity compound of 45 teenth embodiments may be configured to contact the liquid
any of the first to eighth embodiments may comprise at least solvent feed stream with the liquid ethyl acetate product
one of a ketone, an aldehyde, or any combination thereof. In stream using a cross-current flow. In a twenty second
a tenth embodiment, the method of any of the first to ninth embodiment, the extraction unit of any of the eighteenth to
embodiments may comprise drying the purified product. In twenty first embodiments may comprise a liquid-liquid
an eleventh embodiment, the purified product of any of the 50 contact vessel. In a twenty third embodiment, the liquid
first to tenth embodiments may comprise at least about 90% liquid contact vessel of the twenty second embodiment may
ethyl acetate by weight. In a twelfth embodiment, contacting comprise packing. In a twenty fourth embodiment, the
the inlet stream with the solvent in any of the first to eleventh stripping unit of any of the eighteenth to twenty third
embodiments may comprise at least one of contacting the embodiments may comprise a distillation column. In a
inlet stream with the solvent in a counter-current flow, or 55 twenty fifth embodiment, the distillation column of the
contacting the inlet stream with the solvent in a cross-current twenty fourth embodiment may comprise between about 1
flow. In a thirteenth embodiment, the method of any of the and about 50 stages. In a twenty sixth embodiment, the
first to twelfth embodiments can also include feeding a feed system of any of the eighteenth to twenty fifth embodiments
stream comprising ethanol to a reactive distillation column, can also include a cooler, and the cooler can be configured
contacting the ethanol with a catalyst, dehydrogenating 60 to receive the regenerated solvent stream, cool the regener
ethanol over the catalyst, removing ethyl acetate during the ated solvent stream, and provide the cooled regenerated
distillation process as a liquid bottoms product, removing Solvent stream back to the extraction unit. In a twenty
hydrogen during the distillation process as a gaseous top seventh embodiment, the system of any of the eighteenth to
product, and providing the ethyl acetate as the inlet stream. twenty sixth embodiments may also include at least one side
In a fourteenth embodiment, the catalyst of the thirteenth 65 reactor in fluid communication with the reactive distillation
embodiment may be disposed in a side reactor, and the side column. In a twenty eighth embodiment, the system of the
reactor may be in fluid communication with the reactive twenty seventh embodiment may also include a second
 US 9,447,018 B2
41 42
catalyst disposed in the at least one side reactor, wherein the second feed stream with a hydrogenation catalyst during the
catalyst comprises at least one of a dehydrogenation catalyst distillation process. The second feed stream may comprise
or a hydrogenation catalyst. hydrogen.
In a twenty ninth embodiment, a reactive distillation In the preceding discussion and in the claims, the terms
process producing high purity ethyl acetate from ethanol “including and “comprising are used in an open-ended
comprises feeding a feed stream comprising ethanol to a fashion, and thus should be interpreted to mean “including,
reactive distillation column, contacting the ethanol with a but not limited to . . . . At least one embodiment is disclosed
catalyst, dehydrogenating ethanol over the catalyst in the and variations, combinations, and/or modifications of the
liquid phase during the distillation process, removing ethyl embodiment(s) and/or features of the embodiment(s) made
acetate during the distillation process as a bottoms product, 10 by a person having ordinary skill in the art are within the
and removing hydrogen during the distillation process as a scope of the disclosure. Alternative embodiments that result
top product. In a thirtieth embodiment, the reactive distil from combining, integrating, and/or omitting features of the
lation process of the twenty ninth embodiment may also embodiment(s) are also within the scope of the disclosure.
Where numerical ranges or limitations are expressly stated,
include contacting the bottoms stream with a hydrogenation 15 Such express ranges or limitations should be understood to
catalyst and hydrogen, hydrogenating at least a portion of a include iterative ranges or limitations of like magnitude
contaminant in the bottoms stream, and separating the falling within the expressly stated ranges or limitations (e.g.,
hydrogenated portion of the contaminant from the bottoms from about 1 to about 10 includes, 2, 3, 4, etc.; greater than
stream. In a thirty first embodiment, separating the hydro 0.10 includes 0.11, 0.12, 0.13, etc.). For example, whenever
genated portion of the contaminant from the bottoms stream a numerical range with a lower limit, R, and an upper limit,
in the thirtieth embodiment comprises distilling the hydro R, is disclosed, any number falling within the range is
genated portion of the contaminant from the bottoms stream. specifically disclosed. In particular, the following numbers
In a thirty second embodiment, the contacting, the hydro within the range are specifically disclosed: R=R+k*(R-
genating, and the separating in the thirtieth or thirty first R), wherein k is a variable ranging from 1 percent to 100
embodiments may occur downstream of the reactive distil 25 percent with a 1 percent increment, i.e., k is 1 percent, 2
lation column. In a thirty third embodiment, the contaminant percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent, 51
of any of the thirtieth to thirty second embodiments may percent, 52 percent, ... , 95 percent, 96 percent, 97 percent,
comprise a ketone or an aldehyde. In a thirty fourth embodi 98 percent, 99 percent, or 100 percent. Moreover, any
ment, the reactive distillation process of any of the twenty numerical range defined by two R numbers as defined in the
ninth to thirty third embodiments may also include extract 30 above is also specifically disclosed. Use of the term “option
ing at least a portion of a contaminant in the bottoms stream ally’ with respect to any element of a claim means that the
using a solvent to produce an extract stream and a purified element is required, or alternatively, the element is not
product stream, and stripping the portion of the contaminant required, both alternatives being within the scope of the
from the extract stream to produce a contaminant stream and claim. Use of broader terms such as comprises, includes, and
35 having should be understood to provide support for narrower
regenerate the solvent stream. In a thirty fifth embodiment, terms such as consisting of consisting essentially of and
the reactive distillation process of any of the twenty ninth to comprised Substantially of. Accordingly, the scope of pro
thirty fourth embodiments may also include contacting a tection is not limited by the description set out above but is
first fluid drawn from the reactive distillation column with defined by the claims that follow, that scope including all
the catalyst in a side reactor, and introducing the second fluid 40 equivalents of the subject matter of the claims. Each and
to the reactive distillation column during the distillation every claim is incorporated as further disclosure into the
process. The first fluid may react in the presence of the specification and the claims are embodiment(s) of the pres
catalyst to produce a reaction product comprising a second ent invention.
fluid. In a thirty sixth embodiment, the reactive distillation
process of the thirty fifth embodiment may also include 45 What is claimed is:
increasing a contact time between the ethanol and the 1. A method of purifying an ethyl acetate stream com
catalyst, and improving a conversion of ethanol to ethyl prising:
acetate in response to increasing the contact time between contacting an inlet stream with a solvent, wherein the inlet
the ethanol and the catalyst. In a thirty seventh embodiment, stream comprises ethyl acetate and an impurity com
the reactive distillation process of the thirty fifth to thirty 50 pound, wherein the impurity compound comprises at
sixth embodiments may also include contacting the bottoms least one of a ketone, an aldehyde, or any combination
stream with a hydrogenation catalyst and hydrogen, hydro thereof, wherein the impurity compound comprises
genating at least a portion of a contaminant in the bottoms 2-butanone;
stream, and separating the hydrogenated portion of the transferring at least a portion of the impurity compound
contaminant from the bottoms stream. In a thirty eighth 55 from the inlet stream into the solvent to form an extract
embodiment, the bottoms product of any of the twenty ninth and a purified product, wherein the extract comprises
to thirty seventh embodiments may comprise at least about the solvent and the portion of the impurity compound
90% ethyl acetate. In a thirty ninth embodiment, the feed transferred from the inlet stream;
stream comprising ethanol of any of the twenty ninth to separating the extract from the purified product;
thirty eighth embodiments may be the only feed stream fed 60 separating the portion of the impurity compound from the
to the reactive distillation column. In a fortieth embodiment, eXtract;
the catalyst of any of the twenty ninth to thirty ninth forming an impurities stream and a regenerated solvent;
embodiments may be disposed within the reactive distilla and
tion column. In a forty first embodiment, the reactive recycling at least a portion of the regenerated solvent to
distillation process of any of the twenty ninth to fortieth 65 contact the inlet stream.
embodiments may also include introducing a second feed 2. The method of claim 1, wherein the solvent comprises
stream to the reactive distillation column, and contacting the an aqueous fluid.
 US 9,447,018 B2
43 44
3. The method of claim 1, wherein the solvent further contacting a first fluid drawn from the reactive distillation
comprises an extracting agent, wherein the impurity com column with the catalyst in a side reactor, wherein the
pound has a higher solubility in the solvent comprising the first fluid reacts in the presence of the catalyst to
extracting agent than in the solvent without the extracting produce a reaction product comprising a second fluid;
agent. 5 and
4. The method of claim 3, wherein the extracting agent introducing the second fluid to the reactive distillation
comprises sodium hydrogen Sulfite. column during the distillation process.
5. The method of claim 3, wherein the extracting agent 18. The reactive distillation process of claim 17, further
comprises a compound selected from the group consisting comprising:
of hydrosulfite ion, Sulfite ion, hydrazine, hydroxylamine, 10 increasing the contact time between the ethanol and the
semicarbazide, phenylhydrazine, phenylhydroxylamine, catalyst; and
salts thereof, aqueous solutions thereof, and any combina improving the conversion of ethanol to ethyl acetate in
tion thereof. response to increasing the contact time between the
6. The method of claim 3, further comprising reacting the ethanol and the catalyst.
extracting agent and the impurity compound to form an 15 19. The reactive distillation process of claim 17, further
adduct in response to contacting the inlet stream with the comprising:
solvent.
7. The method of claim 6, wherein separating the portion contacting the liquid bottoms product with a hydrogena
of the impurity compound from the extract comprises dis tion catalyst and hydrogen;
Sociating the adduct. hydrogenating at least a portion of a contaminant in the
8. The method of claim 1, wherein the purified product liquid bottoms product; and
comprises at least about 90% ethyl acetate by weight. separating the hydrogenated portion of the contaminant
9. The method of claim 1, wherein contacting the inlet from the liquid bottoms product.
stream with the solvent comprises at least one of contacting 20. The reactive distillation process of claim 14, wherein
the inlet stream with the solvent in a counter-current flow, or the liquid bottoms product comprises at least about 90%
contacting the inlet stream with the solvent in a cross-current 25 ethyl acetate.
flow. 21. The method of claim 1, further comprising: removing
10. The method of claim 1, further comprising: at least a portion of any water in the purified product stream
feeding a feed stream comprising ethanol to a reactive to form a dried purified product stream.
distillation column; 22. The method of claim 1, wherein transferring at least
contacting the ethanol with a catalyst; 30 the portion of the impurity product from the inlet stream into
dehydrogenating ethanol over the catalyst; the Solvent occurs in an extraction unit, and wherein the
removing ethyl acetate during the distillation process as a extraction unit comprises a liquid-liquid contact vessel.
liquid bottoms product; 23. The method of claim 1, wherein separating the portion
removing hydrogen during the distillation process as a of the impurity product from the extract occurs in a stripping
gaseous top product; and 35 unit, and wherein the stripping unit comprises a distillation
providing at least a portion of the ethyl acetate as the inlet column.
Stream.
11. The method of claim 10, wherein the catalyst is 24. A method of purifying an organic stream comprising:
disposed in a side reactor, and wherein the side reactor is in contacting a liquid inlet stream with an aqueous solvent,
fluid communication with the reactive distillation column. wherein the inlet stream comprises: an ester comprising
12. The method of claim 1, wherein separating the portion 40 ethyl acetate, and an impurity compound comprising at
of the impurity compound from the extract comprises: least one of a ketone, an aldehyde, or a combination
contacting the extract with a purge gas, transferring at least thereof, wherein the impurity compound comprises
a portion of the impurity compound from the extract to the 2-butanone;
purge gas, and separating the purge gas from at least the transferring at least a portion of the impurity compound
portion of the impurity compound. 45
from the inlet stream into the solvent to form an extract
13. The method of claim 1, wherein separating the portion and a purified product, wherein the extract comprises
of the impurity compound from the extract occurs at a the solvent and the portion of the impurity compound
pressure of between about 0.001 atm and about 1 atm. transferred from the inlet stream;
14. The method of claim 10, wherein dehydrogenating separating the extract from the purified product;
ethanol over the catalyst occurs in the liquid phase during separating the portion of the impurity compound from the
50
the distillation process. eXtract;
15. The method of claim 14, further comprising: forming an impurities stream and a regenerated solvent;
contacting the liquid bottoms product with a hydrogena and
tion catalyst and hydrogen; recycling at least a portion of the regenerated solvent to
contact the inlet stream.
hydrogenating at least a portion of a contaminant in the 55 25. The method of claim 24, wherein a majority of the
liquid bottoms product, wherein the contaminant com ethyl acetate in the liquid inlet stream is separated into the
prises the impurity compound; and purified product.
separating the hydrogenated portion of the contaminant
from the liquid bottoms product. 26. The method of claim 24, wherein the solvent com
16. The method of claim 15, wherein the contacting of the prises an extracting agent, and wherein the extracting agent
liquid bottoms product with the hydrogenation catalyst and 60 comprises a compound selected from the group consisting
hydrogen, the hydrogenating, and the separating of the of hydrosulfite ion, Sulfite ion, hydrazine, hydroxylamine,
hydrogenated portion of the contaminant occur downstream semicarbazide, phenylhydrazine, phenylhydroxylamine,
of the reactive distillation column. salts thereof, aqueous solutions thereof, and any combina
tion thereof.
17. The reactive distillation process of claim 10, further
comprising: