28/01/2018 EP2371799A1 - Methanol synthesis method using synthesis gas generated by a mixed reforming of natural gas and carbon

and carbon dioxide - Google Patents

 Patents EP2371799A1

Methanol synthesis method using synthesis gas generated by a mixed reforming of natural gas and carbon dioxide

Abstract
EP2371799A1
The present invention relates to a methanol synthesis method using a synthesis gas generated by a
EP Application
mixed reforming of natural gas and carbon dioxide. More particularly, the method of the present
invention seeks to utilize carbon dioxide in an economically advantageous manner, and rstly produces
a synthesis gas by using a catalyst (Ni/Ce/MgAlOx, or Ni/Ce-Zr/MgAlOx) and a reaction process Find Prior Art

condition under which carbon monoxide, carbon dioxide, and hydrogen maintain a speci c ratio
[H2/(2CO+3CO2) = 0.85-1.15] from the mixed reforming wherein the steam reforming of natural gas Other languages: German, French
and the carbon dioxide reforming of methane are carried out at the same time. Subsequently, the thus- Inventor: Jong Wook Bae, Jong Hyeok Oh, Ki Won Jun, Yun Jo
produced synthesis gas is employed to synthesize methanol using a catalyst system (the catalyst Lee, Jun-Ho Ko, Seok-Lyong Song, Keh-Sik Min
consisting of a Cu-Zn-Al-based oxide containing CuO, ZnO, and Al2O3 at a predetermined ratio, and
Current Assignee: Korea Research Institute of Chemical
cerium-zirconium oxide produced by a sol-gel method) which is appropriate for a methanol synthesis Technology , Hyundai Heavy Industries Co Ltd
while producing less by-products. Further, the present invention relates to a methanol synthesis
Original Assignee: Korea Research Institute of Chemical
method using carbon dioxide in which the synthesis gas which is the unreacted material remaining
Technology, Hyundai Heavy Industries Co Ltd
after the completion of said reforming, is e ciently recirculated and reused to improve the carbon use
e ciency (methane and CO2 use e ciency) of the whole process as well as energy e ciency. Priority date: 2008-12-08

Images (2) Family: US (1) JP (1) KR (1) CN (1) EP (1) WO (1)

Date App/Pub Number Status

2009-09-14 EP20090832031 Active

2011-10-05 EP2371799A1 Application

2012-07-18 EP2371799A4 Application

2014-03-05 EP2371799B1 Grant

Classi cations
Info: Patent citations (24), Non-patent citations (3), Cited by (18)
C07C29/154 Preparation of compounds having hydroxy or O-metal groups bound to a carbon , Legal events, Similar documents, Priority and Related
atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon Applications
exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used External links: Espacenet, EPO GPI, EP Register, Global Dossier,
containing copper, silver, gold, or compounds thereof Discuss

View 1 more classi cations

Claims (7)

1. A method for preparing methanol from carbon dioxide, comprising:

preparing synthesis gas via combined reforming, in which steam reforming of natural gas is carried out simultaneously with carbon dioxide reforming of methane, in the
presence of a catalyst of Ni/Ce/MgA10x or Ni/Ce-Zr/MgAlOx;

synthesizing methanol from the obtained synthesis gas in the presence of a catalyst of Cu-ZnO-Al2O3/CeZrOx; and

separating the methanol product from unreacted synthesis gas and recycling the unreacted synthesis gas.

2. The method for preparing methanol from carbon dioxide according to claim 1,
wherein the unreacted synthesis gas separated from the methanol product is recycled to said preparing synthesis gas or said synthesizing methanol.

3. The method for preparing methanol from carbon dioxide according to claim 1,
wherein said preparing synthesis gas is performed by carrying out combined reforming at a reaction temperature of 800 to 1,000 °C under a reaction pressure of 0.5
to 20 atm with a space velocity of 1,000 to 500,000 h-1 in such a condition that molar ratio of CH4/CO2/H2O is within a range of 1/0.3-0.6/1.0-2.0.

4. The method for preparing methanol from carbon dioxide according to claim 1,
wherein said synthesizing methanol is carried out at a reaction temperature of 200 to 400 °C under a reaction pressure of 30 to 60 kg/cm2 with a space velocity of
1,000 to 10,000 h-1.

5. The method for preparing methanol from carbon dioxide according to claim 2,
wherein the unreacted synthesis gas separated from the methanol product is recycled in such a manner that the ratio of synthesis gas recycled to combined
reforming is maintained at 0.0 to 0.2 and that of synthesis gas recycled to methanol synthesis is maintained at 0.8 to 1.0, based on the total unreacted reactants.

6. The method for preparing methanol from carbon dioxide according to claim 1,
wherein said preparing synthesis gas provides a methane conversion of 90% or higher and a carbon dioxide conversion of 40% or higher.

7. The method for preparing methanol from carbon dioxide according to claim 1,
wherein said synthesizing methanol provides a CO conversion of 35% or higher.

Description

[Technical Field]

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28/01/2018 EP2371799A1 - Methanol synthesis method using synthesis gas generated by a mixed reforming of natural gas and carbon dioxide - Google Patents
[0001] The present disclosure relates to a method for methanol synthesis using synthesis gas obtained from combined reforming of natural gas with carbon dioxide.
[Background Art]
[0002] In 2005, as a measure to deal with global warming, the Kyoto protocol regarding reduction of carbon dioxide emission is enacted. Accordingly, there is an imminent
need for providing methods for e cient use of carbon dioxide. In addition, as Clean Development Mechanism (CDM) industries are developed actively, particularly
in advanced countries, carbon emission trading may be allowed according to the reduction of carbon dioxide. Therefore, it is expected that a success in
development of e cient carbon dioxide utilization technologies has a great ripple effect in terms of economy. As processes for converting carbon dioxide, there
have been suggested processes for preparing synthesis gas from combined reforming of natural gas, carbon dioxide and steam, and then producing useful
chemical materials and transportation fuel from synthesis gas. Particularly, a process for synthesizing methanol, one of the most important chemical materials, or
a process for preparing synthetic oil via Fischer-Tropsch synthesis by using synthesis gas obtained from the combined reforming, is getting important because it is
regarded as an e cient way for utilization of carbon dioxide.
[0003] Processes for preparing synthesis gas from natural gas may be classi ed broadly into steam reforming of methane (SRM), partial oxidation of methane (POM) with
oxygen, and carbon dioxide reforming of methane (CDR). The ratio of hydrogen to carbon monoxide (H2/CO) is varied depending on the reforming process and
should be adjusted to the optimal condition required for the subsequent process. In the case of a highly endothermic SRM process, it is possible to obtain a ratio of
H2/CO of 3 or higher. Thus, the process is suitable for hydrogen production and ammonia preparation. In the case of POM, a ratio of H2/CO of about 2 is obtained.
Thus, it is known that POM is suitable for methanol synthesis reaction and hydrocarbon formation through Fischer-Tropsch synthesis. However, POM is
disadvantageous in that it requires a large-scale air-separation unit (ASU).
[0004] Hereinafter, the above-mentioned reforming processes are outlined with their advantages, disadvantages and the values of heat of reactions.
Steam Reforming of Methane (SRM)

CH4 + H2O = 3H2 + CO ΔH = 226 kJ/mol

→ highly endothermic reaction, H2/CO > 3, excess steam is required.

Partial Oxidation of Methane (POM)

CH4 + 0.5O2 = 2H2 + CO ΔH = - 44 kJ/mol

→ mild exothermic reaction, H2/CO = 2, O2 production process is required.

Carbon Dioxide Reforming of Methane (CDR)

CH4 + CO2 = 2H2 + 2CO ΔH = 261 kJ/mol

→ highly endothermic reaction, H2/CO = 1, CO2 addition is required.

[0005] In addition to the above reforming processes, there are known an auto-thermal reforming (ATR) process which is a combination of POM and SRM, a tri-reforming
process which is a combination of POM, SRM and CDR, or the like in order to make an adequate H2/CO ratio as well as to increase energy and carbon e ciency.
Further, it is possible to obtain synthesis gas having different H2/CO ratios depending on the type of reforming process and catalyst. Recently, many patent
applications related to different methods using synthesis gas with such different H2/CO ratios (Korean Unexamined Patent Publication Nos. 2006-0132293 and
2005-0051820 ).
[0006] According to the present disclosure, a nickel-based reforming catalyst (Ni/Ce(Zr)MgAlOx) is used to carry out steam carbon dioxide reforming of methane (SCRM),
wherein the catalyst has high catalytic activity in the combined reforming in which SRM is carried out simultaneously with CDR, as disclosed in Korean Patent
Application No. 2008-0075787 derived from our previous study. In this manner, synthesis gas is prepared to maintain carbon monoxide, carbon dioxide and
hydrogen at a suitable composition [H2/(2CO+3CO2)] and a catalyst for combined reforming, which is suitable for methanol synthesis and Fischer-Tropsch
synthesis using iron-based catalysts, is used. It is shown that the catalyst is inhibited not only from deactivation caused by carbon generation during the reaction
but also from deactivation caused by nickel reoxidation due to water added during the reaction. Thus, the catalyst has excellent reactivity as compared to other
known catalysts for combined reforming processes. In general, it is known that a ratio of H2/(2CO+3CO2) in synthesis gas of about 1.05 is thermodynamically
suitable for methanol synthesis. By adjusting the ratio to an adequate range, it is possible to increase methanol yield and carbon utilization e ciency. Therefore, it
is required to add hydrogen in order to adjust the above ratio, or to modify processing parameters (temperature, pressure, etc.) in order to adjust the CO2 conversion
in CDR.
[0007] In the case of a currently available SRM process, a Ni/Al2O3catalyst system is used at a reaction temperature of 750 to 850 °C under a molar ratio of
steam/methane of 4-6 : 1. However, such a catalyst system is problematic in that it undergoes severe deactivation caused by carbon deposition. Therefore, many
studies have been conducted about catalyst systems containing noble metals or transition metals and alkali metals as co-catalysts (Journal of Molecular Catalysis
A 147 (1999) 41). In addition, in the case of a CDR process, more severe deactivation of catalysts occurs due to carbon deposition. Therefore, in order to inhibit
such catalyst deactivation, many studies have been conducted about noble metal catalysts (Pt/ZrO2) and Ni/MgO or Ni/MgAlO, catalyst systems, to which alkali
metals are added as co-catalysts (Catalysis Today 46 (1998) 203, Catalysis Communications 2 (2001) 49, and Korean Unexamined Patent Publication No. 10-2007-
0043201 ). In general, when using commercially available SRM catalysts directly to CDR and combined CDR and SRM processes, deactivation of catalysts caused
by carbon deposition is accelerated.
[0008] It is generally known that methanol is produced from synthesis gas via the hydrogenation of carbon monoxide or carbon dioxide as depicted in the following
reaction formulae:

CO + 2H2 CH3OH ΔH = -90.8kJ/mol (4)

CO2 + 3H2 CH3OH + H2O ΔH = -49.6kJ/mol (5)

CO + H2O CO2 + H2 ΔH = -41.2kJ/mol (6)

[0009] Reaction formulae (4) and (5) are kinds of the exothermic volume-reducing reactions, and thus they prefer a low temperature and a high pressure
thermodynamically. However, commercial production of methanol has been conducted at an adequate temperature to increase the reaction rate. In addition, the
unreacted gases are recycled and used again in methanol synthesis in order to increase the availability of synthetic gas and to improve the conversion into
methanol. However, water produced according to Reaction Formula (5) causes water gas shift reaction (WGS), such as one as shown in reaction formula (6),
thereby forming an excessive amount of CO2 as a byproduct. Therefore, when introducing a catalyst and process capable of improving the yield of methanol
synthesis by adjusting such parameters adequately, it is possible to improve the carbon utilization and energy utilization e ciency of the overall process. In this
context, many workers have participated in studies for improving the quality of catalysts for methanol synthesis, but complete understanding about the active site
of a catalyst for methanol synthesis cannot be accomplished heretofore. However, it is known that oxidation state of Cu and redox conversion property of reduced
Cu particles play an important role in determining the catalyst quality. It is also known that the activity of a Cu catalyst in a reaction of methanol synthesis is in
proportion to the speci c surface area of Cu of the metal components. For this reason, Cu is used frequently in combination with Zn to prepare the catalyst, and a

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molar ratio of Cu/Zn of 3/7 is known to provide the highest activity. However, it is known that when CO2 is present or when the proportion of oxygen-containing

materials that cover the Cu0 surface increases, the catalyst activity is independent from the Cu0 surface area. Particularly, Korean Patent Application No. 2008-
0072286 , derived from our previous study about methanol synthesis from synthesis gas, discloses a novel catalyst system, including a Cu-Zn-Al oxide containing
CuO, ZnO and Al2O3 in a predetermined ratio, in combination with a cerium-zirconium oxide obtained by a sol-gel process. More particularly, the above patent
application relates to a catalyst for synthesizing methanol from synthesis gas and a method for synthesizing the same, wherein the catalyst is capable of inhibiting
formation of byproducts and improving selectivity toward methanol as compared to the other catalysts using Cu-Zn-Al alone, thereby improving carbon conversion
e ciency and energy e ciency in methanol synthesis.
[0010] In addition to the above, according to the existing patent publications about methanol synthesis from synthesis gas, CO2 is reused in a reformer to minimize
emission of CO2 produced during POM and a cryogenic separation method is employed in such a manner that H2-rich gas is used for methanol synthesis or as fuel,
while CO-rich gas is used in a process for acetic acid preparation, thereby improving the energy e ciency of the overall process ( US Patent No. 7067558 ).
Meanwhile, US Patent No. 6100303 discloses a process for improving energy e ciency and CO2 availability, wherein two different types of reformers, i.e., a
combustion type reformer and a heat exchanger type reformer, are used for steam reforming of natural gas, and purge gas in the unreacted gases is used as a raw
material for reforming/methanol synthesis and as fuel of the reformers in order to reduce the cost required for constructing the processing system and to improve
energy e ciency. However, the process of the US Patent No. 6100303 is different from the present disclosure in terms of the construction of the overall process
and recycling process. Further, US Patent No. 6218439 discloses a method for utilization of CO2 generated during the reaction based on steam reforming alone,
wherein CO2 emission is minimized by refeeding CO2 into reforming or into methanol synthesis after the separation of products. However, the method of the US
Patent No. 6218439 patent uses a catalyst different from the catalyst system disclosed herein and is differentiated from the present disclosure in terms of the
construction of the overall process and recycling process.
[Disclosure] [Technical Problem]
[0011] Under these circumstances, we have focused on a method for improving carbon availability and energy e ciency in a process for methanol preparation using
carbon dioxide. First, synthesis gas is obtained from steam carbon dioxide reforming of methane (SCRM), in which steam reforming of natural gas is carried out
simultaneously with carbon dioxide reforming of methane, by using a catalyst (Ni/Ce/MgAlOx or Ni/Ce-Zr/MgAlOx) and processing condition capable of
maintaining a predetermined ratio of carbon monoxide, carbon dioxide and hydrogen [H2/(2CO+3CO2) = 0.85-1.15]. Next, methanol is synthesized by using the
obtained synthesis gas and a catalyst suitable for methanol synthesis with minimum byproduct formation (a catalyst system including a Cu-Zn-Al oxide containing
CuO, ZnO and Al2O3 in a predetermined ratio, in combination with a cerium-zirconium oxide obtained by a sol-gel process). In addition, unreacted synthesis gas
remaining after the operation of methanol synthesis is recycled e ciently to improve the carbon availability (methane and CO2 availability) and energy e ciency in
the overall process.
[0012] The present disclosure is directed to providing a method for methanol synthesis using synthesis gas obtained from combined reforming of natural gas with carbon
dioxide.
[Technical Solution]
[0013] In one aspect, there is provided a method for methanol preparation from carbon dioxide, including:
preparing synthesis gas via combined reforming, in which steam reforming of natural gas is carried out simultaneously with carbon dioxide reforming of
methane, in the presence of a catalyst of Ni/Ce/MgAlOx or Ni/Ce-Zr/MgAlOx;
synthesizing methanol from the obtained synthesis gas in the presence of a catalyst of Cu-ZnO-Al2O3/CeZrOx; and
separating the methanol product from unreacted synthesis gas and recycling the unreacted synthesis gas.
[Advantageous Effects]
[0014] The present disclosure provides, as a measure of economic utilization of carbon dioxide, an integrated method that includes carrying out combined reforming
(carbon dioxide reforming of methane carried out simultaneously with steam reforming) to produce synthesis gas suitable for methanol synthesis by maintaining a
predetermined ratio of carbon monoxide, carbon dioxide and hydrogen. Herein, a catalyst for combined reforming according to our previous study (Korean Patent
Application No. 2008-0075787 ) and a catalyst for methanol synthesis according to our previous study (Korean Patent Application No. 2008-0072286 ) are used,
and unreacted synthesis gas remaining after the methanol synthesis is recycled at an adequate recycle ratio. In this manner, it is possible to maximize carbon
availability (methane and CO2 availability) and energy e ciency in the overall process. It is expected that such chemical utilization of carbon dioxide reduces
carbon dioxide emission and provides a substitute for methanol imports.
[Description of Drawings]
[0015] Figure 1 is a graph showing methanol yield in a reaction of methanol synthesis as a function of CO/(CO + CO2) ratio;
Figure 2 is a schematic ow chart illustrating methanol synthesis using synthesis gas obtained from combined reforming of carbon dioxide, methane and
water according to an embodiment of the method disclosed herein; and
Figure 3 is a schematic diagram of the method disclosed herein, including preparing synthesis gas via combined reforming, synthesizing methanol from
the synthesis gas, and separating and purifying the product.
[Mode for Invention]
[0016] As mentioned above, one aspect of the present disclosure provides a method for preparing methanol from carbon dioxide, including:
preparing synthesis gas via combined reforming, in which steam reforming of natural gas is carried out simultaneously with carbon dioxide reforming of
methane, in the presence of a catalyst of Ni/Ce/MgAlOx or Ni/Ce-Zr/MgAlOx;
synthesizing methanol from the obtained synthesis gas in the presence of a catalyst of Cu-ZnO-Al2O3/CeZrOx; and
separating the methanol product from unreacted synthesis gas and recycling the unreacted synthesis gas.
[0017] Hereinafter, the method will be explained in more detail.
[0018] First, the method disclosed herein includes preparing synthesis gas according to our previous study (Korean Patent Application No. 2008-0075787 ) from steam
carbon dioxide reforming of methane (SCRM), in which steam reforming of natural gas is carried out simultaneously with carbon dioxide reforming of methane,
while maintaining a predetermined ratio of carbon dioxide, carbon dioxide and hydrogen [H2/(2CO+3CO2) = 0.85-1.15]. In addition, the method disclosed herein
includes synthesizing methanol by using the obtained synthesis gas and a catalyst capable of minimizing byproduct formation according to our previous study
(Korean Patent Application No. 2008-0072286 ). Further, unreacted synthesis gas remaining after the operation of methanol synthesis is recycled with an adequate
ratio to improve the carbon availability (methane and CO2 availability). In this manner, it is possible to prepare methanol from carbon dioxide with improved
methanol yield.
[0019] Generally, in SRM and CDR processes, equilibrium conversion is determined by the ratio of reactants, CH4/CO2/steam, reaction pressure and reaction temperature.
CDR equilibrium conversion decreases and carbon deposition rate increases, as the reaction pressure increases. However, in an industrial plant, reactors are
downsized to reduce the initial cost requirement and reforming is carried out usually at a reaction pressure of 1.0 MPa or higher in order to reduce the cost required
for the subsequent separation operation. In such combined reforming processes, CO2 conversion decreases as the reaction pressure and steam amount in a feed
composition increase. Thus, it is advisable to minimize the use of steam. However, this adversely affects the life of a catalyst due to carbon deposition, and thus
there is a need for developing a catalyst inhibited from deactivation under the above-mentioned conditions. More particularly, as shown in the following Tables 1, 2
and 3, in which equilibrium conversions of combined reforming calculated thermodynamically are described, CO2 conversion in the combined reforming decreases
as the reaction pressure and steam content in the feed composition increase, while CO2 conversion increases as the reaction temperature increases. In addition,
equilibrium conversion of combined reforming and H2/(2CO + 3CO2) ratio are varied with the feed composition and reaction temperature. Therefore, in order to

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allow synthesis gas to maintain a predetermined ratio (H2/(2CO + 3CO2) = 0.85-1.15), it is necessary to adjust the molar ratio of reactants (methane, carbon dioxide
and steam), reaction pressure and reaction temperature, and it is important to employ a suitable catalyst. [Table 1]
Variations in Equilibrium Conversion and Synthesis Gas Ratio Depending on Feed Composition and Temperature/Pressure (Feed Composition: CH4/H2O/CO2 =
1/1.5/x (Molar Ratio) at 900 °C, 0.5-1.0 MPa)
P=0.5MPa P=1.0MPa
CO2 Ratio CH4 Conversion (%) CO2 Conversion (%) CO2 Ratio CH4 Conversion (%) CO2 Conversion (%)

0.3 96.98 36.67 0.3 90.87 32.33

0.4 97.14 40.00 0.4 91.75 40.50
0.5 97.35 43.75 0.5 92.54 44.80
0.6 97.67 47.40 0.6 93.25 47.33
0.7 98.17 49.50 0.7 93.88 48.71
0.8 98.37 50.57 0.8 94.45 49.63
0.9 98.54 51.25 0.9 94.96 50.11
1.0 98.69 51.44 1.0 95.42 50.30
[Table 2]
Variations in Equilibrium Conversion and Synthesis Gas Ratio Depending on Feed Composition and Temperature/Pressure (Feed Composition: CH4/H2O/CO2 =
1/2.0/x (Molar Ratio) at 900 °C, 0.5-1.0 MPa)
P=0.5MPa P=1.0 MPa
CO2 Ratio CH4 Conversion (%) CO2 Conversion (%) CO2 Ratio CH4 Conversion (%) CO2 Conversion (%)

0.3 98.39 8.33 0.3 94.53 6.00

0.4 98.54 21.25 0.4 94.94 19.50
0.5 98.66 28.60 0.5 95.33 27.20
0.6 98.78 33.33 0.6 95.69 32.17
0.7 98.89 36.29 0.7 96.02 35.29
0.8 98.98 38.38 0.8 96.33 37.50
0.9 99.07 39.78 0.9 96.61 38.89
1.0 99.14 40.70 1.0 96.87 40.00
[Table 3]
Variations in Equilibrium Conversion and H2/(2CO+3CO2) Ratio (0.1 MPa) Depending on Feed Composition/Reaction Temperature

Reactant Composition CH4:CO2:H2O (molar ratio) Conversion 700 °C 800 °C 900 °C 1000 °C
(%)

1 : 0.4 : 1 CH4 86 98 100 100

CO2 45 66 73 78

H2/CO 2.31 2.16 2.09 2.05

H2/(2CO+3CO2) 0.88 0.92 0.93 0.93

1 : 0.86 : 2 CH4 74 98 100 100

CO2 15 30 40 48

H2/CO 2.34 2.20 1.99 1.85

H2/(2CO+3CO2) 0.63 0.48 0.39 0.32

1 : 0.44 : 2 CH4 94 98 100 100

CO2 -12 10 25 36

H2/CO 3.24 2.83 2.60 2.45

H2/(2CO+3CO2) 0.88 0.90 0.90 0.90

[0020] As shown in Tables 1, 2 and 3, combined reforming may be operated under a pressure ranging from ambient pressure to 20 atm. However, in the case of low
pressure, equilibrium conversion increases, while the reactor volume increases, resulting in an increase in initial cost. In addition, a high-pressure system is required
additionally for the separation of the product, resulting in degradation of cost-e ciency. On the other hand, under an operating condition above 20 atm, deactivation
of catalyst is accelerated and equilibrium conversion of methane and carbon dioxide decreases. Therefore, it is necessary to maintain an adequate operating
condition. To maintain an optimized feed condition of H2/(2CO + 3CO2) molar ratio of 0.85 to 1.15, it is required for the reforming reactants to maintain a
CH4/CO2/H2O molar ratio of 1/0.3-0.6/1.0-2.0. When the molar ratio of H2O based on methane is 1.0 or less, deactivation of catalyst caused by carbon deposition
becomes severe. On the other hand, when the molar ratio exceeds 2.0, CO2 conversion decreases and CO2 availability also decreases, as demonstrated in Tables 1,
2 and 3.
[0021] In general, as shown in Figure 1, in a reaction for methanol synthesis, methanol yield is improved in the presence of synthesis gas containing a predetermined
amount of CO2 as compared to synthesis gas merely containing CO and H2. It can be seen that methanol yield is maximized under a molar ratio of CO/(CO+CO2) of
0.6 to 0.8. Therefore, the SRM/CDR combined reforming suggested herein allows preparation of synthesis gas suitable for methanol synthesis by maintaining a
predetermined ratio of carbon monoxide, carbon dioxide and hydrogen (H2/(2CO + 3CO2) = 0.85-1.15), making it possible to maximize methanol synthesis
e ciency. In this manner, the method disclosed herein is very useful for processes for preparing methanol from carbon dioxide.
[0022] In addition, as shown in Figure 2, the method disclosed herein includes an integrated process of three main unit operations, i.e., reforming, methanol synthesis and
separation. First, combined reforming (steam carbon dioxide reforming of methane: SCRM) is carried out by using our previous study for combined reforming
(Korean Patent Application No. 2008-0075787 ), wherein steam reforming of natural gas (CH4) (SRM) is performed simultaneously with carbon dioxide reforming of
methane (CDR). Herein, the resultant synthesis gas of carbon monoxide, carbon dioxide and hydrogen is allowed to maintain a predetermined molar ratio (H2/(2CO
+ 3CO2)= 0.85-1.15) so that it is suitable for methanol synthesis. In the subsequent methanol synthesis, a catalyst system for methanol synthesis capable of
minimizing formation of byproducts according to our previous study (Korean Patent Application No. 2008-0072286 ) is used. The method disclosed herein is
characterized by such an integrated process capable of maximizing carbon availability (methane and CO2 availability) and energy e ciency. Before carrying out the
combined reforming, sulfur compounds contained in natural gas is removed by pretreatment using generally known adsorptive desulfurization or
hydrodesulfurization processes to inhibit deactivation of reforming catalyst. In addition, C2-C4 hydrocarbons in natural gas are preliminarily converted in a pre-

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reformer before they are fed into a combined reforming reactor at high temperature, so that catalyst deactivation caused by carbon production is inhibited in the
subsequent operation. The combined reforming is carried out by performing steam reforming of natural gas simultaneously with carbon dioxide reforming of
methane, thereby maximizing carbon dioxide availability. The combined reforming is carried out by using a catalyst obtained by supporting Ni as an active
ingredient on Ce/MgAlOx or Ce-Zr/MgAlOx as a carrier in a weight ratio of 5 to 20 wt% based on the carrier, followed by calcination at 600 to 1,000 °C, and having a

speci c surface area of 80 to 200 m2/g (Korean Patent Application No. 2008-0075787 ). In addition, the catalyst is reduced at a temperature of 700 to 1,000 °C
before the reaction, and then the combined reforming is carried out at a temperature of 800 to 1,000 °C under a reaction pressure of 0.5 to 20 atm with a space
velocity of 1,000 to 500,000 h-1. Then, the resultant synthesis gas is used for the subsequent methanol synthesis while maintaining a predetermined molar ratio
(H2/(2CO + 3CO2)= 0.85-1.15). In the operation of methanol synthesis, a catalyst system including a cerium-zirconium oxide obtained by a sol-gel process in
combination with a Cu-Zn-Al oxide at a weight ratio of 0.1 to 10 based on the cerium-zirconium oxide according to our previous study (Korean Patent Application
No. 2008-0072286 ) is used. Particularly, the cerium-zirconium oxide obtained by a sol-gel process has a Ce/Zr ratio of 0.02 < Ce/Zr < 0.5 and a speci c surface
area of 100 to 300 m2/g, and the nished catalyst for methanol synthesis, Cu-Zn-Al/CeO2-ZrO2 has a speci c surface area of 50 to 250 m2/g. The catalyst for
methanol synthesis is reduced at a temperature ranging from 200 to 500 °C under hydrogen atmosphere, and then a reaction for methanol synthesis is carried out
at a temperature of 200 to 400 °C under a pressure of 30 to 60 kg/cm2 with a space velocity of 1,000 to 10,000 h-1. The nal product, methanol, and unreacted
reactants are separated from each other by a separation process generally known to those skilled in the art, and the unreacted reactants are recycled to the
reactors for combined reforming and methanol synthesis. In this connection, the recycle ratio (RR= recycle ow rate/total ow rate of unreacted reactants) is
controlled adequately to maximize carbon availability and energy e ciency in the overall process. The recycle ratio (RR(2)) of unreacted reactants recycled to
combined reforming and that (RR(1)) of unreacted reactants recycled to methanol synthesis are maintained below 20% and above 80%, respectively, based on the
total recycle ow, so that reutilization of synthesis gas may be maximized in the reactor for methanol synthesis. In this manner, it is possible to improve energy
e ciency and carbon availability in the overall process. For example, when the recycle ratio toward combined reforming is greater than 20%, high energy
consumption is required to increase the temperature to a high temperature of 800 °C or higher before the combined reforming, or synthesis gas, CO or H2,
contained in the recycle ow in an excessive amount may function as a diluting gas, leading to degradation of energy e ciency. In addition, when the recycle ratio
toward methanol synthesis is lower than 80%, the amount of reactants for methanol synthesis is decreased, resulting in a drop in methanol yield. Therefore, it is
required to control the recycle ratio of unreacted reactants adequately, so that the ratio of H2/(2CO+3CO2) is maintained at a range of 0.85 to 1.15 favorable to
methanol synthesis even if CO2 contained in the reactants is concentrated during the recycling. Such control of the recycle ratio increases carbon availability (one-
pass conversion) in methanol synthesis, and thus maximizes energy e ciency and carbon availability.
[0023] Figure 3 is a schematic diagram of the method including combined reforming and methanol synthesis and providing maximized energy e ciency and carbon
availability. The method broadly includes carrying out combined reforming, carrying out methanol synthesis, and carrying out separation and recycling. First, natural
gas is passed into a desulfurizer by way of stream 1. The desulfurization process used herein is a generally known adsorption desulfurization or
hydrodesulfurization process capable of removing sulfur components in natural gas. By doing so, it is possible to inhibit deactivation of reforming catalyst and to
prevent corrosion inside of the reactor and conveying lines. Then, stream 2 free from sulfur components is passed through a pre-reformer, wherein C2-C4
hydrocarbons in natural gas are reformed rst in order to inhibit deactivation of catalyst caused by carbon formation in a combined reforming reactor with high
temperature. Thus, after such pretreatment, stream 3 essentially includes methane and reformed gas. Water (stream 4) as one of the reactants for combined
reforming is subjected to heat exchange and supplied as a reactant in the form of highly pressurized steam. Carbon dioxide reactant, stream 5, is also subjected to
heat exchange, combined with stream 3 and stream 4, and then is fed into the combined reforming reactor heated to 700 °C or higher. Herein, stream 15 composed
of unreacted reactants and containing an excessive amount of CO2 is combined with the above streams, while maintaining a recycle ratio (RR(2)) of 0.2 or less, and
then supplied to the combined reforming reactor. After the combined reforming, the product, stream 6 is passed through a ash column, which is a gas-liquid
separator, and unreacted water and other high-boiling point products passed through the ash column is discharged as stream 8, which, in turn, is puri ed to
provide water capable of being reused as processing water. On the other hand, synthesis gas (stream 7) as a reactant for methanol synthesis is boosted to a high
pressure of 30 atm or higher suitable for methanol synthesis, is subjected to heat exchange, and then is fed to a reactor for methanol synthesis. The reactants for
methanol synthesis is further combined with stream 9 derived from recycling of unreacted synthesis gas after methanol synthesis and maintaining a recycle ratio
of 0.8 or higher, is subjected to heat exchange, and then is fed to the reactor for methanol synthesis along stream 10. Then, stream 11 passed through methanol
synthesis from synthesis gas is sent to a ash column (a gas-liquid separator) to perform gas-liquid separation. After the separation, stream 13 formed of the main
product, methanol, and byproducts essentially including water and CO2 dissolved in stream 13 are sent to the next separation unit. Unreacted synthesis gas is
recycled as stream 12, which, in turn, is reutilized in the combined reforming reactor and reactor for methanol synthesis while maintaining an adequate recycle
ratio. Stream 13 containing the main product is passed through a stripper rst to separate CO2 and is conveyed as stream 14, which, in turn, is combined with
stream 12 to be recycled. Herein, stream 12 and stream 14 are boosted before they are recycled to methanol synthesis in order to compensate for a pressure drop
occurring in the separation. As an alternative, stream 14 is fed merely into the combined reforming reactor so as to inhibit a drop in methanol yield caused by an
increase in CO2 concentration in the reactor for methanol synthesis. Finally, stream 16 passes from the stripper into a separation unit for purifying methanol, so that
high-purity methanol is discharged as stream 17 and water and dissolved CO2 are discharged as stream 18, which, in turn, is puri ed and recycled. Herein, stream 9
and stream 15 are maintained at a recycle ratio of 0.8 or higher and 0.2 or less, respectively, in order to maximize energy e ciency and carbon availability in the
overall process for preparing methanol from carbon dioxide. The catalysts that may be used in the method including carrying out reforming, carrying out methanol
synthesis and carrying out separation are based on our previous studies. First, a catalyst for combined reforming according to our previous study (Korean Patent
Application No. 2008-0075787 ) is used in such a manner that the resultant synthesis gas has a predetermined molar ratio of carbon monoxide, carbon dioxide and
hydrogen (H2/(2CO + 3CO2) = 0.85-1.15). Next, a catalyst for methanol synthesis according to our previous study (Korean Patent Application No. 2008-0072286 ) is
used to minimize formation of byproducts. In addition to the above, unreacted synthesis gas is recycled at an adequate recycle ratio to maximize carbon availability
(methane and CO2 availability) and energy e ciency.
[0024] The examples (and experiments) will now be described. The following examples (and experiments) are for illustrative purposes only and not intended to limit the
scope of the present disclosure.
[Example 1]
[0025] A catalyst for combined reforming is prepared according to our previous study (Korean Patent Application No. 2008-0075787 ).
[0026] First, PURAL MG30 (available from Sasol, speci c surface area: at least 250 m2/g), which is MgAlO (30) with a hydrotalcite structure having an MgO/Al O ratio of
x 2 3
3/7, is provided as a catalyst carrier for combined reforming. Next, the MgAlOx(30) carrier is impregnated with cerium acetate and zirconium acetate in such a
manner that Zr/Ce ratio is 0.25 on the weight basis and Ce-Zr is carried on the MgAlOx(30) carrier at a ratio of 18 wt% based on the total weight of the carrier. At the
same time, nickel nitrate hexahydrate (Ni(NO3)26H2O) as a nickel precursor is supported on the Ce-Zr/MgAlOx(30) carrier at a weight ratio of 15 wt% based on the
total weight of the carrier. Then, the resultant product is agitated in a vacuum drier at 70 °C for 12 hours to remove water as a solvent, further dried in an oven at
100 °C for at least 24 hours, and then calcined at 850 °C for 6 hours to provide a nished catalyst Ni/Ce-Zr/MgAlOx. The catalyst is formed into pellets with a size of

5 mm x 5 mm by using a pelletizer. The resultant catalyst has a speci c surface area of 85 m2/g, pore volume of 0.21 cc/g and an average pore size of 11.5 nm.
Then, 75 g of the catalyst is packed in an Incolloy 800H reactor, and is reduced under hydrogen atmosphere (10 vol% H2/N2) at 750 °C for 5 hours, and a combined
reforming reaction is carried out. To the reforming reactor, reactants including CH4, CO2 and H2O at a xed molar ratio of 1:0.4:1.5 (CH4:CO2:H2O) are fed at a
reaction temperature of 850 °C under a reaction pressure of 0.5 MPa with a space velocity of 1300 L/kg cat/h. The catalyst bed shows a distribution of reaction
temperature ranging from 795 °C to 981 °C.
[0027] Then, a catalyst for methanol synthesis is prepared according to our previous study (Korean Patent Application No. 2008-0072286 ).
[0028] A cerium-zirconium oxide as a carrier is provided by a sol-gel process.

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28/01/2018 EP2371799A1 - Methanol synthesis method using synthesis gas generated by a mixed reforming of natural gas and carbon dioxide - Google Patents
[0029] First, 12.06 g of citric acid and 14.32 g of ethylene glycol are dissolved at 60 °C for 30 minutes under agitation. Next, 2.50 g of cerium nitrate hexahydrate
(Ce(N03)26H2O) as a Ce precursor is dissolved in a minimum amount of water equal to or less than 30 mL so that it is dissolved completely therein, and then the
resultant solution is added gradually to the preformed mixture of citric acid with ethylene glycol to provide solution A. Herein, citric acid is used in a molar amount
corresponding to 10 times of calcium and ethylene glycol is used in a molar amount corresponding to 40 times of calcium. In the same manner, 213.01 g of citric
acid and 252.89 g of ethylene glycol are dissolved at 60 °C for 30 minutes under agitation. Then, 23.56 g of a zirconium (IV) oxychloride octahydrate (ZrCl2O8H2O)
as a Zr precursor is dissolved in 30 mL or less of water so that it is dissolved completely therein, and the resultant solution is added gradually to the preformed
mixture of citric acid with ethylene glycol to provide solution B. Solution A is mixed with solution B and the mixture is agitated at 60 °C for 30 minutes. Then, the
resultant solution is heated at 120 to 130 °C for 5 hours to remove water contained in the solution completely. The obtained sol-like material is maintained at 100
°C, 150 °C, 200 °C and 300 °C, each for 1 hour, at a heating rate of 5 °C/min. Then, the material is maintained at 400 °C for 2 hours so that the surface area of the
carrier may be maximized. Finally, the material is calcined while maintaining the temperature at 500 °C for 4 hours. Herein, the carrier includes 8 wt% of Ce and 92
wt% of Zr (on the metal basis), and has a speci c surface area of 164.5 m2/g.
[0030] Then, 0.8 g of the cerium-zirconium oxide carrier obtained as described above in the form of powder is used together with Cu, Zn and Al precursors. As Cu, Zn and
Al precursors, 5.51 g of copper acetate hydrate (Cu(C2H3O2)2·H2O), 3.03 g of zinc acetate dihydrate (Zn(C2H3O2)2·2H2O), and 2.78 g of aluminum nitrate
nonahydrate (Al(NO3)3·9H2O) are dissolved in 600 mL of deionized water to provide a mixed metal solution having a pH of 5.1. In addition, as a precipitating agent,
5.52 g of sodium carbonate dissolved in 600 mL of deionized water is used, wherein the solution has a pH of 10.2.
[0031] In a 2000 mL ask, at 70 °C, the mixed metal solution and the precipitating agent solution obtained as described above are added gradually to 200 mL of cerium-
zirconium oxide slurried in deionized water at the same time, while maintaining a nal pH of 7.5 to 8.0. Herein, the mixed solution is agitated for about 3 hours at 70
°C, and the resultant catalyst (CuZnAl/Ce0.08Zr0.92Ox) is washed with 2000 mL of deionized water three times or more, ltered, and then dried at 100 °C over at
least 12 hours and calcined at 300 °C for 5 hours under air to provide a catalyst for use in methanol synthesis from synthesis gas. The nished catalyst for
methanol synthesis has a speci c surface area of 123.0 m2/g. The catalyst for methanol synthesis obtained in the form of powder is formed into pellets with a size
of 5 mm x 2.5 mm, and 320 g of the catalyst is charged into a xed bed reactor. Then, the catalyst is reduced under hydrogen atmosphere for 4 hours at 250 °C.
Methanol is synthesized from the synthesis gas obtained from the combined reforming under a pressure of 5.0 MPa with a space velocity of 4300 L/kg cat/h.
Herein, the reactor shows a temperature distribution ranging from 241 °C to 290 °C.
[0032] The catalysts for combined reforming and methanol synthesis are used to carry out an integrated process for preparing methanol from carbon dioxide. The recycle
ratio toward the methanol reactor is 0.94 and 6% of unreacted reactants are not recycled to the reactor but discharged to the exterior. The results are shown in the
following Tables 4 and 5. After carrying out the integrated process, it is shown that CO2 conversion {((supplied CO2 - unconverted CO2)/ supplied CO2) X 100} is
84%, methanol yield (moles of methanol product/supplied (CH4 + CO2) moles) X 100) is about 79%, and methanol production rate is 155 g/h. [Table 4]

Results of Combined Reforming (Example 1)

Space velocity (L/kg cat/h) Molar ratio of reactants (mol%) (CH4/H2O/CO2) Recycle ratio (RR(2)) Conversion (mol%) Molar ratio of synthesis gas

CH4 CO2 CO/(CO + CO2) H2/(2CO + 3CO2)

1300 1/1.5/0.4 0 95 46 0.83 0.91

[Table 5]
Results of Methanol Synthesis (Example 1)
Space velocity (L/kg Molar ratio of reactants CO/(CO + Recycle ratio Conversion Methanol production rate Conversion upon recycling
cat/h) CO2) (RR(1)) (mol%) (g/h) (%)

CO CO2

4300 0.61 0.94 35 7 155 84

[Example 2]
[0033] The integrated process is carried out by using the same catalysts as Example 1, except that the combined reforming is performed under a reaction pressure of 0.65
MPa with a space velocity of 1700 L/kg cat/h by feeding the reactants at a xed molar ratio of CH4:CO2:H2O of 1:0.39:1.5 to the reforming reactor. In addition, the
same catalyst for methanol synthesis as Example 1 is charged to the reactor in an amount of 350 g and the reaction for methanol synthesis is carried out under a
reaction pressure of 5.0 MPa with a space velocity of 4700 L/kg cat/h by using the synthesis gas obtained from the combined reforming. Herein, the combined
reforming reactor shows a temperature distribution of 755 to 990 °C and the catalyst bed of the reactor for methanol synthesis shows a temperature distribution of
223 to 295 °C.
[0034] The catalysts for combined reforming and methanol synthesis are used to carry out an integrated process for preparing methanol from carbon dioxide. The recycle
ratio toward the methanol reactor is 0.81, the recycle ratio toward the combined reforming reactor is 0.12, and the ratio of unreacted reactants discharged to the
exterior is 0.07. The results are shown in the following Tables 6 and 7. After carrying out the integrated process, it is shown that CO2 conversion is 95%, methanol
yield is about 80%, and methanol production rate is 202 g/h. [Table 6]
Results of Combined Reforming (Example 2)
Space velocity (L/kg cat/h) Molar ratio of reactants (mol%) (CH4/H2O/CO2) Recycle ratio (RR(2)) Conversion (mol%) Molar ratio of synthesis gas

CH4 CO2 CO/(CO+CO2) H2/(2CO+3CO2)

1700 1/1.5/0.39 0.12 93 57 0.87 0.93

[Table 7]
Results of Methanol Synthesis (Example 2)
Space velocity (L/kg Molar ratio of reactants Recycle ratio Conversion Methanol production rate Conversion upon recycling
cat/h) CO/(CO+CO2) (RR(1)) (mol%) (g/h) (%)

CO CO2

4700 0.72 0.81 38 3 202 67

[Example 3]
[0035] The integrated process is carried out by using the same catalysts as Example 1, except that the combined reforming is performed under a reaction pressure of 0.55
MPa with a space velocity of 1700 L/kg cat/h by feeding the reactants at a xed molar ratio of CH4:CO2:H2O of 1:0.34:1.5 to the reforming reactor. In addition, the
same catalyst for methanol synthesis as Example 1 is charged to the reactor in an amount of 350 g and the reaction for methanol synthesis is carried out under a
reaction pressure of 5.0 MPa with a space velocity of 4300 L/kg cat/h by using the synthesis gas obtained from the combined reforming. Herein, the combined
reforming reactor shows a temperature distribution of 755 to 995 °C and the catalyst bed of the reactor for methanol synthesis shows a temperature distribution of
216 to 298 °C.
[0036] The catalysts for combined reforming and methanol synthesis are used to carry out an integrated process for preparing methanol from carbon dioxide. The recycle
ratio toward the methanol reactor is 0.90, the recycle ratio toward the combined reforming reactor is 0.08, and the ratio of unreacted reactants discharged to the
exterior is 0.02. The results are shown in the following Tables 8 and 9. After carrying out the integrated process, it is shown that CO2 conversion is 95%, methanol
yield is about 95%, and methanol production rate is 215 g/h. [Table 8]
Results of Combined Reforming (Example 3)

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Space velocity (L/kg cat/h) Molar ratio of reactants Results
(mol%) (CH 4/H2O/COReforming
of Combined 2) Recycle (Example
ratio (RR(2))
3) Conversion (mol%) Molar ratio of synthesis gas

CH4 CO2 CO/(CO+CO ) H2/(2CO+3CO2)

Space velocity (L/kg cat/h) Molar ratio of reactants (mol%) (CH4/H2O/CO2) Recycle ratio (RR(2)) Conversion (mol%) Molar ratio2of synthesis gas
1700 1/1.5/0.34 0.08 97 44 0.84 1.02
CH4 CO2 CO/(CO+CO2) H2/(2CO+3CO2)
[Table 9]
Results of Methanol Synthesis (Example 3)
Space velocity (L/kg Molar ratio of reactants Recycle ratio Conversion Methanol production rate Conversion upon recycling
cat/h) CO/(CO+CO2) (RR(1)) (mol%) (g/h) (%)

CO CO2

4300 0.68 0.90 53 8 215 87

[Example 4]
[0037] To determine the composition in each unit process represented by the ow chart of Figure 2 through modeling using the results of Example 3, ASPEN PLUS is used
to simulate the process, and the results are shown in the following Table 10. To perform the simulation, it is assumed that the recycle ratios toward the reactor for
methanol synthesis and toward the combined reforming reactor are xed at 0.8 and 0.19, respectively, and the ow ratio of unreacted reactants discharged to the
exterior is 0.01. The results are summarized in Table 10. Herein, stream 10 in Figure 3, which is passed through the combined reforming reactor, combined with
unreacted reactants and then fed into the reactor for methanol synthesis, has a H2/(2CO + 3CO2) ratio of 1.22. Such a ratio is slightly away from the range suitable
for methanol synthesis. It is thought that this results from a decrease in recycle ratio toward the reactor for methanol synthesis to 0.8 or less. [Table 10]
Stream # 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Mole Flow (kmol/h ) 1.00 1.50 0.34 6.66 5.90 0.81 7.49 13.39 10.70 9.32 1.38 0.05 1.78 1.33 1.26 0.07
Mole %
CH4 100 0.00 0.00 0.36 0.41 0.00 1.24 0.87 1.08 1.23 0.07 2.08 1.24 0.00 0.00 0.00

H2O 0.00 100 0.00 11.45 0.27 94.2 0 0.01 0.01 0.58 0.01 4.49 0.00 0.01 4.65 0.00 89.8 6

CO 0.00 0.00 0.00 22.37 25.2 4 0.00 12.8 1 18.39 11.21 12.8 6 0.07 2.08 12.8 1 0.00 0.00 0.00
H2 0.00 0.00 0.00 61.21 69.0 8 0.00 75.1 3 72.96 65.78 75.4 9 0.14 4.17 75.1 3 0.00 0.00 0.00

CO2 0.00 0.00 100 4.34 4.90 0.12 10.2 2 7.70 9.01 9.88 3.12 75.00 10.22 0.53 0.00 10.14

CH3OH 0.00 0.00 0.00 0.27 0.10 5.68 0.60 0.08 12.34 0.52 92.10 16.67 0.60 94.82 100 0.00
[0038] In a variant, to perform the simulation, it is assumed that the recycle ratios toward the reactor for methanol synthesis and toward the combined reforming reactor
are xed at 0.90 and 0.09, respectively, and the ow ratio of unreacted reactants discharged to the exterior is 0.01. The results are summarized in Table 11. Herein,
stream 10 in Figure 3, which is passed through the combined reforming reactor, combined with unreacted reactants and then fed into the reactor for methanol
synthesis, has a H2/(2CO + 3CO2) ratio of 0.95. Such a ratio is within the range suitable for methanol synthesis. [Table 11]

Stream # 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Mole Flow (kmol/hr) 1.00 1.50 0.34 5.66 4.93 0.78 7.70 12.6 3 9.91 8.49 1.42 0.07 0.7 7 1.35 1.26 0.09
Mole %
CH4 100 0.00 0.00 0.44 0.51 0.00 2.72 1.86 2.35 2.73 0.07 1.43 2.7 2 0.00 0.00 0.00

H2O 0.00 100 0.00 13.0 0.28 3 94.9 9 0.01 0.01 0.84 0.01 5.86 0.00 0.0 6.09 0.00 1 91.1 1

CO 0.00 0.00 0.00 23.67 27.1 6 0.00 13.70 19.1 11.8 3 4 13.8 0 0.07 1.43 13. 70 0.00 0.00 0.00
H2 0.00 0.00 0.00 57.9 7 66.5 3 0.00 67.85 67.91 58.6 3 68.39 .14 2.86 67. 85 0.00 0.00 0.00

CO2 0.00 0.00 100 4.77 5.47 0.13 15.06 11.0 2 13.0 8 14.5 3 4.38 78.5 7 15. 06 0.59 0.00 8.89

CH3OH 0.00 0.00 0.00 0.12 0.04 4.88 0.65 0.07 13.2 6 0.53 89.48 15.71 0.65 93.32 100 0.00
[0039] As can be seen from the foregoing, in the highly e cient process for preparing methanol using carbon dioxide, it is necessary to maintain the molar ratio of
reactants for combined reforming (CH4/CO2/H2O) at 1/0.3-0.6/1.0-2.0 in order to maintain a predetermined molar ratio of synthesis gas of carbon monoxide,
carbon dioxide and hydrogen (H2/(2CO + 3CO2)= 0.85-1.15) as the products of combined reforming. In addition to this, it is required to control the recycle ratios
toward the reactor for methanol synthesis and toward the combined reforming reactor within an adequate range. Particularly, when the ratio of synthesis gas in the
unreacted reactants remaining after methanol synthesis and recycled toward combined reforming is maintained at 0.0 to 0.2, and the ratio of the unreacted
synthesis gas recycled toward methanol synthesis is maintained at 0.8 to 1.0, it is possible to obtain the ratio of synthesis gas suitable for methanol synthesis
(H2/(2CO + 3CO2) = 0.85-1.15). In conclusion, it is possible to maximize carbon availability (methane and CO2 availability) and energy e ciency by using the
catalyst systems according to our previous studies and by selecting an adequate recycle ratio of unreacted materials.
[Industrial Applicability]
[0040] In 2005, as a measure to deal with global warming, the Kyoto protocol regarding reduction of carbon dioxide emission is enacted. Under these circumstances, it is
getting important gradually to develop technologies of reducing carbon dioxide emission and producing energy-containing materials from carbon dioxide. The
present disclosure provides an integrated process including carrying out combined reforming of carbon dioxide reforming of methane and steam reforming of
methane as a process for economical utilization of carbon dioxide to produce synthesis gas, and synthesizing methanol from the obtained synthesis gas. In this
manner, it is possible to maximize energy e ciency and carbon availability. The primary product, methanol, is useful as a starting material for producing various
industrial products, such as DME, DMC, biodiesel and synthetic gasoline. Further, the synthesis gas obtained from the combined reforming is useful for Fischer-
Tropsch synthesis. Therefore, the method disclosed herein is expected to contribute to development of processes for economical utilization of carbon dioxide.

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KR20160103427A 2015-02-24 2016-09-01 Apparatus for preventing subsea hydrate and topside process hydrate
using are gas

WO2017001987A1 2015-07-01 2017-01-05 Sabic Global Technologies B.V. Dry reformation of methane reaction, nickel and cerium containing core-
shell structured catalysts therefor and their preparation

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KR20080123865A 2008-12-08 2008-12-08 Preparation method of methanol through synthesis gas derived from the combined reforming of methane gas with
mixture of steam and carbon dioxide

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