CN103183346B - Method of reverse water gas shift reaction for reverse water gas shift catalyst - Google Patents
Method of reverse water gas shift reaction for reverse water gas shift catalyst Download PDFInfo
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- CN103183346B CN103183346B CN201210538164.0A CN201210538164A CN103183346B CN 103183346 B CN103183346 B CN 103183346B CN 201210538164 A CN201210538164 A CN 201210538164A CN 103183346 B CN103183346 B CN 103183346B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000002441 reversible effect Effects 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 claims abstract description 43
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 230000004913 activation Effects 0.000 claims abstract description 35
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 20
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 239000006004 Quartz sand Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001994 activation Methods 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003034 coal gas Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000009423 ventilation Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000003252 repetitive effect Effects 0.000 claims description 4
- 238000005201 scrubbing Methods 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003213 activating effect Effects 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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Abstract
The invention discloses a method of reverse water gas shift reaction for reverse water gas shift catalyst. The method comprises the following steps: firstly, catalyst activation: adopting 60 to 100 mesh nickel cerium catalyst as reverse water gas shift catalyst, performing activating treatment to the nickel cerium catalyst for 1 to 2 hours at 600 to 800 DEG C through high-purity carbon dioxide gas; and secondly, reverse water gas shift reaction: uniformly mixing the nickel cerium catalyst conducted to activating treatment and 60 to 100 mesh quartz sand according to the weight ratio of 1:(2.5 to 3), feeding reverse water gas feed gas, and performing catalytic reaction at 600 to 800 DEG C so as to obtain water gas. The method has the advantages that the nickel cerium catalyst is selected for the reverse water gas shift reaction, simultaneously the high-purity carbon dioxide gas is adopted for performing activation, the activation effect is good, the catalytic activity and the thermal stability are good during the catalytic reaction, and the cost is low.
Description
Technical field
The present invention relates to technical field of petrochemical industry, particularly a kind of Reversed Water-gas Shift catalyzer is used for the method for reverse water-gas-shift reaction.
Background technology
Reverse water-gas-shift reaction equation is as follows:
CO
2 + H
2 = CO + H
2O ΔH=+41 kJ/mol
This reaction is a reversible heat absorption reaction with same mole, and high temperature is conducive to the carrying out of reverse water-gas-shift reaction.
In recent years, CO, for solving the problems such as energy shortage, shortage of resources, greenhouse gases effect, is extremely paid close attention in countries in the world
2exploitation research.CO
2as carbon source, be considered to be the inevitable development trend of human use's carbon source.CO in air and water
2carbon content is ten times of oil, Sweet natural gas and coal.Therefore when oil, gas, coal resource shortage, CO
2each goods and materials after good carbon source of can yet be regarded as.At present because the industrialized process in countries in the world is very fast, the consumption growth of the energy also accelerates thereupon.The mineral substance of annual burning makes CO in air
2concentration sharply increases, and will cause so-called Greenhouse effect, thus earth's surface and lower atmosphere layer temperature are raised.
Along with CO
2the Greenhouse effect that a large amount of discharge causes are day by day serious, CO
2conversion and applied research day by day enliven, wherein reverse water-gas-shift reaction (RWGS) is considered to one of reaction having application prospect most.Copper-based catalysts and Ni is catalyst based can be used for reverse water-gas-shift reaction.Reverse water-gas-shift reaction is thermo-negative reaction, and therefore high temperature is conducive to the generation of CO.Copper-based catalysts, due to poor heat stability, is not suitable for pyroreaction.Add Fe auxiliary agent, catalytic activity and the high high-temp stability of copper-based catalysts can be improved, but the activity of catalyzer still has much room for improvement.Ni/Al
2o
3catalyzer is used for reverse water-gas-shift reaction and shows good activity, but in reaction process, create a large amount of methane byproduct.The activation method of catalyzer has material impact to its performance simultaneously, is a key factor needing to consider, existing copper-based catalysts and Ni/Al
2o
3the activation method of catalyzer generally adopts nitrogen or Hydrogen activation, content disclosed in the invention of CN101607206A.At present, not yet CeO is had
2based metal catalysts for the research of high temperature reverse water-gas-shift reaction is reported how to develop CeO
2the effective activation method of based metal catalysts needs to be explored.
Summary of the invention
The object of the present invention is to provide a kind of Reversed Water-gas Shift catalyzer for the method for reverse water-gas-shift reaction, select nickel cerium catalyst for reverse water-gas-shift reaction, adopt special activation method, activation effect is good, there is during catalyzed reaction good catalytic activity, thermostability, and cost is low.
The technical solution adopted for the present invention to solve the technical problems is:
Reversed Water-gas Shift catalyzer is used for a method for reverse water-gas-shift reaction, and described method is:
(1) activation of catalyzer
Adopt 60-100 object nickel cerium catalyst as Reversed Water-gas Shift catalyzer, with high-purity carbon dioxide gas at 600-800 DEG C to nickel cerium catalyst activation treatment 1-2 hour.
(2) reverse water-gas-shift reaction
Mixed according to the part by weight of 1:2.5-3 with 60-100 object quartz sand by nickel cerium catalyst after activation treatment, logical coal gas unstripped gas against the current, at 600-800 DEG C, catalyzed reaction obtains water-gas.Mixed with quartz sand by nickel cerium catalyst, in order to control temperature of reaction that can be accurate, stable when catalyzed reaction, that guarantees to react stablely carries out.
The activation of general catalyzer is logical hydrogen reducing, and the present invention is directed to nickel cerium catalyst, adopt special high-purity carbon dioxide gas to activate, achieve preferably activation effect, and general activation method can not effective activation nickel cerium catalyst.
As preferably, in described nickel cerium catalyst, the mass percent of nickel is 0.25%-0.5%.The mass percent controlling nickel is 0.25%-0.5%, not only catalytic activity is better, simultaneously, the most important thing is that high-purity carbon dioxide gas can carry out effective active to it, although the mass percent of nickel is higher may obtain better catalytic activity, when the mass percent of nickel is more than 0.5%, then high-purity carbon dioxide gas effectively cannot play activation, and easily methanation side reaction occurs, and makes the selectivity of nickel cerium catalyst decline on the contrary.
As preferably, described nickel cerium catalyst adopts coprecipitation method preparation, be specially: after cerous nitrate solution and nickel nitrate solution are mixed, with sodium hydroxide and sodium carbonate for precipitation agent, the mol ratio of sodium hydroxide and sodium carbonate is 1:1, and drip is fixed, in the process, the pH value of precipitated liquid controls in 10 ± 0.1 scopes, stir 4-5h at ambient temperature, age overnight, subsequent filtration, use distilled water repetitive scrubbing, until pH<7.5, dry 20-24 h at 80-100 DEG C, then roasting 3-4 h at 600-800 DEG C in retort furnace, the mass percent obtaining nickel is the Ni – CeO of 0.25%-0.5%
2catalyzer.
As preferably, the purity of described high-purity carbon dioxide gas is more than 99.99%.
As preferably, in step (1), in 1mg nickel cerium catalyst, high-purity carbon dioxide gas ventilation speed is at 2.5-5ml/min.Control amount and the high-purity carbon dioxide gas ventilation speed of nickel cerium catalyst simultaneously, can ensure that nickel cerium catalyst is by effective activation like this, and activation effect is good.High-purity carbon dioxide gas ventilation speed then cannot effective activation lower than 2.5ml/min, high-purity carbon dioxide gas ventilation speed higher than 5ml/min then carbonic acid gas comparatively waste, add production cost.
As preferably, in step (2), in 1mg nickel cerium catalyst, coal gas unstripped gas draft speed is at 5-8ml/min against the current.Control amount and the coal gas unstripped gas draft speed against the current of nickel cerium catalyst simultaneously, the catalytic condition of the best can be ensured like this, play the performance of catalyzer to greatest extent, be conducive to the carrying out of reverse water-gas-shift reaction.
As preferably, in step (2), against the current coal gas unstripped gas consist of 50vol.%CO
2, 50vol.%H
2.
The invention has the beneficial effects as follows: select nickel cerium catalyst for reverse water-gas-shift reaction, adopt high-purity carbon dioxide gas to activate, activation effect is good, have good catalytic activity, thermostability, and cost is low during catalyzed reaction simultaneously.
Accompanying drawing explanation
Fig. 1 is the comparison diagram of the catalytic activity adopting different activation method catalyzer.
Embodiment
Below by specific embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.
In the present invention, if not refer in particular to, the raw material adopted and equipment etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the ordinary method of this area.
Ni – CeO
2the preparation of catalyzer (nickel cerium catalyst)
Prepared by employing coprecipitation method, after cerous nitrate solution and nickel nitrate solution are mixed, with sodium hydroxide and sodium carbonate for precipitation agent, the mol ratio of sodium hydroxide and sodium carbonate is 1:1, and drip is fixed, in the process, the pH value of precipitated liquid controls in 10 ± 0.1 scopes, stir 4-5h at ambient temperature, age overnight, subsequent filtration, use distilled water repetitive scrubbing, until pH<7.5, dry 20-24 h at 80-100 DEG C, then roasting 3-4 h at 600-800 DEG C in retort furnace, the mass percent obtaining nickel is the Ni – CeO of 0.25%-0.5%
2catalyzer.
With the Ni – CeO that nickel mass percent is 0.25%
2catalyzer is example, and use coprecipitation method preparation, concrete steps are as follows:
Measure the Ce (NO of 217.125g/L
3)
36H
2ni (the NO of O solution 46.4ml and 9.910g/L
3)
26H
2o solution 5ml obtains nitrate solution A after they being mixed; The Na of NaOH and 2.120g of 0.800g is taken respectively with electronic balance
2cO
3, join in the deionized water of 200ml and be made into precipitant solution B; By nitrate solution A and precipitant solution B and stream be titrated to 400ml stir deionized water in.In the process, the pH value of precipitated liquid controls in 10 ± 0.1 scopes, till nitrate solution drips off.Then, after stirring 4 h at ambient temperature, 12h is left standstill.Subsequent filtration, uses deionized water repetitive scrubbing, until pH<7.5, is in the loft drier of 80 DEG C of degree dry 24 hours in temperature, finally dried throw out to be put at retort furnace 600 DEG C roasting 4 hours, obtains 0.25%Ni-CeO
2catalyzer.
Embodiment 1
(1) activation of catalyzer
Adopt the nickel cerium catalyst of 60-100 order nickel mass percentage content 0.25% as Reversed Water-gas Shift catalyzer, with the high-purity carbon dioxide gas of purity more than 99.99% at 600 DEG C to nickel cerium catalyst activation treatment 2 hours, in 1mg nickel cerium catalyst, high-purity carbon dioxide gas ventilation speed is at 2.5ml/min.
(2) reverse water-gas-shift reaction
Nickel cerium catalyst after activation treatment is mixed according to the part by weight of 1:2.5 with 60-100 object quartz sand, logical coal gas unstripped gas against the current, in 1mg nickel cerium catalyst, coal gas unstripped gas draft speed is at 5ml/min against the current, against the current coal gas unstripped gas consist of 50vol.%CO
2, 50vol.%H
2; At 600 DEG C, catalyzed reaction obtains water-gas.
Embodiment 2
(1) activation of catalyzer
Adopt the nickel cerium catalyst of 60-100 order nickel mass percentage content 0.5% as Reversed Water-gas Shift catalyzer, with the high-purity carbon dioxide gas of purity more than 99.99% at 800 DEG C to nickel cerium catalyst activation treatment 1 hour, in 1mg nickel cerium catalyst, high-purity carbon dioxide gas ventilation speed is at 5ml/min.
(2) reverse water-gas-shift reaction
Nickel cerium catalyst after activation treatment is mixed according to the part by weight of 1:3 with 60-100 object quartz sand, logical coal gas unstripped gas against the current, in 1mg nickel cerium catalyst, coal gas unstripped gas draft speed is at 8ml/min against the current, against the current coal gas unstripped gas consist of 50vol.%CO
2, 50vol.%H
2; At 800 DEG C, catalyzed reaction obtains water-gas.
After adopting different activation methods to activate nickel cerium catalyst, catalytic activity nickel cerium catalyst being used for reverse water-gas-shift reaction compares, adopt the beautiful GC-7900 type gas-chromatography on-line analysis of sky, Shanghai, TDX-01 chromatographic column, fid detector (band methane reborner).Test result is shown in accompanying drawing 1.As shown in Figure 1, adopt method of the present invention and high-purity carbon dioxide gas activation, the catalytic activity that nickel cerium catalyst is used for reverse water-gas-shift reaction is best, nitrogen, air, hydrogen etc. then obviously cannot effective activation nickel cerium catalysts, after these gas activations, the catalytic activity that nickel cerium catalyst is used for reverse water-gas-shift reaction is low.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (3)
1. Reversed Water-gas Shift catalyzer is used for a method for reverse water-gas-shift reaction, it is characterized in that: described method is:
(1) activation of catalyzer
Adopt 60-100 object nickel cerium catalyst as Reversed Water-gas Shift catalyzer, with high-purity carbon dioxide gas at 600-800 DEG C to nickel cerium catalyst activation treatment 1-2 hour;
(2) reverse water-gas-shift reaction
Mixed according to the part by weight of 1:2.5-3 with 60-100 object quartz sand by nickel cerium catalyst after activation treatment, logical coal gas unstripped gas against the current, at 600-800 DEG C, catalyzed reaction obtains water-gas;
In described nickel cerium catalyst, the mass percent of nickel is 0.25%-0.5%; The purity of described high-purity carbon dioxide gas is more than 99.99%; In step (1), in 1mg nickel cerium catalyst, high-purity carbon dioxide gas ventilation speed is at 2.5-5ml/min; In step (2), in 1mg nickel cerium catalyst, coal gas unstripped gas draft speed is at 5-8ml/min against the current.
2. method according to claim 1, it is characterized in that: described nickel cerium catalyst adopts coprecipitation method preparation, be specially: after cerous nitrate solution and nickel nitrate solution are mixed, with sodium hydroxide and sodium carbonate for precipitation agent, the mol ratio of sodium hydroxide and sodium carbonate is 1:1, and drip is fixed, in the process, the pH value of precipitated liquid controls in 10 ± 0.1 scopes, stir 4-5h at ambient temperature, age overnight, subsequent filtration, use distilled water repetitive scrubbing, until pH<7.5, dry 20-24 h at 80-100 DEG C, then roasting 3-4 h at 600-800 DEG C in retort furnace, the mass percent obtaining nickel is the Ni – CeO of 0.25%-0.5%
2catalyzer.
3. method according to claim 1, is characterized in that: in step (2), against the current coal gas unstripped gas consist of 50vol.%CO
2, 50vol.%H
2.
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| CN106881084B (en) * | 2015-12-10 | 2019-04-30 | 中国科学院大连化学物理研究所 | One kind is for reverse water-gas-shift reaction noble metal catalyst and its preparation and application |
| CN105854914A (en) * | 2016-03-30 | 2016-08-17 | 浙江海洋学院 | Reverse water-gas shift catalyst prepared from crab shells |
| CN106492778B (en) * | 2016-10-28 | 2019-08-30 | 华侨大学 | A kind of doping vario-property nano Ce O2Stick catalyst and its application |
| ES2674434B2 (en) | 2016-12-29 | 2018-12-04 | Consejo Superior De Investigaciones Cientificas | PROCEDURE FOR OBTAINING FORMULA CATALYSTS My (Ce1-xLxO2-x / 2) 1-y FOR USE IN THE REVERSE REACTION OF DISPLACEMENT OF WATER GAS AND PARTIAL OXIDATION OF METHANE TO SYNTHESIS GAS BY METHOD OF COMBUSTION METHOD |
| CN106732743B (en) * | 2016-12-30 | 2019-09-24 | 浙江海洋大学 | A kind of mesoporous Reversed Water-gas Shift catalyst and preparation method thereof |
| CN108529625A (en) * | 2018-06-13 | 2018-09-14 | 昆明理工大学 | A method of preparing carbon monoxide using coal |
| TW202200490A (en) * | 2020-03-31 | 2022-01-01 | 日商大阪瓦斯股份有限公司 | System and method for producing hydrocarbon, and method for operating said system |
| EP4129470A4 (en) * | 2020-03-31 | 2024-04-17 | Osaka Gas Co., Ltd. | Reverse water-gas shift catalyst, electrolytic reaction system, hydrocarbon manufacturing system, and manufacturing methods and use method therefor |
| CN112604691B (en) * | 2020-12-14 | 2022-07-29 | 浙江海洋大学 | Reverse water gas shift catalyst, preparation method and application thereof |
| US11827521B2 (en) | 2021-12-14 | 2023-11-28 | Industrial Technology Research Institute | Method for selectively chemically reducing CO2 to form CO |
| CN114941144B (en) * | 2022-06-08 | 2023-05-30 | 万华化学集团股份有限公司 | Method for electrochemically synthesizing dimethyl sebacate |
| WO2024126607A1 (en) | 2022-12-14 | 2024-06-20 | Basf Se | Process for preparing at least one polyisocyanate from co2 |
| EP4403589A1 (en) | 2023-01-19 | 2024-07-24 | Basf Se | A process for preparing at least one polyisocyanate from solid material w |
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| EP1578529A2 (en) * | 2002-12-20 | 2005-09-28 | Honda Giken Kogyo Kabushiki Kaisha | Platinum and rhodium and/or iron containing catalyst formulations for hydrogen generation |
| CA2675742A1 (en) * | 2002-12-20 | 2004-07-15 | Honda Giken Kogyo Kabushiki Kaisha | Noble metal-free nickel catalyst formulations for hydrogen generation |
| CN101678329B (en) * | 2007-04-27 | 2013-09-18 | 沙特基础工业公司 | Catalytic hydrogenation of carbon dioxide into syngas mixture |
| CN101607206B (en) * | 2009-07-16 | 2012-05-30 | 复旦大学 | Method for increasing the activity of copper-based catalyst in water-gas shift reaction |
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