CN115382544B - Preparation and application of copper-aluminum catalyst for reverse water gas shift reaction - Google Patents
Preparation and application of copper-aluminum catalyst for reverse water gas shift reaction Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 6
- 239000011029 spinel Substances 0.000 claims abstract description 6
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 239000012691 Cu precursor Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000001384 succinic acid Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- -1 copper zinc aluminum Chemical compound 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses preparation and application of a copper-aluminum catalyst for reverse water gas shift reaction, and belongs to the technical field of carbon dioxide conversion. Aiming at the problems of the prior RWGS copper-based catalyst which is lack of high activity and high stability and is renewable and suitable for medium and high temperature conditions, a precursor of Cu, a precursor of Al and an additive are uniformly mixed and then react, and ball milling and drying treatment are carried out to obtain a catalyst precursor; and roasting the catalyst precursor for 0-8 hours at 600-1200 ℃ in inert atmosphere to obtain the copper-aluminum catalyst. The catalyst is prepared by adopting a solid-liquid reaction ball milling method, and the copper-aluminum catalyst with a copper-iron ore structure and a spinel structure can be generated by roasting at a low temperature. The catalyst has high catalytic stability in reverse water gas shift reaction, CO selectivity up to 99% and excellent catalyst reproducibility.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide conversion, and particularly relates to preparation and application of a copper-aluminum catalyst for reverse water gas shift reaction.
Background
Continuous consumption of fossil energy by humans results in a large amount of greenhouse gas CO 2 The emission of carbon dioxide, which has a serious impact on the ecological environment, is a widely accepted concern in industry, as to how to effectively convert carbon dioxide into chemical raw materials or chemical products that can be used by humans.
CO 2 The hydroconversion route mainly comprises: CO 2 Reverse Water Gas Shift (RWGS) and CO 2 Methanol and CO production 2 Methanation reaction and the like。CO 2 The direct hydrogenation to methanol is limited by thermodynamic equilibrium, the methanol yield is low, and the methanol is prepared by hydrogenation after CO is generated by RWGS reaction, so that the methanol yield [ Ind. Eng. Chem. Res.,1999,38:1808-1812 ] can be remarkably improved]Thus, the reverse water gas shift Reaction (RWGS) is considered to be CO 2 The conversion pathway with the most application potential in hydroconversion. At present, the synthesis gas is used for preparing chemicals (such as C x H y The technology of the process technology of olefin, alcohol, formaldehyde and acid) is quite mature, and the technology of converting synthesis gas is coupled through RWGS reaction, so that CO can be realized with low cost 2 Conversion and utilization, thereby effectively reducing CO 2 The emission of the atmosphere is gradually promoted to realize carbon peak and carbon neutralization.
RWGS is an endothermic reaction, and high temperature is favorable for improving CO 2 But the high temperature tends to cause sintering and deactivation of the catalyst. Catalyst developments for RWGS technology, commonly used catalysts include noble metal catalysts and non-noble metal catalysts. Wherein the noble metal catalyst is limited by the factors of small reserve, high price and the like; among the numerous non-noble metal catalysts, copper-based catalysts have been widely studied because of their high activity and low cost, for example: commercial Cu-Zn-Al catalysts are commonly used for CO 2 Hydroconversion, which has higher activity but high temperature>300 ℃ is poor in stability because the Tasmann temperature of metallic copper is low, cu is easy to sinter and grow up in the reaction process, and the catalyst is deactivated; furthermore, with respect to the deactivated Cu-Zn-Al catalyst, it is difficult to redisperse large-particle-diameter Cu therein into small-particle-diameter Cu and maintain the original structure of the fresh catalyst, and thus it is not renewable. Thus, researchers have attempted to improve copper dispersion, alleviate copper sintering by optimizing support, second metal modification, etc. [ chemical progress, 2017,36:2473-2480]However, there remains a challenge to develop a highly active and stable, and renewable RWGS copper-based catalyst suitable for use under medium-high temperature conditions.
Disclosure of Invention
Aiming at the problem that the current commercial copper zinc aluminum catalyst for RWGS is easy to sinter and deactivate, the invention provides a preparation method and application of the copper aluminum catalyst for reverse water gas shift reaction.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a copper-aluminum catalyst for reverse water gas shift reaction having a copper-iron ore structure and a spinel structure, comprising Cu 2 O, cuO and Al 2 O 3 A component (C); the mass fraction of each component is Cu 2 O=3.6%~58.4%、CuO=0%~54.2%、Al 2 O 3 =39.3%~68.1%。
A method for preparing a copper-aluminum catalyst for reverse water gas shift reaction, comprising the following steps:
step 1, uniformly mixing a Cu precursor, an Al precursor and an additive, reacting, and performing ball milling and drying treatment to obtain a catalyst precursor;
and 2, roasting the catalyst precursor for 0 h-8 hours at 600-1200 ℃ in an inert atmosphere to obtain the copper-aluminum catalyst.
Further, the precursor of Cu comprises one or a mixture of a plurality of copper oxide, copper hydroxide or copper acetate in any proportion.
Further, the precursor of Al comprises one or a mixture of several of alumina, aluminum hydroxide or pseudo-boehmite in any proportion.
Further, the additive comprises one or a mixture of several of methanol, ethanol, acetone, ammonium carbonate, ammonium bicarbonate, deionized water, citric acid, oxalic acid, malonic acid or succinic acid in any proportion.
Further, the molar ratio of the additive to the sum of the Cu precursor and the Al precursor is 1 to 5.
Further, the inert atmosphere is nitrogen, argon or helium.
The application of the copper-aluminum catalyst for the reverse water gas shift reaction is applied to the reverse water gas shift reaction.
The application method of copper-aluminum catalyst for reverse water gas shift reaction is that the reaction temperature is 200-600 deg.C, the reaction pressure is 0.1-5.0 MPa, H 2 /CO 2 The molar ratio of (C) is 0.5 to the upperAnd (3) carrying out reverse water gas shift reaction under the conditions of 5.0 and volume space velocity of 3.0L/(g.h) to 12.0L/(g.h).
The method is applied to the regeneration of the copper-aluminum catalyst of the reverse water gas shift reaction, and the regeneration of the copper-aluminum catalyst is completed by roasting for 0 to 8 hours in an inert atmosphere at the temperature of 600 to 1200 ℃.
Compared with the prior art, the invention has the following advantages:
the catalyst has high catalytic stability in reverse water gas shift reaction, CO selectivity up to 99% and excellent catalyst reproducibility.
1. The catalyst is prepared by adopting a solid-liquid reaction ball milling method, and the Cu-Al catalyst with a delafossite structure and a spinel structure can be generated by roasting at a low temperature.
2. The catalyst of the invention has high catalytic activity and stability in the reverse water gas shift reaction, is obviously superior to commercial copper zinc aluminum catalyst, and has the following inherent chemical principles: in the delafossite structure and the spinel structure, cu δ+ With Al 3+ With strong interactions, active Cu generated in situ by the reaction exhibits high activity and stability.
3. The catalyst can realize active regeneration by adopting a simple inert atmosphere roasting method, and the regenerated catalyst has the same crystal phase structure as that of a fresh catalyst, and has the catalytic performance equivalent to that of the fresh catalyst. Therefore, the regeneration performance of the catalyst of the invention is superior to that of commercial copper zinc aluminum catalysts.
4. The catalyst of the invention has high CO selectivity (more than or equal to 99%) for catalyzing reverse water gas shift reaction.
5. The catalyst of the invention can be directly fed for reaction without any pretreatment before use, thereby simplifying the starting process.
Drawings
Figure 1 is an XRD diffractogram of fresh copper aluminium catalyst and regenerated catalyst.
Detailed Description
The invention will be further illustrated by the following examples.
Example 1
Accurately weigh 57.4gCopper hydroxide [ Cu (OH) 2 ]And 42.6g of pseudo-boehmite [ Al (OOH). NH 2 O]Mixing with equal amount of citric acid, ball milling in ball mill for 0.5 hr, and stoving for 0.5 hr to obtain the catalyst precursor. Roasting the precursor for 3 hours at 1100 ℃ in nitrogen atmosphere to obtain a finished catalyst, wherein the composition (mass fraction) is as follows: cu (Cu) 2 O=44.1%、CuO=14.9%、Al 2 O 3 =41.0%。
The fresh catalyst was characterized by X-ray diffraction (XRD) and the results are shown in figure 1. The diffraction peaks in the figure indicate: the synthesized catalyst contains a crystalline phase of delafossite and spinel structure.
Crushing the catalyst, loading 1.0g of the catalyst with 30-40 meshes into a reactor, and starting a feeding reaction when the temperature is raised to 300 ℃, wherein the evaluation conditions and the results are shown in Table 1. The experimental results show that: reaction for 100h, CO 2 The conversion rate is 18.0-18.5%, and the CO selectivity is more than or equal to 99.5%.
Example 2
Accurately weigh 61.1g of copper oxide [ CuO ]]And 38.9g of alumina [ Al 2 O 3 ]Mixing with equal amount of ethanol uniformly, ball milling for 5.0h in a ball mill, and drying for 1.0h to obtain the catalyst precursor. Roasting the precursor in argon atmosphere at 800 ℃ for 5.0h to obtain a finished catalyst, wherein the composition (mass fraction) is as follows: cu (Cu) 2 O=55.1%、 CuO=3.4%、Al 2 O 3 =41.5%. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and the reaction results are shown in Table 1. The experimental results show that: reaction for 100h, CO 2 The conversion rate is 16.3% -16.9%, and the CO selectivity is 100%.
Example 3
Accurately weigh 57.8g of copper acetate [ Cu (CH) 3 COO) 2 ·H 2 O]And 42.2g of pseudo-boehmite [ Al (OOH). NH 2 O]And (3) uniformly mixing the catalyst precursor with the succinic acid with the same amount, ball milling the mixture in a ball mill for 4.0 hours, and drying the mixture for 3 hours to obtain the catalyst precursor. Roasting the precursor in helium atmosphere at 600 ℃ for 1.0h to obtain a finished catalyst, wherein the composition (mass fraction) is as follows: cu (Cu) 2 O=31.3%、CuO=10.6%、Al 2 O 3 =58.1%. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and the reaction results are shown in Table1. The experimental results show that: reaction for 100h, CO 2 The conversion rate is 23.1% -23.5%, and the CO selectivity is more than or equal to 99.7%.
Example 4
Accurately weighing 49.0g of copper hydroxide [ Cu (OH) 2 ]And 51.0g of alumina [ Al ] 2 O 3 ]Mixing with the ammonium carbonate with the same amount uniformly, transferring into a ball mill for ball milling for 7.0h, and then drying for 1.0h to obtain the catalyst precursor. Roasting the precursor for 3.0h at 800 ℃ in an argon atmosphere to obtain a finished catalyst, wherein the composition (mass fraction) is as follows: cu (Cu) 2 O=39.0%、CuO=2.4%、Al 2 O 3 =58.6%. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and the reaction results are shown in Table 1. The experimental results show that: reaction for 100h, CO 2 The conversion rate is 47.7-48.2%, and the CO selectivity is more than or equal to 99.4%.
Example 5
29.5g of copper oxide [ Cu (OH) was weighed out accurately 2 ]And 70.5g of aluminium hydroxide [ Al (OH) 3 ]And (3) uniformly mixing the catalyst precursor with the succinic acid with the same amount, transferring the mixture into a ball mill for ball milling for 5.0h, and then drying for 1.0h to obtain the catalyst precursor. Roasting the precursor in nitrogen atmosphere at 1000 ℃ for 1.0h to obtain a finished catalyst, wherein the composition (mass fraction) is as follows: cu (Cu) 2 O=24.2%、CuO=8.2%、Al 2 O 3 =67.6%. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and the reaction results are shown in Table 1. The experimental results show that: reaction for 100h, CO 2 The conversion rate is 7.2% -7.6%, and the CO selectivity is more than or equal to 99.8%.
Example 6
79.7g of copper acetate [ Cu (CH) 3 COO) 2 ·H 2 O]And 20.3g of alumina [ Al 2 O 3 ]And (3) uniformly mixing the catalyst precursor with the succinic acid with the same amount, transferring the mixture into a ball mill for ball milling for 6.0h, and then drying for 1.0h to obtain the catalyst precursor. Roasting the precursor for 8.0 hours at 800 ℃ in nitrogen atmosphere to obtain a finished catalyst, wherein the composition (mass fraction) is as follows: cu (Cu) 2 O=55.1%、CuO=3.4%、Al 2 O 3 =41.5%. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and the reaction results are shown in Table 1. The experimental results show that: reaction for 100h, CO 2 The conversion rate is 16.3 to 16.8 percent,the CO selectivity is more than or equal to 99.1 percent.
Example 7
Example 1 catalyst was run for 1000 hours, CO 2 The conversion rate is reduced to 9.3%, the catalyst is regenerated, and the catalyst is roasted for 5.0 hours at 1100 ℃ in nitrogen atmosphere. The XRD pattern of the regenerated catalyst obtained was consistent with that of the fresh catalyst (figure 1). The reverse water gas shift reaction was carried out under the same conditions as in example 1. The experimental results show that: reaction for 100h, CO 2 The conversion rate is 17.9-18.3%, and the CO selectivity is more than or equal to 99.5%.
Comparative example 1
The commercial Cu-Zn-Al catalyst was evaluated under the same reaction conditions as in example 1 and compared with the catalyst synthesized in example 1, and it was revealed that CO was reacted on the commercial Cu-Zn-Al catalyst for 80 hours 2 The conversion rate is stabilized at 16.8-17.0%, and the CO selectivity is 31.0-33.4%. After 80h, CO 2 The conversion rate gradually decreases to 100h, CO 2 The conversion rate is reduced to 10.5%, and the CO selectivity is 32.6%. Therefore, the catalyst of the invention shows higher CO selectivity and better catalytic stability.
TABLE 1 reaction conditions and results for the examples
What is not described in detail in the present specification belongs to the prior art known to those skilled in the art. While the foregoing describes illustrative embodiments of the present invention to facilitate an understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, but is to be construed as protected by the accompanying claims insofar as various changes are within the spirit and scope of the present invention as defined and defined by the appended claims.
Claims (9)
1. A copper-aluminum catalyst for reverse water gas shift reaction is characterized in that: the copper-aluminum catalyst has a copper-iron ore structure and a spinel structure, and contains Cu 2 O, cuO and Al 2 O 3 A component (C); the mass fraction of each component is Cu 2 O=3.6%~58.4%、CuO=0%~54.2%、Al 2 O 3 =39.3%~68.1%。
2. A method of preparing a copper-aluminum catalyst for reverse water gas shift reactions according to claim 1, wherein: the method comprises the following steps:
step 1, uniformly mixing a Cu precursor, an Al precursor and an additive, reacting, and performing ball milling and drying treatment to obtain a catalyst precursor;
step 2, roasting the catalyst precursor for 0-8 hours at 600-1200 ℃ in inert atmosphere to prepare a copper-aluminum catalyst;
the additive comprises one or a mixture of several of citric acid, oxalic acid, malonic acid or succinic acid in any proportion.
3. The method for preparing a copper-aluminum catalyst for reverse water gas shift reaction according to claim 2, wherein: the Cu precursor comprises one or a mixture of a plurality of copper oxide, copper hydroxide or copper acetate in any proportion.
4. The method for preparing a copper-aluminum catalyst for reverse water gas shift reaction according to claim 2, wherein: the precursor of Al comprises one or a mixture of more than one of alumina, aluminum hydroxide or pseudo-boehmite in any proportion.
5. The method for preparing a copper-aluminum catalyst for reverse water gas shift reaction according to claim 2, wherein: the mol ratio of the additive to the sum of the Cu precursor and the Al precursor is 1-5.
6. The method for preparing a copper-aluminum catalyst for reverse water gas shift reaction according to claim 2, wherein: the inert atmosphere is nitrogen, argon or helium.
7. Use of a copper-aluminium catalyst for reverse water gas shift reactions according to claim 1, characterized in that: the method is applied to the reverse water gas shift reaction.
8. A method of using the copper-aluminum catalyst for reverse water gas shift reaction according to claim 7, wherein: at the reaction temperature of 200-600 ℃ and the reaction pressure of 0.1-5.0 MPa, H 2 /CO 2 The reverse water gas shift reaction is carried out under the conditions that the molar ratio of the catalyst is 0.5 to 5.0 and the volume space velocity is 3.0L/(g.h) to 12.0L/(g.h).
9. Regeneration of a copper-aluminium catalyst for use in reverse water gas shift reactions according to any one of claims 7 to 8, characterized in that: and roasting for 0-8 h at 600-1200 ℃ in inert atmosphere to finish the regeneration of the copper-aluminum catalyst.
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