CN107159219A - A kind of cobalt-base catalyst and preparation method for acetic acid self-heating reforming hydrogen manufacturing gas - Google Patents
A kind of cobalt-base catalyst and preparation method for acetic acid self-heating reforming hydrogen manufacturing gas Download PDFInfo
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- CN107159219A CN107159219A CN201710355478.XA CN201710355478A CN107159219A CN 107159219 A CN107159219 A CN 107159219A CN 201710355478 A CN201710355478 A CN 201710355478A CN 107159219 A CN107159219 A CN 107159219A
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- catalyst
- cobalt
- acetic acid
- oxide
- acid self
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000001257 hydrogen Substances 0.000 title claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 37
- 238000010438 heat treatment Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000002407 reforming Methods 0.000 title claims abstract description 10
- 239000007789 gas Substances 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011701 zinc Substances 0.000 claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 21
- 239000010941 cobalt Substances 0.000 claims abstract description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- 238000000975 co-precipitation Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 238000002453 autothermal reforming Methods 0.000 claims description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910007570 Zn-Al Inorganic materials 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 16
- 238000005245 sintering Methods 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000008859 change Effects 0.000 abstract description 6
- 238000004220 aggregation Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000011835 investigation Methods 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000001994 activation Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012075 bio-oil Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 229910019114 CoAl2O4 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
Abstract
The present invention relates to a kind of cobalt-base catalyst of acetic acid self-heating reforming hydrogen manufacturing and preparation method.The present invention is directed to existing the catalyst change of catalyst structure and the oxidation of active component and sintering during acetic acid self-heating recapitalization, and there is provided a kind of resistance to sintering, anti-carbon deposit, resistance to oxidation, active high new catalyst the problem of cause catalyst inactivation.The chemical composition of the catalyst of the present invention is CoaZnbAlO7.5 + δ, wherein a is that 0.25 1.00, b is 0.75 5.00.The present invention uses coprecipitation method to be prepared for Zn Al type stratiform hydrotalcite-like compounds for presoma, and introduces active component cobalt, by same order elements of the cobalt to zinc, enters the veneer structure of hydrotalcite-like compound；The composite oxides of fired acquisition, effectively inhibit active component cobalt possible migration, aggregation and sintering under the conditions of pyroreaction, improve the heat endurance of catalyst；Carrier zinc oxide improves the reproducibility, stability and inoxidizability of active component cobalt simultaneously, so as to improve the activity and stability of catalyst.
Description
Technical field
The present invention relates to a kind of cobalt-base catalyst and preparation method for acetic acid self-heating recapitalization hydrogen making, more specifically
Say, be related to a kind of presoma with hydrotalcite-like compound, and cobalt-base catalyst for acetic acid self-heating recapitalization hydrogen making and
Preparation method, belongs to the technical field of acetic acid self-heating recapitalization hydrogen making.
Background technology
Hydrogen is a kind of energy carrier of cleaning, and be particularly suitable for use in fuel cell, is considered as the clean energy resource of future ideality
Carrier.At present, hydrogen is mainly produced from the conversion of the primary energy such as natural gas, coal, and which results in CO in atmosphere2The increasing of content
It is many.The biomass obtained by photosynthesis of plant, is a kind of important regenerative resource.However, biomass energy metric density is low, can
It is changed into energy density through fast pyrolysis and reaches 20 MJ/m3Bio-oil, then concentrate the inexpensive preparing hydrogen of scale conversion
Gas.In bio-oil, acetic acid is as its main liquid phase constituent, and mass fraction, can be through catalytic reforming process up to 30%
Obtain hydrogen.
The main path of acetic acid hydrogen making has steam reforming, partial oxidation and self-heating recapitalization.Vapor reforming hydrogen production
It is a strong endothermic reaction, it is necessary to which outside lasting heat supply carrys out maintenance reaction；Other molecular acid is after catalyst surface activation, warp
Decarboxylation and dehydration, the easily intermediate product such as generation ketenes, occur polycondensation reaction and form carbon deposit to cause catalyst inactivation；
And partial oxidation hydrogen-preparation reaction outside need not continue heat supply, hydrogen yield can be but reduced.For these problems, self-heating can be used
Reformation hydrogen production, i.e., introduce a small amount of oxygen or air in acetic acid steam reforming reaction, combine the steam reforming of heat absorption
Process and the partial oxidation process of heat release, by adjusting the oxygen content in unstripped gas, with adjust overall reaction reach thermal balance or
Gentle heat release；Meanwhile, the introducing of oxygen will influence absorption and activation process of the reactant molecule in catalyst surface, induce
The generation and conversion of product are crossed, the generation of carbon deposit predecessor can be suppressed.But, on the other hand, the introducing of oxygen makes catalyst
Bed front end forms oxidizing atmosphere, local temperature up to more than 1000 degrees Celsius, easily causes the sintering of catalyst carrier, duct
Block and the aggregation of active component becomes big, oxidation, ultimately result in catalyst inactivation.Therefore, development structure stabilization, resistance to oxidation, resistance to
The catalyst of sintering and anti-carbon is the matter of utmost importance that acetic acid autothermal reforming reaction hydrogen making process needs to solve.
Metallic cobalt has the ability of higher fracture C-C keys and c h bond, can be applied in acetic acid catalysis hydrogen production reaction, but also
The problems such as being faced with sintering, carbon distribution.In addition, for catalyst carrier, the optimization of its acid-base property or structure is beneficial to improve cobalt
The performance such as base catalyst activity and anti-carbon.It is used as the Al of carrier2O3, ZnO etc. there is the characteristics of heat endurance is high, wherein Al2O3
The specific surface area of catalyst can be increased, but it has stronger acidity, easily deposits substantial amounts of carbon deposit.ZnO has alkalescence, right
The generation of carbon deposit is inhibited, it is possible to promote the hydrogenation and dehydrogenation reaction in steam reformation；In addition, Co bases Zn-Al
Composite oxides can form spinel structure（AB2O4）, with strong interaction, it is favorably improved the thermally-stabilised of reforming catalyst
Property, anti-sintering and anti-carbon performance.Therefore, ZnO-Al is selected2O3Composite oxides are carrier, can effectively improve catalyst
Catalytic performance.
For the preparation of Zn Al composite oxide, Zn-Al hydrotalcite-like compound presomas can be used.Hydrotalcite is also known as layer
The double hydroxyl composite oxides of shape, it has large specific surface area, the interchangeability of interlayer anion, the controllable of the Nomenclature Composition and Structure of Complexes
Property etc. characteristic, can suppress acid by the modulation of composition, and by Zn in hydrotalcite2+Same order elements, introduce activearm
Point cobalt, it is fired after form high dispersive Zn Al composite oxide cobalt-base catalyst, it is steady with higher specific surface area, good heat
Qualitative, more rich pore structure and stronger alkalescence, so as to the migration of effective inhibitory activity component cobalt, sintering and oxidation,
Acetic acid self-heating recapitalization hydrogen making is conducive to react.
The hydrotalcite structure as made from coprecipitation is complete, crystallinity is high and with good layer structure, is conducive to zinc
The formation of aluminium composite oxide.The present invention is prepared for Zn-Al houghites using coprecipitation（Zn6Al2(OH)16CO3·H2O）
Structured forerunner, introduces active component cobalt, so that the equally distributed composite oxide catalysts of component are obtained, and applied to acetic acid
In the reaction of self-heating recapitalization hydrogen making.
The content of the invention
The technical problems to be solved by the invention are, for existing cobalt-base catalyst during self-heating recapitalization hydrogen making
Structure easily change and active component cobalt be oxidizable and sintering, and the problem of causing catalyst inactivation, there is provided a kind of Stability Analysis of Structures, resistance to
Sintering, resistance to oxidation, activity stabilized new cobalt-base catalyst.
Technical scheme：
Using Zn-Al hydrotalcite-like compounds as the presoma of catalyst, cobalt is introduced as active component, it is fired, contained
CoAl2O4、ZnAl2O4、Co3O4With the composite oxide catalysts such as ZnO, active component Co is highly dispersed in composite oxides,
Improve the activity and stability of acetic acid self-heating recapitalization hydrogen making reaction.The chemical composition of catalyst of the present invention is
CoaZnbAlO7.5 + δ, wherein a is 0.25-1.00, and b is 0.75-5.00.The catalyst oxide composition percentage by weight be：
Cobalt oxide 14.0-14.4%, zinc oxide 46.6-76.4%, aluminum oxide 9.5-39.0%.
Specific preparation method comprises the following steps：
1）Co is constituted according to catalyst chemicalaZnbAlO7.5 + δ, wherein a be 0.25-1.00, b is 0.75-5.00, prepare cobalt, zinc,
The nitrate mixed solution #1 of aluminium；
2）According to carbonate and mol ratio hydroxy 1:16 and metal cation Co, Zn and Al total electrical charge rubbed with hydroxy
You are than being 1:8, prepare the mixed solution #2 of sodium carbonate and sodium hydroxide；
3）Solution #1 and solution #2 is subjected to coprecipitation reaction at 65-80 degrees Celsius, existed so that solution speeds control ph is added dropwise
10.5+In the range of 0.5, and constant temperature is maintained to stir aging 15 ~ 24 hours；Suction filtration, washing three times after, be placed in 105 degrees Celsius
In baking oven, dry 12 hours, obtain the catalyst that hydrotalcite-like compound is main body, its typical hydrotalcite-like compound such as X-ray is spread out
Penetrate figure（Accompanying drawing 1）It is shown；
4）By step 3）The presoma of gained is warming up to 500-800 degrees Celsius with the speed of 10 centigrade per minutes and is calcined 4 hours,
Catalyst of the present invention is obtained, its structure such as X-ray diffractogram（Accompanying drawing 2）It is shown；
5）By step 4）Obtained catalyst（50-200mg）Load fixed bed reactors, be first passed through flow 20mL/min H2
Reduced 1 hour in 600-800 degrees Celsius in atmosphere, carry out activation process, then purged through flow for 30mL/min nitrogen, most
The AC/H after vaporization is passed through afterwards2O/O2/N2Mol ratio be 1.0/ (2.5-5.0)/(0.2-0.5)/(2.5-4.5) mixing
Gas（Wherein AC is acetic acid）, reacted by beds, reaction temperature is 600-800 degrees Celsius.
Beneficial effects of the present invention：
（1）The Zn-Co-Al-O catalyst that the present invention is prepared using coprecipitation, using Zn-Al hydrotalcite-like compounds as presoma,
And active component cobalt is introduced, the part of zinc is replaced by cobalt, into the veneer structure of hydrotalcite-like compound, catalyst is improved
The decentralization of active component, adds the catalytic active center number of catalyst surface, so as to improve the activity of catalyst；It is fired
The composite oxides of acquisition, restrained effectively active component cobalt possible migration, aggregation and sintering under the conditions of pyroreaction,
So as to improve heat endurance of the catalyst during self-heating recapitalization.
（2）Present invention introduces basic supports zinc oxide, the acidity of aluminum oxide is reduced, carbon deposit is effectively inhibited, together
When zinc presence add the reproducibility of cobalt, so as to be effectively improved the activity and stability of catalyst.
（3）Show through acetic acid autothermal reforming reaction result, catalyst of the invention has Stability Analysis of Structures, resistance to sintering, anti-product
The features such as carbon, resistance to oxidation, activity stabilized and high hydrogen yield.
Brief description of the drawings
The presoma X-ray diffraction spectrogram of Fig. 1 catalyst of the present invention.
The X-ray diffraction spectrogram of Fig. 2 catalyst of the present invention.
Reference example 1
Weigh 5.5651 grams of Co (NO3)3.6H2O, 17.0648 grams of Zn (NO3)3.6H2O and 28.6913 gram of Al (NO3)3.9H2O, plus
Enter 153 ml deionized waters and be mixed to form solution #1.30.5943 grams of sodium hydroxides and 5.06656 grams of sodium carbonate are weighed, are added
813 ml deionized waters, form solution #2.By in solution #1 and solution #2 pH be 10.5+In the range of 0.5, at 78 degrees Celsius
Co-precipitation operation is carried out under water-bath, and maintains the temperature to stir aging 24 hours, sediment is obtained and is washed through filtering and deionization
Wash three times, be placed in 105 degrees Celsius of baking ovens and dry 12 hours, obtain houghite presoma, its typical structure such as institute of accompanying drawing 1
Show.The presoma is calcined 4 hours through 700 degrees Celsius, obtains catalyst CDUT-ZC1A, its typical structure is as shown in Figure 2.Through nitrogen
Aspiration is attached/detachment assays, it is 16.28 m as a result to show its specific surface area2/g.The weight of the catalyst is constituted：Cobalt oxide contains
Measure as 14.3%, zinc oxide content be that 46.7%, alumina content is 39.0%.
The acetic acid autothermal reforming reaction activity rating of catalyst is carried out in continuous fixed bed reactor.By catalyst
Grind and tabletting, be sieved into 20-40 mesh, be fitted into reactor, and at a temperature of 700 °C, the H of 20.0mL/min flows2In
Reduction 1 hour.The mixed solution of acetic acid and water is injected into vaporizer after vaporization with syringe pump, mixture of oxygen, and add nitrogen
For internal standard gas, AC/H is formed2O/O2/N2Mol ratio be 1.0/ (2.5-5.0)/(0.2-0.5)/(2.5-4.5) gaseous mixture
Body, and this unstripped gas is imported into reaction bed, reaction condition is normal pressure, air speed 11000-30000mLg-1 h-1, reaction end gas
To configure thermal conductivity detector (TCD) and flame ionization ditector and packed column（Porapaq-QS and 5A）And capillary column（Q-
Plot）Chromatographic.
Catalyst CDUT-ZC1A is investigated through acetic acid autothermal reforming reaction activity, is 650 degrees Celsius, AC/ in reaction temperature
H2O/O2/N2Mol ratio be 1.0/4.0/0.28/3.9, air speed 15000h-1When, the conversion ratio of initial acetic acid is about 96.18%,
The yield of hydrogen is about 2.85 mol-H2/ mol-AC, after the investigation time of 15 hours, hydrogen yield is about 2.51 mol-
H2/ mol-AC, the selectivity of byproduct methane is 2.39%, and the selectivity of acetone is 2.49%.Post catalyst reaction is carried out
XRD, XPS, SEM, TG etc. are characterized, and are as a result shown, the activity reduction in acetic acid autothermal reforming reaction of CDUT-ZC1A catalyst, are
Due to there is the sintering of obvious carbon deposit generation and active component cobalt in course of reaction.
Reference example 2
Weigh 5.4622 grams of Co (NO3)3.6H2O, 27.9172 grams of Zn (NO3)3.6H2O and 7.0406 gram of Al (NO3)3.9H2O, is added
131 ml deionized waters are mixed to form solution #1.12.012 grams of sodium hydroxides and 1.9893 grams of sodium carbonate are weighed, 319 millis are added
Deionized water is risen, solution #2 is formed.By in solution #1 and solution #2 pH be 10.5+In the range of 0.5, under 78 C water baths
Co-precipitation operation is carried out, and maintains the temperature to stir aging 24 hours.Sediment is washed three times through filtering and deionized water, is placed in
Dried 12 hours in 105 degrees Celsius of baking ovens, obtain houghite presoma, its typical structure is as shown in Figure 1.The presoma is passed through
700 degrees Celsius are calcined 4 hours, obtain catalyst CDUT-ZC6A, its typical structure is as shown in Figure 2.It is real through nitrogen adsorption/desorption
Test, it is 11.73 m as a result to show its specific surface area2/g.The weight of the catalyst is constituted：Cobalt oxide content is 14.0%, oxygen
It is that 76.4%, alumina content is 9.6% to change Zn content.
Catalyst CDUT-ZC6A is investigated through acetic acid autothermal reforming reaction activity, is 650 degrees Celsius, AC/ in reaction temperature
H2O/O2/N2Mol ratio be 1.0/4.0/0.28/3.9, air speed 15000h-1When, in the investigation time of 15 hours, acetic acid turns
Rate is initially 99.13%, and hydrogen yield is initially 2.95 mol-H2/ mol-AC, due to the generation of the sintering, carbon distribution of catalyst
And the aggregation increase of active component, the conversion ratio for causing last acetic acid is 94.60%, and hydrogen yield is 2.18 mol-H2/
mol-AC；The selectivity of byproduct methane increases to 3.29% by 1.03%, and the selectivity of acetone increases to 7.31% from 1.12%, and an oxygen
The selectivity for changing carbon reduces to 12.67% by 23.09%, and the selectivity of carbon dioxide reduces to 39.83% by 70.25%.After reaction
Catalyst has carried out the sign such as XRD, XPS, SEM, TG, as a result shows, CDUT-ZC6A catalyst surfaces have obvious carbon deposit to produce
Raw, active component cobalt sintering causes catalyst activity reduction.
Embodiment 1
Weigh 5.5134 grams of Co (NO3)3.6H2O, 22.5415 grams of Zn (NO3)3.6H2O and 17.7653 gram of Al (NO3)3.9H2O, plus
Enter 142 ml deionized waters and be mixed to form solution #1.21.2162 grams of sodium hydroxides and 3.5136 grams of sodium carbonate are weighed, 564 are added
Ml deionized water, forms solution #2.By in solution #1 and solution #2 pH be 10.5+In the range of 0.5, in 78 C water baths
Lower progress co-precipitation operation, and maintain the temperature to stir aging 24 hours.Sediment is washed three times through filtering and deionized water, is put
Dried 12 hours in 105 degrees Celsius of baking ovens, obtain houghite presoma, its typical structure is as shown in Figure 1.The presoma
It is calcined 4 hours through 700 degrees Celsius, obtains catalyst CDUT-ZC2A, its typical structure is as shown in Figure 2.Through nitrogen adsorption/desorption
Experiment, it is 14.89 m as a result to show its specific surface area2/g.The weight of the catalyst is constituted：Cobalt oxide content is 14.2%,
Zinc oxide content is that 61.7%, alumina content is 24.1%.
Catalyst CDUT-ZC2A is investigated through acetic acid autothermal reforming reaction activity, is 650 degrees Celsius, AC/ in reaction temperature
H2O/O2/N2Mol ratio be 1.0/4.0/0.28/3.9, air speed 15000h-1When, in the investigation time of 15 hours, acetic acid turns
Rate is 92.56%, and hydrogen yield is about 2.88 mol-H2/ mol-AC, the selectivity of byproduct methane is 0.92%, acetone
Selectivity is 1.29%.And the selectivity of carbon monoxide is 19.76%-20.40%, the selectivity of carbon dioxide is 55.79%-
58.19%.The sign such as XRD, XPS, SEM, TG has been carried out to post catalyst reaction, has as a result been shown：CDUT-ZC2A catalyst has
Relatively stable structure, does not there is significant change after reaction.
Embodiment 2
Weigh 5.4898 grams of Co (NO3)3.6H2O, 24.9974 grams of Zn (NO3)3.6H2O and 12.8658 gram of Al (NO3)3.9H2O, plus
Enter 137 ml deionized waters and be mixed to form solution #1.17.0113 grams of sodium hydroxides and 2.8172 grams of sodium carbonate are weighed, 452 are added
Ml deionized water, forms solution #2.By in solution #1 and solution #2 pH be 10.5+In the range of 0.5, in 78 C water baths
Lower progress co-precipitation operation, and maintain the temperature to stir aging 24 hours.Sediment is washed three times through filtering and deionized water, is put
Dried 12 hours in 105 degrees Celsius of baking ovens, obtain houghite presoma, its typical structure is as shown in Figure 1.The presoma
It is calcined 4 hours through 700 degrees Celsius, obtains catalyst CDUT-ZC3A, its typical structure is as shown in Figure 2.Through nitrogen adsorption/desorption
Experiment, it is 16.35m as a result to show its specific surface area2/g.The weight of the catalyst is constituted：Cobalt oxide content is 14.1%, oxygen
It is that 68.4%, alumina content is 17.5% to change Zn content.
Catalyst CDUT-ZC3A is investigated through acetic acid autothermal reforming reaction activity, is 650 degrees Celsius, AC/ in reaction temperature
H2O/O2/N2Mol ratio be 1.0/4.0/0.28/3.9, air speed 15000h-1When, within the investigation time of 15 hours, acetic acid
Conversion ratio is 98.88%, and hydrogen yield is 2.85 mol-H2/ mol-AC, byproduct methane and acetone have obtained effective suppression.
The sign such as XRD, XPS, SEM, TG has been carried out to post catalyst reaction, has as a result been shown：CDUT-ZC3A catalyst has stable knot
Structure, active component cobalt valence stability, without obvious carbon deposit.
Embodiment 3
Weigh 5.4770 grams of Co (NO3)3.6H2O, 26.3915 grams of Zn (NO3)3.6H2O and 10.0846 gram of Al (NO3)3.9H2O, plus
Enter 134 ml deionized waters and be mixed to form solution #1.14.6243 grams of sodium hydroxides and 2.4219 grams of sodium carbonate are weighed, 388 are added
Ml deionized water, forms solution #2.By in solution #1 and solution #2 pH be 10.5+In the range of 0.5, in 78 C water baths
Lower progress co-precipitation operation, and maintain the temperature to stir aging 24 hours.Sediment is washed three times through filtering and deionized water, is put
Dried 12 hours in 105 degrees Celsius of baking ovens, obtain houghite presoma, its typical structure is as shown in Figure 1.The presoma
It is calcined 4 hours through 700 degrees Celsius, obtains catalyst CDUT-ZC4A, its typical structure is as shown in Figure 2.Through nitrogen adsorption/desorption
Experiment, it is 11.24m as a result to show its specific surface area2/g.The weight of the catalyst is constituted：Cobalt oxide content is 14.1%, oxygen
It is that 72.2%, alumina content is 13.7% to change Zn content.
Catalyst CDUT-ZC4A is investigated through acetic acid autothermal reforming reaction activity, is 650 degrees Celsius, AC/ in reaction temperature
H2O/O2/N2Mol ratio be 1.0/4.0/0.28/3.9, air speed 15000h-1When, in the investigation time of 15 hours, acetic acid turns
Rate is 100%, and hydrogen yield is about 3.01 mol-H2/ mol-AC, the selectivity of byproduct methane is close to 0%, and acetone is less than inspection
Limit is surveyed, the selectivity of carbon monoxide is stable 26.19%, and the selectivity of carbon dioxide is stable 69.67%；To post catalyst reaction
The sign such as XRD, XPS, SEM, TG has been carried out, has as a result been shown, CDUT-ZC4A catalyst has high stability and activity, is due to
The crystalline structure and Electronic Performance of the catalyst stabilization, during acetic acid heats reformation hydrogen production, with stronger anti-oxidant and
Carbon accumulation resisting ability.
Test result shows that catalyst of the present invention has resistance to sintering, anti-carbon, resistance to oxidation, acetic acid conversion high, active steady
The features such as fixed and hydrogen yield is high.
Claims (6)
1. the cobalt-base catalyst for acetic acid self-heating recapitalization hydrogen making, it is characterised in that：Configure cobalt nitrate, zinc nitrate and nitric acid
The mixed solution #1 of aluminium；It is 1 according to the total electrical charge and mol ratio hydroxy of metal cation cobalt, zinc and aluminium:8 and carbonate
With mol ratio 1 hydroxy:16, the mixed solution #2 of sodium carbonate and sodium hydroxide is prepared, by solution #1 and solution #2 in 65-80
Degree Celsius carry out coprecipitation reaction, control reacting solution pH value 10.5+In the range of 0.5, and maintain stirring in water bath aging 15 ~
24 hours；Suction filtration, washing three times after, in the baking oven for being placed in 105 degrees Celsius, dry 12 hours, produce Zn-Al houghite forerunners
Body sample；It is calcined 4 hours through 500-800 degrees Celsius, produces cobalt-based compound oxide catalyst, its chemical composition is
CoaZnbAlO7.5 + δ, wherein a is 0.25-1.00, and b is 0.75-5.00；It is anti-that the catalyst is used for acetic acid self-heating recapitalization hydrogen making
Answer process.
2. the cobalt-base catalyst of acetic acid self-heating reforming hydrogen manufacturing according to claim 1, it is characterised in that：The catalyst with
The percentage by weight of oxide is constituted：Cobalt oxide 14.0-14.3%, zinc oxide 46.6-76.4%, aluminum oxide 9.5-39.0%.
3. the cobalt-base catalyst of acetic acid self-heating reforming hydrogen manufacturing according to claim 2, it is characterised in that：The catalyst with
The percentage by weight of oxide is constituted：Cobalt oxide is 14.2, and zinc oxide is 61.7%, and aluminum oxide is 24.1%.
4. the cobalt-base catalyst of acetic acid self-heating reforming hydrogen manufacturing according to claim 2, it is characterised in that：The catalyst with
The percentage by weight of oxide is constituted：Cobalt oxide is 14.1%, and zinc oxide is 68.4%, and aluminum oxide is 17.5%.
5. the cobalt-base catalyst of acetic acid self-heating reforming hydrogen manufacturing according to claim 2, it is characterised in that：The catalyst with
The percentage by weight of oxide is constituted：Cobalt oxide is 14.1%, and zinc oxide is 72.2%, and aluminum oxide is 13.7%.
6. the purposes that any one of the claim 1-5 catalyst reacts in acetic acid self-heating reforming hydrogen manufacturing, it is characterised in that：Take
Catalyst described in 50-200mg claim any one of 1-5, is passed through flow 20mL/min H2, in 600-800 degrees Celsius also
Former 1 hour, purged through nitrogen, be passed through the mol ratio of acetic acid/water/oxygen/nitrogen for 1.0/ (2.5-5.0)/(0.2-0.5)/
In the mixed gas of (2.5-4.5), acetic acid autothermal reforming reaction is carried out by beds, reaction temperature is taken the photograph for 600-800
Family name's degree.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718785A (en) * | 2019-02-13 | 2019-05-07 | 成都理工大学 | The derivative cobalt-base catalyst of hydrocalumite for acetic acid self-heating reforming hydrogen manufacturing |
| CN109718790A (en) * | 2019-02-13 | 2019-05-07 | 成都理工大学 | Storage oxygen solid solution for acetic acid self-heating reforming hydrogen manufacturing supports cobalt-base catalyst |
| CN109759070A (en) * | 2019-01-23 | 2019-05-17 | 成都理工大学 | Perovskite type titanium strontium Co catalysts for acetic acid self-heating reforming hydrogen manufacturing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1672789A (en) * | 2004-03-25 | 2005-09-28 | 中国科学院大连化学物理研究所 | Catalyst for autothermal reformation of methanol to prepared hydrogen and its prepn process and application |
| CN101972656A (en) * | 2010-10-20 | 2011-02-16 | 成都理工大学 | Nickel-base catalyst used for autothermal reforming of ethanol for producing hydrogen and preparation method thereof |
| CN102294249A (en) * | 2011-06-16 | 2011-12-28 | 华东理工大学 | Hydrotalcite type catalyst used for carrying out reforming reaction on natural gas and low carbon hydrocarbon (C1-C4) and preparation method thereof |
-
2017
- 2017-05-19 CN CN201710355478.XA patent/CN107159219B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1672789A (en) * | 2004-03-25 | 2005-09-28 | 中国科学院大连化学物理研究所 | Catalyst for autothermal reformation of methanol to prepared hydrogen and its prepn process and application |
| CN101972656A (en) * | 2010-10-20 | 2011-02-16 | 成都理工大学 | Nickel-base catalyst used for autothermal reforming of ethanol for producing hydrogen and preparation method thereof |
| CN102294249A (en) * | 2011-06-16 | 2011-12-28 | 华东理工大学 | Hydrotalcite type catalyst used for carrying out reforming reaction on natural gas and low carbon hydrocarbon (C1-C4) and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ELKA KRALEVA，HEIKE EHRICH: "Synthesis, characterization and activity of Co and Ni catalysts supported on AlMe (Me = Zn, Zr, Ti) mixed oxides", 《J.SOL-GEL SCI.TECHNOL.》 * |
| 周庆等: "层状锌-铝类水滑石材料合成及应用进展", 《广州化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109759070A (en) * | 2019-01-23 | 2019-05-17 | 成都理工大学 | Perovskite type titanium strontium Co catalysts for acetic acid self-heating reforming hydrogen manufacturing |
| CN109718785A (en) * | 2019-02-13 | 2019-05-07 | 成都理工大学 | The derivative cobalt-base catalyst of hydrocalumite for acetic acid self-heating reforming hydrogen manufacturing |
| CN109718790A (en) * | 2019-02-13 | 2019-05-07 | 成都理工大学 | Storage oxygen solid solution for acetic acid self-heating reforming hydrogen manufacturing supports cobalt-base catalyst |
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