CN116060020B - Calcium-chromium-based limonite type nickel-based catalyst for autothermal reforming of acetic acid to prepare hydrogen - Google Patents
Calcium-chromium-based limonite type nickel-based catalyst for autothermal reforming of acetic acid to prepare hydrogen Download PDFInfo
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 36
- 239000001257 hydrogen Substances 0.000 title claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002453 autothermal reforming Methods 0.000 title claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 13
- RQLWXPCFUSHLNV-UHFFFAOYSA-N [Cr].[Ca] Chemical compound [Cr].[Ca] RQLWXPCFUSHLNV-UHFFFAOYSA-N 0.000 title claims abstract description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000011651 chromium Substances 0.000 claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000006200 vaporizer Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 230000009849 deactivation Effects 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 239000006227 byproduct Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- -1 transition metal cations Chemical class 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
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- 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
- B01J23/78—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 alkali- or alkaline earth metals
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a calcium-chromium-based limonite-type nickel-based catalyst for autothermal reforming of acetic acid to prepare hydrogen. The invention provides a novel catalyst with high activity, carbon deposit resistance and oxidation resistance aiming at the deactivation problem of the existing catalyst in the autothermal reforming process of acetic acid. The catalyst of the invention has the chemical composition of (NiO) a (CaO) b (CrO 1.5 ) c Wherein a is 0.38-0.43, b is 0.88-1.33, and c is 1.27-1.61. The invention adopts the Pechni sol-gel method to prepare the Ca with Ni species loaded on the perovskite type Ca 2 Cr 2 O 5 Novel catalysts supported on a carrier and forming Ni-Ca-Cr-O active centers. The catalyst of the invention effectively improves the reaction activity of hydrogen production by autothermal reforming of acetic acid.
Description
Technical Field
The invention relates to a specific Ca oxide of limonite based on Ca and Cr 2 Cr 2 O 5 A preparation method of a supported Ni-based catalyst and application thereof in the process of autothermal reforming of acetic acid belong to the technical field of hydrogen preparation by autothermal reforming of acetic acid.
Background
The use of fossil energy in large quantities brings environmental problems such as greenhouse effect, acid rain, ozone layer destruction, particulate pollution, etc. Hydrogen, which is a clean fuel, has an energy density as high as 122MJ/Kg and is environmentally friendly, is considered as one of the most potential alternative energy sources. At present, common hydrogen production modes include fossil fuel hydrogen production, industrial byproduct hydrogen production, water electrolysis hydrogen production and the like. Fossil fuel hydrogen production has the problems of high byproducts and gas impurities and adverse environmental effects. The hydrogen production modes of industrial by-product hydrogen production, electrolytic hydrogen production and the like have strict requirements on technology and equipment, and have higher cost and limited hydrogen yield. Acetic acid reforming hydrogen production derived from renewable biomass oil is a promising green hydrogen production modality.
When acetic acid is subjected to reforming reaction to produce hydrogen, according to the ratio of acetic acid, water and oxygen which are the raw materials participating in the reaction, the method can be divided into three ways of Steam Reforming (SR), partial oxidation reforming (Partial oxidation, POX) and autothermal reforming (Auto-thermal reforming, ATR). The steam reforming hydrogen production is an endothermic reaction, and external heat is required to be supplied, so that the hydrogen production cost is increased; the oxygen introduced by partial oxidation reforming hydrogen production is easy to cause oxidation deactivation of the catalyst, and the hydrogen yield is not high; the autothermal reforming hydrogen production balances the reaction heat and reduces the hydrogen production cost by introducing proper amount of oxygen.
In the autothermal reforming of acetic acid to produce hydrogen, the catalyst plays a very critical role in the reaction. Reforming catalysts include noble metal catalysts and transition metal catalysts, while nickel-based catalysts are often the subject of investigation because of their good ability to activate the C-C, C-H and O-H bonds in acetic acid molecules, and their high selectivity to hydrogen. However, ni on catalyst for acetic acid 0 CH formed by conversion at active site 3 Intermediate species such as CO are further decomposed to generate CH 3 * The accumulation of species, the dehydrogenation products C, forms char and deposits on Ni 0 Resulting in coverage of the active sites of the catalyst, resulting in deactivation of the catalyst. On the other hand, because the introduced oxygen is mainly consumed at the front end of the reaction, the temperature of the front end of the reaction bed layer is rapidly increased to more than 1000 ℃, active component Ni is easy to aggregate and sinter at the temperature, and meanwhile, the oxidizing atmosphere in the autothermal reforming process is easy to lead to active metal Ni 0 Thereby causing the reaction front to move continuously backward,eventually leading to the deactivation of the whole catalytic bed by sintering and oxidation. Therefore, for improving the coking resistance, sintering resistance, oxidation resistance of the Ni-based catalyst during the autothermal reforming reaction of acetic acid, and reducing the selectivity to byproducts such as methane, acetone, etc., and improving the hydrogen yield are key factors in the autothermal reforming reaction of acetic acid.
To solve the above problems, the present invention creatively introduces a novel optical fiber having A 2 B 2 O 5 Ca of limonite structure 2 Cr 2 O 5 Oxide supported Ni-based catalyst.
First, limonite structure Ca 2 Cr 2 O 5 By introducing an ordered array of oxygen vacancies and forming octahedral and tetrahedrally coordinated transition metal cations Ca 2+ /Cr 3+ Has a structure of alternating layers rich in oxygen vacancies and has stronger lattice oxygen (O) 2- ) The transfer ability, while the active ingredient Ni also plays a positive role in the release of active oxygen, thus promoting the formation of CH during acetic acid conversion x (x=0-3) and other intermediate species, and improving gasification of carbon precursor C to obtain CO/CO 2 The product (C+O → CO, CO+O → CO) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the At the same time, the structural component promotes the WGS reaction (CO+H 2 O→CO 2 +H 2 ) Promotes more hydrogen to be generated, and greatly improves the carbon deposit resistance of the catalyst.
Secondly, limonite type Ca 2 Cr 2 O 5 Has good thermal stability and can provide a stable reaction interface in the conversion process of acetic acid. Wherein, ca species is used as alkaline earth metal, improves the overall alkalinity of the catalyst, is helpful for adsorbing and activating water molecules, and forms intermediate species such as OH and O, wherein the OH species participates in reforming reaction, and the O species is beneficial to gasification of carbon precursor; while the Cr species has thermal stability and variable valence, wherein trivalent Cr 3+ Species can effectively improve reactant H 2 O can promote the adsorption and activation of formaldehyde, acetone, toluene, ethyl acetate and other by-products produced by acetic acid in the autothermal reforming process, so as to raise the selectivity of hydrogen and raise the activity of hydrogenYield; meanwhile, active components Ni, ca and Cr have synergistic effect to form an active center of Ni-Ca-Cr-O, so that the adsorption and activation of reactants acetic acid, water and oxygen are improved, and the CH derived from acetic acid is promoted 3 COO*、CH 3 Formation and conversion of CO-like intermediate species to H 2 And the activity and the carbon deposit resistance of the catalyst are improved by waiting for target products.
Finally, in the preparation process, a novel catalyst with a mesoporous structure is constructed by adopting a Pechni sol-gel method, and the mesoporous structure promotes reactant molecules CH 3 COOH、H 2 O、O 2 And product molecule H 2 、CO、CO 2 Etc.; furthermore, the acetic acid-derived CH is effectively inhibited by the finite field effect of the mesoporous structure 2 CO*、CH 3 OCH 3 The polycondensation effect of the intermediate species effectively inhibits the formation of carbon deposit and improves the reaction product H 2 CO/CO 2 Is selected from the group consisting of (1).
Disclosure of Invention
The invention aims to solve the problems that in the autothermal reforming process of acetic acid, ni-based catalyst is easy to occupy active center by carbon deposit at high temperature, so that the conversion of acetic acid molecules is influenced, and the yield of hydrogen is further influenced.
The invention adopts Ni as an active component, and prepares the Ca-Cr-based limonite type Ca with mesoporous structure by a Pechni sol-gel method 2 Cr 2 O 5 A nickel-based catalyst supported on a carrier; when the catalyst is used in the autothermal reforming reaction of acetic acid, the conversion rate of acetic acid of the catalyst is preferably close to 100% at the reaction temperature of 650 ℃, and the hydrogen yield reaches 2.20mol-H 2 about/mol-HAc.
The technical scheme of the invention is as follows:
aiming at the characteristic of autothermal reforming of acetic acid, the invention prepares the calcium-chromium-based limonite type Ni/Ca by a Pechni sol-gel method 2 Cr 2 O 5 A catalyst. The catalyst of the invention is oxidizedThe molar composition of the material is (NiO) a (CaO) b (CrO 1.5 ) c Wherein a is 0.38-0.43, b is 0.88-1.33, c is 1.27-1.61; the weight percentage composition in terms of oxide is: 14.0 to 16.1 percent of nickel oxide, 24.6 to 37.7 percent of calcium oxide, 48.3 to 61.3 percent of chromium oxide, and the sum of the weight percentages of the components is 100 percent.
The preparation method comprises the following specific steps:
(1) Based on the molar composition of the catalyst (NiO) a (CaO) b (CrO 1.5 ) c Wherein a is 0.38-0.43, b is 0.88-1.33, c is 1.27-1.61, and a proper amount of Ni (NO) 3 ) 2 ·6H 2 O、Ca(NO 3 ) 2 ·4H 2 O and Cr (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water, and stirring until all O is dissolved to obtain a No. 1 solution;
(2) Based on the total number of moles of metal cations: citric acid: preparing a mixed solution 2# of citric acid and ethylene glycol according to the ethylene glycol ratio of 1:1:1, mixing the solution 2# with the solution 1#, then keeping the water bath temperature at 70 ℃, and continuing stirring until sol is formed;
(3) Placing the obtained sol into a 105 ℃ oven for 24 hours, then heating the sol to 750 ℃ from room temperature at a speed of 5 ℃/min in a tube furnace, and calcining and maintaining the sol for 4 hours to obtain the Ni/Ca of the calcium-chromium-based limonite-type nickel-based catalyst 2 Cr 2 O 5 Namely, niO which forms an active center of Ni-Ca-Cr-O is supported on Ca of Ca-Cr-based limonite type 2 Cr 2 O 5 The crystal phase structure of the oxide is shown in figure 1, and a mesoporous structure is constructed, and the pore size distribution of the typical BJH is shown in figure 2;
(4) Catalyst activity test: the catalyst of the invention is used before H 2 Reducing at 500-800 deg.C for 1 hr, injecting the mixed solution of acetic acid and water into vaporizer by constant flow pump, vaporizing, mixing oxygen with nitrogen as internal standard gas to form a molar composition of CH 3 COOH/H 2 O/O 2 /N 2 A reaction raw material gas of 1/(1.3-5.0)/(0.21-0.35)/(2.5-4.5), and the raw material gas is introduced into a reaction bed layer, and the reaction temperature is 500%-800℃。
The invention has the beneficial effects that:
(1) In the calcium-chromium-based limonite type Ni/Ca 2 Cr 2 O 5 In the catalyst, ni-Ca-Cr-O active center is formed, the adsorption and activation of reactant acetic acid, water and oxygen are improved, and the CH derived from acetic acid is promoted 3 COO*、CH 3 Formation and conversion of CO-like intermediate species to H 2 And the activity and the carbon deposit resistance of the catalyst are improved by waiting for target products.
(2) Limonite type Ca in catalyst 2 Cr 2 O 5 In the structure, an ordered array of oxygen vacancies and octahedral and tetrahedrally coordinated transition metal cations Ca are formed 2+ /Cr 3+ Is provided with a strong lattice oxygen (O) 2- ) Transfer ability, promoting formation of CH during acetic acid conversion x (x=0-3) and other intermediate species, improves the gasification of carbon precursor C, and obtains CO/CO 2 The product (C+O → CO, CO+O → CO) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the At the same time, this structure also promotes the WGS reaction (CO+H 2 O→CO 2 +H 2 ) Promotes more hydrogen to be generated, and improves the carbon deposit resistance of the catalyst.
(3) Limonite type Ca of catalyst 2 Cr 2 O 5 The oxide has good thermal stability, provides a stable reaction interface in the conversion process of acetic acid, inhibits the sintering of the active component Ni, and improves the stability of the catalyst. In the structure, ca species are used as alkaline earth metals, so that the overall alkalinity of the catalyst is improved, water molecules are adsorbed and activated, and intermediate species such as OH and O are formed, wherein the OH species participate in reforming reaction, and the O species are beneficial to gasification of carbon deposition precursors; while the Cr species has thermal stability and variable valence, wherein trivalent Cr 3+ Species can effectively improve reactant H 2 O adsorbs and activates, and simultaneously promotes oxidation of byproducts such as formaldehyde, acetone, toluene, ethyl acetate and the like possibly generated in the autothermal reforming process of the acetic acid, so that the selectivity and the yield of hydrogen are improved; active components Ni and Ca 2 Cr 2 O 5 The carriers have strong interaction, so that acetic acid can be effectively adsorbed and activated, and Ni also plays a role in promoting the release of active oxygen, so that the activity of the catalyst and the carbon deposit resistance of the catalyst are effectively improved.
(4) The invention constructs a novel catalyst with a mesoporous structure, and the mesoporous structure promotes a reactant CH 3 COOH、H 2 O、O 2 And product molecule H 2 、CO、CO 2 Etc.; furthermore, the acetic acid-derived CH is effectively inhibited by the finite field effect of the mesoporous structure 2 CO*、CH 3 OCH 3 The polycondensation effect of intermediate species effectively inhibits the occurrence of carbon deposit and improves the reaction product H 2 CO/CO 2 Is selected from the group consisting of (1).
(5) The catalyst of the invention is used in the reaction process of autothermal reforming of acetic acid, and the results show that the catalyst of the invention has the advantages of sintering resistance, carbon deposit resistance, oxidation resistance, high catalytic activity and the like.
Drawings
Fig. 1: x-ray diffraction patterns of the catalyst oxides of the invention
Fig. 2: BJH pore size distribution diagram of the catalyst of the invention
Detailed Description
Reference example 1
12.497g of Al (NO) 3 ) 3 ·9H 2 O and 1.175g of Ni (NO) 3 ) 2 ·6H 2 Pouring O into a beaker, adding a certain amount of deionized water for dissolution to obtain solution 1#; then, 7.849g of citric acid and 2.318g of ethylene glycol are weighed, dissolved and mixed to obtain solution No. 2; then mixing the 2# solution and the 1# solution, and stirring at 70 ℃ until gel is formed; then placing the gel in a 105 ℃ oven, taking out after 24 hours, finally heating to 750 ℃ in a tube furnace at a speed of 5 ℃/min for roasting, and keeping for 4 hours to obtain the CDUT-NA catalyst, thus forming the catalyst loaded on Al 2 O 3 A Ni-based catalyst thereon; the catalyst comprises the following components in percentage by weight in terms of oxide: nickel oxide (NiO) 15.1%, alumina (AlO) 1.5 ) 84.9%.
The acetic acid autothermal reforming reactivity evaluation was performed in a continuous flow fixed bed reactor. Grinding and tabletting the catalyst, sieving to obtain 20-40 mesh granules, weighing 0.2g, loading into a reactor, and heating at 500-800deg.C under H 2 Reducing for 1h; then injecting the mixed solution of acetic acid and water into a vaporizer by a constant flow pump, mixing oxygen and taking nitrogen as an internal standard gas to form a molar composition CH 3 COOH/H 2 O/O 2 /N 2 The reaction raw material gas of 1/(1.3-5.0)/(0.21-0.35)/(2.5-4.5) is led into a reaction bed, the reaction condition is 500-800 ℃, the normal pressure, the space velocity is 10000-35000 ml/(g-catalyst.h), and the reaction tail gas is analyzed on line by a gas chromatograph.
Catalyst CDUT-NA was examined for autothermal reforming activity of acetic acid, the initial conversion of acetic acid was 99.6% at a reaction condition of normal pressure, space velocity 25000 ml/(g-catalyst.h), a reaction temperature of 650 ℃ and feed gas acetic acid/water/oxygen=1/4.0/0.28, and as the reaction proceeded for 10 hours, the conversion of acetic acid was reduced to 64.6%, and the hydrogen yield was gradually reduced to 0.65mol-H 2 /mol-HAc，CO 2 The selectivity of (C) is about 49.0%, the selectivity of CO is about 38.5%, and the selectivity of CH is about 4 The selectivity is 5.6%, and the selectivity of the byproduct acetone is increased to about 35.7%. The characterization results of XRD, BET and the like show that the catalyst has poor stability in the autothermal reforming process of acetic acid, more byproducts and lower activity, and the acetonation reaction is not effectively inhibited, and sintering, carbon deposition and partial oxidation occur.
Example 1
3.043g of Ca (NO) 3 ) 2 ·4H 2 O, 5.156g of Cr (NO) 3 ) 3 ·9H 2 O and 1.162g of Ni (NO) 3 ) 2 ·6H 2 Pouring O into a beaker, adding a certain amount of deionized water for dissolution to obtain solution 1#; then, 6.254g of citric acid and 1.847g of ethylene glycol were weighed, dissolved and mixed to obtain solution # 2; then mixing the 2# solution and the 1# solution, and stirring at 70 ℃ until gel is formed; then placing the gel in a 105 ℃ oven, taking out after 24 hours, and finally heating to 750 ℃ in a tube furnace at a speed of 5 ℃/minRoasting and maintaining for 4 hours to obtain the Ni/Ca catalyst of the calcium-chromium-based limonite type nickel base catalyst 2 Cr 2 O 5 I.e., CDUT-NCC catalyst, whose typical crystal structure is shown in FIG. 1, apparent Ca appears at 24.7 °, 33.7 ° and 49.6 ° 2 Cr 2 O 5 Diffraction peaks of NiO appear at 37.5 degrees, 43.5 degrees and 63.1 degrees, and NiO is supported on Ca of Ca-Cr-based limonite type 2 Cr 2 O 5 The crystal phase structure of the oxide and forms an active center of Ni-Ca-Cr-O; the catalyst is subjected to nitrogen low-temperature physical adsorption test, the pore diameter is intensively distributed at 4nm, and a typical mesoporous structure is shown in figure 2; the catalyst has the molar composition (NiO) 0.40 (CaO) 1.29 (CrO 1.5 ) 1.29 The catalyst comprises the following components in percentage by weight in terms of oxide: nickel oxide (NiO) 14.9%, calcium oxide (CaO) 36.1%, chromium oxide (CrO) 1.5 ) 49.0%.
The catalyst CDUT-NCC is examined by the autothermal reforming activity of acetic acid, when the reaction condition is normal pressure, the space velocity is 25000 ml/(g-catalyst.h), the reaction temperature is 650 ℃, the acetic acid/water/oxygen=1/4.0/0.28 of raw material gas, the conversion rate of the catalyst to acetic acid is about 100%, and the hydrogen yield is 2.2mol-H 2 about/mol-HAc, CO 2 The selectivity is about 45.7 percent, the CO selectivity is about 48.8 percent, CH 4 The selectivity is about 5.6%, and almost no acetone is a byproduct. The CDUT-NCC catalyst is characterized by nitrogen low-temperature physical adsorption, and the result shows that the specific surface area is 2.1m 2 Per gram, pore volume of 0.02cm 3 The pore size distribution is concentrated, the average pore size is 8.3nm, the most probable pore size is 4.0nm, and the mesoporous material belongs to mesoporous materials. The characterization result shows that the catalyst has no sintering phenomenon and no obvious carbon deposit, and the catalyst effectively inhibits the generation of byproduct acetone and has high catalytic activity.
Claims (2)
1. The application of the calcium-chromium-based limonite-based nickel-based catalyst in the acetic acid autothermal reforming hydrogen production process is characterized in that: the calcium-chromium-based limonite-based nickel-based catalyst is treated with H at a temperature of 500-800 DEG C 2 Reducing for 1h, then injecting the mixed solution of acetic acid and water into a vaporizer by a constant flow pumpAfter the chemical reaction, mixing oxygen and taking nitrogen as an internal standard gas to form a molar composition of CH 3 COOH/H 2 O/O 2 /N 2 A reaction feed gas of 1/(1.3-5.0)/(0.21-0.35)/(2.5-4.5), and the feed gas is introduced into a reaction bed layer, wherein the reaction temperature is 500-800 ℃; the catalyst is prepared by the following method: weighing appropriate amount of Ni (NO) 3 ) 2 ·6H 2 O、Ca(NO 3 ) 2 ·4H 2 O and Cr (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water, and stirring until all O is dissolved to obtain a No. 1 solution; based on the total number of moles of metal cations: citric acid: preparing a mixed solution 2# of citric acid and ethylene glycol according to the ethylene glycol ratio of 1:1:1, mixing the solution 2# with the solution 1#, then keeping the water bath temperature at 70 ℃, and continuing stirring until sol is formed; placing the obtained sol into a 105 ℃ oven for 24 hours, then heating the sol to 750 ℃ from room temperature at a speed of 5 ℃/min in a tube furnace, and calcining and maintaining the sol for 4 hours to obtain the Ni/Ca catalyst of the calcium-chromium-based limonite type nickel-based catalyst 2 Cr 2 O 5 Namely, niO which forms an active center of Ni-Ca-Cr-O is supported on Ca of Ca-Cr-based limonite type 2 Cr 2 O 5 A crystalline phase structure of the oxide; the catalyst has the molar composition (NiO) calculated by oxide a (CaO) b (CrO 1.5 ) c Wherein a is 0.38-0.43, b is 0.88-1.33, c is 1.27-1.61; the weight percentage composition in terms of oxide is: 14.0 to 16.1 percent of nickel oxide, 24.6 to 37.7 percent of calcium oxide, 48.3 to 61.3 percent of chromium oxide, and the sum of the weight percentages of the components is 100 percent.
2. Use of a calcium-chromium-based limonite-based nickel-based catalyst according to claim 1 in an autothermal reforming process of acetic acid, characterized in that: the catalyst comprises the following components in percentage by weight in terms of oxide: the nickel oxide is 14.9%, the calcium oxide is 36.1%, and the chromium oxide is 49.0%.
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