CN114931952A - Preparation method of internal heating type integral foam catalyst for hydrogen production by methane steam reforming - Google Patents
Preparation method of internal heating type integral foam catalyst for hydrogen production by methane steam reforming Download PDFInfo
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- CN114931952A CN114931952A CN202210370684.9A CN202210370684A CN114931952A CN 114931952 A CN114931952 A CN 114931952A CN 202210370684 A CN202210370684 A CN 202210370684A CN 114931952 A CN114931952 A CN 114931952A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000010438 heat treatment Methods 0.000 title claims abstract description 59
- 239000006260 foam Substances 0.000 title claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000001257 hydrogen Substances 0.000 title claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000000629 steam reforming Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005187 foaming Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 4
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims abstract description 3
- 239000004088 foaming agent Substances 0.000 claims abstract description 3
- 238000005485 electric heating Methods 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229920000881 Modified starch Polymers 0.000 claims description 7
- 239000004368 Modified starch Substances 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 235000019426 modified starch Nutrition 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 4
- 238000013461 design Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- JZKFHQMONDVVNF-UHFFFAOYSA-N dodecyl sulfate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCCCCCCOS(O)(=O)=O JZKFHQMONDVVNF-UHFFFAOYSA-N 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 5
- 230000003321 amplification Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000011160 research Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001991 steam methane reforming Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- QBKSIHCSDPPLJI-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]tetradecan-1-ol;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCC(CO)N(CCO)CCO QBKSIHCSDPPLJI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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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
- B01J23/83—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 rare earths or actinides
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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
- C01B3/34—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 by reaction of hydrocarbons with gasifying agents
- C01B3/38—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 by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—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 by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
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- 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
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1029—Catalysts in the form of a foam
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C01B2203/1047—Group VIII metal catalysts
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- C01B2203/1076—Copper or zinc-based catalysts
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Abstract
The invention relates to a preparation method of an internal heating type methane steam reforming hydrogen production foam monolithic catalyst, which mainly comprises the following steps: (1) after the heating wire is treated, roasting at high temperature; (2) taking nano Al 2 O 3 Impregnating active components with the powder, drying and roasting to prepare catalyst powder; (3) mixing catalyst powder with an auxiliary agent, and then ball-milling to prepare slurry; (4) adding foaming agent, stirring, ventilating and foaming; (5) slowly adding the prepared foaming material into a die with a fixed heating wire, and ageing; (6) drying the aged green body, and then roasting to obtain an integral catalyst; (7) placing the foam monolithic catalyst into a metal tube, followed byThen loading into a tubular reactor; (8) and connecting the lead with the heating wire. Compared with the traditional fixed bed catalyst, the method has the advantages of small reactor volume, quick catalyst temperature response, simple and convenient process, no amplification effect and the like, and provides a good strategy for realizing efficient, quick, stable and controllable methane hydrogen production.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of an internal heating type methane steam reforming hydrogen production foam monolithic catalyst.
Background
As a clean energy source, hydrogen is expected to become a main energy source in China in 2040 years and is considered as one of important solutions for promoting the realization of carbon peak-to-carbon neutralization. Methane is widely regarded as an important raw material for large-scale industrial production of hydrogen due to its advantages of high hydrogen volume content, perfect transportation and storage facilities, relatively low cost and the like. In the methane hydrogen production technology, the hydrogen production by steam reforming is mature, and is a mainstream hydrogen production mode at home and abroad.
Steam Methane Reforming (SMR) is a highly endothermic process, and in practice, the combustion of natural gas and a portion of the tail gas is usually used to provide heat for the reaction, inevitably producing large quantities of CO 2 Discharge of 1 kg of H per generation, according to incomplete statistics 2 Will release 9kg of CO 2 . At the same time, to ensure uniform temperature inside the reactor, the combustion must be maintained at a fairly high temperature to ensure sufficient inward heat flow, resulting in a large energy waste which will further exacerbate the CO 2 And (4) discharging. Therefore, how to replace fossil fuel for heat supply and reduce CO 2 Emission, referred to as focus of the study.
A large industrial steam methane reformer consists of 100 tubular fixed bed reactors 10-14 meters long, filled with particulate catalyst. In practical application, because the thermal conductivity of the SMR catalyst and the tube wall of the furnace tube is limited, the catalyst inside the reaction tube is often heated unevenly, and strong heat absorption in the reaction process causes a very obvious temperature gradient to be generated on the whole catalyst, so that the utilization rate of the catalyst is further lowered, and the risk of carbon deposition is increased.
How to improve the heat transfer efficiency of the SMR is always the focus of research, the current research mainly comprises new schemes such as catalyst heat transfer performance optimization, reactor temperature management, reactor optimization, low-temperature catalyst design and the like, however, the problems of high design precision, poor consistency, obvious amplification effect, short service life and the like cannot be solved by the new research scheme effectively. In recent years, the internal electric heating type reactor is gradually called as a research hotspot and mainly divided into a built-in heat source (heater) and a pipe wall coating type, and the volume of the reactor is greatly reduced but obvious radial temperature difference exists in the built-in heat source mode due to the low heat exchange area. Although the volume of the reactor is reduced in the pipe wall coating mode, the coating amount is low, and the problems of falling risk, short residence time and the like exist, so that the overall reaction efficiency is low, and the method is always in an experimental research stage.
Therefore, how to improve the effective utilization rate of the methane hydrogen production catalyst, increase the temperature uniformity of the reactor, improve the overall heat efficiency and prolong the service life of the catalyst still needs a great deal of research and innovation.
Based on the problems, the integral methane hydrogen production foam catalyst is prepared on the electric heating wire in one step by adopting a direct foaming method, the built-in electric heating wire quickly heats and provides heat after being electrified, and the heat transfer limitation and the internal temperature difference are solved; the foam catalyst is integrally formed, and the problems of low coating amount, insufficient residence time, low catalyst utilization rate and the like are solved. The preparation method of the internal heating type methane steam reforming hydrogen production foam monolithic catalyst can greatly reduce the volume of a methane hydrogen production catalytic reactor, improve the energy heat efficiency and the catalyst performance, and has very important application value in industry.
Disclosure of Invention
The invention aims to solve the problems of low heat transfer efficiency, low heat efficiency, large reaction temperature difference, low effective utilization rate of the catalyst, large volume of the reactor and the like in the traditional reactor, remarkably reduce the volume of the reactor, improve the residence time of reaction gas and improve the effective utilization rate of the catalyst while ensuring the internal temperature uniformity of the reactor, and provide the preparation method of the internal heating type methane steam reforming hydrogen production foam monolithic catalyst.
The invention relates to a preparation method of an internal heating type integral foam catalyst for hydrogen production by methane steam reforming, which is realized by the following technical scheme:
a preparation method of an internal heating type integral foam catalyst for hydrogen production by methane steam reforming comprises the following technical steps:
(1) treating the electric heating wire in acetone, and roasting at 500-950 ℃ for 30-600 minutes for later use; the shape of the electric heating wire is folded according to the requirement;
(2) taking nano Al 2 O 3 Soaking the powder in a nickel nitrate solution with the mass fraction of 1-30% for 30-180 minutes by adopting an equal-volume soaking method, drying the powder for 30-180 minutes at the temperature of 50-150 ℃, heating the powder to 350-650 ℃ at the speed of 1-10 ℃/min, roasting the powder for 30-360 minutes, and preparing Ni-Al 2 O 3 A catalyst powder;
(3) preparing slurry, wherein the raw materials comprise the following components in percentage by mass:
1 to 10% of glass fiber,
0.5 to 2 percent of N-methyldiethanolamine,
1 to 10 percent of polyethylene glycol,
1 to 10% of polyoxyethylene,
the content of the modified starch ether is 0.1-3%
10 to 40 percent of deionized water,
Ni-Al 2 O 3 the balance of catalyst;
after fully mixing, performing ball milling for 30-180 minutes at the rotating speed of 5-350 r/min, taking out, and aging for 1-12 hours for later use to obtain an aged material;
(4) slowly adding 1-3% by mass of sodium dodecyl sulfate into the aged material prepared in the step (3), uniformly stirring, violently stirring the bottom of the aged material, and rapidly introducing nitrogen gas with the flow rate of 1-500 ml/min into the bottom of the aged material to foam to obtain a foaming material;
(5) slowly adding the foaming material prepared in the step (4) into a mold for fixing the electric heating wire treated in the step (1), and ageing and drying for 1-48 hours at room temperature; obtaining an integral catalyst green body;
(6) drying the integral catalyst blank prepared in the step (5) by adopting a microwave method for 5-30 minutes, then heating to 550-750 ℃ at a speed of 1-10 ℃/min, and roasting for 30-360 minutes to obtain an integral catalyst;
(7) adding a heat insulating material with the thickness of 2-50 mm outside the bulk catalyst prepared in the step (6), and then filling the bulk catalyst into a reactor;
(8) and connecting a lead with the catalyst heating wire to finish the preparation of the self-heating foam monolithic catalyst.
Furthermore, the material of the electric heating wire is Ni-Cr alloy, porous carbon material, which is one or more of FeCrAl alloy.
Furthermore, the design structure of the electric heating wire can be one of monofilament, several, Z, W, I, spiral, folding, sheet and corrugation.
Further, the nano Al 2 O 3 Powder of, optionally, TiO 2 ，CeO 2 ，ZrO 2 Spinel, molecular sieve, and their preparation method is not limited to equal volume impregnation, or kneading, ion exchange, mixing form.
Furthermore, the adopted sizing agent auxiliary agent is one or more of N-methyldiethanolamine, polyethylene glycol, polyethylene oxide and modified starch ether.
Furthermore, the foaming agent is one or more of lauryl sodium sulfate, N-methyldiethanolamine or lauryl triethanolamine sulfate.
Further, the active component is one of nickel nitrate, noble metal platinum nitrate, rhodium nitrate, copper nitrate, ferric nitrate and cobalt nitrate, and the salt of the active component is one or more of sulfate and chlorate.
Compared with the prior art, the invention has the positive effects that:
the invention adopts a direct foaming process to prepare the methane hydrogen production porous foam monolithic catalyst on the structural electric heating wire by a one-step method, and the foam structure effectively increases the loading capacity of the catalyst, improves the reaction residence time, and improves the internal porosity and the specific surface area of the catalyst; the problem of low adhesive force in the conventional method is effectively solved by one-step molding preparation; the built-in electric heating wires which are uniformly distributed generate heat from the inside, and the problem of large temperature difference of the catalyst bed layer is effectively solved. Therefore, compared with the conventional fixed bed catalyst, the built-in electric heating rod type catalyst and the wall-coated type catalyst, the preparation method of the prepared internal heating type methane steam hydrogen production foam monolithic catalyst has the advantages of uniform internal temperature of the catalyst, quick temperature response, small reactor volume, simple preparation process, convenience for large-scale application and the like, provides a good strategy for efficient, quick, stable and controllable internal heating type methane hydrogen production, improves the energy utilization rate, reduces the emission of carbon dioxide, and has a very important application value in the field of natural gas hydrogen production.
Description of the drawings:
FIG. 1: an exemplary figure I of the internal heating type methane steam hydrogen production foam monolithic catalyst;
FIG. 1-1: an exemplary diagram II of the internal heating type methane steam hydrogen production foam monolithic catalyst;
FIG. 2: SEM picture of internal heating type methane steam hydrogen production catalyst;
FIG. 3: a temperature response comparison graph of the internal heating type methane steam hydrogen production foam monolithic catalyst;
Detailed Description
The following provides a specific embodiment of the preparation method of the internal heating type methane steam hydrogen production foam monolithic catalyst.
Example 1
The embodiment provides a preparation method of an internal heating type integral foam catalyst for hydrogen production from methane steam, which comprises the following steps:
as shown in figure 1, the preparation method of the internal heating type integral foam catalyst for hydrogen production by methane steam reforming comprises an electric heating wire (1), a heating power supply lead (2), a foam catalyst (3), an electric heating wire (4) and a reactor wall (5).
(1) Folding the Ni-Cr electric heating wire into a structure in a shape like a Chinese character ji, connecting a plurality of wires into a cylinder, immersing the cylinder in an acetone solution for treatment for 20min, and then roasting at a high temperature of 950 ℃ for 10h for later use;
(2) taking nano Al 2 O 3 Soaking the powder in 30 wt% nickel nitrate solution for 30min by an equal volume soaking method, drying at 50 deg.C for 180min, heating to 650 deg.C at 10 deg.C/min, and calcining for 360min to obtain Ni-Al 2 O 3 A catalyst powder;
(3) taking Ni-Al 2 O 3 50% of catalyst powder, 10% of glass fiber, 2% of N-methyldiethanolamine, 10% of polyethylene glycol, 10% of polyethylene oxide, 3% of modified starch ether and 13% of water are fully mixedBall milling at the rotating speed of 300r/min for 180min, taking out and aging for 12h for later use;
(4) slowly adding 2% of sodium dodecyl sulfate into the aged material, uniformly stirring, violently stirring at the bottom, and simultaneously rapidly introducing nitrogen with the flow rate of 500ml/min at the bottom for foaming;
(5) slowly adding the prepared foaming material into a mold with a fixed heating wire, and ageing and drying for 24 hours at room temperature;
(6) drying the completely dried integral catalyst blank body by adopting a microwave method for 30min, then heating to 550 ℃ at a speed of 10 ℃/min, and roasting for 360min to obtain a bulk catalyst;
(7) uniformly wrapping the prepared self-heating foam monolithic catalyst with a heat insulation material with the thickness of 20mm outside, and then spinning and loading the self-heating foam monolithic catalyst into a 25mm reactor;
(8) and connecting a lead with the catalyst heating wire to finish the preparation of the self-heating foam monolithic catalyst.
The lead is connected with a power supply, the electric heating wire quickly converts the electric energy into heat, the temperature of the foam catalyst is quickly raised to the reaction temperature, and when CH is generated 4 And the mixed gas with water enters the reactor to rapidly react to generate hydrogen.
Comparative example: a25 mm fixed bed reactor is adopted, a commercially available granular catalyst is adopted as the catalyst, the size of the catalyst is 5 x 3mm cylinder, the filling height of the catalyst is consistent with that of the foam catalyst in the example 1, an external electric furnace is adopted to heat the reactor, the heating power of the electric furnace is 2kW, in the comparative example, the methanol steam reforming hydrogen production is taken as an example, a power supply is connected, the heating speed is controlled to be 10-15 ℃/min, the temperature is raised to the target temperature, mixed steam of methanol and water is introduced after the target temperature is reached, and then the reaction is carried out to generate hydrogen. The heating response time is shown in comparison with fig. 3.
Example 2
A preparation method of an internal heating type integral foam catalyst for hydrogen production by methane steam reforming comprises an electric heating wire (1), a heating power supply lead (2), a foam catalyst (3), an electric heating wire (4) and a reactor wall (5). The specific preparation steps of the examples are as follows:
(1) folding an FeCrAl alloy electric heating wire into a Z shape, immersing the electric heating wire in acetone for treatment for 30min, and roasting the electric heating wire at 850 ℃ for 360min for later use;
(2) taking nano CeO 2 Soaking the powder in 1% platinum nitrate solution by an equal volume soaking method for 30min, drying at 65 deg.C for 120min, heating to 550 deg.C at 2 deg.C/min, and calcining for 120min to obtain Pt-CeO 2 A catalyst powder;
(3) taking Pt-CeO 2 40% of catalyst powder, 10% of glass fiber, 2% of N-methyldiethanolamine, 10% of polyethylene glycol, 10% of polyethylene oxide, 3% of modified starch ether and 25% of water are fully mixed, and then the mixture is ball-milled for 30min at the rotating speed of 200r/min, and then taken out and aged for 6h for later use;
(4) slowly adding 2% of lauryl triethanolamine sulfate into the aged material, uniformly stirring, violently stirring the bottom of the aged material, and simultaneously quickly introducing nitrogen gas with the flow of 200ml/min into the bottom of the aged material to foam;
(5) slowly adding the prepared foaming material into a die with a fixed heating wire, and ageing and drying for 48 hours at room temperature;
(6) drying the completely dried monolithic catalyst blank body by adopting a microwave method for 5min, then heating to 550 ℃ at the speed of 5 ℃/min, and roasting for 120min to obtain a bulk catalyst;
(7) uniformly wrapping the prepared self-heating foam monolithic catalyst with a heat insulation material with the thickness of 3mm outside, and then spinning and loading the self-heating foam monolithic catalyst into a 50mm reactor;
(8) and connecting a lead with the catalyst heating wire to finish the preparation of the self-heating foam monolithic catalyst.
The lead is connected with a power supply, the electric heating wire quickly converts the electric energy into heat, the temperature of the foam catalyst is quickly raised to the reaction temperature, and when CH is generated 4 And the mixed gas with water enters the reactor to quickly react to generate hydrogen.
The lead is connected with a power supply, the electric heating wire quickly converts the electric energy into heat, the temperature of the foam catalyst is quickly raised to the reaction temperature, and when CH is generated 4 And the mixed gas with water enters the reactor to rapidly react to generate hydrogen.
Example 3
A preparation method of an internal heating type integral foam catalyst for hydrogen production by methane steam reforming comprises an electric heating wire (1), a heating power supply lead (2), a foam catalyst (3), an electric heating wire (4) and a reactor wall (5). The specific preparation steps of the examples are as follows:
(1) preparing a Ni-Cr alloy into a spiral shape, immersing the spiral shape in acetone for treatment, and then roasting the spiral shape for 120min at 950 ℃ for later use;
(2) taking nano CeO 2 Soaking the powder in 2 wt% copper nitrate solution for 180min by ion exchange, controlling the solution temperature at 75 deg.C, vacuum filtering, drying at 120 deg.C for 120min, heating to 550 deg.C at 5 deg.C/min, and calcining for 120min to obtain Cu-CeO 2 A catalyst powder;
(3) taking Cu-CeO 2 50% of catalyst powder, 5% of glass fiber, 0.5% of N-methyldiethanolamine, 2% of polyethylene glycol, 1.5% of polyethylene oxide, 1% of modified starch ether and 40% of water are fully mixed, and then the mixture is ball-milled for 60min at the rotating speed of 100r/min, and then taken out and aged for 2h for later use;
(4) slowly adding 1% of sodium dodecyl sulfate into the aged material, uniformly stirring, violently stirring at the bottom, and simultaneously rapidly introducing nitrogen with the flow rate of 500ml/min at the bottom for foaming;
(5) slowly adding the prepared foaming material into a mold with a fixed heating wire, and ageing and drying at room temperature for 12 hours;
(6) drying the completely dried monolithic catalyst blank body by adopting a microwave method for 20min, then heating to 750 ℃ at the speed of 2 ℃/min, and roasting for 120min to obtain a bulk catalyst;
(7) uniformly wrapping the prepared self-heating foam monolithic catalyst with a heat insulation material with the thickness of 10mm outside, and then spinning and loading the self-heating foam monolithic catalyst into a 120mm reactor;
(8) and connecting a lead with the catalyst heating wire to finish the preparation of the self-heating foam monolithic catalyst.
The lead is connected with a power supply, the electric heating wire quickly converts the electric energy into heat, the temperature of the foam catalyst is quickly raised to the reaction temperature, and when CH is generated 4 And the mixed gas with water enters the reactor to quickly react to generate hydrogen.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (7)
1. A preparation method of an internal heating type integral foam catalyst for hydrogen production by methane steam reforming is characterized by comprising the following technical steps:
(1) immersing the electric heating wire in acetone for treatment, and then roasting at 500-950 ℃ for 30-600 minutes for later use;
(2) taking nano Al 2 O 3 Soaking the powder in a nickel nitrate solution with the mass fraction of 1-30% for 30-180 minutes by adopting an equal-volume soaking method, drying the powder for 30-180 minutes at 50-150 ℃, heating the powder to 350-650 ℃ at the speed of 1-10 ℃/min, roasting the powder for 30-360 minutes, and preparing Ni-Al 2 O 3 A catalyst powder;
(3) preparing slurry, wherein the raw materials comprise the following components in percentage by mass:
1 to 10% of glass fiber,
0.5 to 2 percent of N-methyldiethanolamine,
1 to 10 percent of polyethylene glycol,
1 to 10% of polyoxyethylene,
the content of the modified starch ether is 0.1-3%
10 to 40 percent of deionized water,
Ni-Al 2 O 3 the balance of catalyst;
after fully mixing, ball-milling for 30-180 minutes at the rotating speed of 5-350 r/min, taking out, and aging for 1-12 hours for later use to obtain an aged material;
(4) slowly adding 1-3% by mass of sodium dodecyl sulfate into the aged material prepared in the step (3), uniformly stirring, violently stirring the bottom of the aged material, and rapidly introducing nitrogen gas with the flow rate of 1-500 ml/min into the bottom of the aged material to foam to obtain a foaming material;
(5) slowly adding the foaming material prepared in the step (4) into a mold for fixing the electric heating wire treated in the step (1), and ageing and drying for 1-48 hours at room temperature; obtaining an integral catalyst green body;
(6) drying the integral catalyst blank prepared in the step (5) by adopting a microwave method for 5-30 minutes, then heating to 550-750 ℃ at a speed of 1-10 ℃/min, and roasting for 30-360 minutes to obtain an integral catalyst;
(7) adding a heat insulating material with the thickness of 2-50 mm outside the bulk catalyst prepared in the step (6), and then filling the bulk catalyst into a reactor;
(8) and connecting a lead with the catalyst heating wire to finish the preparation of the self-heating foam monolithic catalyst.
2. The preparation method of the internally heated foam monolithic catalyst for methane steam reforming hydrogen production according to claim 1, wherein the material of the electric heating wire is one or more of Ni-Cr alloy, porous carbon material and FeCrAl alloy.
3. The preparation method of the internally heated integral foam catalyst for methane steam reforming hydrogen production according to claim 1, wherein the electric heating wire has a design structure of one of monofilament, several, Z, W, I, spiral, folded, sheet and corrugated.
4. The preparation method of the internally heated foam monolithic catalyst for methane steam reforming hydrogen production according to claim 1, wherein the nano Al is 2 O 3 Powder of TiO 2 ，CeO 2 ，ZrO 2 Spinel, molecular sieve, and its preparation method is not limited to equal volume impregnation, or kneading, ion exchange, and mixing.
5. The preparation method of the internally heated integral catalyst for methane steam reforming hydrogen production foam as claimed in claim 1, wherein the slurry auxiliary agent is one or more of N-methyldiethanolamine, polyethylene glycol, polyethylene oxide and modified starch ether.
6. The preparation method of the internally heated integral foam catalyst for methane steam reforming hydrogen production according to claim 1, wherein the foaming agent is one or more of sodium dodecyl sulfate, N-methyldiethanolamine, and triethanolamine dodecyl sulfate.
7. The preparation method of the foam monolithic catalyst for hydrogen production by internal heating type methane steam reforming as claimed in claim 1, wherein the active component is one of nickel nitrate, noble metal platinum nitrate, rhodium nitrate, copper nitrate, ferric nitrate, cobalt nitrate, hydrous or non-hydrous salt, and the active component salt is one or more of sulfate and chlorate.
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