CN114618515B - Catalyst for low-temperature hydrogen production and preparation method and application thereof - Google Patents
Catalyst for low-temperature hydrogen production and preparation method and application thereof Download PDFInfo
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- CN114618515B CN114618515B CN202210260645.3A CN202210260645A CN114618515B CN 114618515 B CN114618515 B CN 114618515B CN 202210260645 A CN202210260645 A CN 202210260645A CN 114618515 B CN114618515 B CN 114618515B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000006260 foam Substances 0.000 claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 claims abstract description 66
- 239000002184 metal Substances 0.000 claims abstract description 66
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 29
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000002195 synergetic effect Effects 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 239000011572 manganese Substances 0.000 claims description 21
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 17
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- SYCBLWWKDXQZRR-UHFFFAOYSA-N [Ni].[W].[Cr] Chemical compound [Ni].[W].[Cr] SYCBLWWKDXQZRR-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims 1
- 239000004917 carbon fiber Substances 0.000 claims 1
- 229910018669 Mn—Co Inorganic materials 0.000 abstract description 29
- 239000003575 carbonaceous material Substances 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000006555 catalytic reaction Methods 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000004506 ultrasonic cleaning Methods 0.000 description 8
- 238000001833 catalytic reforming Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000006057 reforming reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/23—
-
- B01J35/33—
-
- 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
-
- 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
- C01B2203/10—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
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
Abstract
The invention belongs to the technical field of low-temperature hydrogen production, and particularly relates to a low-temperature hydrogen production catalyst, a preparation method and application thereof. The method comprises the following steps: 1) Obtaining a clean foam metal plate with high resistivity; 2) Preparing a foam metal plate loaded with Mn and Co; 3) Growing nano carbon components on the Mn and Co loaded foam metal plate in situ to obtain a catalyst material to be purified, wherein Mn and Co are dispersed on the surface of the nano carbon components, and the nano carbon components are loaded on the foam metal plate; 4) Purifying the catalyst material to be purified to obtain the low-temperature hydrogen production catalyst. The foam metal plate and the nano carbon material have excellent heat conduction and electric conduction performance, and the two ends of the foam metal plate are electrified to generate heat, and the heat and the current are simultaneously acted on Mn-Co active sites dispersed on the nano carbon material, so that a thermal-electric synergistic catalytic hydrogen production reaction occurs.
Description
Technical Field
The invention belongs to the technical field of low-temperature hydrogen production, and particularly relates to a low-temperature hydrogen production catalyst, a preparation method and application thereof.
Background
In the context of carbon peaks and carbon neutralization, the great development of hydrogen energy is an important way to reduce carbon dioxide emissions. Hydrogen is not present in nature as a secondary energy source and needs to be prepared by secondary conversion. The conversion of organic substances such as alcohols (methanol, ethanol) into hydrogen by catalytic reforming reaction is an important method for producing green hydrogen, and is the focus of attention of many researchers. Studies have shown that two major problems are faced in catalytic reforming reactions: 1. the catalytic reforming reaction is a strong endothermic reaction, and a large amount of external heat sources need to be provided; 2. carbon deposition is easy to generate on the catalyst, especially at the reaction temperature of above 600 ℃, which leads to rapid deactivation of the catalyst and reduces the yield of hydrogen. In order to ensure the economy and stability of the hydrogen production system, the reduction of the catalytic reaction temperature has remarkable effects on both the aspects of inhibiting the generation of carbon deposition and reducing the energy consumption of an external heat source. Some researchers have developed a method for preparing hydrogen by low-temperature catalytic reforming, mainly comprising the steps of preparing a single-atom catalyst and a noble metal composite catalyst, wherein the catalytic temperature is reduced, but the catalytic temperature is still higher; and the preparation cost of the noble metal catalyst is high, so that the industrial application is limited.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a catalyst for low-temperature hydrogen production, and a preparation method and application thereof. The self-growing nano carbon material dispersion Mn-Co based composite metal catalyst provided by the invention has double strengthening effects of thermal-electric synergistic catalysis, so that the low-temperature reaction activity of the Mn-Co based catalyst is improved, and the reduction of the reaction temperature of the methanol catalytic reforming hydrogen production to a range of 100-150 ℃ is realized.
The technical scheme provided by the invention is as follows:
the preparation method of the catalyst for low-temperature hydrogen production is characterized by comprising the following steps of:
1) Obtaining a clean foam metal plate with high resistivity;
2) Preparing a foam metal plate loaded with Mn and Co;
3) Growing nano carbon components on the Mn and Co loaded foam metal plate in situ to obtain a catalyst material to be purified, wherein Mn and Co are dispersed on the surface of the nano carbon components, and the nano carbon components are loaded on the foam metal plate;
4) Purifying the catalyst material to be purified to obtain the low-temperature hydrogen production catalyst.
In the technical scheme, the foam metal plate and the nano carbon material have excellent heat conduction and electric conduction performance, the two ends of the foam metal plate are electrified to generate heat, and the heat and the current simultaneously act on Mn-Co active sites dispersed on the nano carbon material, so that a thermal-electric synergistic catalysis hydrogen production reaction occurs.
Specifically, the step 2) includes the following steps:
2a) Immersing the foam metal plate obtained in the step 1) in a mixed solution of Mn salt and Co salt;
2b) Pore-opening is carried out on the impregnated material;
2c) And (3) drying, calcining and reducing the pore-opened material in sequence to activate the pore-opened material, so as to obtain the Mn and Co loaded foam metal plate.
Specific:
in step 2 a), the Mn salt is selected from any one of manganese acetate, manganese nitrate or manganous chloride; the Co salt is selected from any one of cobalt nitrate or cobalt chloride; the total molar concentration of Mn and Co is 0.01-0.5 mol/L; dipping under the ultrasonic condition for 1-2 hours;
in the step 2 c), calcining is carried out under the air condition, the calcining temperature is 500-700 ℃, and the calcining time is 1-3 hours; reducing in the atmosphere of reducing gas at 500-700 deg.c for 1-3 hr.
Specifically, the step 3) includes the following steps: and heating the foam metal plate loaded with Mn and Co in the mixed gas atmosphere containing carbon gas, reducing gas and balance gas for reaction to obtain the catalyst material to be purified, wherein the reaction temperature is 500-700 ℃ and the reaction time is 1-3 hours.
Specifically, the carbon-containing gas is selected from methane, ethylene, acetylene, and the like; the reducing gas being selected from H 2 Or CO, etc.; the balance gas is selected from nitrogen or argon.
Specifically, the step 4) includes the following steps: and (3) electrifying and heating the catalyst material to be purified to 450-650 ℃, then reacting in a mixed atmosphere of water vapor and argon, and oxidizing to remove amorphous carbon on the surface of the material, wherein the volume concentration of the water vapor in the mixed atmosphere is 5-40%.
Specifically, in the low-temperature hydrogen production catalyst, the weight ratio of the nano carbon component to the foam metal plate is (0.1-0.5): 1; the weight ratio of the total mass of Mn and Co to the foam metal plate is (0.05-0.5): 1.
The invention also provides the low-temperature hydrogen production catalyst prepared by the preparation method.
The invention also provides application of the catalyst for hydrogen production.
Specifically, the hydrogen production comprises the following steps: electrifying the catalyst, controlling the temperature to 100-150 ℃, and introducing mixed steam of methanol and water with the molar ratio of (0.3-1): 1 to catalyze hydrogen production.
In the technical scheme, because the foam metal plate and the nano carbon material have excellent heat conduction and electric conduction properties, the two ends of the foam metal plate are electrified to generate heat, and the heat and the current simultaneously act on Mn-Co active sites dispersed on the nano carbon material, so that a thermal-electric synergistic catalysis hydrogen production reaction occurs. Compared with traditional thermocatalysis, the method has the advantages of remarkably reducing the hydrogen production temperature, improving the catalytic efficiency and inhibiting the generation of carbon deposit.
Specifically, the preparation method of the catalyst comprises the following steps:
1) The pretreatment process comprises the following steps: and selecting a foam metal plate with high resistivity (comprising foam nickel-chromium-tungsten, foam nickel-chromium and the like) as a matrix, performing pretreatment of a cleaning-drying step on the matrix, wherein the cleaning comprises the steps of respectively utilizing ethanol, dilute hydrochloric acid and deionized water for cleaning, removing oil stains and oxide layers on the surface of the foam metal, and drying to obtain the pretreated foam metal plate.
2) The modified dipping process comprises the following steps: putting the foam metal plate into a Mn-Co mixed solution, respectively selecting one of manganese acetate, manganese nitrate, manganous chloride and the like, and preparing the Mn-Co mixed solution by one of cobalt nitrate, cobalt chloride and the like, wherein the molar concentration range of Mn and Co is 0.01-0.5 mol/L. The foam metal plate is immersed in the mixed solution for 1-2 hours in an ultrasonic manner, then a sample is taken out, and the foam metal plate is purged by an air compressor to prevent the solution from blocking pores; then the activation treatment of drying, calcining and reducing is carried out, the calcining and reducing temperature is within the range of 500-700 ℃ and the time is 1-4 hours; finally, the foam metal plate loaded with Mn and Co is obtained.
3) The in-situ growth process of the nano carbon material comprises the following steps: will load Mn and Co, placing the foam metal plate into a tube furnace, and introducing carbon-containing gas (such as methane, ethylene, acetylene, etc.)/reducing gas (such as H) 2 And CO and the like)/balance gas (such as nitrogen, argon and the like), heating the tube furnace to 500-700 ℃, and reacting for 1-3 hours, wherein the carbon nano-tube and the multi-layer graphene and other nano-carbon materials grow controllably on the foam metal plate, and the generation amount of the nano-carbon materials is controlled to be 100-500 mg per gram of foam metal. In the self-growth process of the nano carbon material, mn-Co composite metal is highly dispersed on the surface of the nano carbon material, so that the catalyst material to be purified is obtained.
4) The purification treatment process comprises the following steps: connecting two ends of the catalyst material to be purified with electrodes, applying current to enable the foam metal plate with high resistivity to generate a Joule heating effect, and adjusting the current to control the temperature of the catalyst material to be purified. Heating the catalyst material to be purified to 450-650 ℃, and introducing water vapor/argon atmosphere, wherein the concentration of the water vapor is 5-40%. The amorphous carbon which is easy to oxidize on the catalyst material to be purified is removed, the adverse effect of the amorphous carbon on the catalyst activity is reduced, and the purity of the nano carbon material is improved, so that the low-temperature hydrogen production catalyst is prepared.
Specifically, the low-temperature hydrogen production comprises the following steps: the current at two ends of the low-temperature hydrogen production catalyst is regulated, the temperature is controlled to be 100-150 ℃, mixed steam of methanol/water with a certain concentration is introduced, the molar ratio of the methanol to the water is 0.3-1, and the mixed steam carries out catalytic hydrogen production reaction on the catalyst. Methanol is adsorbed, decomposed and desorbed on the surfaces of the Mn-Co composite metal and the nano carbon material to generate small molecular gases such as hydrogen and the like. Because the foam metal plate and the nano carbon material have excellent heat conduction and electric conduction performance, the two ends of the foam metal plate are electrified to generate heat, and the heat and the current are simultaneously acted on Mn-Co active sites dispersed on the nano carbon material, so that a thermal-electric synergistic catalytic hydrogen production reaction occurs. Compared with traditional thermocatalysis, the method has the advantages of remarkably reducing the hydrogen production temperature, improving the catalytic efficiency and inhibiting the generation of carbon deposit.
Drawings
Fig. 1 is a flow chart of the present invention.
FIG. 2 is a scanning electron microscope image of self-grown nanocarbon material on foamed nickel-chromium in example 1.
Fig. 3 is a transmission electron microscopy image of carbon nanotubes, carbon nanofibers and multi-layered graphene on nickel-chromium foam in example 1.
FIG. 4 is a plot of the surface temperature of the low temperature hydrogen production catalyst of example 1 heated in situ at 30A current.
Detailed Description
The principles and features of the present invention are described below with examples only to illustrate the present invention and not to limit the scope of the present invention.
Example 1
The first step: the foam nickel-chromium is selected as a matrix, the thickness of foam metal is 10mm, the foam metal is cut into rectangles 50mm by 20mm, and ethanol, dilute hydrochloric acid and deionized water are sequentially used for cleaning. The specific process comprises the following steps:
placing a plurality of pieces of foam nickel-chromium into a beaker, adding 100ml of dilute hydrochloric acid, wherein the concentration of the dilute hydrochloric acid is 3mol/L, and treating the mixture on an ultrasonic cleaning instrument for 20min; pouring out hydrochloric acid, repeatedly washing with deionized water for 3 times, adding 100ml of absolute ethyl alcohol, and placing on an ultrasonic cleaning instrument for 20min; pouring out absolute ethyl alcohol, repeatedly washing 3 times by using deionized water, adding 100ml of deionized water, and treating on an ultrasonic cleaning instrument for 20min; pouring out deionized water, and drying in a drying oven at 105 ℃ for 12 hours to obtain the pretreated foam nickel-chromium material.
And a second step of: according to the concentration of 0.1mol/L manganese nitrate solution and 0.1mol/L cobalt nitrate solution, preparing 100ml of Mn-Co mixed solution, putting the pretreated foam nickel-chromium plate into the mixed solution, soaking the foam nickel-chromium plate on an ultrasonic cleaning instrument for 1 hour, taking out the metal plate, and purging the metal plate for a plurality of times by using an air compressor. Drying in a drying oven for 12 hr, calcining at 500deg.C in a muffle furnace for 2 hr, and placing in a tube furnace at 10H 2 And (3) reducing for 2 hours at 500 ℃ in Ar atmosphere to obtain the Mn-Co supported foam nickel-chromium sample.
And a third step of: putting the Mn-Co loaded foam nickel-chromium sample into a horizontal tube furnace, checking the air tightness, heating to 600 ℃ in Ar atmosphere, and switching to 10% C 2 H 4 /10％H 2 Reacting in Ar reaction atmosphere for 2 hours, takingAnd (5) outputting. The microscopic morphology of the foamed nickel-chromium surface-grown nanocarbon material was characterized by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), respectively, as shown in fig. 2 and 3. From fig. 2, it is evident that a large amount of fibrous carbon grows on the surface of the foam nickel-chromium, and from fig. 3, it is further seen that the fibrous carbon comprises two forms, namely carbon nanotubes (with a tube diameter of 10-50 nm) with cavities therein and carbon nanofibers with a larger tube diameter (greater than 100 nm), and meanwhile, the generation of multi-layer graphene is observed, as indicated in the figure. Mn-Co composite metal is highly dispersed on the surface of the nano carbon material, and a sample (Mn-Co/nano carbon material@foam metal plate) of the Mn-Co composite metal loaded nano carbon material coated foam nickel-chromium is obtained.
Fourth step: connecting two ends of a sample of Mn-Co/nano carbon material@foam metal plate with electrodes, and applying current to enable the foam metal plate with high resistivity to generate a Joule heating effect. The experiment tests the surface temperature of Mn-Co/nano carbon material @ foam metal plate material under the condition of applying 30A current, and the result is shown in figure 4, and the temperature reaches more than 500 ℃ within 2 seconds of electrifying. The current value of two ends of the Mn-Co/nano carbon material@foam metal plate is regulated, the surface temperature is controlled to be 500 ℃, 200ml/min of mixed gas of water vapor and argon is introduced, the water vapor proportion is 20%, amorphous carbon is removed after purification treatment for 1 hour, and the purity of the nano carbon material is improved, so that the Mn-Co/nano carbon material@foam nickel-chromium plate catalyst for preparing hydrogen by low-temperature catalytic reforming is prepared.
Fifth step: connecting two ends of Mn-Co/nano carbon material@foam nickel-chromium plate catalyst with electrodes, controlling the current value to be 8A, testing the surface temperature of the catalyst by a thermocouple to be 150 ℃, introducing mixed steam of methanol and water after the catalyst is stabilized, preparing mixed solution by the methanol and the water according to the molar ratio of 1:1, injecting the mixed solution into a steam generator at the speed of 50 mu l/min by using an injection pump, heating the mixed solution to 150 ℃ to generate mixed steam, introducing carrier gas of 100ml/min, and carrying the mixed steam into the catalytic reactor. Methanol and water undergo a thermo-electric co-reforming reaction on a catalyst, and the produced gas is collected by a gas bag and analyzed for components by gas chromatography, and the carbon conversion and hydrogen yield are calculated. After 1 hour of reaction, collecting the catalyst after the reaction, and determining the carbon deposition according to the mass of the catalyst before and after the reaction. In order to compare the thermo-electro synergistic catalysis with the traditional thermo-catalysis, the traditional thermo-catalysis experiment ensures that other conditions are unchanged, external heat source is used for heating, and the surface temperature of the catalyst is kept at 150 ℃. The results show that the carbon conversion rate of the thermal-electric synergistic reforming reaction reaches more than 80% at 150 ℃, and the methanol conversion rate of the traditional thermal catalytic reaction is less than 10%, wherein the hydrogen yield of the traditional thermal catalytic reaction is 10 times that of the traditional thermal catalytic reaction, and the carbon deposition is hardly detected after the thermal-electric synergistic catalytic reaction.
Example 2
The first step: the foam nickel-chromium-tungsten is selected as a matrix, the thickness of the foam nickel-chromium-tungsten is 1.5mm, the foam nickel-chromium-tungsten is cut into 50 mm-20 mm rectangles, and ethanol, dilute hydrochloric acid and deionized water are used for cleaning in sequence. The specific process comprises the following steps:
placing a plurality of foam nickel-chromium-tungsten sheets into a beaker, adding 100ml of dilute hydrochloric acid, wherein the concentration of the dilute hydrochloric acid is 3mol/L, and treating the mixture on an ultrasonic cleaning instrument for 20min; pouring out hydrochloric acid, repeatedly washing with deionized water for 3 times, adding 100ml of absolute ethyl alcohol, and placing on an ultrasonic cleaning instrument for 20min; pouring out absolute ethyl alcohol, repeatedly washing 3 times by using deionized water, adding 100ml of deionized water, and treating on an ultrasonic cleaning instrument for 20min; pouring out deionized water, and drying in a drying oven at 105 ℃ for 12 hours to obtain the pretreated foam nickel-chromium-tungsten material.
And a second step of: according to the concentration of 0.2mol/L manganese acetate solution and 0.2mol/L cobalt nitrate solution, preparing 100ml of Mn-Co mixed solution, putting the pretreated foam nickel-chromium-tungsten plate into the mixed solution, soaking the foam nickel-chromium-tungsten plate on an ultrasonic cleaning instrument for 1 hour, taking out the metal plate, and purging the metal plate for a plurality of times by using an air compressor. Drying in a drying oven for 12 hr, calcining at 500deg.C in a muffle furnace for 2 hr, and placing in a tube furnace at 10H 2 And (3) reducing for 2 hours at 500 ℃ in Ar atmosphere to obtain the Mn-Co loaded foam nickel-chromium-tungsten sample.
And a third step of: putting the Mn-Co loaded foam nickel-chromium-tungsten sample into a horizontal tube furnace, checking the air tightness, heating to 500 ℃ in Ar atmosphere, and switching to 10%C 2 H 2 /10％H 2 Reacting in Ar reaction atmosphere for 2 hours, and taking out to obtain Mn-Co composite metal loaded nano carbonThe material wrapped the foam nickel chromium tungsten sample (Mn-Co/nano carbon material @ foam metal plate).
Fourth step: connecting two ends of a sample of Mn-Co/nano carbon material@foam metal plate with electrodes, and applying current to enable the foam metal plate with high resistivity to generate a Joule heating effect. The current value of two ends of the Mn-Co/nano carbon material@foam metal plate is regulated, the surface temperature is controlled to be 500 ℃, 200ml/min of mixed gas of water vapor and argon is introduced, the water vapor proportion is 10%, the amorphous carbon is removed after purification treatment for 1 hour, and the purity of the nano carbon material is improved, so that the Mn-Co/nano carbon material@foam nickel-chromium-tungsten plate catalyst for preparing hydrogen by low-temperature catalytic reforming is prepared.
Fifth step: connecting two ends of Mn-Co/nano carbon material@foam nickel-chromium plate catalyst with electrodes, controlling the current value to be 8A, testing the surface temperature of the catalyst by a thermocouple to be 100 ℃, introducing mixed steam of methanol and water after the catalyst is stabilized, preparing mixed solution by the methanol and the water according to the molar ratio of 1:1, injecting the mixed solution into a steam generator at the speed of 50 mu l/min by using an injection pump, and introducing carrier gas of 100ml/min to carry the mixed steam into the catalytic reactor. Methanol and water undergo a thermo-electric cooperative reforming reaction on a catalyst, and the produced gas is collected by a gas bag and analyzed for components by gas chromatography, and the carbon conversion and the hydrogen yield are calculated. After 1 hour of reaction, collecting the catalyst after the reaction, and determining the carbon deposition according to the mass of the catalyst before and after the reaction. In order to compare the thermo-electro synergistic catalysis with the traditional thermo-catalysis, the traditional thermo-catalysis experiment ensures that other conditions are unchanged, external heat source is used for heating, and the surface temperature of the catalyst is kept to be 100 ℃. The result shows that the carbon conversion rate of the thermal-electric synergistic reforming reaction reaches more than 50% at the temperature of 100 ℃, the methanol conversion rate in the traditional thermal catalytic reaction is close to 0, and no carbon deposit is generated after the thermal-electric synergistic catalytic reaction.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The preparation method of the thermoelectric synergistic low-temperature hydrogen production catalyst is characterized by comprising the following steps of:
1) Obtaining a clean foam metal plate with high resistivity, wherein the foam metal plate is a foam nickel-chromium-tungsten metal plate or a foam nickel-chromium metal plate;
2) Preparing a metal Mn and Co loaded foam metal plate;
3) In-situ growing a nano carbon component on a foam metal plate loaded with Mn and Co to obtain a catalyst material to be purified, wherein Mn and Co are dispersed on the surface of the nano carbon component, the nano carbon component is loaded on the foam metal plate, and the nano carbon component comprises a carbon nano tube, a nano carbon fiber and a multilayer graphene;
4) Purifying the catalyst material to be purified to obtain the low-temperature hydrogen production catalyst, wherein the purifying steps are as follows: heating the catalyst material to be purified to 450-650 ℃ by electrifying, then reacting in a mixed atmosphere of water vapor and argon, oxidizing and removing amorphous carbon on the surface of the material, wherein the volume concentration of the water vapor in the mixed atmosphere is 5-40%;
the low temperature is 100-150 ℃;
in the low-temperature hydrogen production catalyst, the weight ratio of the nano carbon component to the foam metal plate is (0.1-0.5): 1; the weight ratio of the total mass of Mn and Co to the foam metal plate is (0.05-0.5): 1.
2. The method for preparing a thermoelectric synergistic low temperature hydrogen production catalyst according to claim 1, wherein the step 2) comprises the steps of:
2a) Immersing the foam metal plate obtained in the step 1) in a mixed solution of Mn salt and Co salt;
2b) Pore-opening is carried out on the impregnated material;
2c) And (3) drying, calcining and reducing the pore-opened material in sequence to activate the pore-opened material, so as to obtain the Mn and Co loaded foam metal plate.
3. The method for preparing the thermoelectric synergistic low-temperature hydrogen production catalyst according to claim 2, wherein the method comprises the following steps:
in step 2 a), the Mn salt is selected from any one of manganese acetate, manganese nitrate or manganous chloride; the Co salt is selected from any one of cobalt nitrate or cobalt chloride; the total molar concentration of Mn and Co is 0.01-0.5 mol/L; dipping under the ultrasonic condition for 1-2 hours;
in the step 2) c), calcining is carried out under the air condition, wherein the calcining temperature is 500-700 ℃ and the calcining time is 1-3 hours; reducing in the atmosphere of reducing gas at 500-700 ℃ for 1-3 hours.
4. The method for preparing a thermoelectric synergistic low temperature hydrogen production catalyst according to claim 1, wherein the step 3) comprises the steps of: and heating the foam metal plate loaded with Mn and Co in the mixed gas atmosphere of carbon-containing gas, reducing gas and balance gas for reaction to obtain the catalyst material to be purified, wherein the reaction temperature is 500-700 ℃ and the reaction time is 1-3 hours.
5. The method for preparing the thermoelectric synergistic low-temperature hydrogen production catalyst according to claim 4, wherein the method comprises the following steps: the carbon-containing gas is selected from ethylene or acetylene; the reducing gas being selected from H 2 Or CO; the balance gas is selected from nitrogen or argon.
6. A thermoelectric synergistic low temperature hydrogen production catalyst prepared according to the preparation method of any one of claims 1 to 5.
7. Use of a catalyst according to claim 6, characterized in that: is used for producing hydrogen.
8. The use according to claim 7, characterized by the steps of: and electrifying the catalyst, controlling the temperature of the catalyst to be 100-150 ℃, and introducing mixed steam of methanol and water with the molar ratio of (0.3-1): 1 to catalyze the hydrogen production.
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