CN114751373B - Mechanocatalytic method for preparing hydrogen and carbon by methane pyrolysis - Google Patents
Mechanocatalytic method for preparing hydrogen and carbon by methane pyrolysis Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 32
- 239000001257 hydrogen Substances 0.000 title claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 10
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910002065 alloy metal Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 230000008021 deposition Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 229910018487 Ni—Cr Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 4
- 229910001120 nichrome Inorganic materials 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 229910002546 FeCo Inorganic materials 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- 229910002669 PdNi Inorganic materials 0.000 description 3
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- ZDAJWQJFPAOYKS-UHFFFAOYSA-N [Au].C(C)C1=C(C=2C=C3C(=C(C(=CC=4C(=C(C(=CC5=C(C(=C(N5)C=C1N2)CC)CC)N4)CC)CC)N3)CC)CC)CC Chemical compound [Au].C(C)C1=C(C=2C=C3C(=C(C(=CC=4C(=C(C(=CC5=C(C(=C(N5)C=C1N2)CC)CC)N4)CC)CC)N3)CC)CC)CC ZDAJWQJFPAOYKS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
Abstract
The application relates to a mechanical catalysis method for preparing hydrogen and carbon by methane pyrolysis, which timely removes carbon deposition on the surface of a catalyst through mechanical catalysis and prolongs the reaction life of the catalyst; meanwhile, the mechanical energy can effectively activate the reaction molecules, reduce the catalytic reaction energy barrier and moderate the catalytic reaction conditions; finally, only hydrogen and carbon are contained in the methane pyrolysis product, and the mechanical catalysis process of methane pyrolysis is simple to operate and low in energy consumption.
Description
Technical Field
The application belongs to the technical field of methane pyrolysis hydrogen production, and particularly relates to a mechanical catalytic method for preparing hydrogen and carbon by methane pyrolysis.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the application and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The traditional methane cracking thermal catalysis mode cannot effectively get rid of the influence of carbon deposition in the reaction process, so that the cracking catalyst is easy to be deactivated due to the fact that the carbon deposition blocks the pore channels and active sites of the catalyst. In addition, the operation temperature of methane dry gas reforming and methane cracking is higher than 1000 ℃, and the reaction energy consumption is high, so that the exploration of methane hydrogen production technology under mild conditions is a research hot spot in the field.
Disclosure of Invention
In order to improve the reaction efficiency of preparing hydrogen and carbon by methane pyrolysis and reduce the reaction energy consumption and investment cost, the application provides a mechanocatalysis method for preparing hydrogen and carbon by methane pyrolysis. Compared with the traditional catalysis mode, the mechanical catalysis can remove carbon deposition on the surface of the catalyst in time, and the reaction life of the catalyst is prolonged; meanwhile, the mechanical energy can effectively activate the reaction molecules, reduce the catalytic reaction energy barrier and moderate the catalytic reaction conditions; finally, only hydrogen and carbon are contained in the methane pyrolysis product, and the mechanical catalysis process of methane pyrolysis is simple to operate and low in energy consumption.
A mechanocatalytic method for preparing hydrogen and carbon by methane pyrolysis comprises the following steps:
s1: filling a metal alloy catalyst into a mechanical reactor, introducing methane gas from an inlet of the mechanical reactor, and allowing reaction product gas to flow out through an outlet of the mechanical reactor;
s2: the electric motor drives the mechanical reactor to vibrate to control the collision of the metal alloy catalyst in the reactor, and the methane cracking activity is regulated by regulating the temperature of the mechanical reactor and the vibration frequency of the metal alloy catalyst;
s3: and recovering the gas product of methane pyrolysis from the outlet of the mechanical reactor, and directly recovering the carbon powder and the metal alloy catalyst through screening.
Through the technical scheme, hydrogen and carbon can be prepared by methane pyrolysis, the mechanical strength of the catalyst can be improved by using the metal alloy catalyst, the methane pyrolysis reaction can be reduced by introducing mechanical energy to catalyze the methane pyrolysis reaction, carbon deposition on a grinding medium can be effectively removed, the service life of the catalyst is prolonged, and the process is simple to operate and low in investment cost.
Preferably, the reactor in the step S1 is cylindrical in shape, the metal alloy catalyst serves as a grinding medium, the metal alloy catalyst is spherical, and the filling amount of the metal alloy catalyst is 1/20-1/2 of the volume of the reactor.
The reactor structure which has good sealing performance and can be used in the form of a fluidized bed can be used as the reactor of the application, and the reactor is required to have the function of vibrating at a fixed frequency.
Preferably, the metal alloy catalyst in the step S1 comprises an alloy metal carrier and an active component loaded on the carrier, wherein the active component is one or more alloy nano particles or single atoms of iridium, platinum, palladium, nickel, cobalt, iron, gold, gallium, chromium and copper.
The diameter of the alloy metal carrier is 0.1-10cm, more preferably 1-3cm.
Preferably, the alloy metal carrier in the step S1 is an alloy formed by one or more metals of nickel, iron, copper, zinc, chromium and the like, wherein the content of each metal component is in the range of 0-100 wt%.
Preferably, the active ingredient is supported in an amount of 0.0001 to 3wt%.
The metal alloy catalyst is prepared by the following steps:
soaking or ultrasonic treating the metal alloy carrier in one or more metal precursor solutions, and baking at 500-1000 ℃ for 36h in air and at 500-1000 ℃ for 36h in a reducing atmosphere to obtain the metal alloy catalyst of S1.
The metal precursor includes carbonate, nitrate, sulfate, chloride, bromide, or organic complex of the active component, and the like.
S2, controlling the flow rate of methane gas through a mass flowmeter; controlling the temperature of the mechanical reactor through a heating wire; the mechanical reactor is driven to vibrate by the electric motor.
Preferably, in the step S2, the reaction temperature is controlled at 200-1000 ℃, the flow rate of methane is controlled at 0.015L/min, and the vibration frequency of the reactor is controlled at 50-1000Hz.
Preferably, the vibration direction of the reactor in the step S2 is up and down.
Preferably, the pressure in the reactor in step S2 is 0.2MPa.
The application has at least one of the following beneficial technical effects:
the methane is introduced into a mechanical reactor, the reaction temperature for preparing hydrogen and carbon by methane pyrolysis can be reduced by externally applying mechanical force, and meanwhile, reaction products comprise the hydrogen and the carbon, and the product separation process is simple, the energy consumption is low, and the investment cost is low;
the metal alloy grinding medium is used as the catalyst, so that the accumulation of carbon deposition in the methane cracking process can be reduced, and simultaneously, the mechanical force can timely remove the solid carbon on the surface of the catalyst, so that the service life of the catalyst is effectively prolonged.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
The catalytic process of the present application is described in further detail below, with the described embodiments being some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The pretreated metallic nickel spheres (diameter 1 cm) were mixed according to 500g:200mL of solution is soaked in chloroplatinic acid (0.1M) solution for ultrasonic treatment for 1h, then the nickel balls are fished out and dried in a 90 ℃ oven for 2h, and finally the nickel balls are roasted in 600 ℃ air for 6h and then are roasted in 800 ℃ hydrogen for 6h to synthesize the platinum nickel alloy catalyst.
300g of Pt/Ni metal balls are filled in a 2L mechanical reactor, 100mL/min of methane gas is introduced, the reaction is carried out for 100 hours under the conditions of 400 ℃ and 200Hz vibration frequency, the reactor pressure is 0.15MPa, the mechanical reactor drives the metal alloy catalyst to generate mechanical force in a mode of up-and-down vibration, the methane conversion rate is 20%, and the hydrogen selectivity is more than 99%.
Example 2
Pretreated nickel-iron alloy spheres (diameter 2 cm) were prepared at 500g: soaking 300mL of solution in a proportion of chloroiridic acid (0.1M) and chloroplatinic acid (0.1M) solution for ultrasonic treatment for 1h, fishing out nickel iron balls, drying the nickel iron balls in a 90 ℃ oven for 6h, and finally roasting the nickel iron balls in 650 ℃ air for 6h and roasting the nickel iron balls in 900 ℃ hydrogen for 4h to synthesize the platinum-nickel alloy catalyst.
500g of IrPt/NiFe metal balls are filled in a 1.5L mechanical reactor, 50mL/min methane gas is introduced, the reaction is carried out for 100h at 450 ℃ and 500Hz vibration frequency, the reactor pressure is 0.1MPa, the mechanical reactor drives the metal alloy catalyst to generate mechanical force in a vibration mode, the methane conversion rate is 40%, and the hydrogen selectivity is more than 99%.
Example 3
The pretreated copper-iron alloy balls (diameter 3 cm) were mixed according to 500g: soaking 300mL of solution in a ratio of palladium nitrate (0.1M) and nickel acetate (0.1M) solution for ultrasonic treatment for 2 hours, fishing out the copper-iron spheres, drying the copper-iron spheres in a 90 ℃ oven for 6 hours, and finally roasting the copper-iron spheres in 700 ℃ air for 5 hours and roasting the copper-iron spheres in 700 ℃ hydrogen for 6 hours to synthesize the PdNi/CuFe alloy catalyst.
500g of PdNi/CuFe metal balls are filled in a 1L mechanical reactor, 80mL/min methane gas is introduced, the reaction is carried out for 100h under the conditions of 600 ℃ and 1000Hz vibration frequency, the reactor pressure is 0.1MPa, the mechanical reactor drives the metal alloy catalyst to generate mechanical force in a mode that a central rotating shaft extrudes a grinding medium, the methane conversion rate is 40%, and the hydrogen selectivity is more than 99%.
Example 4
The pretreated zinc-chromium alloy balls (diameter 1 cm) were mixed according to 500g:250mL of solution is soaked in a solution of ferric acetate (0.1M) and cobalt acetylacetonate (0.1M) for ultrasonic treatment for 2 hours, then the zinc-chromium balls are fished out and dried in a 90 ℃ oven for 6 hours, and finally the zinc-chromium balls are roasted in 700 ℃ air for 5 hours and then are roasted in 700 ℃ hydrogen for 6 hours to synthesize the FeCo/ZnCr alloy catalyst.
800g FeCo/ZnCr metal balls are filled in a 3L mechanical reactor, 100mL/min methane gas is introduced, the reaction is carried out for 100 hours under the conditions of 900 ℃ and 1300Hz vibration frequency, the reactor pressure is 0.3MPa, the mechanical reactor drives the metal alloy catalyst to generate mechanical force in a centrifugal swing mode, the methane conversion rate is 45%, and the hydrogen selectivity is more than 99%.
Example 5
Pretreated nichrome balls (1.5 cm diameter) were mixed at 500g: the preparation method comprises the steps of immersing 500mL of solution in palladium chloride (0.1M), gold octaethylporphyrin (0.1M) and cobalt acetylacetonate (0.1M) for 2h in proportion, fishing out nickel-chromium balls, drying the nickel-chromium balls in a 90 ℃ oven for 6h, roasting the nickel-chromium balls in 900 ℃ air for 3h, and roasting the nickel-chromium balls in 800 ℃ hydrogen for 6h to synthesize the PdAuCo/NiCr alloy catalyst.
300g of PdAuCo/NiCr metal balls are filled in a 2L mechanical reactor, 500mL/min methane gas is introduced, the reaction is carried out for 100h under the conditions of 1000 ℃ and 1500Hz vibration frequency, the reactor pressure is 0.12MPa, the mechanical reactor drives the metal alloy catalyst to generate mechanical force in a mode of up-and-down vibration, the methane conversion rate is 38%, and the hydrogen selectivity is more than 99%.
Example 6
The pretreated metallic zinc spheres (diameter 2 cm) were prepared according to 500g:200mL of solution is soaked in chloroauric acid (0.1M) solution for ultrasonic treatment for 3h, then the zinc balls are fished out and dried in a 90 ℃ oven for 6h, and finally the zinc balls are roasted in 900 ℃ air for 5h and then in 900 ℃ hydrogen for 6h to synthesize the Au/Zn alloy catalyst.
300g of Au/Zn metal balls are filled in a 2L mechanical reactor, 50mL/min of methane gas is introduced, the reaction is carried out for 100 hours under the conditions of 900 ℃ and 800Hz vibration frequency, the reactor pressure is 0.1MPa, the mechanical reactor drives the metal alloy catalyst to generate mechanical force in a mode of up-and-down vibration, the methane conversion rate is 8%, and the hydrogen selectivity is more than 99%.
The activity test of the methane cracking to prepare hydrogen and carbon is carried out in the above examples 1-6 of the application, and the corresponding test results are shown in the following table 1:
table 1 evaluation of the Activity of each catalyst
| CH 4 Conversion rate | Hydrogen selectivity | Catalyst | |
| Example 1 | 20％ | >99％ | Pt/Ni |
| Example 2 | 40％ | >99％ | IrPt/NiFe |
| Example 3 | 40％ | >99％ | PdNi/CuFe |
| Example 4 | 45％ | >99％ | FeCo/ZnCr |
| Example 5 | 38％ | >99％ | PdAuCo/NiCr |
| Example 6 | 8％ | >99％ | Au/Zn |
The results of the examples in table 1 show that high purity hydrogen products can be obtained using metal alloy catalysts and mechanocatalytic means while the metal alloy catalysts exhibit the technical advantage of not decreasing reactivity after prolonged operation; in addition, the multi-site metal alloy catalyst exhibits higher reactivity.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (6)
1. The mechanocatalytic method for preparing hydrogen and carbon by methane pyrolysis is characterized by comprising the following steps of:
s1: filling a metal alloy catalyst into a mechanical reactor, introducing methane gas from an inlet of the mechanical reactor, and allowing reaction product gas to flow out through an outlet of the mechanical reactor;
s2: the electric motor drives the mechanical reactor to vibrate to control the collision of the metal alloy catalyst in the reactor, and the methane cracking activity is regulated by regulating the temperature of the mechanical reactor and the vibration frequency of the metal alloy catalyst;
s3: recovering a methane cracked gas product from an outlet of a mechanical reactor, and directly recovering carbon powder and a metal alloy catalyst through screening;
the metal alloy catalyst comprises an alloy metal carrier and an active component loaded on the carrier, wherein the active component is one or more alloy nano particles or single atoms of iridium, platinum, palladium, nickel, cobalt, iron, gold, gallium, chromium and copper;
the loading of the active component is 0.0001-3wt%;
the alloy metal carrier is an alloy formed by one or more metals of nickel, iron, copper, zinc and chromium;
the metal alloy catalyst is prepared by the following steps: soaking or ultrasonic processing a metal alloy carrier in one or more metal precursor solutions, and baking for 36 hours at 500-1000 ℃ in air and 36 hours at 500-1000 ℃ in a reducing atmosphere to obtain the metal alloy catalyst;
in the step S2, the reaction temperature is controlled at 400-1000 ℃, and the vibration frequency of the reactor is controlled at 200-1000Hz.
2. The mechanocatalytic process of claim 1 wherein said mechanical reactor is cylindrical in shape and the metal alloy catalyst is spherical in shape and the loading of the metal alloy catalyst is 1/20 to 1/2 of the volume of the mechanical reactor.
3. The mechanocatalytic process of claim 1 wherein said alloy metal support has a diameter of 0.1 cm to 10cm.
4. The mechanocatalytic process of claim 3 for producing hydrogen and carbon by methane pyrolysis wherein said alloy metal support has a diameter of 1-3cm.
5. The mechanocatalytic process of claim 1, wherein said metal precursor comprises a carbonate, nitrate, sulfate, chloride, bromide or organic complex of said active component.
6. Use of the mechanocatalytic process of any of claims 1 to 5 for the production of hydrogen and carbon by methane cracking.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07251070A (en) * | 1994-03-15 | 1995-10-03 | Fuji Electric Co Ltd | Reforming catalyst for fuel cell |
| CN101291732A (en) * | 2005-10-20 | 2008-10-22 | Sk能源 | Nickel based catalyst using hydrotalcite-like precursor and steam reforming reaction of LPG |
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| CN112875724A (en) * | 2021-01-27 | 2021-06-01 | 复旦大学 | Method for synthesizing ammonia by metal oxide catalytic mechanochemistry under normal temperature and pressure water phase condition |
| AU2021105368A4 (en) * | 2021-08-12 | 2021-10-14 | Qingdao University Of Science And Technology | Method for Preparing and Applying Long-life Friction-sensitive Graphdiyne-based Piezoelectric Material |
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| JPH07251070A (en) * | 1994-03-15 | 1995-10-03 | Fuji Electric Co Ltd | Reforming catalyst for fuel cell |
| CN101291732A (en) * | 2005-10-20 | 2008-10-22 | Sk能源 | Nickel based catalyst using hydrotalcite-like precursor and steam reforming reaction of LPG |
| CN102019183A (en) * | 2009-09-22 | 2011-04-20 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen from hydrocarbon steam conversion or carboxyl syngas reaction and preparation method thereof |
| CN102441410A (en) * | 2010-10-15 | 2012-05-09 | 上海欣年石化助剂有限公司 | Catalyst for storing hydrogen by organic matter carrier and preparation method of catalyst |
| CN112875724A (en) * | 2021-01-27 | 2021-06-01 | 复旦大学 | Method for synthesizing ammonia by metal oxide catalytic mechanochemistry under normal temperature and pressure water phase condition |
| AU2021105368A4 (en) * | 2021-08-12 | 2021-10-14 | Qingdao University Of Science And Technology | Method for Preparing and Applying Long-life Friction-sensitive Graphdiyne-based Piezoelectric Material |
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