CN109718782B - Method for preparing hydrogen by reforming methane and hydrogen sulfide - Google Patents
Method for preparing hydrogen by reforming methane and hydrogen sulfide Download PDFInfo
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- CN109718782B CN109718782B CN201711023754.9A CN201711023754A CN109718782B CN 109718782 B CN109718782 B CN 109718782B CN 201711023754 A CN201711023754 A CN 201711023754A CN 109718782 B CN109718782 B CN 109718782B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 35
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 22
- 239000001257 hydrogen Substances 0.000 title claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002407 reforming Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 11
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000006057 reforming reaction Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 144
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 30
- 230000032683 aging Effects 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 11
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 abstract description 38
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 38
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000007789 gas Substances 0.000 abstract description 11
- 239000012752 auxiliary agent Substances 0.000 abstract description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229910001947 lithium oxide Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 49
- 239000012153 distilled water Substances 0.000 description 30
- 239000002243 precursor Substances 0.000 description 30
- 238000003756 stirring Methods 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 7
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
A method for preparing hydrogen by reforming methane and hydrogen sulfide is to contact and react hydrogen sulfide and methane with a catalyst with the following mass composition: fe2O35% -65%, 25% -94% of MgO, and NiO or Li2O1% -10%. The temperature of the methane hydrogen sulfide reforming reaction is 600-1200 ℃, and preferably 600-800 ℃. The catalyst adopted by the method takes iron oxide as an active component, magnesium oxide as a carrier and nickel oxide or lithium oxide as an auxiliary agent, and has the characteristic of high temperature resistance and high-temperature reaction activity; the magnesium oxide can effectively improve the dispersion degree of the iron oxide and inhibit the high-temperature growth of iron oxide grains; the auxiliary agent can improve the alkalinity of the surface of the carrier, and is beneficial to adsorbing and activating the acid gas hydrogen sulfide, so that the conversion rate of the hydrogen sulfide is improved; in addition, the catalyst of the invention has cheap and easily obtained raw materials and simple preparation method, and is suitable for industrial application.
Description
Technical Field
The invention relates to a method for preparing hydrogen by reforming methane hydrogen sulfide, in particular to a method for catalyzing the reforming of methane hydrogen sulfide by adopting a catalyst which takes ferric oxide as an active component, nickel oxide as an auxiliary agent and magnesium oxide as a carrier, belonging to the catalyst technology in the field of hydrogen preparation by reforming methane.
Background
The sulfur in natural gas exists mainly in the form of H2S and the balance of organic sulfur such as mercaptan, thioether and the like, and the organic sulfur can be converted into H through hydrogenation2S。H2S is a gas with strong toxicity, malodor and strong corrosiveness, so the sulfur-containing natural gas can bring a series of complex problems to well drilling, gas production, gas transmission and the like, and can cause the breakage of a drilling tool and the severe corrosion of an oil pipe, a gas pipe and the like, thereby causing huge economic loss. Therefore, H is properly disposed of or utilized2S is also a serious problem in the petrochemical industry in China.
At present, H in China2The S utilization technique is also dominated by the Claus process, with the main product being sulfur. However, the international sulfur market is saturated at present, and the sulfur price drops all the way, so H is used2S is a raw material for producing sulfur, so that development of H is urgently needed2S using a new method. A great deal of H is carried out on Chinese scientists2Hydrogen production by S decompositionIn the case of a double reaction process consisting of a redox reaction and an electrolysis reaction2When the acid tail gas is treated, the sulfur in the acid tail gas is recovered, and high-purity hydrogen can be prepared. The prepared hydrogen can be reused in the hydrodesulfurization process of fuel oil, and the comprehensive utilization of hydrogen is realized. The process is feasible through the research of the enlarged test of Shenghua oil refinery at the university of petroleum (east China). For example, the great-continuous-substance research institute develops a super-adiabatic combustion technology, which is applied to hydrogen sulfide decomposition hydrogen production and utilizes H under the condition of not using a catalyst and an external heating source2S is subjected to super-adiabatic partial oxidative decomposition in a porous medium to remove H2S and hydrogen can be recovered, and the pollution emission is obviously reduced. The technology can be used for treating industrial waste gas containing toxic and harmful components. Up to now, the vast majority of the foreign industrial hydrogen comes from CH4The hydrogen production technology is mature, the production cost is low, but CO and CO are generated in the process2The difficulty is caused to the emission reduction of greenhouse gas, and the raw material also needs to be subjected to a desulfurization process, so that the energy consumption of the whole process is increased.
H2S and CH4The products of reforming are hydrogen and easily liquefiable stored CS2This is H2S is a novel way of utilization and is therefore of particular interest. At present, there is no H in China2S and CH4The reforming hydrogen production aspect of (1). Foreign scientists already in the United states, Mexico, and other countries are engaged in H2S and CH4The research on the reforming hydrogen production process mainly takes kinetics, thermodynamics and simulation as main researches. Thermodynamic analysis was performed by Huang et al in the United states and analysis found that the reaction temperature exceeded 1000 deg.C oC methane can be completely converted, and the conversion rate of hydrogen sulfide is lower, 1000oC is only 30%; Martinez-Salazar et al Pair Mo/La in Mexico2O3-ZrO2The catalyst is subjected to kinetic analysis and simulation, the reaction temperature is 850 ℃ and CH4/H2Methane conversion reached 82% at S = 1/12.
H reported in the literature2S and CH4The reforming catalyst is mainly Fe-based catalyst and Mo-based catalystThe carrier is Al2O3. The reaction is generally carried out at temperatures above 800 ℃ so Al2O3The series of catalysts have the problem of poor high-temperature reaction performance.
Disclosure of Invention
Aims to solve the problem that Al is generally used in the hydrogen production reaction by reforming methane and hydrogen sulfide in the prior art2O3The series of catalysts have poor high-temperature stability, resulting in H2The invention aims to provide a method for preparing hydrogen by reforming methane and hydrogen sulfide, which adopts a catalyst with ferric oxide as an active component, nickel oxide as an auxiliary agent and magnesium oxide as a carrier to catalyze the reforming of the methane and the hydrogen sulfide and has the advantages of good high-temperature stability, high catalyst activity and H2High S conversion rate.
The technical scheme adopted by the invention is as follows:
a method for preparing hydrogen by reforming methane and hydrogen sulfide is to contact and react hydrogen sulfide and methane with a catalyst with the following mass composition:
Fe2O3 5%~65%
MgO 25%~94%
NiO or Li2O 1%~10%。
In the above method, as a further preferable aspect, the catalyst composition is:
Fe2O3 10%~40%
MgO 55%~89%
NiO or Li2O 1%~5%。
In the method, the temperature of the methane hydrogen sulfide reforming reaction is 600-1200 ℃, preferably 700-800 ℃; the reaction pressure is 0.1 to 2MPa, preferably 0.1 to 1 MPa.
In the method, the catalyst is prepared by taking soluble salts of various metals as raw materials and adopting a coprecipitation method, and then drying and roasting the raw materials.
As a more specific embodiment, the specific preparation method of the catalyst is as follows: preparing soluble salt containing iron, magnesium, nickel or lithium into an aqueous solution according to the preset composition of the catalyst, keeping the temperature of the solution at 20-90 ℃, adding a precipitator into the aqueous solution, controlling the pH value to 8-11, and carrying out aging reaction, washing, drying and roasting to obtain the catalyst.
In the above method, in the preparation of the catalyst, the soluble salt containing iron, magnesium, nickel or lithium is preferably nitrate; the precipitant is sodium hydroxide solution, ammonia water or sodium bicarbonate solution, preferably sodium hydroxide; the reaction temperature is preferably 30-60 ℃, and the PH value is preferably controlled at 9-10; the aging time is 1-8 hours, preferably 3-6 hours; the drying temperature is 60-200 ℃, preferably 80-150 ℃, the drying time is 1-36 hours, preferably 8-24 hours, and the roasting is carried out at 400-1000 ℃ for 2-15 hours, preferably at 600-900 ℃ for 3-8 hours.
Compared with the prior art, the invention has the following advantages:
the catalyst adopted by the method takes iron oxide as an active component, magnesium oxide as a carrier and nickel oxide or lithium oxide as an auxiliary agent, and has the characteristic of high temperature resistance and high-temperature reaction activity; the magnesium oxide can effectively improve the dispersion degree of the iron oxide and inhibit the high-temperature growth of iron oxide grains; the auxiliary agent can improve the alkalinity of the surface of the carrier, and is beneficial to adsorbing and activating the acid gas hydrogen sulfide, so that the conversion rate of the hydrogen sulfide is improved; in addition, the catalyst of the invention has cheap and easily obtained raw materials and simple preparation method, and is suitable for industrial application.
Drawings
FIG. 1 TPR spectra of catalysts prepared in example 1 and comparative example 1;
FIG. 2 TPR spectrum of catalyst prepared in example 8.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Catalysts were prepared in examples 1-14 and comparative examples 1-2:
example 1
According to Fe in catalyst2O3The mass fraction of NiO is 40wt%, the mass fraction of NiO is 1%, the mass fraction of MgO is 59wt%, and the corresponding weight is weighedAmount of Fe (NO)3)3、Ni(NO3)2And Mg (NO)3)2Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst C1.
Example 2
According to Fe in catalyst2O3The mass fraction of (1) is 20wt%, NiO is 3 wt%, MgO is 77wt%, and Fe (NO) is weighed in corresponding weight3)3、Ni(NO3)2And Mg (NO)3)2Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst C2.
Example 3
According to Fe in catalyst2O3The mass fraction of the NiO is 10wt%, the NiO is 5wt%, the MgO is 85wt%, and Fe (NO) with the corresponding weight is weighed3)3、Ni(NO3)2And Mg (NO)3)2Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. Then dropwise adding sodium hydroxide solution into the mixed solution while stirring, controlling the pH value at 10, and aging after dropwise addingAnd 3h, taking out, carrying out suction filtration and washing for 3 times, and then putting the obtained product into a drying box at the temperature of 110 ℃ for drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst C3.
Example 4
According to Fe in catalyst2O3The mass fraction of (1) is 20wt%, NiO is 3 wt%, MgO is 77wt%, and Fe (NO) is weighed in corresponding weight3)3、Ni(NO3)2And Mg (NO)3)2Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 600 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 8 hours to obtain the catalyst C4.
Example 5
According to Fe in catalyst2O3The mass fraction of (1) is 20wt%, NiO is 3 wt%, MgO is 77wt%, and Fe (NO) is weighed in corresponding weight3)3、Ni(NO3)2And Mg (NO)3)2Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. And then taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 800 ℃ at the heating rate of 10 ℃/min, and roasting at constant temperature for 3 hours to obtain the catalyst C5.
Example 6
According to Fe in catalyst2O3The mass fraction of NiO is 20wt%, the mass fraction of NiO is 3 wt%, the mass fraction of MgO is 77wt%, and the corresponding weight is weighedFe (NO) of3)3、Ni(NO3)2And Mg (NO)3)2Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a water bath at 50 ℃ with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst C6.
Example 7
According to Fe in catalyst2O3The mass fraction of (1) is 20wt%, NiO is 3 wt%, MgO is 77wt%, and Fe (NO) is weighed in corresponding weight3)3、Ni(NO3)2And Mg (NO)3)2Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a water bath at 60 ℃ with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst C7.
Example 8
According to Fe in catalyst2O310wt% of MgO, 89wt% of Li2O is 1%, and Fe (NO) is weighed according to the weight3)3、Mg(NO3)2And LiNO3Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. Then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3h after the dropwise adding is finished,taking out, filtering, washing for 3 times, placing into a drying oven at 110 ℃, and drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst C8.
Example 9
According to Fe in catalyst2O325wt% of MgO, 74wt% of Li2Weighing Fe (NO) with corresponding weight for 1% of O3)3、Mg(NO3)2And LiNO3Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst C9.
Example 10
According to Fe in catalyst2O340wt% of MgO, 58wt% of Li2O is 2%, and Fe (NO) is weighed according to the weight3)3、Mg(NO3)2And LiNO3Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst C10.
Example 11
According to Fe in catalyst2O320wt% of MgO, 75wt% of Li2O is 5%, and the corresponding weight is weighedAmount of Fe (NO)3)3、Mg(NO3)2And LiNO3Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst C11.
Example 12
According to Fe in catalyst2O320wt% of MgO, 75wt% of Li2The O is 5%, and Fe (NO) is weighed according to the weight3)3、Mg(NO3)2And LiNO3Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 9, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 4 hours to obtain the catalyst C12.
Example 13
According to Fe in catalyst2O310wt% of MgO, 89wt% of Li2O is 1%, and Fe (NO) is weighed according to the weight3)3、Mg(NO3)2And LiNO3Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. Then dropwise adding sodium hydroxide solution into the mixed solution while stirring, controlling the pH value at 10, aging for 3h after dropwise adding, taking out, and vacuum filteringWashed 3 times, and then put into a drying oven at 110 ℃ to be dried overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and roasting at the constant temperature for 8 hours to obtain the catalyst C13.
Example 14
According to Fe in catalyst2O310wt% of MgO, 89wt% of Li2Weighing Fe (NO) with corresponding weight for 1% of O3)3、Mg(NO3)2And LiNO3Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added, and the mixture was placed in a 30 ℃ water bath with a stirring speed of 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. And taking out the dried precursor, placing the precursor in a muffle furnace, raising the temperature to 600 ℃ at the heating rate of 10 ℃/min, and roasting at constant temperature for 3 hours to obtain the catalyst C14.
Comparative example 1
Weighing 116g of MgO pellets of 80-100 meshes, putting the MgO pellets into a flask of a rotary evaporator, and keeping the temperature of a water bath kettle at 65 ℃. 20g Fe (NO) are weighed out3)3·9H2And O is put into a 500mL beaker, 100mL of deionized water is added to prepare a solution, a vacuum pump is turned on after the solution is dissolved, the solution is sucked into the flask, and the rotating speed of the flask is 100 r/min. After the solution is completely evaporated, taking out the MgO pellets, drying the MgO pellets in a drying oven at 110 ℃ for 24 hours, and roasting the MgO pellets in a muffle furnace at 900 ℃ for 3 hours to obtain the catalyst Fe2O3MgO, catalyst D1, where Fe2O3The mass content is 15 percent, and the MgO content is 85 percent.
FIG. 1 shows catalyst C1 Fe of example 12O3NiO/MgO and catalyst D1 Fe of comparative example 12O3TPR comparison of/MgO. As can be seen, Fe2O3The reduction peak on/NiO/MgO is 4 and is more than Fe2O32 reduction peaks on MgO, which shows that the auxiliary NiO and the carrier MgO promote Fe2O3And the reduction peaks not only increased in number but also increased in area, indicating Fe2O3More iron on the/NiO/MgO is reduced to be used as an active component to participate in the reaction, so that the activity of the catalyst is improved.
FIG. 2 shows catalyst C8 Fe of example 82O3/Li2TPR graph of O/MgO. As can be seen, Fe2O3/Li2O/MgO is 300oC and 500oThe C accessory has a reduction peak, the temperature of the reduction peak is relatively low, and Li is shown2O promotes Fe2O3Reduction of (2).
Comparative example 2
Preparation of catalyst Fe2O3/Al2O3: weighing 116g of 80-100 mesh Al2O3The pellets were placed in a flask of a rotary evaporator and the water bath temperature was maintained at 65 ℃. 20g Fe (NO) are weighed out3)3·9H2And O is put into a 500mL beaker, 100mL of deionized water is added to prepare a solution, a vacuum pump is turned on after the solution is dissolved, the solution is sucked into the flask, and the rotating speed of the flask is 100 r/min. After the solution is completely evaporated, taking out Al2O3The pellets are dried in a drying oven at 110 ℃ for 24 hours and roasted in a muffle furnace at 900 ℃ for 3 hours to obtain the catalyst Fe2O3/Al2O3Denoted as catalyst D2, where Fe2O315% by mass of Al2O3The mass content is 85%.
Comparative example 3
Preparation of Mo/La2O3-ZrO2Catalyst: taking Zr (NO)3)3、La(NO3)2Then, the mixture was put into a 500mL beaker, 150mL of distilled water was added thereto, and the beaker was placed in a water bath at 60 ℃ with stirring at 400 rpm. 34.3g of sodium hydroxide was put into a beaker containing 200mL of distilled water, and stirred until all the sodium hydroxide was dissolved. And then dropwise adding a sodium hydroxide solution into the mixed solution while stirring, controlling the pH value to be 10, aging for 3 hours after dropwise adding, taking out, carrying out suction filtration and washing for 3 times, then placing into a drying oven at 110 ℃, and drying overnight. Then taking out the dried precursor and placing the precursor in a muffleHeating to 900 ℃ at a heating rate of 10 ℃/min in a furnace, and roasting at constant temperature for 4 hours to obtain La2O3-ZrO2Wherein La2O3Is 40wt%, ZrO2Is 60 percent. Dipping the ammonium molybdate solution into the La of the carrier by adopting a dipping method2O3-ZrO2Then drying and roasting are carried out to obtain Mo/La2O3-ZrO2Catalyst, catalyst D3, wherein the mass content of molybdenum oxide is 20%, La2O3Is 32wt%, ZrO2The mass fraction of (b) is 48%.
The catalyst is used for catalyzing the hydrogen production reaction of methane and hydrogen sulfide reforming: the test is carried out in a fixed bed reactor, 5mL of catalyst is taken and mixed with quartz sand with the same mesh number according to the volume ratio of 1: 1. The raw material gas is a mixed gas (10 vol% CH) of methane and hydrogen sulfide4，20vol％H2S，70vol%N2) The flow is 100mL/min, and then enters a preheater, the temperature of the preheater is kept at 500 ℃, and then enters a reactor, the reaction temperature is 850 ℃, and the reaction pressure is normal pressure. After the reaction is stable, sampling is started, and SP-3820 type gas chromatography on-line analysis, 5A molecular sieve column and Porapak Q column are adopted, and TCD detection is carried out. The evaluation results after 100h are shown in Table 1.
TABLE 1 reactivity of the catalysts
According to the method, the temperature of the hydrogen production reaction by reforming the methane hydrogen sulfide is changed, the reaction is respectively carried out at 600 ℃, 700 ℃, 800 ℃, 900 ℃ and 1000 ℃, and each catalyst catalyzes H reformed by the methane hydrogen sulfide2The yields are shown in Table 2.
TABLE 2H for reforming of methane hydrogen sulfide catalyzed by each catalyst2Yield of
Claims (10)
1. A method for preparing hydrogen by reforming methane and hydrogen sulfide is to contact and react hydrogen sulfide and methane with a catalyst with the following mass composition:
Fe2O3 5%~65%
MgO 25%~94%
NiO or Li2O 1%~10%。
2. The method of claim 1, wherein the catalyst consists of:
Fe2O3 10%~40%
MgO 55%~89%
NiO or Li2O 1%~5%。
3. The method of claim 1, wherein the temperature of the methane hydrogen sulfide reforming reaction is 600 to 1200 ℃.
4. The method of claim 3, wherein the temperature of the methane hydrogen sulfide reforming reaction is 700 to 800 ℃.
5. The method according to claim 1, wherein the pressure of the methane hydrogen sulfide reforming reaction is 0.1 to 2 MPa.
6. The method of claim 1, wherein the catalyst is prepared by taking soluble salts of each metal as raw materials and adopting a coprecipitation method, and then drying and roasting the raw materials.
7. The method according to claim 6, wherein the catalyst is prepared by the following specific method: preparing soluble salt containing iron, magnesium, nickel or lithium into an aqueous solution according to the preset composition of the catalyst, keeping the temperature of the solution at 20-90 ℃, adding a precipitator into the aqueous solution, controlling the pH value to 8-11, and carrying out aging reaction, washing, drying and roasting to obtain the catalyst.
8. The method according to claim 7, wherein the soluble salt containing iron, magnesium, nickel or lithium is preferably a nitrate salt in the preparation of the catalyst.
9. The method according to claim 7, wherein the precipitant is a sodium hydroxide solution, ammonia water, or sodium bicarbonate solution.
10. The method according to claim 7, wherein the reaction temperature is 30 to 60 ℃ and the pH is controlled to 9 to 10.
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| CN104084211A (en) * | 2014-07-10 | 2014-10-08 | 中国科学院上海高等研究院 | Catalyst for preparing synthesis gas or hydrogen and preparation method and application thereof |
| CN105772016A (en) * | 2016-04-29 | 2016-07-20 | 太原理工大学 | Nickel-based catalyst and preparation method thereof |
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| CN104084211A (en) * | 2014-07-10 | 2014-10-08 | 中国科学院上海高等研究院 | Catalyst for preparing synthesis gas or hydrogen and preparation method and application thereof |
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