CN108421552A - A kind of wide warm high activity synthesis gas catalyst for methanation in presence of sulfur - Google Patents

A kind of wide warm high activity synthesis gas catalyst for methanation in presence of sulfur Download PDF

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CN108421552A
CN108421552A CN201810312192.8A CN201810312192A CN108421552A CN 108421552 A CN108421552 A CN 108421552A CN 201810312192 A CN201810312192 A CN 201810312192A CN 108421552 A CN108421552 A CN 108421552A
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methanation
catalyst
solid
mos
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王玮涵
李振花
王保伟
徐艳
马新宾
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Tianjin University
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a kind of methanation catalysts, are MoS3It is supported on CexZr1‑xO2On solid-solution powder, wherein x is 0.80~0.9, MoS3Load capacity be MoS3 withCexZr1‑xO2Molar ratio is 10~30:1.The invention also discloses the preparation method of the methanation catalyst and for the H of sulfur-bearing2With the purposes of CO gaseous mixture methanation reactions.

Description

A kind of wide warm high activity synthesis gas catalyst for methanation in presence of sulfur
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of wide warm high activity synthesis gas methanation in presence of sulfur catalysis Agent.
Background technology
Methanation reaction refers to the active principle in synthesis gas under the action of certain temperature, pressure and catalyst CO and H2It carries out reaction and generates CH4Process.Reaction equation is represented by：
Methanation catalyst is the key technology in natural gas from coal technique.In existing industry methanation catalyst, with NiO, which is the loaded catalyst of active component, has preferable conversion ratio and selectivity.But nickel catalyst is in synthesis gas original H in material2Activity is very low when/CO ratios are relatively low, and synthesis gas needs to first pass through Water gas shift/WGS by H2/ CO ratios are promoted to 3 or more, It can ensure the activity of nickel catalyst.Meanwhile nickel catalyst is extremely sensitive to sulfur content, raw material of synthetic gas is before use It needs to remove the sour gas such as hydrogen sulfide by fine de-sulfur, and ensures that concentration of hydrogen sulfide is down to 1ppm or less contents, otherwise hold Easily lead to the inactivation of catalyst.Therefore, it develops in low H2All had in/CO ratios and wider hydrogen sulfide content fluctuation range compared with The methanation catalyst of good catalytic activity can greatly reduce production cost.
Patent CN103433026A discloses a kind of ZrO2The high stability catalyst for methanation in presence of sulfur of load, passes through precipitation Method, deposition-precipitation method or sol-gel method for preparing Zr O2Carrier selects commercially available ZrO2Carrier, and pass through infusion process or deposition sedimentation Method is by catalyst activity component MoO3With catalyst promoter Y2O3It is supported on ZrO2On carrier；The catalyst is in high hydrogen sulfide atmosphere In have the characteristics that high methanation reaction catalytic reaction activity, low inverse water gas shift reation activity and good catalytic stability.Specially Sharp CN103157485A discloses a kind of preparation method of load type sulfur-tolerant methanation catalyst, using infusion process or deposition sedimentation Method prepares catalyst, is catalysis with the oxide of Mo, W and/or V using the oxide of Co, Ni, La and/or K as catalyst promoter Agent active component, using the oxide of Ce, Zr, Ti, Mg and/or Si as support modification agent, using the oxide of Ce or Al as catalyst Carrier, compound porous carrier is obtained by coprecipitation, deposition-precipitation method, infusion process or sol-gal process, then passes through leaching Stain method or deposition-precipitation method load catalyst activity component and auxiliary agent on porous support；Catalyst table under the high temperature conditions Reveal excellent catalytic activity, but it is active relatively low under cryogenic.In summary, it needs exist for developing a kind of wide temperature height Active methanation in presence of sulfur catalysts, are provided simultaneously with high catalytic activity and wide temperature adaptability.
Invention content
The purpose of the present invention is to provide a kind of load type sulfur-tolerant methanation catalysts, have in wide temperature fluctuation range There is higher methanation activity, and the purposes of preparation method and methanation reaction is provided.
First aspect present invention discloses a kind of methanation catalyst, is MoS3It is supported on CexZr1-xO2Solid-solution powder On, wherein x is 0.80~0.9, MoS3Load capacity be MoS3Account for MoS3With CexZr1-xO210~30wt% of total amount.
Preferably, the CexZr1-xO2Solid solution is cubic.
Second aspect of the present invention discloses the preparation method of the methanation catalyst, includes the following steps：
(1) a certain amount of cerous nitrate and zirconium nitrate is soluble in water, solution is added dropwise in alkaline precipitating agent at 80 DEG C In, the PH ＞ 11 after precipitating completely are controlled, then aging 24 hours at 100 DEG C；Filtration washing will be precipitated to neutrality, in room temperature It is 12 hours dry, then drying 12 hours at 120 DEG C, it is then calcined 6 hours at 500 DEG C, obtains the oxidation of cubic cerium zirconium Object CexZr1-xO2Solid-solution powder；
(2) a certain amount of ammonium paramolybdate is soluble in water, the Ce for then obtaining a certain amount of step (1)xZr1-xO2Solid solution Powder is evenly spread in molybdenum ammonium solution, is kept for 12 hours in room temperature, then drying 12 hours at 120 DEG C, then 500 It is calcined 6 hours at DEG C, natural cooling obtains load MoO3CexZr1-xO2Solid-solution powder；
(3) solid-solution powder for obtaining step (2) is under 300 DEG C and normal pressure, in 3wt% hydrogen sulfide and 97wt% hydrogen Vulcanize 4h in the atmosphere of gas, is crushed to and obtains the methanation catalyst after 20-80 mesh.Molybdenum oxide largely or entirely by Molybdenum sulfide is replaced.
Preferably, the addition of step (1) cerous nitrate and zirconium nitrate meets x between 0.80-0.9.
Preferably, step (2) ammonium paramolybdate and CexZr1-xO2The addition of solid-solution powder makes MoS3With MoS3 with CexZr1-xO2Molar ratio is 10~30:1.
The third disclosure of the invention of the present invention methanation catalyst is used for the H of sulfur-bearing2It is anti-with CO gaseous mixture methanations The purposes answered.
Preferably, the content of the sulphur is the 0.1~3.0v/v%, the H that gaseous sulphide accounts for gaseous mixture total volume2 Molar ratio with CO is 0.8~1.2:1；The condition of the methanation reaction is：270~650 DEG C, preferably 350~550 DEG C, Pressure is 1.0~6.0MPa.
Beneficial effects of the present invention：
(1) catalyst of the invention not only obtains high catalytic activity and stability using CeO2-ZrO2 solid solution as carrier, but also The dosage for significantly reducing zirconium oxide, reduces catalyst production cost.
(2) catalyst of the invention all has higher in the wider higher range of temperature range and hydrogen sulfide content Methanation activity.
Specific implementation mode
The present invention is described in further detail with reference to specific embodiment, but the following description is only used for Enable general technical staff of the technical field of the invention that the principle of the present invention and marrow is more clearly understood, does not constitute Any restrictions are done to the present invention.
Embodiment 1：It weighs 2.4697g zirconium nitrates to be dissolved in 92 grams of water and stir evenly with 36.1126g cerous nitrates, 80 0.8% potassium hydroxide precipitating reagents of 432mL are added dropwise in solution under the conditions of DEG C, and are vigorously stirred, after control precipitation is complete PH ＞ 11, the aging 24 hours under the conditions of 100 DEG C, will precipitation filtration washing to neutrality, in drying at room temperature 12 hours, at 120 DEG C Lower drying 12 hours is calcined 6 hours at 500 DEG C, you can obtains cubic Ce0.80Zr0.20O2Solid solution support powder.Claim Take 10g support powders and 1.2266g ammonium paramolybdates, it is soluble in water and stir evenly, in drying at room temperature 12 hours, at 120 DEG C It is 12 hours dry, it is calcined 6 hours at 500 DEG C, obtains load 10wt%MoO3Ce0.90Zr0.10O2Solid solution support powder.
Catalyst activity evaluation carries out in fixed bed reactors.Take the catalyst particles of 20-80 mesh (750-178 μm of grain size) Grain is fitted into reactor, is then passed to 3v/v% hydrogen sulfide and 97v/v% hydrogen atmospheres, is vulcanized at 300 DEG C of temperature and normal pressure 4h, the catalyst as vulcanized.After vulcanization, the temperature of catalyst bed is stablized under preset reaction temperature, It is switched to the synthesis gas (H that concentration of hydrogen sulfide is 0.2v/v%2/ CO molar ratios are 1) to be used as unstripped gas, in reaction temperature 350 DEG C, methanation in presence of sulfur reaction is carried out under the conditions of reaction pressure 3.0MPa.The gas of unstripped gas and reactor outlet composition passes through Gas-chromatography on-line checking is analyzed, and the CO conversion ratios and CH of methanation in presence of sulfur reaction is obtained by calculation4Selectivity.Catalyst Activity evaluation for details see attached table 1.
Embodiment 2：It weighs 3.7045g zirconium nitrates to be dissolved in 92 grams of water and stir evenly with 34.1064g cerous nitrates, 80 0.8% potassium hydroxide precipitating reagents of 432mL are added dropwise in solution under the conditions of DEG C, and are vigorously stirred, after control precipitation is complete PH ＞ 11, the aging 24 hours under the conditions of 100 DEG C, will precipitation filtration washing to neutrality, in drying at room temperature 12 hours, at 120 DEG C Lower drying 12 hours is calcined 6 hours at 500 DEG C, you can obtains cubic Ce0.85Zr0.15O2Solid solution support powder.Claim Take 10g support powders and 1.8399g ammonium paramolybdates, it is soluble in water and stir evenly, in drying at room temperature 12 hours, at 120 DEG C It is 12 hours dry, it is calcined 6 hours at 500 DEG C, obtains load 15wt%MoO3Ce0.85Zr0.15O2Solid solution support powder.
Catalyst activity evaluation carries out in fixed bed reactors.Take the catalyst particles of 20-80 mesh (750-178 μm of grain size) Grain is fitted into reactor, is then passed to 3v/v% hydrogen sulfide and 97v/v% hydrogen atmospheres, is vulcanized at 300 DEG C of temperature and normal pressure 4h, the catalyst as vulcanized.After vulcanization, the temperature of catalyst bed is stablized under preset reaction temperature, It is switched to the synthesis gas (H that concentration of hydrogen sulfide is 0.2v/v%2/ CO molar ratios are 1) to be used as unstripped gas, in reaction temperature 450 DEG C, methanation in presence of sulfur reaction is carried out under the conditions of reaction pressure 3.0MPa.The gas of unstripped gas and reactor outlet composition passes through Gas-chromatography on-line checking is analyzed, and the CO conversion ratios and CH of methanation in presence of sulfur reaction is obtained by calculation4Selectivity.Catalyst Activity evaluation for details see attached table 1.
Embodiment 3：It weighs 4.9393g zirconium nitrates to be dissolved in 92 grams of water and stir evenly with 32.1001g cerous nitrates, 80 0.8% potassium hydroxide precipitating reagents of 432mL are added dropwise in solution under the conditions of DEG C, and are vigorously stirred, after control precipitation is complete PH ＞ 11, the aging 24 hours under the conditions of 100 DEG C, will precipitation filtration washing to neutrality, in drying at room temperature 12 hours, at 120 DEG C Lower drying 12 hours is calcined 6 hours at 500 DEG C, you can obtains cubic Ce0.80Zr0.20O2Solid solution support powder.Claim Take 10g support powders and 1.8399g ammonium paramolybdates, it is soluble in water and stir evenly, in drying at room temperature 12 hours, at 120 DEG C It is 12 hours dry, it is calcined 6 hours at 500 DEG C, obtains load 15wt%MoO3Ce0.80Zr0.20O2Solid solution support powder.
Catalyst activity evaluation carries out in fixed bed reactors.Take the catalyst particles of 20-80 mesh (750-178 μm of grain size) Grain is fitted into reactor, is then passed to 3v/v% hydrogen sulfide and 97v/v% hydrogen atmospheres, is vulcanized at 300 DEG C of temperature and normal pressure 4h, the catalyst as vulcanized.After vulcanization, the temperature of catalyst bed is stablized under preset reaction temperature, It is switched to the synthesis gas (H that concentration of hydrogen sulfide is 0.2v/v%2/ CO molar ratios are 1) to be used as unstripped gas, in reaction temperature 400 DEG C, methanation in presence of sulfur reaction is carried out under the conditions of reaction pressure 3.0MPa.The gas of unstripped gas and reactor outlet composition passes through Gas-chromatography on-line checking is analyzed, and the CO conversion ratios and CH of methanation in presence of sulfur reaction is obtained by calculation4Selectivity.Catalyst Activity evaluation for details see attached table 1.
Embodiment 4：It weighs 4.9393g zirconium nitrates to be dissolved in 92 grams of water and stir evenly with 32.1001g cerous nitrates, 80 0.8% potassium hydroxide precipitating reagents of 432mL are added dropwise in solution under the conditions of DEG C, and are vigorously stirred, after control precipitation is complete PH ＞ 11, the aging 24 hours under the conditions of 100 DEG C, will precipitation filtration washing to neutrality, in drying at room temperature 12 hours, at 120 DEG C Lower drying 12 hours is calcined 6 hours at 500 DEG C, you can obtains cubic Ce0.80Zr0.20O2Solid solution support powder.Claim Take 10g support powders and 1.8399g ammonium paramolybdates, it is soluble in water and stir evenly, in drying at room temperature 12 hours, at 120 DEG C It is 12 hours dry, it is calcined 6 hours at 500 DEG C, obtains load 15wt%MoO3Ce0.80Zr0.20O2Solid solution carrier powder.
Catalyst activity evaluation carries out in fixed bed reactors.Take the catalyst particles of 20-80 mesh (750-178 μm of grain size) Grain is fitted into reactor, is then passed to 3v/v% hydrogen sulfide and 97v/v% hydrogen atmospheres, is vulcanized at 300 DEG C of temperature and normal pressure 4h, the catalyst as vulcanized.After vulcanization, the temperature of catalyst bed is stablized under preset reaction temperature, It is switched to the synthesis gas (H that concentration of hydrogen sulfide is 0.2v/v%2/ CO molar ratios are 1) to be used as unstripped gas, in reaction temperature 500 DEG C, methanation in presence of sulfur reaction is carried out under the conditions of reaction pressure 3.0MPa.The gas of unstripped gas and reactor outlet composition passes through Gas-chromatography on-line checking is analyzed, and the CO conversion ratios and CH of methanation in presence of sulfur reaction is obtained by calculation4Selectivity.Catalyst Activity evaluation for details see attached table 1.
Embodiment 5：It weighs 4.9393g zirconium nitrates to be dissolved in 92 grams of water and stir evenly with 32.1001g cerous nitrates, 80 0.8% potassium hydroxide precipitating reagents of 432mL are added dropwise in solution under the conditions of DEG C, and are vigorously stirred, after control precipitation is complete PH ＞ 11, the aging 24 hours under the conditions of 100 DEG C, will precipitation filtration washing to neutrality, in drying at room temperature 12 hours, at 120 DEG C Lower drying 12 hours is calcined 6 hours at 500 DEG C, you can obtains cubic Ce0.80Zr0.20O2Solid solution support powder.Claim Take 10g support powders and 1.8399g ammonium paramolybdates, it is soluble in water and stir evenly, in drying at room temperature 12 hours, at 120 DEG C It is 12 hours dry, it is calcined 6 hours at 500 DEG C, obtains load 15wt%MoO3Ce0.80Zr0.20O2Solid solution carrier powder End.
Catalyst activity evaluation carries out in fixed bed reactors.Take the catalyst particles of 20-80 mesh (750-178 μm of grain size) Grain is fitted into reactor, is then passed to 3v/v% hydrogen sulfide and 97v/v% hydrogen atmospheres, is vulcanized at 300 DEG C of temperature and normal pressure 4h, the catalyst as vulcanized.After vulcanization, the temperature of catalyst bed is stablized under preset reaction temperature, It is switched to the synthesis gas (H that concentration of hydrogen sulfide is 0.2v/v%2/ CO molar ratios are 1) to be used as unstripped gas, in reaction temperature 550 DEG C, methanation in presence of sulfur reaction is carried out under the conditions of reaction pressure 3.0MPa.The gas of unstripped gas and reactor outlet composition passes through Gas-chromatography on-line checking is analyzed, and the CO conversion ratios and CH of methanation in presence of sulfur reaction is obtained by calculation4Selectivity.Catalyst Activity evaluation for details see attached table 1.
Embodiment 6：It weighs 4.9393g zirconium nitrates to be dissolved in 92 grams of water and stir evenly with 32.1001g cerous nitrates, 80 0.8% potassium hydroxide precipitating reagents of 432mL are added dropwise in solution under the conditions of DEG C, and are vigorously stirred, after control precipitation is complete PH ＞ 11, the aging 24 hours under the conditions of 100 DEG C, will precipitation filtration washing to neutrality, in drying at room temperature 12 hours, at 120 DEG C Lower drying 12 hours is calcined 6 hours at 500 DEG C, you can obtains cubic Ce0.80Zr0.20O2Solid solution support powder.Claim Take 10g support powders and 3.0665g ammonium paramolybdates, it is soluble in water and stir evenly, in drying at room temperature 12 hours, at 120 DEG C It is 12 hours dry, it is calcined 6 hours at 500 DEG C, obtains load 25wt%MoO3Ce0.80Zr0.20O2Solid solution support powder.
Catalyst activity evaluation carries out in fixed bed reactors.Take the catalyst particles of 20-80 mesh (750-178 μm of grain size) Grain is fitted into reactor, is then passed to 3v/v% hydrogen sulfide and 97v/v% hydrogen atmospheres, is vulcanized at 300 DEG C of temperature and normal pressure 4h, the catalyst as vulcanized.After vulcanization, the temperature of catalyst bed is stablized under preset reaction temperature, It is switched to the synthesis gas (H that concentration of hydrogen sulfide is 0.2v/v%2/ CO molar ratios are 1) to be used as unstripped gas, in reaction temperature 400 DEG C, methanation in presence of sulfur reaction is carried out under the conditions of reaction pressure 3.0MPa.The gas of unstripped gas and reactor outlet composition passes through Gas-chromatography on-line checking is analyzed, and the CO conversion ratios and CH of methanation in presence of sulfur reaction is obtained by calculation4Selectivity.Catalyst Activity evaluation for details see attached table 1.
Table 1 is the catalytic condition and knot for the unstripped gas that catalyst prepared by the method for the present invention is used for different concentration of hydrogen sulfide Fruit.Catalyst produced by the present invention is provided with good adaptability as shown in Table 1, and still with higher under the conditions of low hydrogen-carbon ratio Methanation activity.
Table 1：The methanation in presence of sulfur catalytically active assessment result of embodiment catalyst
Embodiment Catalyst forms Reaction temperature (DEG C) CO conversion ratios (%) CH4Selectivity (%)
1 10MoS3/Ce0.90Zr0.80O2 350 70.4 88.0
2 15MoS3/Ce0.85Zr0.15O2 450 80.2 94.2
3 15MoS3/Ce0.80Zr0.20O2 400 75.5 89.8
4 15MoS3/Ce0.80Zr0.20O2 500 80.1 96.8
5 15MoS3/Ce0.80Zr0.20O2 550 80.9 97.6
6 25MoS3/Ce0.80Zr0.20O2 400 78.2 90.7

Claims (7)

1. a kind of methanation catalyst, which is characterized in that it is MoS3It is supported on CexZr1-xO2On solid-solution powder, wherein x is 0.80~0.9, MoS3Load capacity account for MoS3With CexZr1-xO210~30wt% of total amount.
2. methanation catalyst according to claim 1, which is characterized in that the CexZr1-xO2Solid solution is cubic crystal Type.
3. a kind of preparation method of methanation catalyst according to claim 1, which is characterized in that include the following steps：
(1) a certain amount of cerous nitrate and zirconium nitrate is soluble in water, alkaline precipitating agent is added dropwise in solution at 80 DEG C, is controlled The PH ＞ 11 after precipitating completely are made, then aging 24 hours at 100 DEG C；Filtration washing will be precipitated to neutrality, in drying at room temperature 12 hours, then drying 12 hours at 120 DEG C, it is then calcined 6 hours at 500 DEG C, obtains cubic cerium zirconium oxide CexZr1-xO2Solid-solution powder；
(2) a certain amount of ammonium paramolybdate is soluble in water, the Ce for then obtaining a certain amount of step (1)xZr1-xO2Solid-solution powder It evenly spreads in molybdenum ammonium solution, is kept for 12 hours in room temperature, then drying 12 hours at 120 DEG C, then at 500 DEG C Calcining 6 hours, natural cooling obtain load MoO3CexZr1-xO2Solid-solution powder；
(3) solid-solution powder for obtaining step (2) is under 300 DEG C and normal pressure, in the gas of 3wt% hydrogen sulfide and 97wt% hydrogen Vulcanize 4h in atmosphere, is crushed to and obtains the methanation catalyst after 20-80 mesh.
4. preparation method according to claim 3, which is characterized in that the addition of step (1) cerous nitrate and zirconium nitrate Amount meets x between 0.80~0.9.
5. preparation method according to claim 3, which is characterized in that step (2) ammonium paramolybdate and CexZr1-xO2Gu The addition of solution powder makes MoS3Account for MoS3With CexZr1-xO210~30wt% of total amount.
6. a kind of methanation catalyst according to claim 1 is used for the H of sulfur-bearing2With the use of CO gaseous mixture methanation reactions On the way.
7. purposes according to claim 6, which is characterized in that the content of the sulphur is that gaseous sulphide accounts for gaseous mixture totality 0.1 long-pending~3.0v/v%, the H2Molar ratio with CO is 0.8~1.2:1；The condition of the methanation reaction is：270~ 650 DEG C, pressure is 1.0~6.0MPa.
CN201810312192.8A 2018-04-09 2018-04-09 A kind of wide warm high activity synthesis gas catalyst for methanation in presence of sulfur Pending CN108421552A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110152651A (en) * 2019-05-17 2019-08-23 太原理工大学 Applied to the sulfur resistant catalyst and its preparation method of synthesis gas methanation and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110152651A (en) * 2019-05-17 2019-08-23 太原理工大学 Applied to the sulfur resistant catalyst and its preparation method of synthesis gas methanation and application

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