CN101745401B - Load type sulfur-tolerant methanation catalyst and preparation method and application thereof - Google Patents
Load type sulfur-tolerant methanation catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a load type sulfur-tolerant methanation catalyst, which is characterized by taking a main metal M as an active component, a second metal M1 as an auxiliary agent and S as a carrier, and consisting of the metal M, the metal M1 and the carrier S, wherein the mass ratio of the M1 to the M to the S is 0.01-39:1-30:0.01-90; the main metal M is one or more of Mo, W and V; the second metal M1 is one or more of Fe, Co, Ni, Cr, Mn, La, Y or Ce; and the carrier S is SiO2, ZrO2, Al2O3, MgO or TiO2. The load type sulfur-tolerant methanation catalyst is prepared by a sol-gel method. The metallic carbide catalyst prepared by the method has the advantages of low cost, high specific area, small particles, high methane selectivity and better sulfur tolerance when used for CO hydrogenation methanation reaction, and the like.
Description
Technical field
The present invention relates to a kind of methanation catalyst and its preparation method and application, is a kind of catalyst for methanation in presence of sulfur and its preparation method and application specifically.
Background technology
Coal, oil and natural gas are three large pillars of 21 century world energy supplies.At present, in world's energy consumption structure, oil accounts for 39 seven percent, natural gas accounts for 23 two percent, considerable scale has been had in the development and utilization of natural gas, but natural gas proportion in the China energy consumption structure only is about 2 percent five, far below world average level and Asia average level ten Percent point one.Natural gas singly is not the fuel of high-quality, and is the important source material of chemical industry.Along with continuous discovery and the exploitation of natural gas resource, the scope of utilizing of natural gas also progressively enlarges, and demonstrates important function in China's economic construction.The expert estimates that the proportion of natural gas in the China energy consumption structure will reach 6 percent, 2020 years and will reach ten Percent in 2010.When the time comes, being applied in that China might approach or surpassing oil of natural gas realizes the target that energy structure in China rationally changes to " efficient, economic, clean, safety ".
Always take temperature from the conventional energy resource resource (comprising coal, oil, G﹠W energy) of China, roughly account for 10% ~ 11% of the similar total resources in the world.In Chinese conventional energy resource, coal accounts for 88.5%, oil accounts for 3.7%, natural gas accounts for 1.4%, water can 6.4%.Also have in addition nuclear energy, biomass energy, solar energy and wind energy etc., but these energy portions do not have by a relatively large margin rising in a short time.Therefore, China still has to take coal as main energy sources quite over a long time at one, and this just provides possibility for Coal Gasification production substitute natural gas.Consider that from present coal chemical technology development level and economy Coal Gasification Polygeneration System is approach very likely.Poly-generation is take coal gasification as core, to produce the multiple products such as clean fuel, chemical products, generating, heating power, refrigeration as target, by the coupling of kinds of processes, realizes economic benefit and the maximized New Coal Chemical of social benefit system.
In existing technology, Coal Gasification production substitute natural gas mainly contains non-methanation in presence of sulfur technology and methanation in presence of sulfur technology.For non-methanation in presence of sulfur technology, mainly be to utilize nickel-base catalyst.Patent CN91106812 and 97108002 discloses this type of nickel-base catalyst, but this type of catalyst is to the H in the unstripped gas
2/ CO ratio is had relatively high expectations; Not anti-sulphur, the unstripped gas desulfurization requires very high, desulfurization to H
2The volume fraction of S is less than 0.1 * 10
-6Anti-carbon deposition ability is poor.In the production, unstripped gas will carry out the above desulfurization of two-stage before entering methanator, and wants deoxidation, interpolation steam.During operation, stop production and need use nitrogen replacement, hydrogen shield when resuming production, flow process is complicated, investment is large, the operating cost height causes gas cost higher.In order to reduce the purification cost of coal gasification gas, people have begun the research and development to catalyst for methanation in presence of sulfur.At present, the used catalyst of methanation in presence of sulfur technology mainly contains two kinds.A kind of is the nickel-base catalyst of modification: the people such as Wang Minwei have studied Ni-Mo-La/-Al
2O
3The performance of catalyst methanation in sulfur-containing coal gas; People's researchs such as Japan Betta are with ZrO
2Contain the methanation of Ni catalyst in 10-100ppm sulphur for carrier; The people such as Stencel study NiO/Cr
2O
3/ MgSiO
3System and Ni/Cr
2O
3/ MgAl
2O
4The methanation in presence of sulfur behavior of System Catalyst.Although this class catalyst is anti-sulphur to a certain extent, the anti-sulfur content of catalyst ubiquity is little, the shortcomings such as the easy inactivation of course of reaction.Another kind of sulfur resistant catalyst is catalyst with base of molybdenum: U.S. coal gas research institute (GRI) and catalyst research company (CRC) and Gas Research Institute, Chicago (IGT) have developed jointly with MoS
3Be main catalyst for methanation in presence of sulfur, anti-sulfur content reaches 1%; " methanation process of halophile and catalyst " patent disclosure of Gaz de France comprehensive development company (GI) application a kind of Mo (V, W or Co, Ni)/ZrO
2Catalyst, catalyst is at H
2S, COS, CS
2Still has good catalytic performance in the sulfides.This class molybdenum base sulfur resistant catalyst was molybdenum oxide before reaction, must use high concentration H before using
2S and H
2Presulfurization, prereduction have brought great inconvenience for the application of catalyst.
Summary of the invention
The purpose of this invention is to provide and a kind ofly have efficient sulfur tolerance, good stability, do not need pretreated catalyst for methanation in presence of sulfur and its preparation method and application before using.
Catalyst for methanation in presence of sulfur provided by the invention adds M on this basis take the M metal as main active component
1Metal is as auxiliary agent, and carrier is S, and catalyst is by M metal, M
1Metal and carrier S form, wherein M
1: M: the S mass ratio is (0.01-39): (1-30): (0.01-90);
Wherein M is main metal, and M can be one or more of Mo, W and V;
M
1Be the second metal, M
1Can be one or more of Fe, Co, Ni, Cr, Mn, La, Y or Ce;
S is carrier, and S can be SiO
2, ZrO
2, Al
2O
3, MgO or TiO
2
The preparation method of catalyst of the present invention may further comprise the steps:
1. first support oxide is carried out calcination process, with support oxide at 400-800 ℃ of calcination process 2-24 hour.
2. under 20-60 ℃, under the stirring condition, with the chelating agent wiring solution-forming, between acid or alkali regulator solution pH=0.5-10, with precursor solution and second metal M of main metal M
1Precursor solution successively slowly is added drop-wise in the mentioned solution, continue to stir 1-24 hour, then the carrier S of under stirring condition calcination process being crossed adds in the mentioned solution, continuation in 60-90 ℃ of water-bath evaporating solvent to forming viscous solution, the product that obtains at 60-150 ℃ of dry 4-48 hour, can be obtained M-M
1/ S presoma, wherein M
1: M: the S mass ratio is (0.01-39): (1-30): (0.01-90);
3. the presoma that obtains being ground to particle diameter is placed in the quartz reactor less than 0.25mm, pass into inert gas or carbonaceous gas, flow velocity is 60-150ml/min, adopt two sections temperature programming controls, rise to 400 ℃ with 0.2-10 ℃ heating rate from room temperature, and then after continuing to rise to 500-800 ℃ with 0.2-10 ℃ of heating rate constant temperature 1-8 hour;
4. after temperature programming reaction finishes, with step 3. material in inert atmosphere or carbonaceous gas, be cooled to room temperature;
5. under the room temperature condition, in passivation atmosphere, 4. material was carried out passivation 1-8 hour, namely obtain metal carbide catalyst.
As above 2. the presoma of described main metal M can be: the presoma (nitric acid tungsten, ammonium tungstate, tungsten fluoride, sodium tungstate etc.) of the presoma of molybdenum (ammonium molybdate and molybdenum chloride), tungsten, the presoma (ammonium vanadate etc.) of vanadium etc.
As above 2. described the second metal M
1Presoma can be: the presoma (ferric nitrate of iron, iron chloride etc.), presoma (the cobalt nitrate of cobalt, cobalt chloride etc.), the presoma of nickel (nickel nitrate etc.), presoma (the chromic nitrate of chromium, ammonium chromate etc.), presoma (the manganese nitrate of manganese, manganese chloride etc.), presoma (the lanthanum nitrate of lanthanum, lanthanum chloride etc.), presoma (the yttrium nitrate of yttrium, yttrium chloride, yttrium fluoride etc.), presoma (the cerous nitrate of cerium, cerous sulfate, cerous carbonate, cerium chloride etc.) etc.
As above 2. described solvent can be: a kind of or mixture in deionized water, the ethanol etc., the mass ratio of deionized water and ethanol is 1: (0.01-100).
As above 2. described, acid is nitric acid, acetic acid etc., and alkali is ethylenediamine, ammoniacal liquor, sodium hydroxide solution, potassium hydroxide solution etc.
As above 2. described, chelating agent is citric acid, tartaric acid, benzoglycolic acid, malic acid, EDTA (ethylenediamine tetra-acetic acid) etc.
As above 2. described, chelating agent: (M+M
1) mol ratio is 1: 0.2-8
As above 3., 4. described inert gas can be: one or more of nitrogen, argon gas, helium, wherein oxygen content requires to be lower than 0.1%.
As above 3., 4. described carbonaceous gas can be: CO/H
2, CH
4/ H
2, C
2H
6/ H
2, C
2H
4/ H
2, C
4H
10/ H
2One or more, carbonaceous gas/H wherein
2Mol ratio is 1: 1-4.
As above 5. described passivation gas can be the mixture of air and nitrogen, argon gas or helium, or the mixture of oxygen and nitrogen, argon gas or helium.
The application conditions of catalyst of the present invention is: reaction raw materials is synthesis gas, H
2/ CO mol ratio is 1.0-3.0, and sulfur content is 1-5% in the unstripped gas, and reaction temperature is 220-360 ℃, and pressure is 0.1-10.0MPa, and volume space velocity is 1000-8000h
-1
The present invention compared with prior art has following characteristics:
(1) the present invention prepares many metal carbides presoma by sol-gel process, and each metal component is realized the abundant mixing of atom or molecular level, has greatly reduced the presoma particle diameter; And by adding SiO
2Carry out load in carrier, increased specific area, improved the active component utilization rate.
(2) presoma of the present invention preparation contains organic matter and can be used as carbon source, does not need additionally to add carbonaceous gas in the temperature programming carbonisation again, realizes in-situ carburization, can greatly reduce preparation cost.
(3) catalyst provided by the invention has higher methane selectively in the higher reactivity of maintenance.
(4) catalyst provided by the invention has good sulfur tolerance, and sulfur content 1-5% in the unstripped gas, catalyst still have very high activity, selective and life-span.
Coal Gasification production substitute natural gas (SNG) sulfur resistant catalyst, this catalyst agent is used for methanation reaction, has good reactivity and methane selectively.
The specific embodiment:
The analysis that the present invention adopts and being calculated as follows:
Gas and product liquid adopt Shimadzu GC-8A gas chromatograph to analyze.Thermal conductivity detector (TCD) (TCD) detects CO, the CO in the gas
2, H
2, CH
4Volume content and the H in the product liquid
2O, CH
3The percentage by weight of OH, its chromatographic column use respectively carbon molecular sieve and the TDX401 packed column of 2m, and column temperature is 100 ℃.Hydrocarbon in the gas and the mixed alcohol in the liquid are then detected by hydrogen flame ionization detector, and its chromatographic column is the Porapak Q packed column of 2m.
Gas-phase product is that intermediate carries out related normalizing calculating by methane gas, and liquid product is that the related normalizing of intermediate calculates by methyl alcohol.
For explaining in detail the feature of this catalyst, now be described as follows in conjunction with the embodiments:
Embodiment 1
Prescription: citric acid/(Ni+Mo) mol ratio is 1: 0.5, Ni: Mo: TiO
2Mass ratio is 1: 10: 30
First with TiO
2Carrier was 400 ℃ of calcination process 2 hours, and the catalyst preparation is as follows by the prescription implementation:
Under 35 ℃ of stirring conditions, preparation citric acid, water/alcohol mixed solution (H
2O/C
2H
5OH=1: 10w/w), with red fuming nitric acid (RFNA) regulator solution pH=1.5; In mentioned solution, add respectively Ni (NO
3)
36H
2O solution and (NH
4)
6Mo
7O
244H
2O solution continues to stir 14 hours, the TiO after the adding calcination process
2Continue to stir 5 hours, and continued under 60 ℃ of conditions evaporating solvent to viscous solution, the product that obtains 140 ℃ of dryings 4 hours, is obtained Ni-Mo/TiO
2Presoma.The presoma that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.25mm, pass into argon gas, flow velocity is 120mL/min, adopt two sections temperature programming controls to rise to 400 ℃ with the heating rate of 4 ℃/min from room temperature, and then constant temperature 4 hours after rising to 750 ℃ with 2 ℃/min heating rate, be down to the O take the carrier of oxygen volume concentrations as 2v/v% after the room temperature
2/ Ar mist purges passivation and namely got Ni-Mo/TiO in 4 hours
2(Ni: Mo: TiO
2Mass ratio is 1: 10: 30) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, evaluating catalyst condition: H
2/ CO mol ratio is 2.0, and reaction temperature is 340 ℃, and pressure is 8.0MPa, and volume space velocity is 2000h
-1, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 2
Prescription: citric acid/(Ni+Mo) mol ratio is 1: 0.5, Fe: Mo: SiO
2Mass ratio is 1: 5: 30
First with SiO
2Carrier is 800 ℃ of calcination process 24 hours,, the catalyst preparation is as follows by the prescription implementation:
Under 20 ℃ of stirring conditions, preparation citric acid, water/alcohol mixed solution (H
2O/C
2H
5OH=10: 1w/w), with red fuming nitric acid (RFNA) regulator solution pH=1.5; In mentioned solution, add respectively Fe (NO
3)
39H
2O solution and (NH
4)
6Mo
7O
244H
2O solution continues to stir 24 hours, the SiO after the adding calcination process
2Continue to stir 24 hours, and continued under 90 ℃ of conditions evaporating solvent to viscous solution, the product that obtains 140 ℃ of dryings 24 hours, is obtained Fe-Mo/SiO
2Presoma.The presoma that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.25mm, pass into argon gas, flow velocity is 150mL/min, adopt two sections temperature programming controls to rise to 400 ℃ with the heating rate of 10 ℃/min from room temperature, and then constant temperature 1 hour after rising to 800 ℃ with 2 ℃/min heating rate, be down to the O take the carrier of oxygen volume concentrations as 0.5v/v% after the room temperature
2/ Ar mist purges passivation and namely got Fe-Mo/SiO in 8 hours
2(Fe: Mo: SiO
2Mass ratio is 1: 5: 30) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 360 ℃, and pressure is 10.0MPa, and volume space velocity is 8000h
-1, H
2/ CO mol ratio is 3.0, and the catalytic perfomance evaluation is listed in the table 1.
Embodiment 3
Prescription: tartaric acid/(Co+Mo) mol ratio is 1: 0.2, Co: Mo: Al
2O
3Mass ratio is 0.01: 30: 90
First with Al
2O
3Carrier was 500 ℃ of calcination process 12 hours, and the catalyst preparation is as follows by the prescription implementation:
Under 60 ℃ of stirring conditions, preparation tartaric acid, water mixed solution are with acetic acid regulator solution pH=1.5; In mentioned solution, add respectively Co (NO
3)
36H
2O solution and (NH
4)
6Mo
7O
244H
2O solution continues to stir 1 hour, the Al after the adding calcination process
2O
3Continue to stir 1 hour, and continued under 60 ℃ of conditions evaporating solvent to viscous solution, the product that obtains 60 ℃ of dryings 24 hours, is obtained Co-Mo/Al
2O
3Presoma.The presoma that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.25mm, pass into nitrogen, flow velocity is 60mL/min, adopt two sections temperature programming controls to rise to 400 ℃ with the heating rate of 0.2 ℃/min from room temperature, and then constant temperature 8 hours after rising to 500 ℃ with 10 ℃/min heating rate, be down to the O take the carrier of oxygen volume concentrations as 1.0v/v% after the room temperature
2/ N
2Mist purges passivation and namely got Co-Mo/Al in 1 hour
2O
3(Co: Mo: Al
2O
3Mass ratio is 0.01: 30: 90) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 220 ℃, and pressure is 0.1MPa, and volume space velocity is 1000h
-1, H
2/ CO mol ratio is 1.0, and the catalytic perfomance evaluation is listed in the table 1.
Embodiment 4
Prescription: the mol ratio of malic acid/(Co+Mn+Mo) 1: 2, Co: Mn: Mo: ZrO
2Mass ratio is 0.02: 10: 20: 0.01
First with ZrO
2Carrier was 600 ℃ of calcination process 20 hours, and the catalyst preparation is as follows by the prescription implementation:
Under 40 ℃ of stirring conditions, preparation malic acid, water mixed solution are with ammoniacal liquor regulator solution pH=3.5; In mentioned solution, add respectively Co (NO
3)
36H
2O solution, Mn (NO
3)
26H
2O and (NH
4)
6Mo
7O
244H
2O solution continues to stir 3 hours, the ZrO after the adding calcination process
2Continue to stir 1 hour, and continued under 80 ℃ of conditions evaporating solvent to viscous solution, the product that obtains 80 ℃ of dryings 24 hours, is obtained Co-Mn-Mo/ZrO
2Presoma.The presoma that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.25mm, pass into helium, flow velocity is 120mL/min, adopt two sections temperature programming controls to rise to 400 ℃ with the heating rate of 2 ℃/min from room temperature, and then constant temperature 4 hours after rising to 700 ℃ with 5 ℃/min heating rate, be down to the air/N take volume of air concentration as 2.0v/v% after the room temperature
2Mist purges passivation and namely got Co-Mn-Mo/ZrO in 2 hours
2(Co: Mn: Mo: ZrO
2Mass ratio is 0.02: 10: 20: 0.01) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 240 ℃, and pressure is 2.0MPa, and volume space velocity is 2000h
-1, H
2/ CO mol ratio 1.5, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 5
Prescription: the mol ratio of benzoglycolic acid/(Cr+Mn+W) 1: 1, Cr: Mn: W: the MgO mass ratio is 1: 2: 20: 30
First with the MgO carrier 400 ℃ of calcination process 20 hours, the catalyst preparation is as follows by the prescription implementation:
Under 50 ℃ of stirring conditions, preparation benzoglycolic acid, water mixed solution are with ethylenediamine regulator solution pH=2.5; In mentioned solution, add respectively Cr (NO
3)
39H
2O solution, Mn (NO
3)
26H
2O and (NH
4)
10H
2(W
2O
7)
6Solution continue to stir 6 hours, and the MgO that adds after the calcination process continues to stir 10 hours, continued under 70 ℃ of conditions evaporating solvent to viscous solution, and the product that obtains 90 ℃ of dryings 10 hours, is obtained the Cr-Mn-W/MgO presoma.The presoma that obtains is ground to particle diameter is placed in the crystal reaction tube less than 0.25mm, pass into CH
4/ H
2(1/4v/v) gas, flow velocity is 100mL/min, adopt two sections temperature programmings control to rise to 400 ℃ with the heating rate of 5 ℃/min from room temperature, and then constant temperature 2 hours after rising to 650 ℃ with 1 ℃/min heating rate, be down to the O take the carrier of oxygen volume concentrations as 2.0v/v% after the room temperature
2The passivation of/He mist purging namely got Cr-Mn-W/MgO in 3 hours, and (Cr: Mn: W: the MgO mass ratio is 1: 2: 20: 30) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 260 ℃, and pressure is 6.0MPa, and volume space velocity is 4000h
-1, H
2/ CO mol ratio 1.5, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 6
Prescription: EDTA/ (Co+La+V) mol ratio 1: 3, Co: La: V: SiO
2Mass ratio is 30: 1: 1: 10
First with SiO
2Carrier was 700 ℃ of calcination process 24 hours, and the catalyst preparation is as follows by the prescription implementation:
Under 40 ℃ of stirring conditions, preparation EDTA, water/alcohol mixed solution (H
2O/C
2H
5OH=1: 0.01w/w), with NaOH regulator solution pH=10; In mentioned solution, add respectively Co (NO
3)
36H
2O solution, La (NO
3)
36H
2O and NH
4VO
3Solution continues to stir 10 hours, the SiO after the adding calcination process
2Continue to stir 9 hours, and continued under 90 ℃ of conditions evaporating solvent to viscous solution, the product that obtains 130 ℃ of dryings 48 hours, is obtained Co-La-V/SiO
2Presoma.The presoma that obtains is ground to particle diameter is placed in the crystal reaction tube less than 0.25mm, pass into C
2H
6/ H
2(1/4v/v) gas, flow velocity is 130mL/min, adopt two sections temperature programmings control to rise to 400 ℃ with the heating rate of 4 ℃/min from room temperature, and then constant temperature 3 hours after rising to 800 ℃ with 5 ℃/min heating rate, be down to the O take the carrier of oxygen volume concentrations as 1.0v/v% after the room temperature
2/ Ar mist purges passivation and namely got Co-La-V/SiO in 2 hours
2(Co: La: V: SiO
2Mass ratio is 30: 1: 1: 10) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 300 ℃, and pressure is 7.0MPa, and volume space velocity is 6000h
-1, H
2/ CO mol ratio 2, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 7
Prescription: EDTA/ (Ni+Ce+Mo) mol ratio 1: 5, Ni: Ce: Mo: SiO
2Mass ratio is 5: 5: 30: 10
First with SiO
2Carrier was 550 ℃ of calcination process 12 hours, and the catalyst preparation is as follows by the prescription implementation:
Under 50 ℃ of stirring conditions, preparation EDTA, water/alcohol mixed solution (H
2O/C
2H
5OH=1: 0.1w/w), with NaOH regulator solution pH=9; In mentioned solution, add respectively Ni (NO
3)
36H
2O solution, Ce (NO
3)
36H
2O and (NH
4)
6Mo
7O
244H
2O solution continues to stir 20 hours, the SiO after the adding calcination process
2Continue to stir 2 hours, and continued under 80 ℃ of conditions evaporating solvent to viscous solution, the product that obtains 100 ℃ of dryings 36 hours, is obtained Ni-Ce-Mo/SiO
2Presoma.The presoma that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.25mm, pass into argon gas, flow velocity is 70mL/min, adopt two sections temperature programming controls to rise to 400 ℃ with the heating rate of 6 ℃/min from room temperature, and then constant temperature 6 hours after rising to 600 ℃ with 7 ℃/min heating rate, be down to the O take the carrier of oxygen volume concentrations as 1.5v/v% after the room temperature
2/ Ar mist purges passivation and namely got Ni-Ce-Mo/SiO in 3 hours
2(Ni: Ce: Mo: SiO
2Mass ratio is 5: 5: 30: 10) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 320 ℃, and pressure is 8.0MPa, and volume space velocity is 3000h
-1, H
2/ CO mol ratio 1.5, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 8
Prescription: EDTA/ (Mn+Ce+Mo) mol ratio 1: 4, Mn: Ce: Mo: ZrO
2Mass ratio is 5: 10: 28: 50
First with ZrO
2Carrier was 450 ℃ of calcination process 15 hours, and the catalyst preparation is as follows by the prescription implementation:
Under 35 ℃ of stirring conditions, preparation EDTA, water/alcohol mixed solution (H
2O/C
2H
5OH=1: 1w/w), with potassium hydroxide regulator solution pH=7; In mentioned solution, add respectively Mn (NO
3)
26H
2O solution, Ce (NO
3)
36H
2O and (NH
4)
6Mo
7O
244H
2O solution continues to stir 15 hours, the ZrO after the adding calcination process
2Continue to stir 4 hours, and continued under 90 ℃ of conditions evaporating solvent to viscous solution, the product that obtains 135 ℃ of dryings 24 hours, is obtained Mn-Ce-Mo/ZrO
2Presoma.The presoma that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.25mm, pass into argon gas, flow velocity is 80mL/min, adopt two sections temperature programming controls to rise to 400 ℃ with the heating rate of 1 ℃/min from room temperature, and then constant temperature 5 hours after rising to 700 ℃ with 5 ℃/min heating rate, be down to the O take the carrier of oxygen volume concentrations as 1.0v/v% after the room temperature
2/ Ar mist purges passivation and namely got Mn-Ce-Mo/ZrO in 2 hours
2(Mn: Ce: Mo: ZrO
2Mass ratio is 5: 10: 28: 50) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 280 ℃, and pressure is 4.0MPa, and volume space velocity is 6000h
-1, H
2/ CO mol ratio 2.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 9
Prescription: the mol ratio of citric acid/(Fe+Ce+Mo) 1: 2.5, Fe: Ce: Mo: ZrO
2Mass ratio is 10: 5: 30: 24
First with ZrO
2Carrier was 500 ℃ of calcination process 18 hours, and the catalyst preparation is as follows by the prescription implementation:
Under 45 ℃ of stirring conditions, preparation citric acid, alcohol mixed solution are with red fuming nitric acid (RFNA) regulator solution pH=0.5; In mentioned solution, add respectively Fe (NO
3)
29H
2O solution, Ce (NO
3)
36H
2O and (NH
4)
6Mo
7O
244H
2O solution continues to stir 3 hours, the ZrO after the adding calcination process
2Continue to stir 20 hours, and continued under 80 ℃ of conditions evaporating solvent to viscous solution, the product that obtains 150 ℃ of dryings 40 hours, is obtained Fe-Ce-Mo/ZrO
2Presoma.The presoma that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.25mm, pass into argon gas, flow velocity is 150mL/min, adopt two sections temperature programming controls to rise to 400 ℃ with the heating rate of 0.3 ℃/min from room temperature, and then constant temperature 4 hours after rising to 550 ℃ with 1 ℃/min heating rate, be down to the O take the carrier of oxygen volume concentrations as 1.0v/v% after the room temperature
2/ Ar mist purges passivation and namely got Fe-Ce-Mo/ZrO in 7 hours
2(Fe: Ce: Mo: ZrO
2Mass ratio is 10: 5: 30: 24) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 270 ℃, and pressure is 6.0MPa, and volume space velocity is 4500h
-1, H
2/ CO mol ratio 2.5, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 10
Prescription: the mol ratio of citric acid/(Fe+Y+Mo) 1: 2.5, Fe: Y: Mo: SiO
2Mass ratio is 10: 1: 30: 25
First with SiO
2Carrier was 400 ℃ of calcination process 8 hours, and the catalyst preparation is as follows by the prescription implementation:
Under 40 ℃ of stirring conditions, preparation citric acid, alcohol mixed solution are with red fuming nitric acid (RFNA) regulator solution pH=1.5; In mentioned solution, add respectively Fe (NO
3)
29H
2O solution, Y (NO
3)
36H
2O and (NH
4)
6Mo
7O
244H
2O solution continues to stir 24 hours, the SiO after the adding calcination process
2Continue to stir 24 hours, and continued under 90 ℃ of conditions evaporating solvent to viscous solution, the product that obtains 90 ℃ of dryings 35 hours, is obtained Fe-Y-Mo/SiO
2Presoma.The presoma that obtains is ground to particle diameter is placed in the crystal reaction tube less than 0.25mm, pass into CO/H
2(1/1v/v) gas, flow velocity is 60mL/min, adopt two sections temperature programmings control to rise to 400 ℃ with the heating rate of 0.5 ℃/min from room temperature, and then constant temperature 8 hours after rising to 600 ℃ with 1.5 ℃/min heating rate, be down to the O take the carrier of oxygen volume concentrations as 1.5v/v% after the room temperature
2/ Ar mist purges passivation and namely got Fe-Y-Mo/SiO in 8 hours
2(Fe: Y: Mo: SiO
2Mass ratio is 10: 1: 30: 25) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 230 ℃, and pressure is 5.0MPa, and volume space velocity is 7000h
-1, H
2/ CO mol ratio 3.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 11
Prescription: the mol ratio of citric acid/(Fe+Ni+W) 1: 7, Fe: Ni: W: the MgO mass ratio is 5: 7: 30: 40
First with the MgO carrier 500 ℃ of calcination process 5 hours, the catalyst preparation is as follows by the prescription implementation:
Under 50 ℃ of stirring conditions, preparation citric acid, alcohol mixed solution are with red fuming nitric acid (RFNA) regulator solution pH=1.0; In mentioned solution, add respectively Fe (NO
3)
29H
2O solution, Ni (NO
3)
36H
2O and (NH
4)
10H
2(W
2O
7)
6Solution continue to stir 5 hours, and the MgO that adds after the calcination process continues to stir 6 hours, continued under 60 ℃ of conditions evaporating solvent to viscous solution, and the product that obtains 60 ℃ of dryings 48 hours, is obtained the Fe-Ni-W/MgO presoma.The presoma that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.25mm, pass into nitrogen, flow velocity is 150mL/min, adopt two sections temperature programming controls to rise to 400 ℃ with the heating rate of 10 ℃/min from room temperature, and then constant temperature 7 hours after rising to 750 ℃ with 1 ℃/min heating rate, be down to the O take the carrier of oxygen volume concentrations as 1.5v/v% after the room temperature
2The passivation of/Ar mist purging namely got Fe-Ni-W/MgO in 1 hour, and (Fe: Ni: W: the MgO mass ratio is 5: 7: 30: 40) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 250 ℃, and pressure is 6.5MPa, and volume space velocity is 6000h
-1, H
2/ CO mol ratio 2.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 12
Prescription: the mol ratio of citric acid/(Fe+Ni+V) 1: 5, Fe: Ni: V: TiO
2Mass ratio is 0.01: 0.02: 30: 90
First with TiO
2Carrier was 800 ℃ of calcination process 3 hours, and the catalyst preparation is as follows by the prescription implementation:
Under 20 ℃ of stirring conditions, preparation citric acid, water mixed solution are with red fuming nitric acid (RFNA) regulator solution pH=2.0; In mentioned solution, add respectively Fe (NO
3)
29H
2O solution, Ni (NO
3)
36H
2O and NH
4VO
3Solution continues to stir 4 hours, the TiO after the adding calcination process
2Continue to stir 20 hours, and continued under 70 ℃ of conditions evaporating solvent to viscous solution, the product that obtains 70 ℃ of dryings 32 hours, is obtained Fe-Ni-V/TiO
2Presoma.The presoma that obtains is ground to particle diameter is placed in the crystal reaction tube less than 0.25mm, pass into C
2H
4/ H
2(1/2v/v) gas, flow velocity is 100mL/min, adopt two sections temperature programmings control to rise to 400 ℃ with the heating rate of 5 ℃/min from room temperature, and then constant temperature 6 hours after rising to 700 ℃ with 6 ℃/min heating rate, be down to the O take the carrier of oxygen volume concentrations as 1.0v/v% after the room temperature
2/ N
2Mist purges passivation and namely got Fe-Ni-V/TiO in 2 hours
2(Fe: Ni: V: TiO
2Mass ratio is 0.01: 0.02: 30: 90) catalyst.Be ground to the 60-80 order with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 290 ℃, and pressure is 6.0MPa, and volume space velocity is 5000h
-1, H
2/ CO mol ratio 2.0, the catalytic perfomance evaluation is listed in the table 1.
Claims (1)
1. the application of a load type sulfur-tolerant methanation catalyst, it is characterized in that application conditions is: reaction raw materials is synthesis gas, H
2/ CO mol ratio is 1.0-3.0, and sulfur content is 1-5% in the unstripped gas, and reaction temperature is 220-360 ℃, and pressure is 0.1-10.0MPa, and volume space velocity is 1000-8000h
-1
Wherein catalyst is take main metal M as active component, and the second metal M 1 is as auxiliary agent, and carrier is S, and catalyst is comprised of M metal, M1 metal and carrier S, wherein M1: M: the S mass ratio is 0.01-39: 1-30: 0.01-90; Wherein main metal M is one or more of Mo, W and V; The second metal M 1 is one or more of Fe, Co, Ni, Cr, Mn, La, Y or Ce; Carrier S is SiO
2, ZrO
2, Al
2O
3, MgO or TiO
2
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101371988A (en) * | 2008-05-14 | 2009-02-25 | 大连理工大学 | Method for preparing transitional metal carbides catalytic material and use |
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- 2009-12-07 CN CN 200910175308 patent/CN101745401B/en active Active
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