CN102513124A - Catalyst for methanating coke oven gas and preparation method thereof - Google Patents
Catalyst for methanating coke oven gas and preparation method thereof Download PDFInfo
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- CN102513124A CN102513124A CN2011104212937A CN201110421293A CN102513124A CN 102513124 A CN102513124 A CN 102513124A CN 2011104212937 A CN2011104212937 A CN 2011104212937A CN 201110421293 A CN201110421293 A CN 201110421293A CN 102513124 A CN102513124 A CN 102513124A
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Abstract
The invention relates to a technology for manufacturing artificial natural gas by methanating oxycarbide and provides a catalyst for methanating coke oven gas and a preparation method thereof. The catalyst is a gamma-aluminum oxide or a TiO2 carrier for carrying an active component and an addition agent, wherein the active component is Ni and the addition agent is composed of a first addition agent and a second addition agent; the first addition agent is a rare-earth element and the second addition agent is one or combination of more of Sr, Mn, V, Zr, Ce and Cr. The catalyst provided by the invention has good coke oven gas methanation activity and selectivity, and has the advantages of good high-temperature resistance, low-temperature activity and higher use space velocity; and the catalyst can be applied to various coke oven gas methanation processes including heat-insulating circulation, heat-insulating non-circulation, heat-exchange reactors and the like, and operation space velocities in the processes are more than 5000 per hour.
Description
Technical field
The present invention relates to the oxycarbide methanation and produce the artificial natural gas technology, a kind of gas employing methanation of coke oven Catalysts and its preparation method is provided.
Technical background
The comprehensive utilization of coke gas is the key subjects of coking industry always, oven gas (the calorific value 16.746MJ/Nm that the coking industry by-product is a large amount of
3).By the about 400m of coke by-product per ton
3Oven gas calculates, the annual by-product coke furnace gas of independent coal chemical enterprise 89,400,000,000 m
3About.At present, oven gas utilizes approach to mainly contain in the industry: as gas; Generating; From oven gas, carry hydrogen; Produce methyl alcohol, dimethyl ether or synthetic ammonia etc. behind the deep purifying.But these efficient and capacity usage ratios that utilize method to have are lower, and the bad economic benefit in the market that has is relatively poor.And the characteristics of oven gas are hydrogen many carbon are few, are fit to very much methanation reaction, can be through methanation reaction with CO, CO
2Deng being converted into CH
4, and obtain CH through separation means such as transformation absorption
4The natural gas of volume fraction more than 90%, therefore, adopting the coke-oven gas methanation synthetic natural gas is an environmental friendliness technology, the component in the oven gas can be utilized effectively, and improves capacity usage ratio greatly.
Coke-stove gas synthesizing methane metallization processes generally includes three parts of high efficiency separation of methane after raw material gas purifying, methanation and the methanation; Wherein purification of raw materials technology and methane purification technique are ripe relatively; Therefore methanation technology is the core of gas employing methanation of coke oven technology; Present gas employing methanation of coke oven technology mainly contain adiabatic circulation technology-operating temperature be 400-500 ℃, thermal insulation not circulation technology-operating temperature be that 500-600 ℃ and heat transfer reactor technology-operating temperature are 250-300 ℃; Whether different process circulates and aspect such as methanator structure emphasizes particularly on different fields to meet the different needs at unstripped gas, therefore needs methanation catalyst to have good adaptability to satisfy the requirement of different process.
Chinese patent CN 101391218 discloses a kind of gas employing methanation of coke oven Catalysts and its preparation method, and as carrier, the dipping nickel nitrate is after make finished product after dry and the roasting with the composite oxides of magnesia-alumina spinel structure for this catalyst.This catalyst shows good activity stability in 120 hours, 400 ℃ life test.But it is not provided at the stability data of (more than 400 ℃) under the higher temperature and the activity data of (below 350 ℃) under the low temperature more; Generally speaking thermal insulation do not circulate in the methanation process operating temperature can be in operating temperature more than 500 ℃ and in the heat transfer reactor methanation process below 300 ℃; The operating temperature of having only the circulation adiabatic methanation process is between 400-500 ℃, and this just causes the disclosed methanation catalyst of this patent possibly only be applicable to the circulation adiabatic methanation process; In addition its volume space velocity lower-4000h
-1, volume space velocity is low to mean that catalyst amount is big, the methanator volume also will increase, and causes the increase of catalyst purchase cost and the increase of equipment investment.
Summary of the invention
The purpose of this invention is to provide a kind of gas employing methanation of coke oven Catalysts and its preparation method.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
A kind of catalyst that is used for gas employing methanation of coke oven, catalyst are gama-alumina or the TiO that supports active component and auxiliary agent
2Carrier; Wherein active component is Ni, and auxiliary agent is that first auxiliary agent and second auxiliary agent are formed, and wherein first auxiliary agent is a rare earth element, and second auxiliary agent is the one or more combination among Sr, Mn, V, Zr, Ce, the Cr.
Said catalyst is made up of active component, first auxiliary agent, second auxiliary agent and carrier, by mass percentage, 5-50% active component, 0.5-10% first auxiliary agent, 2-20% second auxiliary agent, surplus is a carrier.Said first auxiliary agent is La; Second auxiliary agent is one or more among Ce, Mn, Zr, the Sr.Said second auxiliary agent is one or more among Sr, Zr, the Mn.
Said catalyst is made up of active component, first auxiliary agent, second auxiliary agent and carrier, by mass percentage, 20-40% active component, 1-6% first auxiliary agent, 6-15% second auxiliary agent, surplus is a carrier.
The Preparation of catalysts method that is used for gas employing methanation of coke oven; According to the above ratio, place stirred tank to stir and the adding carrier solubilization of active ingredient, then add first auxiliary agent, second auxiliary agent and the alkaline solution that have dissolved one by one and make it produce deposition; With washing of precipitate; Under 100-150 ℃, carried out dry 6-10 hour, dry back promptly obtains the catalyst precursor with 500-800 ℃ of roasting 3-5 hour efflorescence then, forming processes.
With above-mentioned gained catalyst precursor with 300-500 ℃ at H
2Or under the effect of coke-stove gas it is reduced to the catalyst finished product.Said gained catalyst precursor with 350-450 ℃ at H
2Under the effect of gas it is reduced to the catalyst finished product.
The solvent of said lytic activity component, first auxiliary agent and second auxiliary agent is metallic salt material or deionized water, and said metallic salt material is nitrate, formates or oxalates.Said metallic salt material is a nitrate.
Said alkaline solution liquid is NaOH solution, NH
4HCO
3, urea, ammoniacal liquor or Na
2CO
3Solution.Said alkaline solution liquid is Na
2CO
3Solution or ammoniacal liquor.
Said sediment was 110-130 ℃ of drying 8 hours.Said dried 600-700 ℃ of roasting 4 hours that are deposited in.
The present invention has the following advantages
1. the present invention is through introducing two auxiliary agents, and the synergy of first, second auxiliary agent has been improved heat endurance, low temperature active and the source of the gas adaptability of catalyst, has kept the high activity under the catalyst low temperature simultaneously, and the operation air speed is higher.
2. the present invention adopts the manufacture craft of co-precipitation to widen the serviceability temperature of catalyst and has improved the stability and the grain structure of catalyst structure.
3. the present invention can be applicable to the gas employing methanation of coke oven technology of various different operating temperature than this catalyst of other catalyst.
4. have good heat-resistant stability and the high activity in 250-600 ℃ wide temperature range through the inventive method gained catalyst; Thereby can adapt to various gas employing methanation of coke oven technologies; Comprise that operating temperature is that 400-500 ℃ the adiabatic technology of circulation, operating temperature is that 500-600 ℃ do not circulate adiabatic technology and operating temperature is 250 ℃ heat transfer reactor technology, and the operation air speed is all at 5000h
-1More than.
Description of drawings
Long-time stability design sketch under the gas employing methanation of coke oven catalyst experiment chamber condition that Fig. 1 provides for the embodiment of the invention, (wherein, the mole of unstripped gas is formed: 43.7%H
2, 3.29%N
2, 5.38%CO, 20.86%CH
4, 1.77%CO
2, 25%H
2O.550 ℃ of reaction temperatures, reaction pressure 0.4MPa, butt reaction velocity 10000h
-1).
Fig. 2 for the embodiment of the invention provide the sideline test process chart.
Industrial side line experiment CO total conversion, CO that Fig. 3 provides for the embodiment of the invention
2(wherein, unstrpped gas consists of the total conversion design sketch: 55-60%H
2, 24-28%CH
4, 6-9%CO, 2-3.5%CO
2, 3-5%N
2, the water vapour additional amount is 20% of a gas gross.Pressure 0.4～0.6MPa, 250 ℃-270 ℃ of intake air temperature, the bed hot(test)-spot temperature is 540-555 ℃).
The specific embodiment
Be the characteristic of this catalyst of detailed presentations, combine Comparative Examples, embodiment and comparative example to specify as follows at present.
Embodiment 1
With 90g Na
2CO
3Be dissolved in the 350ml deionized water subsequent use.With 198g Ni (NO
3)
26H
2O, 31g La (NO
3)
36H
2O is dissolved in the 400ml deionized water and stirs and forms solution 1,78gMn (NO
3)
2(50% content), 19g Zr (NO
3)
25H
2O is dissolved in the 200ml deionized water and stirs and forms solution 2.Under stirring condition with 114g Al
2O
3Powder slowly adds solution 1 and stirs.In this solution, add solution 2 earlier and add Na subsequently
2CO
3Solution fully precipitates metal ion, continues to stir 30 minutes.Sediment through after washing, the drying was dried 8 hours under 120 ℃ of conditions, afterwards sediment was carried out roasting 4 hours in 600 ℃ of Muffle furnaces, made φ 3 * 3mm cylinder shape catalyst through beating blade technolgy.At 400 ℃, hydrogen atmosphere reduction down obtained final gas employing methanation of coke oven catalyst in 4 hours with above-mentioned catalyst.
The active testing result: the CO conversion ratio is 85.28%, CH
4Selectivity is 85.36%; The CO conversion ratio is 87.93% under this condition of Theoretical Calculation, CH
4Selectivity is: 91.24%.
Embodiment 2
With 103g Na
2CO
3Be dissolved in the 350ml deionized water subsequent use.With 200g Ni (NO
3)
26H
2O is dissolved in the 400ml deionized water and stirs and forms solution 1, with 20g La (NO
3)
36H
2O, 10g Sr (NO
3)
24H
2O, 15g Zr (NO
3)
25H
2O is dissolved in the 100ml deionized water and stirs and forms solution 2.Under stirring condition with 120g Al
2O
3Powder slowly adds solution 1 and stirs, and in this solution, adds Na simultaneously
2CO
3Solution and compounding agent solution 2 fully precipitate metal ion, continue to stir 30 minutes.Sediment through after washing, the drying was dried 8 hours under 120 ℃ of conditions, afterwards sediment was carried out roasting 4 hours in 600 ℃ of Muffle furnaces, made φ 3 * 3mm cylinder shape catalyst through beating blade technolgy.At 400 ℃, hydrogen atmosphere reduction down obtained final gas employing methanation of coke oven catalyst in 4 hours with above-mentioned catalyst.
The active testing result: the CO conversion ratio is 84.17%, CH
4Selectivity is 81.9%; The CO conversion ratio is 87.93% under this condition of Theoretical Calculation, CH
4Selectivity is: 91.24%.
Embodiment 3
Be dissolved in the 350ml deionized water 70g NaOH subsequent use.With 200g Ni (NO
3)
26H
2O, 10g La (NO
3)
36H
2O, 10g Zr (NO
3)
25H
2O, 7g Ce (NO
3)
36H
2O is dissolved in the 400ml deionized water and stirs.Under stirring condition, slowly add 132g Al
2O
3Powder stirs.In this solution, add NaOH solution metal ion is fully precipitated, continue to stir 30 minutes.Sediment through after washing, the drying was dried 8 hours under 120 ℃ of conditions, afterwards sediment was carried out roasting 4 hours in 600 ℃ of Muffle furnaces, made φ 3 * 3mm cylinder shape catalyst through beating blade technolgy.At 400 ℃, hydrogen atmosphere reduction down obtained final gas employing methanation of coke oven catalyst in 4 hours with above-mentioned catalyst.
The active testing result: the CO conversion ratio is 80.35%, CH
4Selectivity is 77.56%; The CO conversion ratio is 87.93% under this condition of Theoretical Calculation, CH
4Selectivity is: 91.24%.
Embodiment 4
With 90g Na
2CO
3Be dissolved in the 350ml deionized water subsequent use.With 198g Ni (NO
3)
26H
2O, 15g La (NO
3)
36H
2O, 70g Mn (NO
3)
2(50% content), 10g Sr (NO
3)
24H
2O is dissolved in the 400ml deionized water and stirs.Under stirring condition, slowly add 113g Al
2O
3Powder stirs.In this solution, add Na
2CO
3Solution fully precipitates metal ion, continues to stir 30 minutes.Sediment through after washing, the drying was dried 8 hours under 120 ℃ of conditions, afterwards sediment was carried out roasting 4 hours in 600 ℃ of Muffle furnaces, made φ 3 * 3mm cylinder shape catalyst through beating blade technolgy.At 400 ℃, hydrogen atmosphere reduction down obtained final gas employing methanation of coke oven catalyst in 4 hours with above-mentioned catalyst.
The active testing result: the CO conversion ratio is 83.6%, CH
4Selectivity is 81.35%; The CO conversion ratio is 87.93% under this condition of Theoretical Calculation, CH
4Selectivity is: 91.24%.
Embodiment 5
With 90g Na
2CO
3Be dissolved in the 350ml deionized water subsequent use.With 200g Ni (NO
3)
26H
2O, 25g La (NO
3)
36H
2O, 80g Mn (NO
3)
2(50% content), 14g Ce (NO
3)
36H
2O is dissolved in the 400ml deionized water and stirs.Under stirring condition, slowly add 114g Al
2O
3Powder stirs.In this solution, slowly drip Na
2CO
3Solution fully precipitates metal ion, continues to stir 30 minutes.Sediment through after washing, the drying was dried 8 hours under 120 ℃ of conditions, afterwards sediment was carried out roasting 4 hours in 600 ℃ of Muffle furnaces, made φ 3 * 3mm cylinder shape catalyst through beating blade technolgy.At 400 ℃, hydrogen atmosphere reduction down obtained final gas employing methanation of coke oven catalyst in 4 hours with above-mentioned catalyst.
The active testing result: the CO conversion ratio is 84.51%, CH
4Selectivity is 83.46%; The CO conversion ratio is 87.93% under this condition of Theoretical Calculation, CH
4Selectivity is: 91.24%.
Embodiment 6
Be dissolved in the 350ml deionized water 250ml concentrated ammonia liquor (concentration is 25%) subsequent use.With 200gNi (NO
3)
26H
2O, 45g La (NO
3)
36H
2O, 90g Mn (NO
3)
2(50% content) is dissolved in the 400ml deionized water and stirs and form solution 1, with 15g NH
4VO
3Be dissolved in the 100ml deionized water and stir and form solution 2.With 115g Al
2O
3Powder slowly adds solution 1 and stirs, first compounding agent solution 2 in this solution, and then the ammoniacal liquor that adds dilution fully precipitates metal ion, continues to stir 30 minutes.Sediment through after washing, the drying was dried 8 hours under 120 ℃ of conditions, afterwards sediment was carried out roasting 4 hours in 600 ℃ of Muffle furnaces, made φ 3 * 3mm cylinder shape catalyst through beating blade technolgy.At 400 ℃, hydrogen atmosphere reduction down obtained final gas employing methanation of coke oven catalyst in 4 hours with above-mentioned catalyst.
The active testing result: the CO conversion ratio is 84.51%, CH
4Selectivity is 83.46%; The CO conversion ratio is 87.93% under this condition of Theoretical Calculation, CH
4Selectivity is: 91.24%.
Embodiment 7
Be dissolved in the 350ml deionized water 150g urea subsequent use.With 200g Ni (NO
3)
26H
2O, 60g La (NO
3)
36H
2O, 80g Mn (NO
3)
2(50% content), 32g Cr (NO
3)
39H
2O is dissolved in the 400ml deionized water and stirs.Under stirring condition, slowly add 115g Al
2O
3Powder stirs.In this solution, add urea liquid metal ion is fully precipitated, continue to stir 30 minutes.Sediment through after washing, the drying was dried 8 hours under 120 ℃ of conditions, afterwards sediment was carried out roasting 4 hours in 600 ℃ of Muffle furnaces, made φ 3 * 3mm cylinder shape catalyst through beating blade technolgy.At 400 ℃, hydrogen atmosphere reduction down obtained final gas employing methanation of coke oven catalyst in 4 hours with above-mentioned catalyst.
The active testing result: the CO conversion ratio is 83.26%, CH
4Selectivity is 80.39%; The CO conversion ratio is 87.93% under this condition of Theoretical Calculation, CH
4Selectivity is: 91.24%.
Embodiment 8
Be dissolved in the 350ml deionized water 250ml concentrated ammonia liquor (concentration is 25%) subsequent use.With 275g Ni (NO
3)
26H
2O, 45g La (NO
3)
36H
2O, 90g Mn (NO
3)
2(50% content), 20g Zr (NO
3)
25H
2O is dissolved in the 500ml deionized water and stirs.Under stirring condition, slowly add 100g Al
2O
3Powder stirs.The ammoniacal liquor that in this solution, adds dilution fully precipitates metal ion, continues to stir 30 minutes.Sediment through after washing, the drying was dried 8 hours under 120 ℃ of conditions, afterwards sediment was carried out roasting 4 hours in 600 ℃ of Muffle furnaces, made φ 3 * 3mm cylinder shape catalyst through beating blade technolgy.At 400 ℃, hydrogen atmosphere reduction down obtained final gas employing methanation of coke oven catalyst in 4 hours with above-mentioned catalyst.
The active testing result: the CO conversion ratio is 85.62%, CH
4Selectivity is 85.46%; The CO conversion ratio is 87.93% under this condition of Theoretical Calculation, CH
4Selectivity is: 91.24%.
Embodiment 9
The catalyst of choosing according to embodiment 1 described method preparation carries out the methanation experiment, and reaction velocity is 20000h
-1, the remaining reaction condition is with embodiment 1-8.The active testing result: the CO conversion ratio is 83.93%, CH
4Selectivity is 84.76%; The CO conversion ratio is 87.93% under this condition of Theoretical Calculation, CH
4Selectivity is: 91.24%.
The catalyst of choosing according to embodiment 1 described method preparation carries out life experiment, and appreciation condition is with embodiment 1-8.The test experiments result sees Fig. 1.Can find out that by Fig. 1 in 1000 hours experimentation, the CO conversion ratio fluctuates between 83-90%.Show based on the result that bed temperature is measured that in addition bed temperature is stable in the whole test process, hotspot location does not obviously move down, and illustrates that catalyst has good heat-resistant stability.
Embodiment 11
The catalyst of choosing according to embodiment 1 described method preparation carries out the methanation experiment, and the catalyst activity appreciation condition is following:
Reactor is 28 isothermal reactors that tubulation constitutes of φ 32mm by internal diameter, and loaded catalyst is 60ml in the every pipe, and the water vapour with fluidized state between reactor removes reaction heat.The concrete constituent content of unstripped gas is: H
2: 55.1%; N
2: 7.9%; CO:6.1%; CH
4: 25.2%; CO
2: 3.0%; 250 ℃ of reaction temperatures, reaction pressure 0.8Mpa, reaction velocity 8000h
-1The CO conversion ratio is 100%, CO
2Conversion ratio is 99%.
Embodiment 12
Employing is carried out industrial sideline test according to the catalyst of the described method preparation of embodiment 1, before the test in pure hydrogen atmosphere reductase 12 4 hours.Fig. 2 is seen in technological process.Purify the back coke-stove gas and add water vapour (vapour gas volume ratio=0.15～0.3) back entering electric heater; After being heated to 250～280 ℃, mist gets into methanator I; Carry out methanation; After getting into water cooler then and being cooled to 250～280 ℃, get into the further methanation of methanator II again, go out methanator II gas and get into water cooler II and be cooled to normal temperature.All load this catalyst in two reactors.Reactor is the fixed bed reactors of internal diameter 307mm, the loading height 300mm of catalyst, and loadings is 20L.The treating capacity of coke-stove gas is 150m
3/ h, gas composition is: 55-60%H
2, 24-28%CH
4, 6-9%CO, 2-3.5%CO
2, 3-5%N
2, the water vapour additional amount is 20% of a gas gross.Pressure 0.4～0.6MPa, 250 ℃-270 ℃ of intake air temperature, the bed hot(test)-spot temperature is 540-555 ℃.
The gas composition of I section reactor inlet, the outlet of I section and II section reactor outlet adopts the beautiful gas-chromatography of producing in sky, Shanghai to analyze, and model is 7890T, and argon gas is done carrier gas; Electric current is 70mA; Column temperature is 140 ℃, and the sample introduction temperature is 100 ℃, and detector temperature is 150 ℃.
Test activity change situation in service and see Fig. 3.Can find out that by Fig. 3 in the test run 1000 hours, the CO total conversion is near 100%.In early stage during pressure-raising, CO
2Total conversion raises gradually, CO after 100 hours
2Conversion ratio is along with the raw material fluctuation is fluctuateed in the 60-80% scope, and this conversion ratio result is near the equilibrium conversion that calculates.
In addition, the interior bed temperature distribution of two towers does not have obvious variation in the process of the test.The interior hotspot location of two towers does not obviously move down in the entire test, explains that once more catalyst has good stable property.
The appreciation condition of catalyst is among the foregoing description 1-8: reactor is the stainless steel tube of φ 32mm internal diameter 23mm, and catalyst size is φ 3.0 * 3.0, and former particle packing amount is 20ml.Unstripped gas adds part steam according to the coke-stove gas proportioning and forms, and concrete constituent content is: H
2: 43.7%; N
2: 3.29%; CO:5.38%; CH
4: 20.86%; CO
2: 1.77%; H
2O:25%.550 ℃ of reaction temperatures, reaction pressure 0.4MPa, reaction velocity 10000h
-1
The composition of unstripped gas and tail gas adopts the method for online sampling analysis, uses the TDX packed column of internal diameter φ 3mm, long 1.5m in thermal conductance (TCD) detector, to detect.
Comparative example 1
With 91.8g Na
2CO
3Be dissolved in the 350ml deionized water subsequent use.With 200g Ni (NO
3)
26H
2O is dissolved in the 400ml deionized water and stirs.Under stirring condition, slowly add 150g Al
2O
3Powder stirs.In this solution, add Na
2CO
3Solution fully precipitates metal ion, continues to stir 30 minutes.Sediment through after washing, the drying was dried 8 hours under 120 ℃ of conditions, afterwards sediment was carried out roasting 4 hours in 600 ℃ of Muffle furnaces, made φ 3 * 3mm cylinder shape catalyst through beating blade technolgy.At 400 ℃, hydrogen atmosphere reduction down obtained final gas employing methanation of coke oven catalyst in 4 hours with above-mentioned catalyst.
The active testing result: the CO conversion ratio is 50.28%, CH
4Selectivity is 80.36%; The CO conversion ratio is 87.93% under this condition of Theoretical Calculation, CH
4Selectivity is: 91.24%.
Comparative example 2
With 91.8g Na
2CO
3Be dissolved in the 350ml deionized water subsequent use.With 200g Ni (NO
3)
26H
2O, 30g La (NO
3)
36H
2O is dissolved in the 400ml deionized water and stirs.Under stirring condition, slowly add 140g Al
2O
3Powder stirs.In this solution, add Na
2CO
3Solution fully precipitates metal ion, continues to stir 30 minutes.Sediment through after washing, the drying was dried 8 hours under 120 ℃ of conditions, afterwards sediment was carried out roasting 4 hours in 600 ℃ of Muffle furnaces, made φ 3 * 3mm cylinder shape catalyst through beating blade technolgy.At 400 ℃, hydrogen atmosphere reduction down obtained final gas employing methanation of coke oven catalyst in 4 hours with above-mentioned catalyst.
The active testing result: the CO conversion ratio is 70.30%, CH
4Selectivity is 82.36%; The CO conversion ratio is 87.93% under this condition of Theoretical Calculation, CH
4Selectivity is: 91.24%.
Compare with comparative example 1, add La
2O
3Comparative example 2 higher methanation activity is arranged.
Comparative example
Chinese patent CN101391218A discloses a kind of gas employing methanation of coke oven catalyst, with Al
2O
3Be carrier, active component is present in the catalyst with the NiO form, and carrier and auxiliary agent MgO form the carrier structure of magnesium aluminate spinel.The mass percent of each component is: NiO is 5-20%, Al
2O
3Be 30-80%, the content of MgO is 1-50%.The activity rating condition is: reaction temperature is that 400 ℃, pressure are that 1Mpa, air speed are 4000h
-1, unstripped gas consists of: 55.04%H
2, 30%CH
4, 7.06%CO, 3.03%CO
2, 4%N
2, 0.42%O
2, the water vapour additional amount is 20% of a gas gross.There is not tangible decay of activity in 120 hours the life test.But it is not provided at the stability data of (more than 400 ℃) under the higher temperature and the activity data of (below 350 ℃) under the low temperature more; Generally speaking thermal insulation do not circulate in the methanation process operating temperature can be in operating temperature more than 500 ℃ and in the heat transfer reactor methanation process below 300 ℃; The operating temperature of having only the circulation adiabatic methanation process is between 400-500 ℃, and this just causes the disclosed methanation catalyst of this patent possibly only be applicable to the circulation adiabatic methanation process; In addition its volume space velocity lower-4000h
-1, volume space velocity is low to mean that catalyst amount is big, the methanator volume also will increase, and causes the increase of catalyst purchase cost and the increase of equipment investment.By comparison, outstanding advantage of the present invention is to use that air speed is higher, heat-resistant stability is better, low temperature active is good, serviceability temperature is wideer.
Claims (14)
1. catalyst that is used for gas employing methanation of coke oven, it is characterized in that: catalyst is gama-alumina or the TiO that supports active component and auxiliary agent
2Carrier; Wherein active component is Ni, and auxiliary agent is that first auxiliary agent and second auxiliary agent are formed, and wherein first auxiliary agent is a rare earth element, and second auxiliary agent is the one or more combination among Sr, Mn, V, Zr, Ce, the Cr.
2. by the described catalyst that is used for gas employing methanation of coke oven of claim 1; It is characterized in that: said catalyst is made up of active component, first auxiliary agent, second auxiliary agent and carrier; By mass percentage; 5-50% active component, 0.5-10% first auxiliary agent, 2-20% second auxiliary agent, surplus is a carrier.
3. by the described catalyst that is used for gas employing methanation of coke oven of claim 1, it is characterized in that: said first auxiliary agent is La; Second auxiliary agent is one or more among Ce, Mn, Zr, the Sr.
4. by the described catalyst that is used for gas employing methanation of coke oven of claim 1, it is characterized in that: said second auxiliary agent is one or more among Sr, Zr, the Mn.
5. by claim 2 or the 3 described catalyst that are used for gas employing methanation of coke oven; It is characterized in that: said catalyst is made up of active component, first auxiliary agent, second auxiliary agent and carrier; By mass percentage; 20-40% active component, 1-6% first auxiliary agent, 6-15% second auxiliary agent, surplus is a carrier.
6. described Preparation of catalysts method that is used for gas employing methanation of coke oven of claim 1; It is characterized in that: according to the above ratio, place stirred tank to stir and the adding carrier solubilization of active ingredient, then add first auxiliary agent, second auxiliary agent and the alkaline solution that have dissolved one by one and make it produce deposition; With washing of precipitate; Under 100-150 ℃, carried out dry 6-10 hour, dry back promptly obtains the catalyst precursor with 500-800 ℃ of roasting 3-5 hour efflorescence then, forming processes.
7. by the described Preparation of catalysts method that is used for gas employing methanation of coke oven of claim 6, it is characterized in that: with above-mentioned gained catalyst precursor with 300-500 ℃ at H
2Or under the effect of coke-stove gas it is reduced to the catalyst finished product.
8. by the described Preparation of catalysts method that is used for gas employing methanation of coke oven of claim 7, it is characterized in that: said gained catalyst precursor with 350-450 ℃ at H
2Under the effect of gas it is reduced to the catalyst finished product.
9. by the described Preparation of catalysts method that is used for gas employing methanation of coke oven of claim 6; It is characterized in that: the solvent of said lytic activity component, first auxiliary agent and second auxiliary agent is metallic salt material or deionized water; Said metallic salt material is nitrate, formates or oxalates.
10. by the described Preparation of catalysts method that is used for gas employing methanation of coke oven of claim 9, it is characterized in that: said metallic salt material is a nitrate.
11. by the described Preparation of catalysts method that is used for gas employing methanation of coke oven of claim 6, it is characterized in that: said alkaline solution liquid is NaOH solution, NH
4HCO
3, urea, ammoniacal liquor or Na
2CO
3Solution.
12. by the described Preparation of catalysts method that is used for gas employing methanation of coke oven of claim 11, it is characterized in that: said alkaline solution liquid is Na
2CO
3Solution or ammoniacal liquor.
13. by the described Preparation of catalysts method that is used for gas employing methanation of coke oven of claim 6, it is characterized in that: said sediment was 110-130 ℃ of drying 8 hours.
14. by the described Preparation of catalysts method that is used for gas employing methanation of coke oven of claim 6, it is characterized in that: the said dried 600-700 of being deposited in ℃ roasting 4 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921429A (en) * | 2012-11-09 | 2013-02-13 | 西南化工研究设计院有限公司 | Coal-derived natural gas catalytic agent and preparation method thereof |
| CN105618068A (en) * | 2014-12-01 | 2016-06-01 | 中国科学院大连化学物理研究所 | Metal wall-supported type high-temperature synthetic gas methanation catalyst as well as preparation method and application thereof |
| WO2018141649A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Manganese-doped nickel-methanation catalysts |
| WO2018141646A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Nickel methanation catalysts doped with iron and manganese |
| CN110639543A (en) * | 2019-09-30 | 2020-01-03 | 四川蜀泰化工科技有限公司 | Methanation catalyst and preparation method thereof |
| CN113941335A (en) * | 2021-11-11 | 2022-01-18 | 曲靖市麒麟气体能源有限公司 | Improved method for producing methanation series catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040054016A1 (en) * | 2002-06-12 | 2004-03-18 | National University Of Singapore | Supported nickel catalyst for synthesis gas preparation |
| CN101468311A (en) * | 2007-12-29 | 2009-07-01 | 大连普瑞特化工科技有限公司 | Catalyst for methanation of coal gas and preparation method thereof |
| CN102029162A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院大连化学物理研究所 | Wide-temperature full methanation catalyst and preparation method thereof |
| CN102139218A (en) * | 2011-03-22 | 2011-08-03 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for complete methanation of synthesis gas from coal and preparation method thereof |
-
2011
- 2011-12-15 CN CN2011104212937A patent/CN102513124A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040054016A1 (en) * | 2002-06-12 | 2004-03-18 | National University Of Singapore | Supported nickel catalyst for synthesis gas preparation |
| CN101468311A (en) * | 2007-12-29 | 2009-07-01 | 大连普瑞特化工科技有限公司 | Catalyst for methanation of coal gas and preparation method thereof |
| CN102029162A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院大连化学物理研究所 | Wide-temperature full methanation catalyst and preparation method thereof |
| CN102139218A (en) * | 2011-03-22 | 2011-08-03 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for complete methanation of synthesis gas from coal and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921429A (en) * | 2012-11-09 | 2013-02-13 | 西南化工研究设计院有限公司 | Coal-derived natural gas catalytic agent and preparation method thereof |
| CN105618068A (en) * | 2014-12-01 | 2016-06-01 | 中国科学院大连化学物理研究所 | Metal wall-supported type high-temperature synthetic gas methanation catalyst as well as preparation method and application thereof |
| CN105618068B (en) * | 2014-12-01 | 2018-07-10 | 中国科学院大连化学物理研究所 | Metallic walls carry formula synthesis gas high-temperature methanation catalyst and its preparation method and application |
| WO2018141649A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Manganese-doped nickel-methanation catalysts |
| WO2018141646A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Nickel methanation catalysts doped with iron and manganese |
| US10888846B2 (en) | 2017-01-31 | 2021-01-12 | Clariant Produkte (Deutschland) Gmbh | Manganese-doped nickel-methanation catalysts |
| CN110639543A (en) * | 2019-09-30 | 2020-01-03 | 四川蜀泰化工科技有限公司 | Methanation catalyst and preparation method thereof |
| CN113941335A (en) * | 2021-11-11 | 2022-01-18 | 曲靖市麒麟气体能源有限公司 | Improved method for producing methanation series catalyst |
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