CN102489340B - Method for preparing catalyst used for one-carbon chemical reactions through coprecipitation - Google Patents
Method for preparing catalyst used for one-carbon chemical reactions through coprecipitation Download PDFInfo
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Abstract
A method for preparing a catalyst used for one-carbon chemical reactions through coprecipitation belongs to the technical field of catalysts and comprises the following steps: at 0-150 DEG C, pretreating soluble metal compounds with alcohol, after pretreatment, diluting alcoholic solution of the metal compounds with water, then slowly mixing the solution and a precipitant to enter a precipitationreactor for a coprecipitation reaction at 0-120 DEG C and at a pH value of 7-13, after the coprecipitation reaction, and subject to ageing, suction filtration, washing, drying, roasting, tabletting, pelleting and reduction, obtaining the catalyst with high catalytic property and used for one-carbon chemical reactions of fischer tropsch, methanol synthesis, steam methane reformation and the like. The precipitation catalyst prepared with method is high in catalytic activity and has stable reaction performance, and conversion rate can reach high level.
Description
Technical field
The present invention relates to a kind of new catalyst preparation method, relate in particular to the method that a kind of coprecipitation prepares the one-carbon chemical catalyst.This method for preparing catalyst can be widely used in that Fischer-Tropsch is synthetic, methyl alcohol synthetic and the one-carbon chemical catalysts such as methane reforming, belongs to catalyst technical field.
Technical background
The reaction that reactant only contains a carbon atom in the chemical reaction process is referred to as one-carbon chemical.The main purpose of one-carbon chemical is to save coal and petroleum resources, generates many fuel with few carbon raw material, offers the mankind.
One-carbon chemical reacts since a hydrocarbonize.To contain the compound of a carbon atom---methane (CH
4), synthesis gas (CO and H
2), CO
2, CH
3OH, HCHO etc. are initial reactant, the synthetic a series of important industrial chemicals of reaction and the chemistry of fuel.The backbone material of one-carbon chemical is CO and H
2, be can both hold facilely from any carbon resource that contains, this is the maximum reason of the one-carbon chemical core that can be in following chemical industry.
In 20 century 70 mid-terms, the concept of C1 chemistry has been proposed in Japan at first.Meanwhile, About Monsanto Chemicals is produced the acetic acid technology with the low pressure methanol carbonylation and is obtained commercial Application; U.S. Mobile chemical company ZSM-5 molecular sieve catalyst successfully is applied to methanol conversion gasoline processed; The country that the gas production such as the Middle East, Canada is abundant is accelerated to improve by methanol from natural gas production capacity, causes a large amount of methyl alcohol to come into the market.Therefore, the C1 chemistry is not only studied with synthesis gas in recent years, and research with methyl alcohol as important basic material, synthesize a series of take ethene as basic material productions the basic organic chemical industry products.
In fact one carbonizer is exactly a kind of Coal Chemical Industry and gas chemical industry of a new generation.At present product mainly comprises liquid fuel and fuel additive, low-carbon alkene, synthesis of low-carbon alcohol, also comprises the six large class chemical products such as methyl alcohol and series of products thereof, formaldehyde and series of products thereof.The key of holding one-carbon chemical is catalyst, therefore how to develop about good catalyst the success or failure of one-carbon chemical.
Summary of the invention
The precipitation method are normally mixed the material of different chemical composition under solution state, add suitable precipitating reagent and prepare the presoma sediment in mixed liquor, again sediment are carried out drying or calcination, thereby make corresponding powder granule.
The coprecipitation that the present invention adopts refers to contain one or more cations in solution, they exist in solution with homogeneous phase, add precipitating reagent, after precipitation reaction, can obtain the precipitation of the homogeneous of various compositions, it is the method that preparation contains the catalyst of one or more metallic elements.The advantage of coprecipitation is: the first directly obtains the nano-powder material of chemical composition homogeneous by the various chemical reactions in the solution, and it two is nano-powder materials that easy prepared sizes are little and be evenly distributed.
Another feature of the present invention is to utilize a certain amount of metallic compound of various pure preliminary treatment.For be evenly distributed degree and improve performance of the particle size that improves the preparation powder sample, reduce particle size, we improve coprecipitation, and purpose is with the nucleation of crystal grain and growth course separately, rapid, high volume nucleation, evenly growth.In precipitation process, the size of particle is mainly determined by nucleation rate and nuclear growth rate, therefore just can control the performance of deposit seed by control nucleation rate and nuclear growth rate.Owing to the existence of alcohol in the precipitation solution, changed the concentration of precipitation solution, effectively controlled nucleation rate, alcoholic solution is coated on around the crystal grain simultaneously, suppressed the speed that nuclear increases, prevented the secondary agglomeration of particle, distributed and suitable particle size thereby obtained uniform particle size.
The purpose of this invention is to provide a kind of preparation method of the new catalyst for one-carbon chemical reaction, the method can be applied to Fischer-Tropsch synthesis cobalt-based catalyst and ferrum-based catalyst, methane reforming nickel-base catalyst and cobalt-base catalyst, synthesizing methanol copper-based catalysts, the CO cupric oxide is catalyst based and the preparation of the one-carbon chemical catalysts such as cobalt-base catalyst.
Main purpose of the present invention can be achieved through the following technical solutions:
A kind of new method of coprecipitation Kaolinite Preparation of Catalyst is characterized in that, may further comprise the steps:
(1) utilize the metallic compound of pure preliminary treatment water-soluble, pretreatment temperature is controlled between 0-150 ℃, and the time obtained the alcoholic solution of metallic compound at 0.1-8 hour, and concentration is 10wt%-80wt%;
(2) water is diluted to suitable concentration with the alcoholic solution of metallic compound again, and the concentration of metallic compound is between 0.1wt%-40wt%;
(3) step (2) gained solution and precipitating reagent slowly are mixed in the precipitation reactor, the control precipitation temperature is between 0-120 ℃, and pH value is between 7-13; Wore out 2-48 hour after precipitation finishes, aging temperature is between 0-80 ℃;
(4) will precipitate after suction filtration, the washes clean dryly, baking temperature is 40-150 ℃, constant temperature 4-48 hour, put into again the Muffle furnace roasting, and sintering temperature is 200-800 ℃, constant temperature 2-20 hour;
Through compressing tablet, granulation, reduction obtains preformed catalyst again;
Alcohol can be methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol in the above-mentioned steps (1), propane diols, in the various isomers of glycerine, butanediol, polyethylene glycol and above alcohol a kind of, two or more.
Described precipitating reagent can be in potash, sodium carbonate, carbonic acid ammonia, urea, the ammoniacal liquor a kind of.Precipitating reagent adds with the form of solution, and concentration is at 1wt%-50wt%.
Described metallic compound comprises the soluble compound of a kind of, two or more metals in iron, copper, cobalt, nickel, zinc, manganese, cerium, magnesium, aluminium, the zirconium, preferably contains at least a kind of in iron, copper, cobalt, the nickel.
In the step (3) solution just add with the feed way of precipitating reagent, counter add and and flow, be preferably co-precipitation.
A kind of precipitation method prepare the method for ferrum-based catalyst, and its step is as follows,
(1) utilize the metallic compound of pure preliminary treatment water-soluble, pretreatment temperature is controlled between 0-150 ℃, and the time obtained the alcoholic solution of metallic compound at 0.1-8 hour, and concentration is 10wt%-80wt%;
(2) water is diluted to suitable concentration with the alcoholic solution of metallic compound again, and the concentration of metallic compound is between 0.1wt%-40wt%;
(3) step (2) gained solution and precipitating reagent slowly are mixed in the precipitation reactor, the control precipitation temperature is between 0-120 ℃, and pH value is between 7-13; Wore out 2-48 hour after precipitation finishes, aging temperature is between 0-80 ℃;
(4) will precipitate after suction filtration, the washes clean dryly, baking temperature is 40-150 ℃, constant temperature 4-48 hour, put into again the Muffle furnace roasting, and sintering temperature is 200-800 ℃, constant temperature 2-20 hour;
Through compressing tablet, granulation, reduction obtains preformed catalyst again;
Its pretreated alcohol of method that the above-mentioned precipitation method prepare ferrum-based catalyst can be methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol, propane diols, in the various isomers of glycerine, butanediol, polyethylene glycol and above alcohol a kind of, two or more.
The above-mentioned precipitation method prepare the method for ferrum-based catalyst, described metallic compound comprises the soluble compound of one or more metals of the soluble compound of active component iron and Cu additives, cobalt, manganese, magnesium, zinc, and soluble compound comprises one or more in nitrate compound, acetic acid compound, carbonyls, pure oxo-compound, sulphate, the oxalate compound.
The described precipitating reagent of method that the above-mentioned precipitation method prepare ferrum-based catalyst is one or more in potash, sodium carbonate, carbonic acid ammonia, urea, the ammoniacal liquor.
A kind of precipitation method prepare the method for copper-based catalysts, and its step is as follows,
(1) utilize the metallic compound of pure preliminary treatment water-soluble, pretreatment temperature is controlled between 0-150 ℃, and the time obtained the alcoholic solution of metallic compound at 0.1-8 hour, and concentration is 10wt%-80wt%;
(2) water is diluted to suitable concentration with the alcoholic solution of metallic compound again, and the concentration of metallic compound is between 0.1wt%-40wt%;
(3) step (2) gained solution and precipitating reagent slowly are mixed in the precipitation reactor, the control precipitation temperature is between 0-120 ℃, and pH value is between 7-13; Wore out 2-48 hour after precipitation finishes, aging temperature is between 0-80 ℃;
(4) will precipitate after suction filtration, the washes clean dryly, baking temperature is 40-150 ℃, constant temperature 4-48 hour, put into again the Muffle furnace roasting, and sintering temperature is 200-800 ℃, constant temperature 2-20 hour;
Through compressing tablet, granulation, reduction obtains preformed catalyst again;
Its pretreated alcohol of method that the above-mentioned precipitation method prepare copper-based catalysts can be methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol, propane diols, in the various isomers of glycerine, butanediol, polyethylene glycol and above alcohol a kind of, two or more.
The described metallic compound of method that the above-mentioned precipitation method prepare copper-based catalysts comprises one or more the soluble compound in active ingredient copper and auxiliary agent zinc, aluminium, zirconium, the cerium, and soluble compound comprises one or more in nitrate, acetate, carbonyls, pure oxygen base salt, sulfate, the oxalates.
The above-mentioned precipitation method prepare the method for copper-based catalysts, and described precipitating reagent is one or more in potash, sodium carbonate, carbonic acid ammonia, urea, the ammoniacal liquor.
A kind of precipitation method prepare the method for cobalt-base catalyst, and its its step is as follows,
(1) utilize the metallic compound of pure preliminary treatment water-soluble, pretreatment temperature is controlled between 0-150 ℃, and the time obtained the alcoholic solution of metallic compound at 0.1-8 hour, and concentration is 10wt%-80wt%;
(2) water is diluted to suitable concentration with the alcoholic solution of metallic compound again, and the concentration of metallic compound is between 0.1wt%-40wt%;
(3) step (2) gained solution and precipitating reagent slowly are mixed in the precipitation reactor, the control precipitation temperature is between 0-120 ℃, and pH value is between 7-13; Wore out 2-48 hour after precipitation finishes, aging temperature is between 0-80 ℃;
(4) will precipitate after suction filtration, the washes clean dryly, baking temperature is 40-150 ℃, constant temperature 4-48 hour, put into again the Muffle furnace roasting, and sintering temperature is 200-800 ℃, constant temperature 2-20 hour;
Through compressing tablet, granulation, reduction obtains preformed catalyst again;
The above-mentioned precipitation method prepare cobalt-base catalyst its pretreated alcohol of method can in the various isomers of methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol, propane diols, glycerine, butanediol, polyethylene glycol and above alcohol a kind of, two or more.
The described metallic compound of method that the above-mentioned precipitation method prepare cobalt-base catalyst comprises one or more compounds in the compound of active component cobalt and auxiliary agent nickel, manganese, cerium, the aluminium, and compound comprises one or more in nitrate, acetate, carbonyls, pure oxygen base salt, sulfate, the oxalates.
The above-mentioned precipitation method prepare the method for cobalt-base catalyst, and described precipitating reagent is one or more in potash, sodium carbonate, carbonic acid ammonia, urea, the ammoniacal liquor.
A kind of precipitation method prepare the method for nickel-base catalyst, and its step is as follows,
(1) utilize the metallic compound of pure preliminary treatment water-soluble, pretreatment temperature is controlled between 0-150 ℃, and the time obtained the alcoholic solution of metallic compound at 0.1-8 hour, and concentration is 10wt%-80wt%;
(2) water is diluted to suitable concentration with the alcoholic solution of metallic compound again, and the concentration of metallic compound is between 0.1wt%-40wt%;
(3) step (2) gained solution and precipitating reagent slowly are mixed in the precipitation reactor, the control precipitation temperature is between 0-120 ℃, and pH value is between 7-13; Wore out 2-48 hour after precipitation finishes, aging temperature is between 0-80 ℃;
(4) will precipitate after suction filtration, the washes clean dryly, baking temperature is 40-150 ℃, constant temperature 4-48 hour, put into again the Muffle furnace roasting, and sintering temperature is 200-800 ℃, constant temperature 2-20 hour;
Through compressing tablet, granulation, reduction obtains preformed catalyst again;
Its pretreated alcohol of method that the above-mentioned precipitation method prepare nickel-base catalyst can be methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol, propane diols, glycerine, butanediol, in the various isomers of polyethylene glycol, polyethylene glycol and above alcohol a kind of, two or more.
The above-mentioned precipitation method prepare the method for nickel-base catalyst, described metallic compound comprises one or more soluble compounds in the compound of active component nickel and Cu additives, cerium, magnesium, the zirconium, and soluble compound comprises one or more in nitrate, acetate, carbonyls, pure oxygen base salt, sulfate, the oxalates.
The above-mentioned precipitation method prepare the method for nickel-base catalyst, and described precipitating reagent is one or more in potash, sodium carbonate, carbonic acid ammonia, urea, the ammoniacal liquor.
Main advantage of the present invention is:
(1) the prepared precipitated catalyst catalytic activity of the present invention is very high, and conversion ratio can reach higher level.
(2) the prepared precipitated catalyst of the present invention has comparatively stable reactivity worth.
(3) catalyst raw materials of the present invention cheap, be easy to get, preparation technology is simple, the catalyst prod cost is low, is suitable for suitability for industrialized production.
The specific embodiment
Method for preparing catalyst of the present invention is not defined as any concrete carbon catalysts, but following will the description the present invention with regard to an a kind of carbon catalysts at least.But protection scope of the present invention is not limited in this.
Embodiment 1
Ferrum-based catalyst preparation: take by weighing ferric nitrate, copper nitrate, potassium nitrate, manganese nitrate, magnesium nitrate, 200: 3: 4 in molar ratio: with propyl alcohol be mixed with the solution of concentration 10wt% at 100: 20, carry out preliminary treatment in container, be heated with stirring to 150 ℃, constant temperature is after 1 hour, treat that solution is down to room temperature, add a certain amount of water, be mixed with the solution of concentration 3wt%, after mixing, slowly be mixed in the precipitation reactor with sodium carbonate liquor, control precipitation pH value is 10, and precipitation temperature is 90 ℃.After finishing, precipitation wore out 2 hours 70 ℃ of aging temperatures.To precipitate after suction filtration, the washes clean dryly, baking temperature is 80 ℃, and constant temperature 48 hours is put into the Muffle furnace roasting again, and sintering temperature is 500 ℃, constant temperature 5 hours.Through compressing tablet, granulation, obtain preformed catalyst again.
Get above-mentioned catalyst 1g synthesis gas (CO/H
2=1) reduce in fixed bed, reducing condition is 500 ℃, 0.1MPa, 5000h
-1(V/V), constant temperature 10h.After reduction is finished, the catalyst that has reduced is down to room temperature in nitrogen stream, then nitrogen is switched to synthesis gas (H
2/ CO=1), begin to carry out Fischer-Tropsch synthesis.Reaction condition is 300 ℃, 1.5MPa, 2500h
-1(V/V), reaction result sees Table 1.
Comparative Examples 1
Catalyst preparation: take by weighing ferric nitrate, copper nitrate, potassium nitrate, manganese nitrate, magnesium nitrate, 200: 3: 4 in molar ratio: be mixed with the aqueous solution of concentration 3wt% at 100: 20, after mixing, add in the precipitation reactor, again sodium carbonate liquor is added in the precipitation reactor, control precipitation pH value is 8, and precipitation temperature is 60 ℃.After finishing, precipitation wore out 2 hours 30 ℃ of aging temperatures.To precipitate after suction filtration, the washes clean dryly, baking temperature is 120 ℃, and constant temperature 12 hours is put into the Muffle furnace roasting again, and sintering temperature is 600 ℃, constant temperature 2 hours.Through compressing tablet, granulation, obtain preformed catalyst again.
Get above-mentioned catalyst 1g synthesis gas (CO/H
2=1) reduce in fixed bed, reducing condition is 500 ℃, 0.1MPa, 5000h
-1(V/V), constant temperature 10h.After reduction is finished, the catalyst that has reduced is down to room temperature in nitrogen stream, then nitrogen is switched to synthesis gas (H
2/ CO=1), begin to carry out Fischer-Tropsch synthesis.Reaction condition is 300 ℃, 1.5MPa, 2500h
-1(V/V), reaction result sees Table 1.
Table 1 fischer-tropsch synthetic catalyst reaction result
Embodiment 2
Copper-based catalysts preparation: take by weighing copper nitrate and zinc nitrate, be the copper nitrate zinc nitrate solution that 1: 1 and amylalcohol are mixed with total concentration 30wt% in molar ratio, carry out preliminary treatment and be heated with stirring to 30 ℃ in container, constant temperature is after 8 hours, treats that solution is down to room temperature, add a certain amount of water, be mixed with the copper nitrate zinc nitrate solution of concentration 15wt%, after mixing, slowly be mixed in the precipitation reactor with ammonia spirit, control precipitation pH value is 7, and precipitation temperature is 100 ℃.Wore out 10 hours after precipitation finishes, aging temperature is 60 ℃.To precipitate after suction filtration, the washes clean dryly, baking temperature is 120 ℃, and constant temperature 10 hours is put into the Muffle furnace roasting again, and sintering temperature is 400 ℃, constant temperature 3 hours.Through compressing tablet, granulation, obtain preformed catalyst again.
Get above-mentioned catalyst 1g gaseous mixture (V (H
2)/V (N
2)=5: 95) by 150 ℃, 180 ℃, after the heating schedule of 210 ℃ and 240 ℃ reduces in fixed bed, lower the temperature, reducing gases is switched to synthesis gas (V (H
2)/V (CO)/V (CO
2)/V (N
2)=65.9/27.1/2.9/4.1) begins to carry out the methyl alcohol synthetic reaction.Reaction condition is 210 ℃-270 ℃, 5.0MPa, 500h
-1(V/V), reaction result sees Table 2.
Comparative Examples 2
The catalyst preparation: taking by weighing copper nitrate and zinc nitrate, is the copper nitrate zinc nitrate aqueous solution that is mixed with concentration 15wt% at 1: 1 in molar ratio, slowly is mixed in the precipitation reactor with urea liquid, and control precipitation pH value is 9, and precipitation temperature is 50 ℃.Wore out 30 hours after precipitation finishes, aging temperature is 25 ℃.To precipitate after suction filtration, the washes clean dryly, baking temperature is 100 ℃, and constant temperature 24 hours is put into the Muffle furnace roasting again, and sintering temperature is 400 ℃, constant temperature 3 hours.Through compressing tablet, granulation, obtain preformed catalyst again.
Get above-mentioned catalyst 1g gaseous mixture (V (H
2)/V (N
2)=5: 95) by 150 ℃, 180 ℃, after the heating schedule of 210 ℃ and 240 ℃ reduces in fixed bed, lower the temperature, reducing gases is switched to synthesis gas (V (H
2)/V (CO)/V (CO
2)/V (N
2)=65.9/27.1/2.9/4.1) begins to carry out the methyl alcohol synthetic reaction.Reaction condition is 210 ℃-270 ℃, 5.0MPa, 500h
-1(V/V), reaction result sees Table 2.
Table 2 methanol synthesis catalyst reaction result
Embodiment 3
Nickel-base catalyst preparation: take by weighing nickel nitrate and magnesium nitrate, be the solution that 1: 4 and butanediol are mixed with total concentration 80wt% in molar ratio, be heated with stirring to 60 ℃ in container, constant temperature is after 0.5 hour, treats that solution is down to room temperature, add a certain amount of water, be mixed with nickel nitrate and the magnesium nitrate solution of concentration 40wt%, after mixing, slowly be mixed in the precipitation reactor with sal volatile, control precipitation pH value is 12, and precipitation temperature is 120 ℃.Wore out 48 hours after precipitation finishes, aging temperature is 5 ℃.To precipitate after suction filtration, the washes clean dryly, baking temperature is 150 ℃, and constant temperature 24 hours is put into the Muffle furnace roasting again, and sintering temperature is 700 ℃, constant temperature 2 hours.Through compressing tablet, granulation, obtain preformed catalyst again.
Get above-mentioned catalyst 0.2g and place quartz tube reactor, after 3 hours, pass into reaction gas CO 700 ℃ of lower reduction with hydrogen
2/ CH
4(1/1), begins to carry out methane reforming reaction.Reaction condition is 700 ℃, 0.1MPa, 10000h
-1(V/V), reaction result sees Table 3.
Comparative Examples 3
Catalyst preparation: take by weighing nickel nitrate and magnesium nitrate, be nickel nitrate and the magnesium nitrate aqueous solution that is mixed with concentration 40wt% at 1: 4 in molar ratio, after mixing, add and be equipped with in the precipitation reactor of sal volatile, control precipitation pH value is 12, and precipitation temperature is 65 ℃.Wore out 48 hours after precipitation finishes, aging temperature is 60 ℃.To precipitate after suction filtration, the washes clean dryly, baking temperature is 120 ℃, and constant temperature 15 hours is put into the Muffle furnace roasting again, and sintering temperature is 400 ℃, constant temperature 5 hours.Through compressing tablet, granulation, obtain preformed catalyst again.
Get above-mentioned catalyst 0.2g and place quartz tube reactor, after 3 hours, pass into reaction gas CO 700 ℃ of lower reduction with hydrogen
2/ CH
4(1/1), begins to carry out methane reforming reaction.Reaction condition is 700 ℃, 0.1MPa, 10000h
-1(V/V), reaction result sees Table 3.
Table 3 methane reforming catalyst reaction result
Embodiment 4
The cobalt-base catalyst preparation: take by weighing cobalt octacarbonyl, manganese nitrate is the cobalt octacarbonyl manganese nitrate solution that 1: 4 and glycerine are mixed with concentration 20wt% in molar ratio, in container, carry out preliminary treatment, be heated with stirring to 120 ℃, constant temperature is after 1.5 hours, treats that solution is down to room temperature, add a certain amount of water, be mixed with the cobalt nitrate solution of concentration 10wt%, after mixing, slowly be mixed in the precipitation reactor with sodium carbonate liquor, control precipitation pH value is 10, and precipitation temperature is 70 ℃.After finishing, precipitation wore out 20 hours 70 ℃ of aging temperatures.To precipitate after suction filtration, the washes clean dryly, baking temperature is 90 ℃, and constant temperature 48 hours is put into the Muffle furnace roasting again, and sintering temperature is 350 ℃, constant temperature 20 hours.Through compressing tablet, granulation, obtain preformed catalyst again.
Get above-mentioned catalyst 1g and reduce in fixed bed with hydrogen, reducing condition is 500 ℃, 0.1MPa, 5000h
-1(V/V), constant temperature 10h.After reduction is finished, the catalyst that has reduced is down to room temperature in nitrogen stream, then nitrogen is switched to synthesis gas (H
2/ CO=0.5), begin to carry out Fischer-Tropsch synthesis.Reaction condition is 250 ℃, 1.5MPa, 2500h
-1(V/V), reaction result sees Table 4.
Comparative Examples 4
Catalyst preparation: take by weighing cobalt octacarbonyl, manganese nitrate, be the cobalt octacarbonyl cobalt that is mixed with concentration 10wt% at 1: 4 in molar ratio, manganese nitrate aqueous solution, after mixing, add in the precipitation reactor, again sodium carbonate liquor is added in the precipitation reactor, control precipitation pH value is 10, and precipitation temperature is 60 ℃.After finishing, precipitation wore out 2 hours 30 ℃ of aging temperatures.To precipitate after suction filtration, the washes clean dryly, baking temperature is 80 ℃, and constant temperature 4 hours is put into the Muffle furnace roasting again, and sintering temperature is 500 ℃, constant temperature 2 hours.Through compressing tablet, granulation, obtain preformed catalyst again.
Get above-mentioned catalyst 1g and reduce in fixed bed with hydrogen, reducing condition is 500 ℃, 0.1MPa, 5000h
-1(V/V), constant temperature 10h.After reduction is finished, the catalyst that has reduced is down to room temperature in nitrogen stream, then nitrogen is switched to synthesis gas (H
2/ CO=0.5), begin to carry out Fischer-Tropsch synthesis.Reaction condition is 300 ℃, 1.5MPa, 2500h
-1(V/V), reaction result sees Table 4.
Table 4 fischer-tropsch synthetic catalyst reaction result
Claims (10)
1. a coprecipitation is characterized in that for the preparation of the method for the catalyst of one-carbon chemical reaction, may further comprise the steps:
(1) utilize the metallic compound of pure preliminary treatment water-soluble, pretreatment temperature is controlled between 30-150 ℃, and the time obtained the alcoholic solution of metallic compound at 0.1-8 hour, and concentration is 10wt%-80wt%;
(2) water is diluted to suitable concentration with the alcoholic solution of metallic compound again, and the concentration of metallic compound is between 0.1wt%-40wt%;
(3) step (2) gained solution and precipitating reagent slowly are mixed in the precipitation reactor, the control precipitation temperature is between 0-120 ℃, and the pH value is between 7-13; Wore out 2-48 hour after precipitation finishes, aging temperature is between 0-80 ℃;
(4) will precipitate after suction filtration, the washes clean dryly, baking temperature is 40-150 ℃, constant temperature 4-48 hour, put into again the Muffle furnace roasting, and sintering temperature is 200-800 ℃, constant temperature 2-20 hour; Through compressing tablet, granulation, reduction obtains final catalyst again;
In the above-mentioned steps (1) alcohol be in the various isomers of methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol, propane diols, glycerine, butanediol, polyethylene glycol and above alcohol a kind of, two or more.
2. in accordance with the method for claim 1, it is characterized in that, described precipitating reagent is one or more in potash, sodium carbonate, carbonic acid ammonia, urea, the ammoniacal liquor.
3. in accordance with the method for claim 1, it is characterized in that, described metallic compound comprises the compound of a kind of, two or more metals in iron, copper, cobalt, nickel, zinc, manganese, cerium, magnesium, aluminium, the zirconium.
4. in accordance with the method for claim 1, it is characterized in that, described compound comprises one or more in nitrate, acetate, carbonyls, pure oxygen base salt, sulfate, the oxalates.
5. in accordance with the method for claim 1, it is characterized in that, in the step (3) feed way of solution and precipitating reagent for just add, instead add, and flow in a kind of.
6. in accordance with the method for claim 5, it is characterized in that, the feed way of solution and precipitating reagent is for just adding in the step (3).
7. according to the preparation method of the described arbitrary catalyst of claim 1-5, it is characterized in that, described catalyst is ferrum-based catalyst, and metallic compound comprises the compound of one or more metals of the compound of active component iron and Cu additives, cobalt, manganese, magnesium, zinc.
8. according to the preparation method of the described arbitrary catalyst of claim 1-5, it is characterized in that, described catalyst is copper-based catalysts, and metallic compound comprises one or more compounds of active component cupreous compound and auxiliary agent zinc, aluminium, zirconium, cerium.
9. according to the preparation method of the described arbitrary catalyst of claim 1-5, it is characterized in that, described catalyst is cobalt-base catalyst, and metallic compound comprises one or more compounds in the compound of active component cobalt and auxiliary agent nickel, manganese, cerium, the aluminium.
10. according to the preparation method of the described arbitrary catalyst of claim 1-5, it is characterized in that, described catalyst is nickel-base catalyst, and metallic compound comprises one or more soluble compounds in the compound of active component nickel and Cu additives, cerium, magnesium, the zirconium.
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| CN102489340B (en) * | 2011-12-02 | 2013-10-16 | 北京化工大学 | Method for preparing catalyst used for one-carbon chemical reactions through coprecipitation |
| CN104096570A (en) * | 2013-04-02 | 2014-10-15 | 北京化工大学 | Iron-based catalyst for production of low carbon olefin by Fischer Tropsch synthesis, preparation method and application thereof |
| CN104588079B (en) * | 2013-11-03 | 2017-02-15 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst and preparation method thereof |
| CN104069863B (en) * | 2014-07-09 | 2016-03-30 | 太原理工大学 | Slurry bed system synthesis gas produces CuZnAl catalyst and the methods for making and using same of pentane |
| CN105435807B (en) * | 2014-07-22 | 2018-10-23 | 北京化工大学 | A kind of unsupported catalyst and its preparation method and application |
| CN104624196B (en) * | 2015-02-05 | 2017-06-16 | 中科合成油技术有限公司 | A kind of high-specific surface area fischer-tropsch synthetic catalyst and preparation method and application |
| CN107043319B (en) * | 2016-02-05 | 2024-05-24 | 高化学株式会社 | Method for producing methanol |
| CN110270368B (en) * | 2018-03-14 | 2020-09-04 | 北京化工大学 | Method for synthesizing carbon-chemical embedded catalyst material by solution-free method |
| CN110314688A (en) * | 2018-03-28 | 2019-10-11 | 国家能源投资集团有限责任公司 | Methanol synthesis catalyst and preparation method thereof |
| CN109158107B (en) * | 2018-08-17 | 2021-03-16 | 中国科学院化学研究所 | Method for preparing liquid hydrocarbon by directly hydrogenating carbon dioxide |
| CN111298796A (en) * | 2020-04-14 | 2020-06-19 | 郑州大学 | Preparation process and application of catalyst for preparing low-carbon olefin by industrial-grade catalytic hydrogenation |
| CN113058613B (en) * | 2021-03-18 | 2022-08-26 | 浙江师范大学 | Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof |
| CN115582131B (en) * | 2022-10-13 | 2023-12-19 | 浙江新和成股份有限公司 | Copper-manganese catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101927156A (en) * | 2010-06-11 | 2010-12-29 | 清华大学 | Method for preparing zirconia catalyst used for preparation of C2-C4 low-carbon olefins by CO hydrogenation |
| CN102000578A (en) * | 2010-09-29 | 2011-04-06 | 大连理工大学 | Catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and preparing method thereof |
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| CN102000578A (en) * | 2010-09-29 | 2011-04-06 | 大连理工大学 | Catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and preparing method thereof |
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| Title |
|---|
| 李冬丽等.沉淀转化法制备NiO催化剂及其催化性能研究.《应用化工》.2008,第37卷(第8期),902-905. |
| 沉淀转化法制备NiO催化剂及其催化性能研究;李冬丽等;《应用化工》;20080831;第37卷(第8期);902-905 * |
| 第3页第[0024]-[0026]段. |
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