CN102989511A - Fischer-Tropsch synthesis catalyst, and preparation and application thereof - Google Patents
Fischer-Tropsch synthesis catalyst, and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a Fischer-Tropsch synthesis catalyst, and a preparation and an application thereof. The catalyst comprises a carrier, an active metal component, and an organic substance I. The active metal component is selected from iron and/or cobalt. With the catalyst as a standard and calculated according to oxide, the content of the active metal component is 2-50wt%. A molar ratio of the organic substance I to the active metal component is 0.01-5. Compared with prior arts, the performance of the catalyst provided by the invention is substantially improved.
Description
Invention field
The present invention relates to a kind of fischer-tropsch synthetic catalyst and preparation thereof and application.
Background technology
Fischer-Tropsch synthetic (FTS, FT is synthetic) refers to synthesis gas (CO+H
2) changing into the reaction of hydro carbons at catalyst, product comprises alkane and alkene, and by-product CO
2, H
2The organic oxygen-containing compounds such as O and alcohol, aldehyde, acid, ketone and ester, product can obtain the high-quality liquid fuel through deep processing, such as gasoline, diesel oil and aviation kerosine etc.From FT synthetic be found to the history that eight more than ten years were arranged now, South Africa is since the industrial utilization FT synthetic technology fifties in last century, always development so far.
The consumption of petroleum resources increases increasingly, and people become increasingly active in the effort of seeking replacement resources; And the continuous increase of coal and natural gas proved reserves makes the research in synthetic this field of FT very active.Moreover, the World Refining already is faced with and produces low-sulfur and super-low sulfur vapour, diesel oil to satisfy the challenge of day by day harsh environmental legislation.Because FT is synthetic to have and not to rely on oil, product cleaning advantages such as (not sulfur-bearing, nitrogen), along with the world energy sources structure from single oil dependent form to coal, the transformation of natural gas and oil alliance type, the FT synthetic technology will be developed rapidly.Wherein, conversion of natural gas is that the cobalt-based FT synthesis technique of high-quality diesel oil and high-quality wax product especially attracts people's attention, and it is all significant for Reasonable Utilization of Natural Gas resource and following clean coal technology.Yet the core of its Efficient Conversion remains the catalysis problem relevant with the research of FT synthetic catalyst.Improve activity, the reduction CO of FT synthetic catalyst
2And CH
4Selective and improve C
5 +Hydro carbons selectively be the core content of FT synthetic catalyst research and development, this is related to effective utilization of synthesis gas and the reduction of production cost.
Summary of the invention
The technical problem to be solved in the present invention is fischer-tropsch synthetic catalyst, its preparation and the application that provides on the basis of existing technology a kind of performance to obtain modification.
The present invention relates to following invention:
1, a kind of fischer-tropsch synthetic catalyst, contain carrier, active metal component and organic matter I, wherein, described active metal component chosen from Fe and/or cobalt, take catalyst as benchmark, take the content of the described active metal component of oxide as the 2-50 % by weight, the mol ratio of described organic matter I and described active metal component is 0.01-5.
According to 1 described catalyst, it is characterized in that 2, take catalyst as benchmark, take the content of the described active metal component of oxide as the 5-40 % by weight, the mol ratio of described organic matter I and described active metal component is 0.02-3.
According to 2 described catalyst, it is characterized in that 3, take catalyst as benchmark, take the content of the described active metal component of oxide as the 10-30 % by weight, the mol ratio of described organic matter I and described active metal component is 0.1-2.
According to 1,2 or 3 each described catalyst, it is characterized in that 4, described organic matter I is selected from water-soluble one or more that contain in oxygen and/or the organic compounds containing nitrogen.
According to 4 described catalyst, it is characterized in that 5, described water-soluble oxygen-containing organic compound is selected from one or more in Organic Alcohol and the organic acid; Described water-soluble organic compounds containing nitrogen is selected from one or more in the organic amine.
According to 1 described catalyst, it is characterized in that 6, described carrier is selected from one or more in aluminium oxide, silica-alumina, alumina silicate or the silica.
7, according to 6 described catalyst, it is characterized in that described alumina catalyst support.
8, according to 7 described catalyst, it is characterized in that, described aluminium oxide be selected from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.
9, according to 1 described catalyst, it is characterized in that, also contain one or more adjuvant components that are selected among La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and the Pd, in element and take catalyst as benchmark, the content of described auxiliary agent is no more than 25 % by weight.
According to 9 described catalyst, it is characterized in that 10, in element and take catalyst as benchmark, the content of described adjuvant component is the 0.01-10 % by weight.
11, a kind of preparation method of fischer-tropsch synthetic catalyst comprises: (1) preparation contains the hybrid infusion solution of chosen from Fe and/or cobalt compound and organic matter I, and uses this solution impregnating carrier; (2) impregnation product that obtains of drying steps (1); Wherein, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 2-50 % by weight, and the mol ratio of described organic matter I and described active metal component is 0.01-5.
12, according to 11 described methods, it is characterized in that, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 5-40 % by weight, and the mol ratio of described organic matter I and described active metal component is 0.02-3.
13, according to 12 described methods, it is characterized in that, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 10-30 % by weight, and the mol ratio of described organic matter I and described active metal component is 0.1-2.
According to 11,12 or 13 each described methods, it is characterized in that 14, described organic matter I is selected from water-soluble one or more that contain in oxygen and/or the organic compounds containing nitrogen; Described drying condition comprises: temperature is 80-300 ℃, and be 0.5-72 hour drying time.
According to 14 described methods, it is characterized in that 15, described water-soluble oxygen-containing organic compound is selected from one or more in Organic Alcohol and the organic acid; Described water-soluble organic compounds containing nitrogen is selected from one or more in the organic amine; Described drying condition comprises: temperature is 100-250 ℃, and be 1-12 hour drying time.
According to 11 described methods, it is characterized in that 16, described carrier is selected from one or more in aluminium oxide, silica-alumina, alumina silicate or the silica.
17, according to 16 described methods, it is characterized in that described alumina catalyst support.
18, according to 17 described methods, it is characterized in that, described aluminium oxide be selected from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.
19, according to 11 described methods, it is characterized in that, also comprise in carrier and introduce the step that is selected from one or more adjuvant components among La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and the Pd, in element and take catalyst as benchmark, the introducing amount of described adjuvant component is no more than 25 % by weight.
According to 19 described methods, it is characterized in that 20, in element and take catalyst as benchmark, the introducing amount of described adjuvant component is the 0.01-10 % by weight.
21, a kind of preparation method of fischer-tropsch synthetic catalyst comprises: (1) preparation contains the dipping solution of chosen from Fe and/or cobalt compound, and uses this solution impregnating carrier; (2) dry, roasting or the not impregnation product that obtains of calcination steps (1); (3) preparation contains the maceration extract of organic matter I, and the product that obtains with this solution impregnation step (2); (4) impregnation product that obtains of drying steps (3); Wherein, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 2-50 % by weight; The dipping of described step (3) makes that the mol ratio of organic matter I and described active metal component is 0.01-5 in the final catalyst.
According to 21 described methods, it is characterized in that 22, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 5-40 % by weight; The dipping of described step (3) makes that the mol ratio of organic matter I and described active metal component is 0.02-3 in the final catalyst.
According to 22 described methods, it is characterized in that 23, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 10-30 % by weight; The dipping of described step (3) makes that the mol ratio of organic matter I and described active metal component is 0.1-2 in the final catalyst.
According to 21,22 or 23 described methods, it is characterized in that 24, described organic matter I is selected from water-soluble one or more that contain in oxygen and/or the organic compounds containing nitrogen; The dipping of described step (3) makes that the mol ratio of organic matter I and described active metal component is 0.1-2 in the final catalyst; Described drying condition comprises: temperature is 80-300 ℃, and be 0.5-72 hour drying time; Described roasting condition comprises: temperature is 120-600 ℃, and the time is 1-8 hour.
According to 24 described methods, it is characterized in that 25, described water-soluble oxygen-containing organic compound is selected from one or more in Organic Alcohol and the organic acid; Described water-soluble organic compounds containing nitrogen is selected from one or more in the organic amine; Described drying condition comprises: temperature is 100-250 ℃, and be 1-12 hour drying time; Described roasting condition comprises: temperature is 150-450 ℃, and the time is 2-6 hour.
According to 21 described methods, it is characterized in that 26, described carrier is selected from one or more in aluminium oxide, silica-alumina, alumina silicate or the silica.
27, according to 26 described methods, it is characterized in that described alumina catalyst support.
28, according to 27 described methods, it is characterized in that, described aluminium oxide be selected from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.
29, according to 21 described methods, it is characterized in that, also comprise in carrier and introduce the step that is selected from one or more adjuvant components among La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and the Pd, in element and take catalyst as benchmark, the introducing amount of described adjuvant component is no more than 25 % by weight.
According to 29 described methods, it is characterized in that 30, in element and take catalyst as benchmark, the introducing amount of described adjuvant component is the 0.01-10 % by weight.
31, a kind of preparation method of fischer-tropsch synthetic catalyst, comprise: (1) uses the liquid infiltration carrier that is selected from the liquid of organic matter II or contains organic matter II, by volume and take the water absorption rate ω of described carrier as benchmark, described dipping makes the hold-up σ of liquid described in the carrier of Unit Weight be no more than 50% of ω; (2) preparation contains the dipping solution ε of chosen from Fe and/or cobalt compound, and use this solution impregnating carrier, described dipping so that finally in the catalyst take the content of the described active metal component of oxide as the 2-50 % by weight; (3) impregnation product that obtains of dry and calcination steps (2); (4) preparation contains the maceration extract of organic matter I, and the product that obtains with this solution impregnation step (3), and described dipping makes that the mol ratio of organic matter I and described active metal component is 0.01-5 in the final catalyst; (5) impregnation product that obtains of drying steps (4).
According to 31 described methods, it is characterized in that 32, it is the 2-30% of ω that the dipping of described step (1) makes the hold-up σ of liquid described in the carrier of Unit Weight.
According to 32 described methods, it is characterized in that 33, it is the 5-20% of ω that the dipping of described step (1) makes the hold-up σ of liquid described in the carrier of Unit Weight.
According to 31 described methods, it is characterized in that 34, the amount of described step (2) preparation maceration extract ε is that (ω-σ), n is the consumption of described carrier by weight to n.
According to 31 described methods, it is characterized in that 35, the described liquid that contains organic matter II is the aqueous solution of organic matter II.
According to 31 or 35 described methods, it is characterized in that 36, described organic matter II is selected from one or more in hydrocarbon, alcohol, organic acid or the organic amine.
According to 36 described methods, it is characterized in that 37, described organic matter II is selected from one or more in alcohol, organic acid or the organic amine.
According to 37 described methods, it is characterized in that 38, described organic matter II is selected from one or more compounds in alcohol, acid or the organic amine of being selected from that boiling point is higher than water.
According to 31 described methods, it is characterized in that 39, the dipping of described step (2) makes in the final catalyst content take the described active metal component of oxide as the 5-40 % by weight; The dipping of described step (4) makes that the mol ratio of organic matter I and described active metal component is 0.02-3 in the final catalyst.
According to 39 described methods, it is characterized in that 40, the dipping of described step (2) makes in the final catalyst content take the described active metal component of oxide as the 10-30 % by weight; The dipping of described step (4) makes that the mol ratio of organic matter I and described active metal component is 0.1-2 in the final catalyst.
According to 31,39 or 40 described methods, it is characterized in that 41, described organic matter I is selected from water-soluble one or more that contain in oxygen and/or the organic compounds containing nitrogen; The dipping of described step (4) makes that the mol ratio of organic matter I and described active metal component is 0.1-2 in the final catalyst; Described drying condition comprises: temperature is 80-300 ℃, and be 0.5-72 hour drying time; Described roasting condition comprises: temperature is 120-600 ℃, and the time is 1-8 hour.
According to 41 described methods, it is characterized in that 42, described water-soluble oxygen-containing organic compound is selected from one or more in Organic Alcohol and the organic acid; Described water-soluble organic compounds containing nitrogen is selected from one or more in the organic amine; Described drying condition comprises: temperature is 100-250 ℃, and be 1-12 hour drying time; Described roasting condition comprises: temperature is 150-450 ℃, and the time is 2-6 hour.
According to 31 described methods, it is characterized in that 43, described carrier is selected from one or more in aluminium oxide, silica one aluminium oxide, alumina silicate or the silica.
44, according to 43 described methods, it is characterized in that described alumina catalyst support.
45, according to 44 described methods, it is characterized in that, described aluminium oxide be selected from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.
46, according to 31 described methods, it is characterized in that, also comprise in carrier and introduce the step that is selected from one or more adjuvant components among La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and the Pd, in element and take catalyst as benchmark, the introducing amount of described adjuvant component is no more than 25 % by weight.
According to 46 described methods, it is characterized in that 47, in element and take catalyst as benchmark, the introducing amount of described adjuvant component is the 0.01-10 % by weight.
48. a Fischer-Tropsch synthesis method is included under the Fischer-Tropsch synthesis condition, will contain hydrogen and contact with catalyst with CO gas, wherein, described catalyst is the described catalyst of 1-10 any one claim.
According to catalyst provided by the invention, wherein, described organic matter I is selected from water miscible one or more that contain in oxygen and/or the organic compounds containing nitrogen, and preferred water miscible oxygen-containing organic compound is selected from one or more in the pure and mild organic acid; Preferred water miscible organic compounds containing nitrogen is selected from one or more in the organic amine.For example, oxygen-containing organic compound can be ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartaric acid, the malic acid; Organic compounds containing nitrogen can be ethylenediamine, EDTA and ammonium salt thereof.In preferred embodiment, the organic matter I in the described catalyst and the mol ratio of described active metal component are preferably 0.01-5, are preferably 0.02-3, more preferably 0.1-2.
Described carrier can for being suitable for arbitrarily preparing the carrier that fischer-tropsch synthetic catalyst is used, for example, be selected from one or more in aluminium oxide, silica-alumina, alumina silicate or the silica.Preferred aluminium oxide wherein, further preferably from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.They can be commercially available commodity or adopt arbitrarily prior art preparation.
Optionally, described carrier can be the article shaped that is fit to arbitrarily operation, for example, and sphere, compressing tablet and bar shaped.Described moulding can be carried out according to a conventional method, as passing through the method moulding such as compressing tablet, spin, extrusion.Take the extruded moulding thing of aluminium oxide as example, when moulding, carry out smoothly for the described moulding of assurance, can add entry, extrusion aid and/or adhesive, contain or not contain expanding agent in the precursor of described aluminium oxide and/or aluminium oxide, drying and roasting are carried out in then extrusion molding afterwards.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art.For example, common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, the PVOH, described peptizing agent can be inorganic acid and/or organic acid, and described expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and the surfactant.Synthetic cellulose wherein is preferably one or more in CMC, methylcellulose, ethyl cellulose, the hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in polyethylene glycol, poly-propyl alcohol, the polyvinyl alcohol, and surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight is the propenyl copolymer of 200-10000 and one or more in the maleic acid copolymer.The temperature of described drying can be 40-350 ℃, is preferably 100-200 ℃, and the time is 1-24 hour, is preferably 2-12 hour; Sintering temperature is 350-1000 ℃, is preferably 600-950 ℃, and roasting time is 1-10 hour, is preferably 2-6 hour.Wherein, the precursor of described aluminium oxide is selected from hibbsite, monohydrate alumina and the amorphous hydroted alumina or several mixtures.They can be that commercially available commodity also can be by any one method preparation in the prior art.
According to catalyst provided by the present invention, the kind of wherein said active metal component and content are usual kind and the content that fischer-tropsch synthetic catalyst adopts.Preferred described active metal component is iron or cobalt and their combination, further is cobalt; In oxide and take catalyst as benchmark, the content of described active metal component can be the 2-50 % by weight, is preferably the 5-40 % by weight, more preferably the 10-30 % by weight.
According to catalyst provided by the invention, can also contain any material that maybe can improve described catalyst performance that do not affect.As introducing one or more adjuvant components that are selected among La, Zr, Ce, W, Cu, Mn or the K; Introducing is selected from one or more adjuvant components among Ru, Re, Pt and the Pd, and in element and take catalyst as benchmark, the introducing amount of above-mentioned auxiliary agent is the 0.001-25 % by weight, is preferably the 0.01-10 % by weight.
According to method for preparing catalyst provided by the invention, under the prerequisite that is enough to described active metal component and organic matter I be carried on the described carrier, the introducing method of described active metal component and organic matter I is not particularly limited preferred infusion process.
One preferred embodiment in, the preparation method of catalyst of the present invention comprises: (1) preparation contains the hybrid infusion solution of chosen from Fe and/or cobalt compound and organic matter I, and uses this solution impregnating carrier; (2) impregnation product that obtains of drying steps (1); Wherein, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 2-50 % by weight, and the mol ratio of described organic matter I and described active metal component is 0.01-5.
Another preferred embodiment in, the preparation method of catalyst of the present invention comprises: (1) preparation contains the dipping solution of chosen from Fe and/or cobalt compound, and uses this solution impregnating carrier; (2) dry, roasting or the not impregnation product that obtains of calcination steps (1); (3) preparation contains the maceration extract of organic matter I, and the product that obtains with this solution impregnation step (2); (4) impregnation product that obtains of drying steps (3); Wherein, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 2-50 % by weight; The dipping of described step (3) makes that the mol ratio of organic matter I and described active metal component is 0.01-5 in the final catalyst.
Wherein, the described compound that contains active metal component is one or more in their soluble compound, as contains water-soluble salt of active metal component, one or more in the complex compound.Described organic matter I is selected from water miscible one or more the organic compound that contains in oxygen and/or the organic compounds containing nitrogen, and preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol and the organic acid; Preferred organic compounds containing nitrogen is selected from one or more in the organic amine.For example, oxygen-containing organic compound can be selected from ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, in 2-CDTA, citric acid, tartaric acid, the malic acid one or more, organic compounds containing nitrogen can be selected from ethylenediamine, EDTA and ammonium salt thereof.
When containing one or more adjuvant components that are selected among La, Zr, Ce, W, Cu, Mn or the K in the described catalyst, and when being selected from one or more adjuvant components in the components such as Ru, Re, Pt and Pd, the present invention is not particularly limited its introducing method.For example, can be will contain the compound of described adjuvant component introduce described carrier after being mixed with hybrid infusion solution with the compound that contains active metal component and organic matter I; Can also be to introduce described carrier and roasting behind the independent obtain solution of the compound that contains described auxiliary agent.When described auxiliary agent and described reactive metal group and organic matter I introduce described carrier respectively, preferably flood described carrier and dry with the compound solution that contains described auxiliary agent.Described drying condition comprises: temperature is 80-300 ℃, is preferably 100-250 ℃, and be 0.5-72 hour drying time, is preferably 1-12 hour; Preferably flood described carrier and roasting with the compound solution that contains described auxiliary agent.Described sintering temperature is 120-600 ℃, is preferably 150-450 ℃, and roasting time is 1-8 hour, is preferably 2-6 hour.In element and take catalyst as benchmark, the introducing amount of above-mentioned auxiliary agent is the 0.001-25 % by weight, is preferably the 0.01-10 % by weight.
The inventor is surprised to find, before usefulness contains the dipping solution impregnated carrier of reactive metal and/or organic matter I, with the liquid of a certain amount of organic matter II or contain the liquid infiltration carrier of organic matter II, in the identical situation of active metallic content, the performance of catalyst is obviously improved first.Be enough to realize that under the prerequisite of this purpose, the present invention is not particularly limited described liquid.For example, can be to be liquid organic mixture under one or more normal temperature; Can be water and be at normal temperatures one or more the mixed solution in the liquid organic matter.The organic matter of described liquid state can be one or more that are selected from hydrocarbon, alcohol, acid or the organic amine.Preferred one or more in alcohol, acid or organic amine.Wherein, described alcohol can be one or more (for example, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol, glycerine, the xylitols etc.) in monohydric alcohol, dihydroxylic alcohols, trihydroxylic alcohol and/or the polyalcohol; Described acid is one or more (for example, they can be formic acid, acetic acid, oxalic acid, citric acid, maleic acid, malic acid etc.) in monoacid, binary acid, ternary acid and/or the polyacid; Described organic amine can be one or more (for example, they can be n-butylamine, hexamethylene diamine, diethanol amine, triethanolamine, propionamide, butyramide, isobutyramide, acrylamide, caprolactam, dimethyl formamide, diphenylamines, benzidine, o-phenylenediamine etc.) that comprise in fatty amines, alcamines, amide-type, the aromatic amine.When the liquid of described organic matter II is water and organic mixture, in preferred embodiment, the organic matter of described liquid state further preferably is higher than one or more compounds in alcohol, acid or the organic amine of being selected from of water from boiling point, wherein, organic content is less than or equal to the hold-up σ of the described liquid of expection.
Preparation method according to catalyst of the present invention, when with comprising with the liquid of organic matter II before containing the dipping solution impregnated carrier of reactive metal and/or organic matter I or when containing the liquid infiltration carrier of organic matter II, one preferred embodiment in, described method comprises: (1) uses the liquid infiltration carrier that is selected from the liquid of organic matter II or contains organic matter II, by volume and take the water absorption rate ω of described carrier as benchmark, described dipping makes the hold-up σ of liquid described in the carrier of Unit Weight be no more than 50% of ω; (2) preparation contains the dipping solution ε of chosen from Fe and/or cobalt compound, and use this solution impregnating carrier, described dipping so that finally in the catalyst take the content of the described active metal component of oxide as the 2-50 % by weight; (3) impregnation product that obtains of dry and calcination steps (2); (4) preparation contains the maceration extract of organic matter I, and the product that obtains with this solution impregnation step (3), and described dipping makes that the mol ratio of organic matter I and described active metal component is 0.01-5 in the final catalyst; (5) impregnation product that obtains of drying steps (4).
The assay method of the water saturation adsorbance ω of described carrier comprises: the carrier (testing sample is at first in 120 ℃ of oven dry 4 hours) of getting a certain amount of (being 20 grams among the embodiment), be weighed as G, this carrier is placed in the container (such as graduated cylinder, beaker etc.), add water until carrier is not had by water logging fully, placed four hours; Filter, solid phase drains 5 minutes, obtains inhaling water saturated carrier, is weighed as B.Water absorption rate ω=(B-G)/G.Herein, the density of setting water is 1, (B-G) be carrier suction volume, the dimension of water absorption rate ω be " volume/weight " for example be " ml/g " (or ml/g).
By volume and take the water absorption rate ω of described carrier as benchmark, described dipping makes the hold-up σ of liquid described in the carrier of Unit Weight be no more than 50% of ω, is preferably the 2-30% of ω, more preferably the 5-20% of ω.Can realize control to described liquid hold-up σ in carrier by mode arbitrarily, as adopt excessive as described in carrier as described in the liquid infiltration, evaporate afterwards described liquid hold-up σ in carrier met the demands; Or realize with the method for the described amount of liquid σ direct impregnation carrier of required delay.When adopting the described carrier of excessive described liquid infiltration, the method for evaporating afterwards and described liquid is during for alcohol, acid or hydrocarbon compound, described evaporation take the reaction of alcohol or hydrocarbon compound does not occur as decompose and/or oxidation reaction as prerequisite.Being generally baking temperature is 80-300 ℃, is preferably 100-250 ℃, and be 0.5-72 hour drying time, is preferably 1-12 hour.σ can adopt following method to measure, comprise the water absorption rate ω that measures described carrier, again according to aforesaid method with described liquid infiltration carrier, afterwards, measure the water absorption rate ω 1 that is detained the carrier that described liquid is arranged, σ=((ω-ω 1)/ω) * 100%.
The dipping method of described step (2) can be the Kaolinite Preparation of Catalyst conventional method, for example, can be the mode that adopts excessive liquid dipping, the method for saturated dipping etc.When described dipping adopted saturated dipping method, the amount of the dipping solution of preferred described step (2) preparation satisfies ε=n, and (ω-σ), n wherein was the consumption of described carrier.
According to the invention provides catalyst, be used for need in the presence of hydrogen, carrying out reduction activation before the Fischer-Tropsch synthesis, reducing condition is: reduction temperature is 100 ℃ to 800 ℃, is preferably 200 ℃ to 600 ℃, more preferably 300 ℃ to 450 ℃; Recovery time is 0.5-72 hour, be preferably 1-24 hour, more preferably 2-8 hour, described reduction can be carried out in pure hydrogen, also can in the gaseous mixture of hydrogen and inert gas, carry out, as carrying out in the gaseous mixture of hydrogen and nitrogen and/or argon gas, Hydrogen Vapor Pressure is 0.1-4MPa, is preferably 0.1-2MPa.
According to Fischer-Tropsch synthesis method provided by the invention, described mixture and the catalytic condition of described catalyst with carbon monoxide and hydrogen: preferred temperature is 160～280 ℃, more preferably 190～250 ℃, pressure is preferably 1～8MPa, 1-5MPa more preferably, the mol ratio of hydrogen and carbon monoxide is 0.4～2.5, is preferably 1.5～2.5, more preferably 1.8～2.2, the space-time speed of gas is 200 hours
-1～10000 hours
-1, be preferably 500 hours
-1～8000 hours
-1
Described contact can be carried out in the reactor of any type, for example fixed bed reactors, slurry attitude bed tank reactor, fluidized-bed reactor or bubbling bed reactor and corresponding scheme.Obviously, the granular size of catalyst changes according to the reaction scheme of their employings.Given reaction scheme is selected only catalyst granules granularity, relate to reactant and the product diffusion problem in catalyst granules, beds and reaction medium, this belongs to those skilled in the art's general knowledge.
Compared with prior art, the invention provides catalyst performance be improved significantly.
The specific embodiment
The following examples will the present invention will be further described.
Embodiment and Comparative Examples used carrier are all the by the following method aluminium oxide of preparation: get the commercial boehmite products C 1 powder 500g that Condea company sells, mixed solution with 7.5 gram nitric acid and 400g deionized water, C1 powder and mixed solution are mixed, kneading is plastic on double screw banded extruder afterwards, and be extruded into the clover shape bar of 1.2 millimeters of Φ, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 4 hours, obtain carrier, this carrier is characterized by gama-alumina through XRD, and water absorption rate is 0.72.
Comparative Examples 1
Take by weighing the Al of 20g
2O
3Carrier.Take by weighing the cobalt nitrate of 18.7g, water is dissolved into 14.4 milliliters of maceration extracts, floods this alumina support with this maceration extract, then dries by the fire 4h in baking oven under 120 ℃, and the 250 ℃ of roasting 4h in Muffle furnace that continue obtain reference catalyst DC1.Cobalt oxide content is listed in the table 1 among the catalyst DC1.The catalyst composition analysis adopts the X-fluorescence method to measure (together lower).
Comparative Examples 2
Take by weighing the Al of 20g
2O
3Carrier.Take by weighing cobalt nitrate and the 0.060g ruthenic chloride of 18.7g, water is dissolved into 14.4 milliliters of maceration extracts, floods this alumina support with this maceration extract, then dries by the fire 4h in baking oven under 120 ℃, and the 250 ℃ of roasting 4h in Muffle furnace that continue obtain reference catalyst DC2.Cobalt oxide and ruthenium-oxide content are listed in the table 1 among the catalyst DC2.
Embodiment 1
Take by weighing the Al of 20g
2O
3Carrier.Take by weighing the cobalt nitrate of 18.7g, water is dissolved into 14.4 milliliters of maceration extract a; Take by weighing the 1.0g glycerine, water is dissolved into 14.4 milliliters of maceration extract b; At first flood this alumina support with maceration extract a, afterwards 120 ℃ of lower 4h, 300 ℃ of roasting 4h in Muffle furnace that continue of drying by the fire in baking oven; After being down to room temperature, with maceration extract b dipping, 150 ℃ of dry 4h in baking oven obtain catalyst C1 afterwards again.The mol ratio of cobalt oxide content and glycerine and cobalt is listed in the table 1 among the catalyst C1.
Embodiment 2
Take by weighing the Al of 20g
2O
3Carrier.Take by weighing the cobalt nitrate of 18.7g, water is dissolved into 14.4 milliliters of maceration extract a; Take by weighing the 5.9g glycerine, water is dissolved into 14.4 milliliters of maceration extract b; At first flood this alumina support with maceration extract a, afterwards 120 ℃ of lower 4h, 250 ℃ of roasting 4h in Muffle furnace that continue of drying by the fire in baking oven; After being down to room temperature, again with maceration extract b dipping, afterwards in baking oven respectively at 150 ℃ of roasting 4h, obtain catalyst C2.The mol ratio of cobalt oxide content and glycerine and cobalt is listed in the table 1 among the catalyst C2.
Embodiment 3
Take by weighing the Al of 20g
2O
3Carrier.Take by weighing the cobalt nitrate of 18.7g, water is dissolved into 14.4 milliliters of maceration extract a; Take by weighing 7.0g ethylene glycol, water is dissolved into 14.4 milliliters of maceration extract b; At first flood this alumina support with maceration extract a, afterwards 120 ℃ of lower 4h, 230 ℃ of roasting 4h in Muffle furnace that continue of drying by the fire in baking oven; After being down to room temperature, again with maceration extract b dipping, 120 ℃ of lower dry 8h in baking oven obtain catalyst C3 afterwards.The mol ratio of cobalt oxide content and ethylene glycol and cobalt is listed in the table 1 among the catalyst C3.
Embodiment 4
Take by weighing the Al of 20g
2O
3Carrier.Take by weighing respectively cobalt nitrate and the 6.3g citric acid of 23.0g, water is dissolved into 14.4 milliliters of maceration extracts, floods this alumina support with this maceration extract, and 160 ℃ of roasting 6h in baking oven obtain catalyst C4 afterwards.The mol ratio of cobalt oxide content and ethylene glycol and cobalt is listed in the table 1 among the catalyst C4.
Embodiment 5
Take by weighing the Al of 20g
2O
3Carrier.Take by weighing cobalt nitrate and the 0.060g ruthenic chloride of 18.7g, water is dissolved into 14.4 milliliters of maceration extract a; Take by weighing 4.0g ethylene glycol, water is dissolved into 14.4 milliliters of maceration extract b; At first flood this alumina support with maceration extract a, afterwards 120 ℃ of lower 4h, 210 ℃ of roasting 4h in Muffle furnace that continue of drying by the fire in baking oven; After being down to room temperature, again with maceration extract b dipping, in the inherent 160 ℃ of roasting 4h of baking oven, obtain catalyst C5 afterwards.The mol ratio of cobalt oxide content and ethylene glycol and cobalt is listed in the table 1 among the catalyst C5.
Embodiment 6
Take by weighing the gamma-aluminium oxide carrier of 40g, take by weighing 4.0g ethylene glycol, add water and become 28.8 milliliters of maceration extract a; Flood this alumina support with half of maceration extract a, afterwards 120 ℃ of lower baking 3h in baking oven.After being down to room temperature, half of getting wherein carried out the water absorption rate test, and water absorption rate is about 0.60.Cobalt nitrate and the 0.060g ruthenic chloride of 18.7g got in weighing, and water is dissolved into 13.0 milliliters of maceration extract ε, floods remaining carrier with maceration extract ε, descends dry 4h at 140 ℃ afterwards in baking oven.Take by weighing 4.0g ethylene glycol, water is dissolved into 14.4 milliliters of maceration extract c; Flood this sample with maceration extract c, then, at 160 ℃ of dry 4h, obtain catalyst C6.The mol ratio of cobalt oxide content and ethylene glycol and cobalt is listed in the table 1 among the catalyst C6.
Embodiment 7
Take by weighing the Al of 20g
2O
3Carrier.Take by weighing cobalt nitrate and the 0.060g ruthenic chloride of 18.7g, water is dissolved into 14.4 milliliters of maceration extract a; Take by weighing the 3.5g malic acid, water is dissolved into 14.4 milliliters of maceration extract b; At first flood this alumina support with maceration extract a, afterwards 120 ℃ of lower 4h, 280 ℃ of roasting 4h in Muffle furnace that continue of drying by the fire in baking oven; After being down to room temperature, again with maceration extract b dipping, afterwards in baking oven respectively at 120 ℃ of lower dry 4h, at 140 ℃ of roasting 4h.Obtain catalyst C7, its composition is listed in the table 1.
Embodiment 8
Take by weighing the Al of 20g
2O
3Carrier.Take by weighing cobalt nitrate and the 0.060g ruthenic chloride of 18.7g, water is dissolved into 14.4 milliliters of maceration extract a; Take by weighing the 10.3g maleic acid, water is dissolved into 14.4 milliliters of maceration extract b; At first flood this alumina support with maceration extract a, afterwards 120 ℃ of lower 4h, 240 ℃ of roasting 4h in Muffle furnace that continue of drying by the fire in baking oven; After being down to room temperature, again with maceration extract b dipping, afterwards in baking oven respectively at 120 ℃ of lower dry 4h, at 150 ℃ of roasting 4h.Obtain catalyst C8, its composition is listed in the table 1.
Catalyst performance evaluation:
Evaluation response carries out in fixed bed reactors, and catalyst is 40-60 order particle, consumption 2.5ml.
Catalyst reduces under the nitrogen atmosphere that flows and activates, and reduction and activation condition comprise: reduction temperature is 400 ℃, and pressure is 0.2MPa, and hydrogen space-time speed is 1000Nl/g/h, and the recovery time is 4h.
The Fischer-Tropsch synthesis condition comprises: temperature is 210 ℃, and pressure is 2.0MPa, and the mol ratio of hydrogen and carbon monoxide is generally 2.0 in the synthesis gas, and the space-time speed of forming gas is 500Nl/g/h.
Each evaluating catalyst the results are shown in table 1.
The FT of table 1 catalyst synthesizes results of property
* the molar ratio of organic matter and reactive metal feeds intake as calculating according to actual.
The result who is provided by table 1 can show, compares with reference catalyst, is obviously improved by the performance that the invention provides the catalyst agent.
Claims (48)
1. fischer-tropsch synthetic catalyst, contain carrier, active metal component and organic matter I, wherein, described active metal component chosen from Fe and/or cobalt, take catalyst as benchmark, take the content of the described active metal component of oxide as the 2-50 % by weight, the mol ratio of described organic matter I and described active metal component is 0.01-5.
2. according to 1 described catalyst, it is characterized in that take catalyst as benchmark, take the content of the described active metal component of oxide as the 5-40 % by weight, the mol ratio of described organic matter I and described active metal component is 0.02-3.
3. according to 2 described catalyst, it is characterized in that take catalyst as benchmark, take the content of the described active metal component of oxide as the 10-30 % by weight, the mol ratio of described organic matter I and described active metal component is 0.1-2.
4. according to 1,2 or 3 each described catalyst, it is characterized in that described organic matter I is selected from water-soluble one or more that contain in oxygen and/or the organic compounds containing nitrogen.
5. according to 4 described catalyst, it is characterized in that described water-soluble oxygen-containing organic compound is selected from one or more in Organic Alcohol and the organic acid; Described water-soluble organic compounds containing nitrogen is selected from one or more in the organic amine.
6. according to 1 described catalyst, it is characterized in that described carrier is selected from one or more in aluminium oxide, silica-alumina, alumina silicate or the silica.
7. according to 6 described catalyst, it is characterized in that described alumina catalyst support.
8. according to 7 described catalyst, it is characterized in that, described aluminium oxide be selected from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.
9. according to 1 described catalyst, it is characterized in that also contain one or more adjuvant components that are selected among La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and the Pd, in element and take catalyst as benchmark, the content of described auxiliary agent is no more than 25 % by weight.
10. according to 9 described catalyst, it is characterized in that in element and take catalyst as benchmark, the content of described adjuvant component is the 0.01-10 % by weight.
11. the preparation method of a fischer-tropsch synthetic catalyst comprises: (1) preparation contains the hybrid infusion solution of chosen from Fe and/or cobalt compound and organic matter I, and uses this solution impregnating carrier; (2) impregnation product that obtains of drying steps (1); Wherein, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 2-50 % by weight, and the mol ratio of described organic matter I and described active metal component is 0.01-5.
12. according to 11 described methods, it is characterized in that, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 5-40 % by weight, and the mol ratio of described organic matter I and described active metal component is 0.02-3.
13. according to 12 described methods, it is characterized in that, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 10-30 % by weight, and the mol ratio of described organic matter I and described active metal component is 0.1-2.
14., it is characterized in that described organic matter I is selected from water-soluble one or more that contain in oxygen and/or the organic compounds containing nitrogen according to 11,12 or 13 each described methods; Described drying condition comprises: temperature is 80-300 ℃, and be 0.5-72 hour drying time.
15., it is characterized in that described water-soluble oxygen-containing organic compound is selected from one or more in Organic Alcohol and the organic acid according to 14 described methods; Described water-soluble organic compounds containing nitrogen is selected from one or more in the organic amine; Described drying condition comprises: temperature is 100-250 ℃, and be 1-12 hour drying time.
16., it is characterized in that described carrier is selected from one or more in aluminium oxide, silica-alumina, alumina silicate or the silica according to 11 described methods.
17., it is characterized in that described alumina catalyst support according to 16 described methods.
18. according to 17 described methods, it is characterized in that, described aluminium oxide be selected from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.
19. according to 11 described methods, it is characterized in that, also comprise in carrier and introduce the step that is selected from one or more adjuvant components among La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and the Pd, in element and take catalyst as benchmark, the introducing amount of described adjuvant component is no more than 25 % by weight.
20., it is characterized in that in element and take catalyst as benchmark, the introducing amount of described adjuvant component is the 0.01-10 % by weight according to 19 described methods.
21. the preparation method of a fischer-tropsch synthetic catalyst comprises: (1) preparation contains the dipping solution of chosen from Fe and/or cobalt compound, and uses this solution impregnating carrier; (2) dry, roasting or the not impregnation product that obtains of calcination steps (1); (3) preparation contains the maceration extract of organic matter I, and the product that obtains with this solution impregnation step (2); (4) impregnation product that obtains of drying steps (3); Wherein, the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 2-50 % by weight; The dipping of described step (3) makes that the mol ratio of organic matter I and described active metal component is 0.01-5 in the final catalyst.
22., it is characterized in that the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 5-40 % by weight according to 21 described methods; The dipping of described step (3) makes that the mol ratio of organic matter I and described active metal component is 0.02-3 in the final catalyst.
23., it is characterized in that the dipping of described step (1) makes in the final catalyst content take the described active metal component of oxide as the 10-30 % by weight according to 22 described methods; The dipping of described step (3) makes that the mol ratio of organic matter I and described active metal component is 0.1-2 in the final catalyst.
24., it is characterized in that described organic matter I is selected from water-soluble one or more that contain in oxygen and/or the organic compounds containing nitrogen according to 21,22 or 23 described methods; The dipping of described step (3) makes that the mol ratio of organic matter I and described active metal component is 0.1-2 in the final catalyst; Described drying condition comprises: temperature is 80-300 ℃, and be 0.5-72 hour drying time; Described roasting condition comprises: temperature is 120-600 ℃, and the time is 1-8 hour.
25., it is characterized in that described water-soluble oxygen-containing organic compound is selected from one or more in Organic Alcohol and the organic acid according to 24 described methods; Described water-soluble organic compounds containing nitrogen is selected from one or more in the organic amine; Described drying condition comprises: temperature is 100-250 ℃, and be 1-12 hour drying time; Described roasting condition comprises: temperature is 150-450 ℃, and the time is 2-6 hour.
26., it is characterized in that described carrier is selected from one or more in aluminium oxide, silica-alumina, alumina silicate or the silica according to 21 described methods.
27., it is characterized in that described alumina catalyst support according to 26 described methods.
28. according to 27 described methods, it is characterized in that, described aluminium oxide be selected from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.
29. according to 21 described methods, it is characterized in that, also comprise in carrier and introduce the step that is selected from one or more adjuvant components among La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and the Pd, in element and take catalyst as benchmark, the introducing amount of described adjuvant component is no more than 25 % by weight.
30., it is characterized in that in element and take catalyst as benchmark, the introducing amount of described adjuvant component is the 0.01-10 % by weight according to 29 described methods.
31. the preparation method of a fischer-tropsch synthetic catalyst, comprise: (1) uses the liquid infiltration carrier that is selected from the liquid of organic matter II or contains organic matter II, by volume and take the water absorption rate ω of described carrier as benchmark, described dipping makes the hold-up σ of liquid described in the carrier of Unit Weight be no more than 50% of ω; (2) preparation contains the dipping solution ε of chosen from Fe and/or cobalt compound, and use this solution impregnating carrier, described dipping so that finally in the catalyst take the content of the described active metal component of oxide as the 2-50 % by weight; (3) impregnation product that obtains of dry and calcination steps (2); (4) preparation contains the maceration extract of organic matter I, and the product that obtains with this solution impregnation step (3), and described dipping makes that the mol ratio of organic matter I and described active metal component is 0.01-5 in the final catalyst; (5) impregnation product that obtains of drying steps (4).
32., it is characterized in that it is the 2-30% of ω that the dipping of described step (1) makes the hold-up σ of liquid described in the carrier of Unit Weight according to 31 described methods.
33., it is characterized in that it is the 5-20% of ω that the dipping of described step (1) makes the hold-up σ of liquid described in the carrier of Unit Weight according to 32 described methods.
34., it is characterized in that the amount of described step (2) preparation maceration extract ε is that (ω-σ), n is the consumption of described carrier by weight to n according to 31 described methods.
35., it is characterized in that the described liquid that contains organic matter II is the aqueous solution of organic matter II according to 31 described methods.
36., it is characterized in that described organic matter II is selected from one or more in hydrocarbon, alcohol, organic acid or the organic amine according to 31 or 35 described methods.
37., it is characterized in that described organic matter II is selected from one or more in alcohol, organic acid or the organic amine according to 36 described methods.
38., it is characterized in that described organic matter II is selected from one or more compounds in alcohol, acid or the organic amine of being selected from that boiling point is higher than water according to 37 described methods.
39., it is characterized in that the dipping of described step (2) makes in the final catalyst content take the described active metal component of oxide as the 5-40 % by weight according to 31 described methods; The dipping of described step (4) makes that the mol ratio of organic matter I and described active metal component is 0.02-3 in the final catalyst.
40., it is characterized in that the dipping of described step (2) makes in the final catalyst content take the described active metal component of oxide as the 10-30 % by weight according to 39 described methods; The dipping of described step (4) makes that the mol ratio of organic matter I and described active metal component is 0.1-2 in the final catalyst.
41., it is characterized in that described organic matter I is selected from water-soluble one or more that contain in oxygen and/or the organic compounds containing nitrogen according to 31,39 or 40 described methods; The dipping of described step (4) makes that the mol ratio of organic matter I and described active metal component is 0.1-2 in the final catalyst; Described drying condition comprises: temperature is 80-300 ℃, and be 0.5-72 hour drying time; Described roasting condition comprises: temperature is 120-600 ℃, and the time is 1-8 hour.
42., it is characterized in that described water-soluble oxygen-containing organic compound is selected from one or more in Organic Alcohol and the organic acid according to 41 described methods; Described water-soluble organic compounds containing nitrogen is selected from one or more in the organic amine; Described drying condition comprises: temperature is 100-250 ℃, and be 1-12 hour drying time; Described roasting condition comprises: temperature is 150-450 ℃, and the time is 2-6 hour.
43., it is characterized in that described carrier is selected from one or more in aluminium oxide, silica-alumina, alumina silicate or the silica according to 31 described methods.
44., it is characterized in that described alumina catalyst support according to 43 described methods.
45. according to 44 described methods, it is characterized in that, described aluminium oxide be selected from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.
46. according to 31 described methods, it is characterized in that, also comprise in carrier and introduce the step that is selected from one or more adjuvant components among La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and the Pd, in element and take catalyst as benchmark, the introducing amount of described adjuvant component is no more than 25 % by weight.
47., it is characterized in that in element and take catalyst as benchmark, the introducing amount of described adjuvant component is the 0.01-10 % by weight according to 46 described methods.
48. a Fischer-Tropsch synthesis method is included under the Fischer-Tropsch synthesis condition, will contain hydrogen and contact with catalyst with CO gas, wherein, described catalyst is the described catalyst of 1-10 any one claim.
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