CN102441402B - Fischer-Tropsch synthesis catalyst and application thereof - Google Patents
Fischer-Tropsch synthesis catalyst and application thereof Download PDFInfo
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Abstract
A Fischer-Tropsch synthesis catalyst and application thereof. The catalyst contains a carrier, an active metal component loaded on the carrier and selected from iron and / or cobalt and an auxiliary agent metal component selected from one or a plurality of precious metals, wherein the auxiliary agent metal component accounts for 0.01-0.3 wt%, calculated by element and using the catalyst as a reference. The preparation method of the catalyst comprises steps of: (1) carrying out a dipping reaction on a solution containing iron compound and / or cobalt compound and the carrier; (2) drying and roasting products obtained from the step (1); (3) carrying out a dipping reaction on a solution containing at last one precious metal compound and the products obtained from the step (2); (4) drying and roasting products obtained from the step (3); and the solution in the step (3) contains alkali, and a molar ratio of the alkali and the precious metals is 20-200. Compared with a prior art, the catalyst provided by the invention has improved Fischer-Tropsch synthesis performance.
Description
Invention field
The present invention relates to a kind of fischer-tropsch synthetic catalyst and application thereof.
Background technology
Coal and oil are the main energy sources that current mankind is used, and are difficult to change within the quite long period of history.The Fischer-Tropsch synthetic technology is risen in people to the research of colliery engineering, and its core is that the Raw material processings such as coal, natural gas or living beings (cellulose, hemicellulose, lignin) are made synthesis gas (comprises H
2And CO), then through the catalytic action of catalyst synthesis gas is changed into liquid hydrocarbon product.The fuel product that this technology is produced does not contain S, N, aromatic hydrocarbons etc., can effectively reduce atmosphere pollution, satisfies people's requirement day by day harsh to environmental protection.At first the Fischer-Tropsch synthetic technology realizes industrialization in the Germany of 1930s, and various countries begin to set up artificial oil factory subsequently.
The carrier of fischer-tropsch synthetic catalyst is with Al
2O
3, SiO
2, TiO
2, ZrO
2Deng being main, Al
2O
3Good with its wearability, the advantage that mechanical strength is high and extensive use.The common active metal component that is used for the FT synthetic catalyst is mainly Fe and/or Co.For making up the deficiency of single-activity metal, often introduce other metals as auxiliary agent in the catalyst preparation, thus life-extending, gain in strength, carry high activity and stability.
Studies show that: precious metal additive is to the activity of FT reaction and selectively having a great impact of liquid hydrocarbon.Goodwin etc. (Catal.125 (1996) 160) have studied the performance impact of auxiliary agent Ru to the alumina load cobalt-base catalyst, and Ru adds reduction degree and the CO conversion ratio that has increased reactive metal.(Catal., 2001,199 (2): 236～264) studied Pt, Pd, Ru to Co/SiO such as Tsubaki
2The impact of catalyst performance finds that its active order is: RuCo＞PdCo＞PtCo＞Co.(the AppliedCatalysis A:General such as Jacobs, 2009,361:137～151) studied Ag, the Au auxiliary agent effect to cobalt-based alumina load catalyst, find to increase adding of a small amount of Au, Ag the density of Co metal surface active sites, catalyst activity significantly improves, and methane selectively has small size decline.In addition, the patent US 4585798 of the patent US 5939350 of part foreign patent such as Sasol company and Shell company also discloses the positive impact of precious metal additive Ru to FT synthetic catalyst performance.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, a kind of new, active better fischer-tropsch synthetic catalyst is provided and adopts this catalyst to carry out the synthetic method of Fischer-Tropsch.
The invention provides a kind of fischer-tropsch synthetic catalyst, the promoter metal component that this catalyst contains carrier and loads on chosen from Fe and/or the cobalt active metal component on this carrier and be selected from noble metal one or more, in element and take described catalyst as benchmark, the content of described promoter metal component is 0.01 % by weight-0.3 % by weight; The preparation method of described catalyst comprises:
(1) iron containing compounds and/or cobalt compound solution and carrier are carried out impregnation;
(2) product that obtains of dry and calcination steps (1);
(3) will contain the solution of at least a compound that is selected from noble metal and the product that step (2) obtains and carry out impregnation;
(4) product that obtains of dry and calcination steps (3);
Wherein, the solution of described step (3) contains alkali, and the mol ratio of described alkali and noble metal is 20～200.
The present invention further provides a kind of Fischer-Tropsch synthesis method, be included under the Fischer-Tropsch synthesis condition mixture and the catalyst haptoreaction of carbon monoxide and hydrogen, it is characterized in that, described catalyst is aforementioned catalyst provided by the invention.
Compared with prior art, the synthetic performance of Fischer-Tropsch that the invention provides catalyst obtains modification, and particularly when promoter metal content is relatively low, the performance that the invention provides catalyst obviously is better than the catalyst according to the conventional method preparation.
The specific embodiment
According to catalyst provided by the invention, wherein, described noble metal comprises the noble metal that is selected from VIII family and IB, for example, be selected from noble ruthenium, rhodium, palladium, osmium, iridium, the platinum of VIII family, be selected from noble silver, the gold of IB family, preferred noble metal is one or more in ruthenium, platinum and gold.In element and take described catalyst as benchmark, the content of described promoter metal component is 0.01 % by weight-0.3 % by weight, is preferably 0.02 % by weight-0.15 % by weight.
According to catalyst provided by the invention, in the preparation method of described catalyst, the alkali in the solution of described step (3) and the mol ratio of noble metal are 20-200, are preferably 60-120.
Described alkali is selected from the compound of react acid in the aqueous solution arbitrarily, for example, can be one or more the mixture in ammoniacal liquor, urea, potassium hydroxide, sodium carbonate and monoethanolamine, preferred urea and/or ammoniacal liquor wherein.
Impregnation in described step (1) and step (3) can adopt dipping method and condition habitual in prior art, and to this, the present invention is not particularly limited.And in step (1) or step (3), contain the concentration of described purpose component composition and the consumption of solution by controlling in maceration extract, the active metal component of content and the catalyst of promoter metal component are specified in preparation, be easily to realize to those skilled in the art, do not give unnecessary details here.
In a concrete embodiment, the preferred impregnation condition of described step (3) comprises: the impregnation temperature is 20 ℃-90 ℃, is preferably 60 ℃-80 ℃, and the time is 0.5 hour-72 hours, is preferably 2 hours-48 hours.
When described alkali is selected from potassium hydroxide, sodium carbonate etc. and contains through the inexpungible component of roasting, also comprise afterwards the step that adopts the conventional process washing in described step (3), to remove this component.
Drying in described step (2) or step (4) and the method for roasting and condition are the synthetic habitual drying of preparation Fischer-Tropsch and method and the condition of roasting.For example, adopt the method for heat drying, when adopting heating means dry, the condition of described drying comprises: baking temperature is 100 ℃-300 ℃, and preferred 110 ℃-150 ℃, be 0.5 hour-48 hours drying time, preferred 2 hours-12 hours.The condition of described roasting comprises: sintering temperature is 150 ℃-800 ℃, and preferred 300 ℃-600 ℃, roasting time is 0.5 hour-48 hours, preferred 2 hours-12 hours.
According to catalyst provided by the invention, wherein, the content of described chosen from Fe and/or cobalt active metal component is customary amount, in oxide and take catalyst as benchmark, the content of preferred active metal component is 5～70 % by weight, more preferably 10～50 % by weight, more be preferably 12～30 % by weight.
Under the prerequisite that is enough to described active metal component is carried on described carrier, the present invention is not particularly limited the method that described active metal component is carried on described carrier.For example, can be enough to effective dose active metal component be deposited under condition on described carrier, the solution of described carrier with the compound of the active metal component that contains that contains effective dose is contacted, as passing through the methods such as dipping, co-precipitation, preferred infusion process is carried out drying, roasting afterwards.The condition of described drying for the habitual condition of this type of catalyst of preparation, is 80～350 ℃ as baking temperature, is preferably 100～300 ℃, and be 1～24 hour drying time, is preferably 2～12 hours.When described catalyst need to carry out roasting, described temperature was preferably 100-700 ℃, and roasting time is 1～6 hour, and further preferred temperature is preferably 200-500 ℃, and roasting time is 2～4 hours.
One or more in described their soluble compound of compound that contains active metal component, as contain water-soluble salt of active metal component, one or more in complex compound.
Described carrier can be selected from silica, aluminium oxide, titanium oxide, zirconia, zinc oxide, magnesia, and one or more in their modifier, or their mixture.Preferential oxidation silicon, aluminium oxide, further preferential oxidation aluminium, for example gama-alumina.
According to catalyst provided by the invention, optionally can be made into the article shaped of convenient operation arbitrarily, as microballoon, compressing tablet and bar shaped, become the carrier that preparation the invention provides catalyst after article shaped drying, roasting.Described moulding can be carried out according to a conventional method, as all can by methods such as spray-drying (preparing microsphere supported), compressing tablet, spin, extrusions.For slurry attitude bed, the particle diameter of described microspherical catalyst is preferably 20 microns-150 microns, more preferably 30 microns-80 microns when described catalyst.Wherein, the evaluation particle diameter of described carrier adopts ISO 13320-1 grain size analysis one laser diffraction method to measure.The temperature of described drying can be 100-200 ℃, is preferably 120-150 ℃; Sintering temperature is 350-950 ℃, is preferably 450-900 ℃, and roasting time is 1-12 hour, is preferably 2-8 hour.
Being selected from one or more adjuvant components in Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Zr, Ti, REO, Re, Hf, Ce, Mn, V, is the adjuvant component that is usually used in fischer-tropsch synthetic catalyst known in the art.According to catalyst of the present invention, optionally optionally contain one or more that are selected from above-mentioned adjuvant component.In oxide and take catalyst as benchmark, the content of described adjuvant component preferably below 30 % by weight, more preferably below 20 % by weight, more is preferably below 15 % by weight.
When also containing one or more adjuvant components that are selected from Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Zr, Ti, REO, Re, Hf, Ce, Mn, V in described catalyst, also be included in the step that catalyst is introduced described adjuvant component in the preparation method of described catalyst.According to the conventional method of preparation fischer-tropsch synthetic catalyst, described adjuvant component can be introduced in the process of preparation carrier, also can be before the carried metal component, introduce afterwards or simultaneously.For example, directly adjuvant component or the compound that contains adjuvant component are mixed with carrier to be formed and/or precursor when extruded moulding, afterwards extruded moulding again.Or with the solution that contains described adjuvant component compound before the carried metal component, afterwards or simultaneously the method for dipping is introduced.
In a concrete embodiment, described carrier is a kind of aluminium oxide by comprising one or more promoter metal component modifications that are selected from zinc, cobalt and nickel, in oxide and take described carrier as benchmark, the described content that is selected from one or more the promoter metal components in zinc, cobalt and nickel is 0.5 % by weight-15 % by weight; The preparation method of described modified aluminas comprises:
(1) preparation contains alkali and contains one or more the aqueous solution in the compound that is selected from zinc, cobalt or nickel;
(2) the solution impregnation aluminium oxide for preparing with step (1);
(3) will the dry and roasting through the aluminium oxide of step (2) dipping.
Wherein, the alkali in the preparation method's of described modified aluminas step (1) is selected from one or more in ammonia, ammoniacal liquor and organic amine, and the consumption of described alkali makes the pH value of described solution be 7.5-14, is preferably 8.5-13, more preferably 9-12.5.Described roasting condition comprises: sintering temperature is 500-900 ℃, is preferably 550-850 ℃, and more preferably 600-800 ℃, roasting time is 0.5 hour-8 hours, is preferably 1 hour-6 hours, more preferably 2 hours-4 hours.
According to the invention provides catalyst, need to be under hydrogen exist before being used for Fischer-Tropsch synthesis, the cobalt of oxidation state is carried out reduction activation, reducing condition is: reduction temperature is 100 ℃ to 800 ℃, be 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 carry out in the gaseous mixture of hydrogen and inert gas, 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 FT synthetic 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
The present invention will be further described for the following examples, and still, therefore the present invention is not restricted.
Embodiment 1:
(1) catalyst preparation
Take 20 gram γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size is 40～80 microns), 24.6 gram cabaltous nitrate hexahydrates are dissolved in 10 ml deionized water, make maceration extract, with the aforesaid alumina support of this solution impregnation, after standing 2 hours, 120 ℃ of dryings are 4 hours in baking oven, be placed on afterwards in tube furnace, obtained sample A1 in 4 hours in 450 ℃ of roastings.
Successively with HAuCl
44H
2O (containing golden percetage by weight greater than 47.8%) 0.02 gram, urea 0.17 gram is water-soluble, makes 250 ml water solution (mol ratio of urea and the gold atom ratio of 60: 1), and 20 gram A1 are mixed with this solution, be warming up to 80 ℃, under agitation impregnation is 4 hours.Afterwards, wash with dope filtration and with deionized water and detect without chlorion to filtrate that (filtrate is with the liquor argenti nitratis ophthalmicus titration of 0.1mol/L, without turbid phenomenon, lower same), filter cake after 2 hours, at 350 ℃ of roasting 3h of tube furnace, makes catalyst C1 in 120 ℃ of dryings of baking oven.In catalyst C1, the content of Co is that the content of 20%, Au is 0.05% (in catalyst, the content of metal component is calculated value, and is lower same).
(2) catalyst is used and performance
Evaluating catalyst carries out in autoclave, takes catalyst 5 grams, with catalyst under pure hydrogen atmosphere 400 ℃ the reduction 5 hours, heating rate is 6.0 ℃/min, hydrogen gas space velocity be 15 the mark liter/gram-catalyst/hour, then catalyst is transferred in the autoclave that fills 250 gram medium waxes, begin to be warming up to 110 ℃ after airtight having checked, and begin to stir, continue to be warming up to 160 ℃, afterwards, pass into synthesis gas, controlled pressure is 2.5MPa, and synthesis gas composition is: H
2: CO: N
2=56: 28: 16, the synthesis gas air speed was 5 mark liter/gram-catalyst/hour (NL/g-cat/h), continues to be warming up to 220 ℃, at 220 ℃ of stable reaction 48h, utilized online gas-chromatography to carry out the tail gas composition analysis.Evaluation result sees Table 1, wherein, and X
COBe illustrated in the molar ratio of CO inversion quantity and CO air inflow under above-mentioned FT synthetic reaction condition, S
C5+Being illustrated under above-mentioned FT synthetic reaction condition and generating carbon number is that the ratio that the CO of the hydro carbons 5 or more accounts for the CO inversion quantity is listed as, S
CH4+The CO that expression is converted into methane accounts for the ratio of CO inversion quantity.
Embodiment 2:
(1) catalyst preparation
Take 20 gram γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size is 40～80 microns), take again the 24.6g cabaltous nitrate hexahydrate and be dissolved in 10 ml deionized water, make maceration extract, with the aforesaid alumina support of this solution impregnation, after standing 2h, 120 ℃ of dry 4h in baking oven, be placed on afterwards in tube furnace, obtained sample A1 in 4 hours in 450 ℃ of roastings.
Successively with HAuCl
44H
2O (containing golden percetage by weight greater than 47.8%) 0.04 gram, urea 0.70 gram is water-soluble, makes 250 ml water solution (mol ratio of urea and the gold atom ratio of 120: 1), and 20 gram A1 are mixed with this solution, be warming up to 80 ℃, under agitation impregnation is 4 hours.Afterwards, wash to filtrate with dope filtration and with deionized water and detect without chlorion, filter cake after 3 hours, at 350 ℃ of roasting 3h of tube furnace, makes catalyst C2 in 120 ℃ of dryings of baking oven.In catalyst C2, the content of Co is that the content of 20%, Au is 0.1%.
(2) catalyst is used and performance
According to the method identical with embodiment 1 and condition evaluating catalyst C2, evaluation result sees Table 1.
Embodiment 3:
(1) catalyst preparation
Take 20 gram γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size is 40～80 microns), take again the 24.6g cabaltous nitrate hexahydrate and be dissolved in the 10ml deionized water, make maceration extract, with the aforesaid alumina support of this solution impregnation, after standing 2h, 120 ℃ of dry 4h in baking oven, be placed on afterwards in tube furnace, obtained sample A1 in 4 hours in 450 ℃ of roastings.
Take 0.94g platinum chloride ammonia solution (concentration is 1.07gPt/100g solution), be settled to the 250ml aqueous solution, the ammoniacal liquor that dropwise adds 0.5mol/L is 6mL (mol ratio of ammoniacal liquor and pt atom is 60: 1) approximately.20g A1 is mixed with this solution, and under agitation impregnation is 4 hours.Afterwards, wash to filtrate with dope filtration and with deionized water and detect without chlorion, filter cake at 350 ℃ of roasting 3h of tube furnace, makes catalyst C3 after 120 ℃ of dry 2h of baking oven.In catalyst C3, the content of Co is that the content of 20%, Pt is 0.05%.
(2) catalyst is used and performance
According to the method identical with embodiment 1 and condition evaluating catalyst C3, evaluation result sees Table 1.
Embodiment 4:
(1) catalyst preparation
Take 20 gram γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size is 40～80 microns), take again the 24.6g cabaltous nitrate hexahydrate and be dissolved in the 10ml deionized water, make maceration extract, with the aforesaid alumina support of this solution impregnation, after standing 2h, 120 ℃ of dry 4h in baking oven, be placed on afterwards in tube furnace, obtained sample A1 in 4 hours in 450 ℃ of roastings.
Take 1.87g platinum chloride ammonia solution (concentration is 1.07gPt/100g solution), be settled to the 250ml aqueous solution, dropwise add the ammoniacal liquor 12mL (mol ratio of ammoniacal liquor and pt atom is 60: 1) of 0.5mol/L.20g A1 is mixed with this solution, and under agitation impregnation is 4 hours.Afterwards, wash to filtrate with dope filtration and with deionized water and detect without chlorion, filter cake at 350 ℃ of roasting 3h of tube furnace, makes catalyst C4 after 120 ℃ of dry 2h of baking oven.In catalyst C4, the content of Co is that the content of 20%, Pt is 0.1%.
(2) catalyst is used and performance
According to the method identical with embodiment 1 and condition evaluating catalyst C4, evaluation result sees Table 1.
Embodiment 5:
(1) catalyst preparation
Take 20 gram γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size is 40～80 microns), take again the 24.6g cabaltous nitrate hexahydrate and be dissolved in the 10ml deionized water, make maceration extract, with the aforesaid alumina support of this solution impregnation, after standing 2h, 120 ℃ of dry 4h in baking oven, be placed on afterwards in tube furnace, obtained sample A1 in 4 hours in 450 ℃ of roastings.
Take 0.027g hydrate ruthenium trichloride (ruthenium content is greater than 37.3%), be settled to the 250ml aqueous solution, dropwise add the ammonia spirit 12ml (mol ratio of ammoniacal liquor and ruthenium atom is 60: 1) of 0.5mol/L.20g A1 is mixed with this solution, and under agitation impregnation is 4 hours.Afterwards, wash to filtrate with dope filtration and with deionized water and detect without chlorion, filter cake at 350 ℃ of roasting 3h of tube furnace, makes catalyst C5 after 120 ℃ of dry 2h of baking oven.In catalyst C5, the content of Co is that the content of 20%, Ru is 0.05%.
(2) catalyst is used and performance
According to the method identical with embodiment 1 and condition evaluating catalyst C5, evaluation result sees Table 1.
Embodiment 6
(1) modified aluminas and preparation thereof
75 milliliters of concentrated ammonia liquors (mass fraction 25%) are added in 75 ml deionized water, and add 23.44 gram zinc nitrate hexahydrates dissolvings to obtain alkaline Zn solution, pH approximately 12.100 gram gama-aluminas (sasol alumina powder, 55 microns of average grain diameters) are added mentioned solution, stir lower the placement 6 hours.After suction filtration, filter cake is put into 140 ℃ of baking oven inner dryings after 6 hours, put into 800 ℃ of Muffle furnace roastings 4 hours.Obtain thus the alumina support that Zn content is 2.27% (calculated value).
(2) catalyst preparation
Take the 24.6g cabaltous nitrate hexahydrate and be dissolved in the 10ml deionized water, make maceration extract, with the 20g alumina support after the aforementioned roasting of this solution impregnation, after standing 2h, 120 ℃ of dry 4h in baking oven are placed in tube furnace afterwards, obtain sample A2 in 4 hours in 450 ℃ of roastings.
Take 0.027g hydrate ruthenium trichloride (ruthenium content is greater than 37.3%), be settled to the 250ml aqueous solution, dropwise add the ammonia spirit 12ml (mol ratio of ammoniacal liquor and ruthenium atom is 60: 1) of 0.5mol/L.20g A2 is mixed with this solution, and under agitation impregnation is 4 hours.Afterwards, wash to filtrate with dope filtration and with deionized water and detect without chlorion, filter cake at 350 ℃ of roasting 3h of tube furnace, makes catalyst C6 after 120 ℃ of dry 2h of baking oven.In catalyst C6, the content of Co is that the content of 20%, Ru is 0.05%.
(3) catalyst is used and performance
According to the method identical with embodiment 1 and condition evaluating catalyst C6, evaluation result sees Table 1.
Comparative Examples 1:
(1) catalyst preparation
Carrier adopts γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size is 40～80 μ m), first take this alumina powder of 20g, take again the 24.6g cabaltous nitrate hexahydrate and be dissolved in the 10ml deionized water, make maceration extract, with the aforesaid alumina support of this solution impregnation, after standing 2h, 120 ℃ of dry 4h in baking oven are placed in tube furnace afterwards, obtain reference catalyst BC1 in 4 hours in 450 ℃ of roastings.In catalyst B C1, the content of Co is 20%.
(2) catalyst is used and performance
According to the method identical with embodiment 1 and condition evaluating reference catalyst BC1, evaluation result sees Table 1.
Comparative Examples 2:
(1) catalyst preparation
Carrier adopts γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size are 40～80 μ m) is with 24.6 gram cabaltous nitrate hexahydrates and 0.02 gram HAuCl
44H
2O (containing golden percetage by weight greater than 47.8%) is dissolved in 10 ml deionized water, make maceration extract, with the aforesaid alumina support of this solution impregnation, after standing 2 hours, 120 ℃ of dryings are 4 hours in baking oven, be placed on afterwards in tube furnace, obtained reference catalyst BC2 in 4 hours in 450 ℃ of roastings.In catalyst B C2, the content of Co is that the content of 20%, Au is 0.05%.
(2) catalyst is used and performance
According to the method identical with embodiment 1 and condition evaluating reference catalyst BC2, evaluation result sees Table 1.
Comparative Examples 3:
Take 20 gram γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size are 40～80 microns) is with 24.6 gram cabaltous nitrate hexahydrates and 0.05 gram HAuCl
44H
2O (containing golden percetage by weight greater than 47.8%) is dissolved in 10 ml deionized water, make maceration extract, with the aforesaid alumina support of this solution impregnation, after standing 2 hours, 120 ℃ of dryings are 4 hours in baking oven, be placed on afterwards in tube furnace, obtained reference catalyst BC3 in 4 hours in 450 ℃ of roastings.In catalyst B C3, the content of Co is that the content of 20%, Au is 0.1%.
(2) catalyst is used and performance
According to the method identical with embodiment 1 and condition evaluating reference catalyst BC3, evaluation result sees Table 1.
Table 1
Claims (19)
1. fischer-tropsch synthetic catalyst, the promoter metal component that contains carrier and load on chosen from Fe and/or the cobalt active metal component on this carrier and be selected from noble metal one or more, in element and take described catalyst as benchmark, the content of described promoter metal component is 0.01 % by weight-0.3 % by weight; The preparation method of described catalyst comprises:
(1) iron containing compounds and/or cobalt compound solution and carrier are carried out impregnation;
(2) product that obtains of dry and calcination steps (1);
(3) will contain the solution of at least a compound that is selected from noble metal and the product that step (2) obtains and carry out impregnation;
(4) product that obtains of dry and calcination steps (3);
Wherein, the solution of described step (3) contains alkali, and the mol ratio of described alkali and noble metal is 20～200.
2. catalyst according to claim 1, it is characterized in that, described noble metal is selected from one or more in Ru, Rh, Pd, Os, Ir, Pt, Ag or Au, and in element and take described catalyst as benchmark, the content of described promoter metal component is 0.02 % by weight-0.15 % by weight.
3. catalyst according to claim 2, is characterized in that, described noble metal is selected from one or more in Ru, Pt or Au.
4. catalyst according to claim 1, is characterized in that, the alkali in the solution of described step (3) and the mol ratio of noble metal are 60-120.
5. according to claim 1 or 4 described catalyst, is characterized in that, described alkali is urea and/or ammoniacal liquor.
6. catalyst according to claim 1, is characterized in that, the impregnation condition of described step (3) comprising: the impregnation temperature is 20 ℃-90 ℃, and the time is 0.5 hour-72 hours.
7. catalyst according to claim 6, is characterized in that, the impregnation condition of described step (3) comprising: the impregnation temperature is 50 ℃-80 ℃, and the time is 2 hours-48 hours.
8. catalyst according to claim 1, it is characterized in that, drying condition in described step (2) or step (4) comprises: temperature is 100 ℃-300 ℃, time is 0.5 hour-48 hours, the condition of roasting comprises: temperature is 150 ℃-800 ℃, and the time is 0.5 hour-48 hours.
9. catalyst according to claim 8, it is characterized in that, drying condition in described step (2) or step (4) comprises: temperature is 110 ℃-150 ℃, time is 2 hours-12 hours, the condition of roasting comprises: temperature is 300 ℃-600 ℃, and roasting time is 2 hours-12 hours.
10. catalyst according to claim 1, is characterized in that, described carrier is selected from silica, aluminium oxide, titanium oxide, zirconia, zinc oxide, magnesia, and one or more in their modifier.
11. catalyst according to claim 10 is characterized in that, described carrier is aluminium oxide.
12. according to claim 10 or 11 described catalyst, it is characterized in that, described carrier is a kind of aluminium oxide by comprising one or more promoter metal component modifications that are selected from zinc, cobalt and nickel, in oxide and take described carrier as benchmark, the described content that is selected from one or more the promoter metal components in zinc, cobalt and nickel is 0.5 % by weight-15 % by weight; The preparation method of described modified aluminas comprises:
(1) preparation contains alkali and contains one or more the aqueous solution in the compound that is selected from zinc, cobalt or nickel;
(2) the solution impregnation aluminium oxide for preparing with step (1);
(3) will the dry and roasting through the aluminium oxide of step (2) dipping.
13. catalyst according to claim 12 is characterized in that, the alkali in the preparation method's of described modified aluminas step (1) is selected from one or more in ammonia, ammoniacal liquor and organic amine, and the consumption of described alkali makes the pH value of described solution be 7.5-14.
14. catalyst according to claim 13 is characterized in that, described alkali is selected from ammonia or ammoniacal liquor, and the consumption of described alkali makes the pH value of described solution be 8.5-13.
15. catalyst according to claim 14 is characterized in that, the consumption of described alkali makes the pH value of described solution be 9-12.5.
16. catalyst according to claim 12 is characterized in that, described roasting condition comprises: sintering temperature is 500-900 ℃, and roasting time is 0.5-8.
17. catalyst according to claim 16 is characterized in that, described roasting condition comprises: sintering temperature is 550-850 ℃, and roasting time is 1-6.
18. catalyst according to claim 17 is characterized in that, described roasting condition comprises: sintering temperature is 600-800 ℃, and roasting time is 2-4.
19. a Fischer-Tropsch synthesis method is included under the Fischer-Tropsch synthesis condition mixture and the catalyst haptoreaction of carbon monoxide and hydrogen, it is characterized in that, described catalyst is the described catalyst of aforementioned claim 1-18 any one claim.
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| CN103769085B (en) * | 2012-10-23 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for catalytic combustion |
| CN104549359B (en) * | 2013-10-28 | 2017-06-20 | 中国石油化工股份有限公司 | Production light olefins catalyst, the preparation method and its application method of catalyst |
| CN104549358B (en) * | 2013-10-28 | 2017-03-15 | 中国石油化工股份有限公司 | The catalyst of synthesizing low-carbon alkene, preparation method and its using method |
| CN104549315B (en) * | 2013-10-28 | 2017-10-27 | 中国石油化工股份有限公司 | Preparation of low carbon olefines by synthetic gas catalyst, preparation method and its application method |
| CN104289231B (en) * | 2014-10-09 | 2017-02-08 | 武汉凯迪工程技术研究总院有限公司 | High-dispersity cobalt-based Fischer-Tropsch synthesis catalyst as well as preparation method and application thereof |
| CN106607051B (en) * | 2015-10-21 | 2019-06-11 | 中国石油化工股份有限公司 | The catalyst and preparation method thereof of one step producing light olefins of synthesis gas |
| CN107774259B (en) * | 2016-08-30 | 2020-09-22 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst and application thereof |
| CN107790153B (en) * | 2016-08-30 | 2020-10-27 | 中国石油化工股份有限公司 | Silicon modified Fischer-Tropsch synthesis catalyst and application thereof |
| CN108262044B (en) * | 2016-12-30 | 2021-06-11 | 中国石油化工股份有限公司 | Preparation method of Fischer-Tropsch synthesis catalyst and prepared Fischer-Tropsch synthesis catalyst |
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| CN101134164A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Co-based fischer-tropsch synthesis catalyst and method for preparing the same |
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| CN101134164A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Co-based fischer-tropsch synthesis catalyst and method for preparing the same |
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