CN102441402A - Fischer-Tropsch synthesis catalyst and application thereof - Google Patents
Fischer-Tropsch synthesis catalyst and application thereof Download PDFInfo
- Publication number
- CN102441402A CN102441402A CN2010105036529A CN201010503652A CN102441402A CN 102441402 A CN102441402 A CN 102441402A CN 2010105036529 A CN2010105036529 A CN 2010105036529A CN 201010503652 A CN201010503652 A CN 201010503652A CN 102441402 A CN102441402 A CN 102441402A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hours
- catalyst according
- solution
- roasting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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 in the quite long period of history, are difficult to change.The Fischer-Tropsch synthetic technology is risen in the research of people to colliery engineering, and its core is that coal, natural gas or living beings raw materials such as (cellulose, hemicellulose, lignin) is processed into synthesis gas (comprises H
2And CO), the catalytic action of process catalyst changes into liquid hydrocarbon product with synthesis gas again.The fuel product that this technology is produced does not contain S, N, aromatic hydrocarbons etc., can reduce atmosphere pollution effectively, satisfies people's requirement harsh day by day to environmental protection.The Fischer-Tropsch synthetic technology at first 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 mainly is Fe and/or Co.For remedying the deficiency of single-activity metal, in Preparation of Catalyst, often introduce other metals as auxiliary agent, thereby life-saving is gained in strength raising activity and stable.
Research shows: precious metal additive has very big influence to the selectivity of FT reactive activity and 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 the adding of Ru has increased the reduction degree and the CO conversion ratio of reactive metal.(Catal., 2001,199 (2): 236～264) studied Pt, Pd, Ru such as Tsubaki to Co/SiO
2The influence of catalyst performance finds that its active order is: RuCo＞PdCo＞PtCo＞Co.(AppliedCatalysis A:General such as Jacobs; 2009; 361:137～151) studied Ag, Au auxiliary agent effect to cobalt-based alumina load catalyst; Find that the adding of a small amount of Au, Ag can increase 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 that the present invention will solve 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 present invention provides a kind of fischer-tropsch synthetic catalyst; This catalyst contains carrier and the promoter metal component that loads on chosen from Fe and/or the cobalt active metal component on this carrier and be selected from the noble metal one or more; In element and with said catalyst is benchmark, and said promoter metal components contents is 0.01 weight %-0.3 weight %; Said Preparation of catalysts method comprises:
(1) iron containing compounds and/or cobalt compound solution and carrier are flooded reaction;
(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 flood reaction;
(4) product that obtains of dry and calcination steps (3);
Wherein, the solution of said step (3) contains alkali, and the mol ratio of said alkali and noble metal is 20～200.
The present invention further provides a kind of Fischer-Tropsch synthesis method, is included under the Fischer-Tropsch synthesis condition the mixture and the catalyst haptoreaction of carbon monoxide and hydrogen, it is characterized in that said catalyst is aforementioned catalyst provided by the invention.
Compared with prior art, the present invention provides the synthetic performance of the Fischer-Tropsch of catalyst to obtain modification, and particularly when promoter metal content was relatively low, the present invention provided the performance of catalyst obviously to be superior to 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, the noble metal that is selected from IB family is silver-colored, golden, and preferred noble metal is one or more in ruthenium, platinum and the gold.In element and with said catalyst is benchmark, and said promoter metal components contents is 0.01 weight %-0.3 weight %, is preferably 0.02 weight %-0.15 weight %.
According to catalyst provided by the invention, in said Preparation of catalysts method, the alkali in the solution of said step (3) and the mol ratio of noble metal are 20-200, are preferably 60-120.
Said 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 the monoethanolamine, preferred urea and/or ammoniacal liquor wherein.
Dipping reaction in said step (1) and the step (3) can be adopted dipping method and condition habitual in the prior art, to this, and the not special restriction of the present invention.And in step (1) or step (3); Through containing the concentration of said purpose component composition and the consumption of solution in the control maceration extract; The active metal component of content and the catalyst of promoter metal component are specified in preparation, are to those skilled in the art to realize easily, do not give unnecessary details here.
In a concrete embodiment, said step (3) is preferably flooded reaction condition and comprised: the dipping reaction 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 the step that adopts the conventional process washing afterwards in said step (3), to remove this component.
The drying in said step (2) or the step (4) and the method for roasting and condition are the synthetic habitual drying of preparation Fischer-Tropsch and the method and the condition of roasting.For example, adopt the method for heat drying, when adopting heating means dry, the condition of said 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 said 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 said chosen from Fe and/or cobalt active metal component is customary amount, in oxide and with catalyst be benchmark, the content of preferred active metal component is 5～70 weight %; Further be preferably 10～50 weight %, more be preferably 12～30 weight %.
Described active metal component is carried under the prerequisite on the said carrier being enough to, the present invention is carried on the not special restriction of method on the said carrier to described active metal component.For example; Can be enough to effective dose active metal component be deposited under the condition on the said 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 methods such as dipping, co-precipitation, preferred infusion process is carried out drying, roasting afterwards.The condition of said drying is 80～350 ℃ for the habitual condition of this type of catalyst of preparation like baking temperature, is preferably 100～300 ℃, and be 1～24 hour drying time, is preferably 2～12 hours.When said catalyst need 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.
In said their soluble compound of compound that contains active metal component one or more, as contain water-soluble salt of active metal component, in the complex compound one or more.
Described carrier can be selected from silica, aluminium oxide, titanium oxide, zirconia, zinc oxide, magnesia, and in their modifier one or more, or their mixture.Preferred silica, aluminium oxide, further preferred aluminium oxide, for example gama-alumina.
According to catalyst provided by the invention, optionally can be made into and be convenient to the article shaped of operating arbitrarily, like microballoon, compressing tablet and bar shaped, article shaped becomes the carrier that preparation the present invention provides catalyst after dry, roasting.Said moulding can be undertaken by conventional method, as all can through methods such as spray-drying (preparing microsphere supported), compressing tablet, spin, extrusions.When said catalyst is used to starch the attitude bed, the particle diameter of said microspherical catalyst is preferably 20 microns-150 microns, further is preferably 30 microns-80 microns.Wherein, the evaluation particle diameter of said carrier adopts ISO 13320-1 grain size analysis one laser diffraction method to measure.The temperature of said 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 among Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Zr, Ti, REO, Re, Hf, Ce, Mn, the V, is the adjuvant component that is usually used in fischer-tropsch synthetic catalyst known in the art.According to catalyst according to the invention, optionally can randomly contain and be selected from the above-mentioned adjuvant component one or more.In oxide and with catalyst be benchmark, the content of said adjuvant component preferably below 30 weight %, further is preferably below the 20 weight %, more is preferably below the 15 weight %.
When also containing one or more adjuvant components that are selected among Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Zr, Ti, REO, Re, Hf, Ce, Mn, the V in the said catalyst, also be included in the step that catalyst is introduced said adjuvant component in the said Preparation of catalysts method.According to the conventional method of preparation fischer-tropsch synthetic catalyst, said 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, when extruded moulding, directly adjuvant component or the compound that contains adjuvant component are mixed with carrier to be formed and/or precursor, afterwards extruded moulding again.Or with the solution that contains said adjuvant component compound before the carried metal component, afterwards or simultaneously the method for dipping is introduced.
In a concrete embodiment; Said carrier is a kind of by comprising the aluminium oxide that is selected from one or more promoter metal component modifications in zinc, cobalt and the nickel; In oxide and with said carrier is benchmark, and said one or more promoter metal components contents that are selected from zinc, cobalt and the nickel are 0.5 weight %-15 weight %; The preparation method of said modified aluminas comprises:
(1) preparation contains the alkali and one or more the aqueous solution that contains in the compound that is selected from zinc, cobalt or nickel;
(2) the solution impregnation aluminium oxide for preparing with step (1);
(3) will dry and roasting through the aluminium oxide of step (2) dipping.
Wherein, the alkali in the preparation method's of said modified aluminas the step (1) is selected from one or more in ammonia, ammoniacal liquor and the organic amine, and the consumption of said alkali makes the pH value of said solution be 7.5-14, is preferably 8.5-13, further is preferably 9-12.5.Described roasting condition comprises: sintering temperature is 500-900 ℃, is preferably 550-850 ℃, further is preferably 600-800 ℃, and roasting time is 0.5 hour-8 hours, is preferably 1 hour-6 hours, further is preferably 2 hours-4 hours.
According to the present invention catalyst is provided; In that be used for before the Fischer-Tropsch synthesis need be in the presence of hydrogen, the cobalt of oxidation state is carried out reduction activation, reducing condition is: reduction temperature is 100 ℃ to 800 ℃; Be preferably 200 ℃ to 600 ℃, further be preferably 300 ℃ to 450 ℃; Recovery time is 0.5-72 hour; Be preferably 1-24 hour, further be preferably 2-8 hour, said reduction can be carried out in pure hydrogen; Also can in the gaseous mixture of hydrogen and inert gas, carry out; As in the gaseous mixture of hydrogen and nitrogen and/or argon gas, carrying out, Hydrogen Vapor Pressure is 0.1-4MPa, is preferably 0.1-2MPa.
According to FT synthetic method provided by the invention, said mixture and the catalytic condition of said catalyst with carbon monoxide and hydrogen: preferred temperature is 160～280 ℃, further is preferably 190～250 ℃; Pressure is preferably 1～8MPa; Further be preferably 1-5MPa, the mol ratio of hydrogen and carbon monoxide is 0.4～2.5, is preferably 1.5～2.5; Further be 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
Following embodiment further specifies the present invention, and still, therefore the present invention is not restricted.
Embodiment 1:
(1) Preparation of Catalyst
Take by weighing 20 gram γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size are 40～80 microns) is dissolved in 10 ml deionized water with 24.6 gram cabaltous nitrate hexahydrates; Process maceration extract; With this solution impregnation aforesaid alumina support, leave standstill 2 hours after, 120 ℃ of dryings are 4 hours in baking oven; Be placed on afterwards in the 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, processes 250 ml water solution (60: 1 ratio of the mol ratio of urea and gold atom), and 20 gram A1 are mixed with this solution, is warming up to 80 ℃, dipping reaction under agitation 4 hours.Afterwards, with dope filtration and spend the no chlorion of deionised water to filtrating detect (filtrating is with the liquor argenti nitratis ophthalmicus titration of 0.1mol/L, no turbid phenomenon, under together), filter cake after 2 hours, at 350 ℃ of roasting 3h of tube furnace, makes catalyst C1 in 120 ℃ of dryings of baking oven.The content of Co is 20% among the catalyst C1, and the content of Au is 0.05% (content of metal component is calculated value in the catalyst, down together).
(2) catalyst applications and performance thereof
Evaluating catalyst carries out in autoclave, takes by weighing catalyst 5 gram, and with catalyst 400 ℃ of reduction 5 hours under pure hydrogen atmosphere, heating rate is 6.0 ℃/min; Hydrogen gas space velocity be 15 mark liters/gram-catalyst/hour, then catalyst is transferred to and fills 250 and restrain in the autoclave of 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; Feed synthesis gas, controlled pressure is 2.5MPa, and synthesis gas consists of: 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 stopping reaction 48h, utilizes online gas-chromatography to carry out the tail gas composition analysis.Evaluation result is seen table 1, wherein, and X
COBe illustrated in the molar ratio of CO inversion quantity and CO air inflow under the above-mentioned FT synthetic reaction condition, S
C5+Being illustrated under the 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) Preparation of Catalyst
Take by weighing 20 gram γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size are 40～80 microns) takes by weighing the 24.6g cabaltous nitrate hexahydrate again and is dissolved in 10 ml deionized water; Process maceration extract; With this solution impregnation aforesaid alumina support, leave standstill 2h after, 120 ℃ of dry 4h in baking oven; Be placed on afterwards in the 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, processes 250 ml water solution (120: 1 ratio of the mol ratio of urea and gold atom), and 20 gram A1 are mixed with this solution, is warming up to 80 ℃, dipping reaction under agitation 4 hours.Afterwards, with dope filtration and spend deionised water to filtrating no chlorion detect, filter cake after 3 hours, at 350 ℃ of roasting 3h of tube furnace, makes catalyst C2 in 120 ℃ of dryings of baking oven.The content of Co is 20% among the catalyst C2, and the content of Au is 0.1%.
(2) catalyst applications and performance thereof
According to method and the condition evaluating catalyst C2 identical with embodiment 1, evaluation result is seen table 1.
Embodiment 3:
(1) Preparation of Catalyst
Take by weighing 20 gram γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size are 40～80 microns) takes by weighing the 24.6g cabaltous nitrate hexahydrate again and is dissolved in the 10ml deionized water; Process maceration extract; With this solution impregnation aforesaid alumina support, leave standstill 2h after, 120 ℃ of dry 4h in baking oven; Be placed on afterwards in the tube furnace, obtained sample A1 in 4 hours in 450 ℃ of roastings.
Take by weighing 0.94g platinum chloride ammonia solution (concentration is 1.07gPt/100g solution), be settled to the 250ml aqueous solution, dropwise add the about 6mL of ammoniacal liquor (mol ratio of ammoniacal liquor and pt atom is 60: 1) of 0.5mol/L.20g A1 is mixed dipping reaction under agitation 4 hours with this solution.Afterwards, with dope filtration and spend deionised water to filtrating no chlorion detect, filter cake at 350 ℃ of roasting 3h of tube furnace, makes catalyst C3 behind 120 ℃ of dry 2h of baking oven.The content of Co is 20% among the catalyst C3, and the content of Pt is 0.05%.
(2) catalyst applications and performance thereof
According to method and the condition evaluating catalyst C3 identical with embodiment 1, evaluation result is seen table 1.
Embodiment 4:
(1) Preparation of Catalyst
Take by weighing 20 gram γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size are 40～80 microns) takes by weighing the 24.6g cabaltous nitrate hexahydrate again and is dissolved in the 10ml deionized water; Process maceration extract; With this solution impregnation aforesaid alumina support, leave standstill 2h after, 120 ℃ of dry 4h in baking oven; Be placed on afterwards in the tube furnace, obtained sample A1 in 4 hours in 450 ℃ of roastings.
Take by weighing 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 dipping reaction under agitation 4 hours with this solution.Afterwards, with dope filtration and spend deionised water to filtrating no chlorion detect, filter cake at 350 ℃ of roasting 3h of tube furnace, makes catalyst C4 behind 120 ℃ of dry 2h of baking oven.The content of Co is 20% among the catalyst C4, and the content of Pt is 0.1%.
(2) catalyst applications and performance thereof
According to method and the condition evaluating catalyst C4 identical with embodiment 1, evaluation result is seen table 1.
Embodiment 5:
(1) Preparation of Catalyst
Take by weighing 20 gram γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size are 40～80 microns) takes by weighing the 24.6g cabaltous nitrate hexahydrate again and is dissolved in the 10ml deionized water; Process maceration extract; With this solution impregnation aforesaid alumina support, leave standstill 2h after, 120 ℃ of dry 4h in baking oven; Be placed on afterwards in the tube furnace, obtained sample A1 in 4 hours in 450 ℃ of roastings.
Take by weighing 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 dipping reaction under agitation 4 hours with this solution.Afterwards, with dope filtration and spend deionised water to filtrating no chlorion detect, filter cake at 350 ℃ of roasting 3h of tube furnace, makes catalyst C5 behind 120 ℃ of dry 2h of baking oven.The content of Co is 20% among the catalyst C5, and the content of Ru is 0.05%.
(2) catalyst applications and performance thereof
According to method and the condition evaluating catalyst C5 identical with embodiment 1, evaluation result is seen 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 and obtain alkaline Zn solution, pH about 12.100 gram gama-aluminas (sasol alumina powder, 55 microns of average grain diameters) are added above-mentioned solution, stirred held 6 hours.Behind the 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 the alumina support that Zn content is 2.27% (calculated value) thus.
(2) Preparation of Catalyst
Take by weighing the 24.6g cabaltous nitrate hexahydrate and be dissolved in the 10ml deionized water, process maceration extract, with the 20g alumina support after the aforementioned roasting of this solution impregnation; After leaving standstill 2h; 120 ℃ of dry 4h in baking oven are placed in the tube furnace afterwards, obtain sample A2 in 4 hours in 450 ℃ of roastings.
Take by weighing 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 dipping reaction under agitation 4 hours with this solution.Afterwards, with dope filtration and spend deionised water to filtrating no chlorion detect, filter cake at 350 ℃ of roasting 3h of tube furnace, makes catalyst C6 behind 120 ℃ of dry 2h of baking oven.The content of Co is 20% among the catalyst C6, and the content of Ru is 0.05%.
(3) catalyst applications and performance thereof
According to method and the condition evaluating catalyst C6 identical with embodiment 1, evaluation result is seen table 1.
Comparative Examples 1:
(1) Preparation of Catalyst
Carrier adopts γ-Al
2O
3Powder (sasol aluminium oxide, particle mean size are 40～80 μ m) takes by weighing this alumina powder of 20g earlier; Take by weighing the 24.6g cabaltous nitrate hexahydrate again and be dissolved in the 10ml deionized water, process maceration extract, with the aforesaid alumina support of this solution impregnation; After leaving standstill 2h; 120 ℃ of dry 4h in baking oven are placed in the tube furnace afterwards, obtain reference catalyst BC1 in 4 hours in 450 ℃ of roastings.The content of Co is 20% among the catalyst B C1.
(2) catalyst applications and performance thereof
According to method and the condition evaluating reference catalyst BC1 identical with embodiment 1, evaluation result is seen table 1.
Comparative Examples 2:
(1) Preparation of Catalyst
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, processes maceration extract, with the aforesaid alumina support of this solution impregnation; After leaving standstill 2 hours; 120 ℃ of dryings are 4 hours in baking oven, are placed on afterwards in the tube furnace, obtain reference catalyst BC2 in 4 hours in 450 ℃ of roastings.The content of Co is 20% among the catalyst B C2, and the content of Au is 0.05%.
(2) catalyst applications and performance thereof
According to method and the condition evaluating reference catalyst BC2 identical with embodiment 1, evaluation result is seen table 1.
Comparative Examples 3:
Take by weighing 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, processes maceration extract, with the aforesaid alumina support of this solution impregnation; After leaving standstill 2 hours; 120 ℃ of dryings are 4 hours in baking oven, are placed on afterwards in the tube furnace, obtain reference catalyst BC3 in 4 hours in 450 ℃ of roastings.The content of Co is 20% among the catalyst B C3, and the content of Au is 0.1%.
(2) catalyst applications and performance thereof
According to method and the condition evaluating reference catalyst BC3 identical with embodiment 1, evaluation result is seen table 1.
Table 1
Claims (19)
1. fischer-tropsch synthetic catalyst; Contain carrier and the promoter metal component that loads on chosen from Fe and/or the cobalt active metal component on this carrier and be selected from the noble metal one or more; In element and with said catalyst is benchmark, and said promoter metal components contents is 0.01 weight %-0.3 weight %; Said Preparation of catalysts method comprises:
(1) iron containing compounds and/or cobalt compound solution and carrier are flooded reaction;
(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 flood reaction;
(4) product that obtains of dry and calcination steps (3);
Wherein, the solution of said step (3) contains alkali, and the mol ratio of said alkali and noble metal is 20～200.
2. catalyst according to claim 1; It is characterized in that; Said noble metal is selected from one or more among Ru, Rh, Pd, Os, Ir, Pt, Ag or the Au, is benchmark in element and with said catalyst, and said promoter metal components contents is 0.02 weight %-0.15 weight %.
3. catalyst according to claim 2 is characterized in that said noble metal is selected from one or more among Ru, Pt or the Au.
4. catalyst according to claim 1 is characterized in that, the alkali in the solution of said step (3) and the mol ratio of noble metal are 60-120.
5. according to claim 1 or 4 described catalyst, it is characterized in that said alkali is urea and/or ammoniacal liquor.
6. catalyst according to claim 1 is characterized in that, the dipping reaction condition of said step (3) comprising: the dipping reaction temperature is 20 ℃-90 ℃, and the time is 0.5 hour-72 hours.
7. catalyst according to claim 6 is characterized in that, the dipping reaction condition of said step (3) comprising: the dipping reaction temperature is 50 ℃-80 ℃, and the time is 2 hours-48 hours.
8. catalyst according to claim 1; It is characterized in that the drying condition in said step (2) or the step (4) comprises: temperature is 100 ℃-300 ℃, and the 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 the drying condition in said step (2) or the step (4) comprises: temperature is 110 ℃-150 ℃, and the 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 in their modifier one or more.
11. catalyst according to claim 10 is characterized in that, said carrier is an aluminium oxide.
12. according to claim 10 or 11 described catalyst; It is characterized in that; Said carrier is a kind of by comprising the aluminium oxide that is selected from one or more promoter metal component modifications in zinc, cobalt and the nickel; In oxide and with said carrier is benchmark, and said one or more promoter metal components contents that are selected from zinc, cobalt and the nickel are 0.5 weight %-15 weight %; The preparation method of said modified aluminas comprises:
(1) preparation contains the alkali and one or more the aqueous solution that contains in the compound that is selected from zinc, cobalt or nickel;
(2) the solution impregnation aluminium oxide for preparing with step (1);
(3) will 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 said modified aluminas the step (1) is selected from one or more in ammonia, ammoniacal liquor and the organic amine, and the consumption of said alkali makes the pH value of said 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 said alkali makes the pH value of said solution be 8.5-13.
15. catalyst according to claim 14 is characterized in that, the consumption of said alkali makes the pH value of said 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 the mixture and the catalyst haptoreaction of carbon monoxide and hydrogen, it is characterized in that said catalyst is the described catalyst of each claim of aforementioned claim 1-18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010503652 CN102441402B (en) | 2010-10-12 | 2010-10-12 | Fischer-Tropsch synthesis catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010503652 CN102441402B (en) | 2010-10-12 | 2010-10-12 | Fischer-Tropsch synthesis catalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102441402A true CN102441402A (en) | 2012-05-09 |
| CN102441402B CN102441402B (en) | 2013-11-06 |
Family
ID=46004634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010503652 Active CN102441402B (en) | 2010-10-12 | 2010-10-12 | Fischer-Tropsch synthesis catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102441402B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769085A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for catalytic combustion |
| CN104289231A (en) * | 2014-10-09 | 2015-01-21 | 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 |
| CN104549315A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparation of low-carbon olefin from synthesis gas as well as preparation method and 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 |
| CN106607051A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for one-step preparation of low-carbon olefin from synthetic gas and preparation method thereof |
| 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 |
| CN107774259A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of fischer-tropsch synthetic catalyst and its application |
| CN107790153A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of fischer-tropsch synthetic catalyst of Si modification and its application |
| CN108262044A (en) * | 2016-12-30 | 2018-07-10 | 中国石油化工股份有限公司 | The preparation method of fischer-tropsch synthetic catalyst and prepared fischer-tropsch synthetic catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1981927A (en) * | 2005-12-14 | 2007-06-20 | 中国石油化工股份有限公司 | Cobalt-based Fischer-Tropasch synthetic catalyst and its production |
| 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 |
-
2010
- 2010-10-12 CN CN 201010503652 patent/CN102441402B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1981927A (en) * | 2005-12-14 | 2007-06-20 | 中国石油化工股份有限公司 | Cobalt-based Fischer-Tropasch synthetic catalyst and its production |
| 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 |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769085A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | 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 |
| 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 |
| CN104549315A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparation of low-carbon olefin from synthesis gas as well as preparation method and 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 |
| 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 |
| CN104289231A (en) * | 2014-10-09 | 2015-01-21 | 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 |
| CN106607051A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for one-step preparation of low-carbon olefin from synthetic gas and preparation method 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 |
| CN107774259A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of fischer-tropsch synthetic catalyst and its application |
| CN107790153A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of fischer-tropsch synthetic catalyst of Si modification and its application |
| 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 |
| CN108262044A (en) * | 2016-12-30 | 2018-07-10 | 中国石油化工股份有限公司 | The preparation method of fischer-tropsch synthetic catalyst and prepared fischer-tropsch synthetic catalyst |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102441402B (en) | 2013-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102441402B (en) | Fischer-Tropsch synthesis catalyst and application thereof | |
| CN102441393B (en) | A kind of take modified aluminas as fischer-tropsch synthetic catalyst and the application thereof of carrier | |
| CN103203238B (en) | A kind of fischer-tropsch synthetic catalyst and Synthesis and applications thereof | |
| AU2010214972B2 (en) | Fischer-Tropsch synthesis Fe-based catalyst, process of preparation and application thereof | |
| CN102553579B (en) | Preparation method of high-dispersity supported nano metal catalyst | |
| US8618182B2 (en) | Process for synthesizing C5+ hydrocarbons in the presence of a catalyst prepared using at least one cyclic oligosaccharide | |
| CN111229215B (en) | Metal high-dispersion supported catalyst based on carbon quantum dot induction and preparation method and application thereof | |
| CN101698152A (en) | Cobalt-based compounded catalyst and preparing method and application thereof | |
| WO2013150305A2 (en) | Alcohol production process | |
| CN112755996A (en) | Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application | |
| CN103418388B (en) | A kind of fischer-tropsch synthetic catalyst and Synthesis and applications thereof | |
| CN110787789A (en) | Preparation and application of catalyst for preparing methanol by carbon dioxide hydrogenation | |
| CN103962130B (en) | A kind of Catalysts and its preparation method for oxalate synthetic reaction | |
| CN102671665A (en) | Co-based Fischer-Tropsch synthesis catalyst with high Co content, as well as preparation method and application thereof | |
| CN109718787B (en) | Cerium/yttrium stabilized zirconia support and catalyst | |
| CN101890361A (en) | Catalyst for use in highly selective preparation of gasoline fractions from synthesis gas and preparation method thereof | |
| CN103846110B (en) | The activation method of a kind of fischer-tropsch synthetic catalyst and application thereof | |
| CN101214455A (en) | Preparation method of supported nano hydrogenation catalyst | |
| CN102441386A (en) | Novel Fischer Tropsch synthesis method | |
| CN103589446B (en) | A kind of method of iron-based liquid hydrocarbon | |
| CN113058613B (en) | Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof | |
| CN108114729A (en) | A kind of anthraquinone hydrogenation catalyst and its preparation method and application | |
| CN109529912A (en) | Furfural hydrogenation prepares furfuryl alcohol composite nanostructure copper catalyst and preparation method thereof | |
| CN102671673B (en) | Cobalt-base Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN100493705C (en) | Swollen vermiculite loading NiB amorphous alloy catalyst preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |