CN1764499A - Catalyst for fischer-tropsch synthesis and process for producing hydrocarbon - Google Patents
Catalyst for fischer-tropsch synthesis and process for producing hydrocarbon Download PDFInfo
- Publication number
- CN1764499A CN1764499A CN200480008020.8A CN200480008020A CN1764499A CN 1764499 A CN1764499 A CN 1764499A CN 200480008020 A CN200480008020 A CN 200480008020A CN 1764499 A CN1764499 A CN 1764499A
- Authority
- CN
- China
- Prior art keywords
- metal
- catalyst
- silica
- base carrier
- cobalt
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalyst for Fischer-Tropsch synthesis which attains a low selectivity to methane and a high probability of chain growth alpha in a region where the conversion of Co is high. The catalyst for Fischer-Tropsch synthesis is obtained by depositing two or more precursor compounds containing a metal selected among cobalt, nickel, and ruthenium on a silica-based support containing 0.03 to 0.30 mass % alkali metal and/or alkaline earth metal.
Description
Technical field
The present invention relates to a kind of being used for by comprising hydrogen and an oxidation carbon method as catalyst and this Preparation of Catalyst hydrocarbon of a kind of usefulness of the synthesis gas preparation hydrocarbon of main component.
Background technology
Reaction by the synthetic hydrocarbon of the synthesis gas that comprises hydrogen and carbon monoxide is called as " Fischer-Tropsch synthetic (FT is synthetic) ", is well-known in this former document.Fischer-Tropsch synthesis is (for example Japan Patent postpone to disclose No.4-227847 disclosed) by using that the catalyst that obtained to the carrier as silica and aluminium oxide by the reactive metal of load such as iron and cobalt carries out.
FT synthetic reaction carbon monoxide conversion ratio (CO conversion ratio), methane selectively and chain growth factor-alpha characterize.Term " low methane selectively " is meant the reaction that generates methane, i.e. the side reaction of Fischer-Tropsch reaction is suppressed to low-level.Term " chain growth factor-alpha " is used for estimating the molecular weight of product hydrocarbon, that is to say, α meaned near 1.0 o'clock can obtain the more hydrocarbon of HMW.
The FT synthetic product subsequently stage usually by hydrocracking, then as clean fuel liquid.In recent years, to the midbarrel in these liquid fuels, for example kerosene and light gas oil have higher demand.In order to improve the productive rate of these midbarrels, need lower methane selectively and the chain growth factor-alpha of Geng Gao.Therefore, have higher CO conversion ratio, lower methane selectively, the expense one holder synthetic reaction of higher chain growth factor-alpha has become the target that industrial quarters is made great efforts, and it can be promoted by the catalyst that improves in the FT synthetic method.
Yet not only methane selectively has with the CO conversion ratio and improves the trend increase, and CO conversion ratio and chain growth factor-alpha are in these those relations of growing that disappear.Especially it is to be noted, also do not obtain a kind of catalyst that has low methane selectively and high chain growth factor-alpha at high CO zone of transformation so far.This is to utilize to use this synthetic method to produce biggest obstacle in clean fuel liquid method in the synthetic and reality of FT.
Summary of the invention
The purpose of this invention is to provide a kind of new FT synthetic catalyst, it has low methane selectively and high chain growth factor-alpha at high CO zone of transformation, has therefore overcome the biggest obstacle in the synthetic practical application of FT.
After having carried out big quantity research, the inventor has finished the present invention, therefrom find and to overcome the problems referred to above by the catalyst that employing comprises two or more precursor compound, described precursor compound contains a kind of specific reactive metal that loads on the silica base carrier, and described silica base carrier contains respectively in mass 〉=0.03% and≤0.30% alkali metal and/or alkaline-earth metal.
That is to say, according to first of the present invention, a kind of catalyst for fischer-tropsch synthesis now is provided, this catalyst comprises two or more precursor compound, described precursor compound contains a kind of reactive metal that is selected from cobalt, nickel and ruthenium that loads on the silica base carrier, and described silica base carrier contains in mass 〉=0.03% and≤0.30% alkali metal and/or alkaline-earth metal.
According to another part of the present invention, the catalyst that is provided be impregnated into by the precursor compound that will be selected from the metal of cobalt, nickel and ruthenium comprising of two or more comprise in mass 〉=0.03% and≤0.30% alkali metal and/or the silica base carrier of alkaline-earth metal on, dry then and roasting prepares.
According to a part more of the present invention, in the catalyst that is provided, alkali metal and/or alkaline-earth metal are that one or more are selected from the alkali metal of lithium, sodium and potassium and/or one or both are selected from the alkaline-earth metal of magnesium and calcium.
According to a part more of the present invention, in the catalyst that is provided, the precursor compound that comprises the metal that is selected from cobalt, nickel and ruthenium is selected from the nitrate of these metals, hydrochloride, sulfate, formates, acetate, propionate, oxalates, acetoacetate.
According to a part more of the present invention, in the catalyst that is provided, the described load capacity that is selected from the metal of cobalt, nickel and ruthenium is 3-50 quality %, based on the silica base carrier, calculates with metal.
According to another part of the present invention, in the catalyst that is provided, the average grain diameter of described silica base carrier be 10 μ m to 10mm, specific area is 100 to 500m
2/ g.
The present invention also relates to a kind of by utilizing aforementioned catalyst to make hydrogen and carbon monoxide carry out synthetic reaction to prepare the method for hydrocarbon.
Be to more detailed description of the present invention below.
Term used herein " silica base carrier " is represented silica or comprises silica to remove through alkali metal and/or alkali-earth metal modified carrier as main group.
The alkali metal preferred lithium, sodium and the potassium that are used for improved silica.The alkaline-earth metal preferably magnesium and the calcium that are used for improved silica.
Method with alkali metal and/or alkali-earth metal modified silica has no particular limits.Therefore, any traditional method of modifying, for example infusion process or metal alkoxide method can be selected for use.Particularly preferred method is an infusion process.In infusion process, incipient wetness method most preferably.
Silica is after flooding with alkali metal and/or alkaline-earth metal, and then drying and roasting are to carry out modification.
The drying means that floods back silica is had no particular limits, and therefore air dry and exhaust drying in a vacuum can in air.Usually under air atmosphere, at 100-200 ℃, preferred 110-150 ℃ was descended preferred 5-24 hour dry 0.5-48 hour.Usually under air atmosphere, at 300-600 ℃, preferred 400-450 ℃ following roasting 0.5-10 hour, preferred 1-5 hour.
The amount that is used for the alkali metal of improved silica and/or alkaline-earth metal in mass for 〉=0.03% and≤0.30% or, preferably be in mass 〉=0.04% and≤0.20% or, more preferably be in mass 〉=0.05% or and≤0.13% or.The amount of alkali metal and/or alkaline-earth metal is invalid providing when reducing methane selectively and increasing the chain growth factor-alpha, yet when their amount surpasses 0.30% in mass, will reduces the CO conversion ratio in mass less than 0.03% o'clock.
The average pore size of the silica that the present invention is used can be 8-20nm, preferred 10-18nm, more preferably 11-16nm.The value that terminology used here " average pore size " expression measures by the nitrogen adsorption method.
The silica of the present invention's use and the shape of silica base carrier are had no particular limits.Therefore, silica and silica base carrier can be any shapes that is applicable to the technology that will adopt, and can be selected from the goods of different shape, for example spherical or Powdered goods and column moldings.Average grain diameter to silica and silica base carrier has no particular limits.Generally have from 10 μ m to 10mm, preferred 50 μ m can select for use according to the technology that will adopt to any carrier of the average grain diameter of 5mm.
Specific area to silica and silica base carrier has no particular limits.Generally have from 100 to 500m
2/ g, preferred 200 to 400m
2Any carrier of the specific area of/g can adopt.
Term " comprises a kind of precursor compound that is impregnated into the metal that is selected from cobalt, nickel and ruthenium on the silica base carrier " and represents that all contain the compound of described slaine or its compound in molecule.Though preferably nitrate, hydrochloride, sulfate, formates, acetate, propionate, oxalates and acetoacetate have no particular limits the type of this compound.Feature of the present invention just is to have adopted the precursor compound of the reactive metal that exemplifies previously comprising of two or more.Though the only combination of two kinds of precursor compounds preparation easily usually if desired, also can be made up the precursor compound more than three kinds or three kinds.Carefully closing of precursor compound had no particular limits.Carefully closing of two kinds of precursor compounds is preferably nitrate and formates; Nitrate and acetate; And nitrate and acetoacetate.Particularly preferred combination is nitrate and formates; And nitrate and acetate.Most preferred combination is nitrate and acetate.
Beneficial effect of the present invention can be impregnated into by the precursor compound of the metal that comprises given activity with two or more on silica base carrier of the alkali metal that contains certain content and/or alkaline-earth metal and obtain.
The reactive metal that loads on the silica base carrier can be selected from cobalt, nickel and ruthenium.In these metals, more preferably cobalt and ruthenium, most preferably cobalt.In general, in the solution of the precursor compound that contains described metal by the silica base carrier being dipped into two or more, make these compounds impregnated and load on the carrier, then drying and roasting is so that reactive metal is loaded on the silica base carrier with the form of metal oxide.
Drying means is had no particular limits, and therefore, air dry and exhaust drying in a vacuum can in air.Usually under air atmosphere, at 100-200 ℃, under preferred 110-150 ℃, dry 0.5-48 hour, preferred 5-24 hour.Roasting usually under air atmosphere, at 300-600 ℃, under preferred 400-450 ℃, roasting 0.5-10 hour, preferred 1-5 hour.
The amount that loads on the reactive metal on the silica base carrier is had no particular limits.Yet, based on the silica base carrier, to calculate with metal, the load capacity of reactive metal is generally 3-50 quality %, preferred 5-40 quality %, the amount of preferred especially 10-30 quality %.Because reactive metal load capacity in mass caused catalyst to have very poor activity less than 3% o'clock and reactive metal load capacity in mass surpasses 50% gathering in a large number, can not obtain beneficial effect of the present invention this moment.
If desired, can be promoter, for example zirconia and lanthana load on the silica base carrier.Based on the silica base carrier, to calculate with metal, the amount of this promoter is generally 1-20 quality %.
Adopt catalyst of the present invention, can make hydrogen and carbon monoxide, synthetic hydrocarbon under low methane selectively and the high alpha-value at high CO conversion ratio.
When catalyst of the present invention is used for the FT synthetic reaction, in advance can be preferably to its reduction with hydrogen.
When adopting catalyst of the present invention, the raw material when the FT synthetic reaction is implemented is not particularly limited, as long as they are to comprise hydrogen and carbon monoxide is just passable as the synthesis gas of main more composition.Yet the mol ratio of hydrogen and carbon monoxide is 1.5 to 2.5, preferred 1.8 to 2.2.
Catalyst of the present invention is applicable to any known FT synthesis process, for example fixed bed, overcritical fixed bed, slurry attitude bed, fluidized bed type reaction process.Though without limits, preferred fixed bed, overcritical fixed bed, slurry attitude bed type reaction process, preferred especially fixed bed, overcritical fixed-bed type reaction process, most preferably fixed-bed type reaction process.
Reaction condition to the FT synthetic reaction has no particular limits, and therefore, can carry out under the condition of routine.This reaction usually can be in 200-280 ℃ temperature range and 1,000-3,000h
-1Gaseous hourly space velocity under carry out.
Industrial applicability
As mentioned above, the FT synthetic reaction that has low methane selectively and high chain growth factor-alpha at high CO zone of transformation can be finished by adopting FT synthetic catalyst of the present invention, described catalyst be by with comprising of two or more a kind of precursor compound that is selected from the metal of cobalt, nickel and ruthenium be impregnated into comprise in mass 〉=0.03% and≤the silica base carrier of 0.30% alkali metal and/or alkaline-earth metal on, dry then and the roasting acquisition.
The preferred forms of invention
To make more detailed description according to subsequently embodiment and comparative example the present invention, but the invention is not restricted to this.
(embodiment 1)
5.0g average pore size is 15.2nm and specific area is 320m
2The silica of/g is flooded by the aqueous solution by incipient wetness method, and it is benchmark that the described aqueous solution comprises with silica, calculates the sodium acetate of 0.04 quality % and is benchmark with silica by sodium metal, calculates the magnesium nitrate of 0.04 quality % by magnesium metal.Then, under 120 ℃ temperature, spend the night dry moisture content.Under 450 ℃ temperature, by two hours roasting, silica is carried out modification had the silica base carrier of sodium and magnesium to obtain load.The alkali metal of silica base carrier and the content of alkaline-earth metal adopt the metal analysis Instrumental Analysis to measure.As a result, confirm that total metal content is 0.08% in mass.The silica base carrier is flooded by the aqueous solution by incipient wetness method, and it is benchmark that the described aqueous solution comprises with the carrier, calculates the cobalt nitrate of 10.0 quality % and is benchmark with the carrier by metallic cobalt, calculates the cobalt acetate of 10.0 quality % by metallic cobalt.Then, under 120 ℃ temperature, spend the night dry moisture.The silica base carrier is 450 ℃ roasting temperature 2 hours, to obtain the catalyst of load cobalt.Before reaction beginning, the catalyst that obtains is added in the fixed bed annular reactor, under 400 ℃ temperature with hydrogen stream reductase 12 hour.Then, with 2,000h
-1The gaseous hourly space velocity supply to comprise mol ratio be 2/1 the hydrogen and the material mixed gas of carbon monoxide, under the pressure of 250 ℃ temperature and 1MPa, begin reaction.At any time use the gas composition of gas chromatographic analysis reactor exit.According to the conventional method, utilize analysis data computation CO conversion ratio, methane selectively and the chain growth factor-alpha that obtains.The result is presented in the table 1.
(embodiment 2)
Except adopting average pore size is that 12.8nm and specific area are 347m
2Outside the silica of/g, repeat embodiment 1 to determine CO conversion ratio, methane selectively and chain growth factor-alpha.The result is presented in the table 1.
(embodiment 3)
The silica base carrier that comprises alkali metal and the alkaline-earth metal of 0.04 quality % except employing, it is base that described carrier comprises with silica by employing, calculate the sodium acetate of 0.02 quality % and be base with silica by sodium metal, the aqueous solution that calculates the magnesium nitrate of 0.02 quality % by magnesium metal obtains, repeat embodiment 1 to determine CO conversion ratio, methane selectively and chain growth factor-alpha.The result is presented in the table 1.
(embodiment 4)
The silica base carrier that comprises alkali metal and the alkaline-earth metal of 0.16 quality % except employing, it is base that described carrier comprises with silica by employing, calculate the sodium acetate of 0.08 quality % and be base with silica by sodium metal, the aqueous solution of pressing the magnesium nitrate of magnesium metal calculating 0.08% obtains, repeat embodiment 1 to determine CO conversion ratio, methane selectively and chain growth factor-alpha.The result is presented in the table 1.
(embodiment 5)
The silica base carrier that comprises alkali metal and the alkaline-earth metal of 0.10 quality % except employing, it is base that described carrier comprises with silica by employing, calculate the sodium acetate of 0.05 quality % and be base with silica by sodium metal, the aqueous solution that calculates the magnesium nitrate of 0.05 quality % by magnesium metal obtains, repeat embodiment 1 to determine CO conversion ratio, methane selectively and chain growth factor-alpha.The result is presented in the table 1.
(embodiment 6)
The silica base carrier that comprises alkali metal and the alkaline-earth metal of 0.24 quality % except employing, it is base that described carrier comprises with silica by employing, calculate the sodium acetate of 0.12 quality % and be base with silica by sodium metal, the aqueous solution that calculates the magnesium nitrate of 0.12 quality % by magnesium metal obtains, repeat embodiment 1 to determine CO conversion ratio, methane selectively and chain growth factor-alpha.The result is presented in the table 1.
(comparative example 1)
Comprise alkali metal and alkaline-earth metal that total amount is 0.02 quality %, average pore size is that 15.2nm, specific area are 320m
2The silica base carrier of/g is by incipient wetness method water solution impregnation, it is base that the described aqueous solution comprises with dioxy voltinism base carrier, cobalt nitrate and the silica base carrier of calculating 10.0 quality % by metallic cobalt are base, calculate the cobalt acetate of 10.0 quality % by metallic cobalt.Then, under 120 ℃ temperature, spend the night, remove moisture content.The silica base carrier is 450 ℃ roasting temperature 2 hours, to obtain the catalyst of load cobalt.Before reaction beginning, the gained catalyst is added in the fixed bed annular reactor, under 400 ℃ temperature with hydrogen stream reductase 12 hour.Then, with 2,000h
-1The gaseous hourly space velocity supply to comprise mol ratio be 2/1 the hydrogen and the material mixed gas of carbon monoxide, under the pressure of 250 ℃ temperature and 1MPa, begin reaction.At any time use the gas composition of gas chromatographic analysis reactor exit.According to the conventional method, utilize analysis data computation CO conversion ratio, methane selectively and the chain growth factor-alpha that obtains.The result is presented in the table 1.
(comparative example 2)
Except employing comprises alkali metal and the alkaline-earth metal of 0.02 quality %, average pore size is that 12.8nm, specific area are 347m
2Outside the silica base carrier of/g, repeat comparative example 1 to determine CO conversion ratio, methane selectively and chain growth factor-alpha.The result is presented in the table 1.
(comparative example 3)
The alkali metal and the alkaline-earth metal that comprise 0.32 quality % except employing, comprising with silica by employing is base, calculate the sodium acetate of 0.16 quality % and be base with silica by sodium metal, calculate by magnesium metal outside the silica base carrier of aqueous solution preparation of magnesium nitrate of 0.16 quality %, repeat embodiment 1 to determine CO conversion ratio, methane selectively and chain growth factor-alpha.The result is presented in the table 1.
(comparative example 4)
Before modification, only having with silica is base, and the cobalt nitrate that calculates 20.0 quality % by metallic cobalt repeats embodiment 1 to determine CO conversion ratio, methane selectively and chain growth factor-alpha outside loading on the silica base carrier.The result is presented in the table 1.
Can confirm from the result of table 1, by adopt two or more precursor compound that comprises the metal that is selected from cobalt, nickel and ruthenium loaded to comprise in mass 〉=0.03% and≤catalyst for preparing on the silica base carrier of 0.30% alkali metal and/or alkaline-earth metal, can obtain gratifying high CO conversion ratio, low methane selectively and high chain growth factor-alpha simultaneously.
Table 1
| Catalyst | CO conversion ratio % | Methane selectively % | The chain growth factor-alpha |
| Embodiment 1 | 89.3 | 13.6 | 0.89 |
| Embodiment 2 | 90.0 | 14.0 | 0.87 |
| Embodiment 3 | 84.0 | 13.7 | 0.88 |
| Embodiment 4 | 85.0 | 13.6 | 0.89 |
| Embodiment 5 | 90.0 | 9.0 | 0.91 |
| Embodiment 6 | 83.3 | 14.0 | 0.89 |
| Comparative example 1 | 85.2 | 17.2 | 0.86 |
| Comparative example 2 | 90.0 | 20.0 | 0.81 |
| Comparative example 3 | 78.0 | 11.0 | 0.89 |
| Comparative example 4 | 64.0 | 13.5 | 0.88 |
Claims (7)
1, a kind of catalyst for fischer-tropsch synthesis, comprise two or more precursor compound, described precursor compound contains a kind of metal that is selected from cobalt, nickel and ruthenium that loads on the silica base carrier, described silica base carrier comprises in mass 〉=0.03% and≤0.30% alkali metal and/or alkaline-earth metal.
2, according to the catalyst of claim 1, wherein said catalyst be by two or more is comprised a kind of precursor compound that is selected from the metal of cobalt, nickel and ruthenium be impregnated into comprise in mass 〉=0.03% and≤0.30% alkali metal and/or the silica base carrier of alkaline-earth metal on, dry then and roasting prepares.
3, according to the catalyst of claim 1 or 2, wherein said alkali metal and/or alkaline-earth metal are one or more alkali metal that is selected from lithium, sodium and potassium and/or one or both the alkaline-earth metal that is selected from magnesium and calcium.
4,, describedly comprise nitrate, hydrochloride, sulfate, formates, acetate, propionate, oxalates and the acetoacetate that a kind of precursor compound that is selected from the metal of cobalt, nickel and ruthenium is selected from described metal according to each described catalyst of claim 1-3.
5, according to each described catalyst of claim 1-4, the described load capacity that is selected from the metal of cobalt, nickel and ruthenium is calculated as the 3-50% quality by metal, is base with described silica base carrier.
6, according to each described catalyst of claim 1-5, the average grain diameter of described silica base carrier be 10 μ m to 10mm, specific area is 100-500m
2/ g.
7, a kind of method for preparing hydrocarbon makes hydrogen and reaction of carbon monoxide with synthetic described hydrocarbon by adopting each described catalyst of claim 1-6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003086024 | 2003-03-26 | ||
| JP086024/2003 | 2003-03-26 | ||
| PCT/JP2004/003750 WO2004085055A1 (en) | 2003-03-26 | 2004-03-19 | Catalyst for fischer-tropsch synthesis and process for producing hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1764499A true CN1764499A (en) | 2006-04-26 |
| CN1764499B CN1764499B (en) | 2010-04-28 |
Family
ID=33095048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200480008020.8A Expired - Fee Related CN1764499B (en) | 2003-03-26 | 2004-03-19 | Catalyst for fischer-tropsch synthesis and process for producing hydrocarbon |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4911974B2 (en) |
| CN (1) | CN1764499B (en) |
| AU (1) | AU2004224536B2 (en) |
| MY (1) | MY141118A (en) |
| WO (1) | WO2004085055A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462079B (en) * | 2007-12-20 | 2011-07-20 | 中国石油化工股份有限公司 | Method for preparing catalyst with lamella distribution |
| CN101195553B (en) * | 2006-12-07 | 2011-08-10 | 中国石油化工股份有限公司 | Hydrocarbon synthesizing method |
| CN102039133B (en) * | 2009-10-13 | 2012-11-14 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesized Co-based fluidized bed catalyst and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004089540A1 (en) | 2003-04-07 | 2004-10-21 | Nippon Steel Corporation | Catalyst for producing hydrocarbon from synthesis gas and method for producing catalyst |
| JP6839602B2 (en) * | 2017-05-01 | 2021-03-10 | 日鉄エンジニアリング株式会社 | A method for producing a catalyst for producing a hydrocarbon from a synthetic gas, and a method for producing a hydrocarbon for producing a hydrocarbon from a synthetic gas. |
| JP7145653B2 (en) * | 2018-06-08 | 2022-10-03 | 日鉄エンジニアリング株式会社 | Method for producing catalyst for producing hydrocarbons from synthesis gas, and method for producing hydrocarbons from synthesis gas |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9103417D0 (en) * | 1991-02-19 | 1991-04-03 | Shell Int Research | Washing treatment for catalysts and/or catalyst precursors |
| US6117814A (en) * | 1998-02-10 | 2000-09-12 | Exxon Research And Engineering Co. | Titania catalysts their preparation and use in fischer-tropsch synthesis |
-
2004
- 2004-03-19 WO PCT/JP2004/003750 patent/WO2004085055A1/en active Application Filing
- 2004-03-19 JP JP2005504025A patent/JP4911974B2/en not_active Expired - Fee Related
- 2004-03-19 AU AU2004224536A patent/AU2004224536B2/en not_active Ceased
- 2004-03-19 CN CN200480008020.8A patent/CN1764499B/en not_active Expired - Fee Related
- 2004-03-24 MY MYPI20041046 patent/MY141118A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195553B (en) * | 2006-12-07 | 2011-08-10 | 中国石油化工股份有限公司 | Hydrocarbon synthesizing method |
| CN101462079B (en) * | 2007-12-20 | 2011-07-20 | 中国石油化工股份有限公司 | Method for preparing catalyst with lamella distribution |
| CN102039133B (en) * | 2009-10-13 | 2012-11-14 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesized Co-based fluidized bed catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1764499B (en) | 2010-04-28 |
| AU2004224536B2 (en) | 2009-07-30 |
| WO2004085055A1 (en) | 2004-10-07 |
| AU2004224536A1 (en) | 2004-10-07 |
| JP4911974B2 (en) | 2012-04-04 |
| JPWO2004085055A1 (en) | 2006-06-29 |
| MY141118A (en) | 2010-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108144644B (en) | hydroisomerization catalyst, preparation and application thereof | |
| CN1942243A (en) | Catalyst for fischer-tropsch synthesis and process for producing hydrocarbons | |
| CN108144651B (en) | Hydroisomerization catalyst and preparation and application thereof | |
| CN103007982B (en) | Fischer-Tropsch synthesis catalyst comprising zeolite molecular sieve, and preparation method and application thereof | |
| CN103008001B (en) | Fischer-Tropsch synthesis catalyst comprising composite molecular sieve, and preparation method and application thereof | |
| CN101134164B (en) | Co-based fischer-tropsch synthesis catalyst and method for preparing the same | |
| CN1059918C (en) | Improved steam reforming catalysts for lower hydrocarbons | |
| CN101864324B (en) | Method for synthesizing liquid hydrocarbon | |
| CN106944159B (en) | A kind of preparation method of catalyst for hydrogen production from methane vapor reforming | |
| EP2301663B1 (en) | Catalyst for fischer-tropsch synthesis and method for producing hydrocarbons | |
| CN102441400B (en) | Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas | |
| CN1764499A (en) | Catalyst for fischer-tropsch synthesis and process for producing hydrocarbon | |
| CN1260007C (en) | Micro-ball iron-based catalyst for Fischer-Tropsch synthesis and its preparation and use | |
| JP2003024786A (en) | Catalyst for fischer-tropsch synthesis and method for producing hydrocarbon | |
| CN1883804A (en) | Catalyst for preparation of dimethyl ether from synthesis gas | |
| CN1247305C (en) | Method for deoxidizing iron base catalyst of Fisher-Tropsch synthesis in slurry bed | |
| CN1176746C (en) | Fischer-Tropsch catalyst and its preparing process | |
| CN103008000B (en) | Fischer-Tropsch synthesis catalyst comprising non-zeolite molecular sieve, and preparation method and application thereof | |
| CN106807421B (en) | A kind of catalyst and its preparation method and application for synthesis gas mixed alcohol | |
| CN108654637B (en) | Cobalt-based catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method | |
| CN105727954A (en) | Preparation method of catalyst for synthetic gas to natural gas | |
| KR101988370B1 (en) | Catalysts for methanation of carbon dioxide and the manufacturing method of the same | |
| CN111434382A (en) | Carrier-supported vanadium oxide promoted Rh-based catalyst and preparation method and application thereof | |
| CN106475106B (en) | A kind of preparation method of synthesis gas preparing natural gas by methanation catalyst | |
| CN110280303B (en) | Catalyst for preparing liquefied petroleum gas from synthesis gas and preparation method thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100428 Termination date: 20190319 |