CN104437489B - Ferrum-based Fischer-Tropsch synthesis catalyst and preparation and application thereof - Google Patents
Ferrum-based Fischer-Tropsch synthesis catalyst and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a ferrum-based Fischer-Tropsch synthesis catalyst and preparation and application thereof. The catalyst contains an aluminum oxide carrier and an active metal component ferrum, wherein the carrier has a bimodal pore structure, characterized by a mercury intrusion method, the carrier has the pore volume of 0.6-1.4 ml/g and the specific surface area of 80-400 m＜2＞/g, the volume of pores with the diameter of 5-20 nm accounts for 30-60% the total pore volume, and the volume of pores with the diameter of 100-300 nm accounts for 15-45% the total pore volume. Compared with the prior art, the catalyst provided by the invention has better Fischer-Tropsch synthesis performance.
Description
Technical field
The present invention relates to fischer-tropsch synthetic catalyst and its preparation and application, synthesize more specifically to a kind of iron-base fischer-tropsch
Catalyst and its preparation and application.
Background technology
Nineteen twenty-three, Fischer and Tropsch are found that CO and H2Mixture Synthin product method（F-T is closed
Into）.In recent years, with being becoming tight the day of petroleum resources, the soaring progressively harsh and coal to demanded fuel of crude oil price and
Being continuously increased for natural gas proved reserves, makes the research that F-T synthesizes this field enliven very much, and many companies are in F-T synthesis
Researched and developed.Good F-T synthetic catalysts, it should to CO and H2There is adsorption activity, the CO to adsorbing has hydrogenation to make
With, contributing to chain growth, leniently promotion is hydrogenated, while and should not hydrogenate too strong, Water gas shift/WGS excessively and form non-live
Property carbide etc..The first step of F-T synthesis is CO and H2Chemisorbed, from terms of structural chemistry viewpoint, with 3d and 4f keys and
The transition elements of energy level, are used as the active component of F-T synthetic catalysts mostly.Wherein with regard to Ni, Fe, Co, Ru research compared with
It is many.Except Ni as hydrogenation activity is too strong, make chain growth probability too big, be mainly used in methanation, uncomfortable cooperation synthesizes macromolecule wax
Outside the active component of hydrocarbon catalyst, its excess-three kind metallic catalyst all can be used for F-T synthesis.And there is commercial application value be
Co and Fe catalyst, wherein as the F-T synthesizing activities of Co are high, reaction condition is gentle, and water gas shift reaction is few, and performance is steady
Fixed, the life-span is longer, therefore people have carried out wider research to Co catalyst in research and application.Co for F-T is urged
Agent, the DNAcarrier free oxide of early application, such as pure cobalt/cobalt oxide, cobalt-chromated oxide and cobalt-zinc oxide etc.；Sent out later
Thorium oxide and magnesium oxide is now added, the activity of catalyst can be increased；Co catalyst carrier loaded at present is that research and industry should
Main flow.For F-T synthesis uses Co catalyst, researcher to select various auxiliary agents to modify which, to expect to improve which
Catalytic performance.
A kind of method for preparing catalyst and using method is disclosed in CN89109859 and CN93106465, the catalyst bag
Include the cobalt of the catalysis activity amount on the alumina support of load and also sensitive to load capacity selected from platinum, iridium, rhodium and its mixture
Second metal.Metal oxide promoters can be added.
CN01810769.9 and CN01810773 disclose a kind of method for preparing catalyst and using method, the catalyst bag
The cobalt of catalysis activity amount is included, its content is 5gCo/100g-70gCo/100g carriers, it is also possible to add Pd and Pt, as having
Strengthen the dopant of Co reducing powers.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of performance on the basis of existing technology to obtain modified Fischer-Tropsch
The preparation method and application of synthetic catalyst and the catalyst.
Inventor's research finds, when F-T synthetic catalysts are prepared using a kind of carrier with structure of double peak holes, catalysis
The F-T synthetic reaction performances of agent, such as C5 +Selectivity substantially improved.
Content according to the present invention includes：
1. a kind of iron-base fischer-tropsch synthesis catalyst, containing alumina support and active metal component ferrum, wherein, the carrier
With structure of double peak holes, characterized with mercury injection method, the pore volume of the carrier is 0.6-1.4 ml/g, and specific surface area is 80-400
Rice2/ gram, the pore volume in a diameter of 5-20nm holes accounts for the 30-60% of total pore volume, and the pore volume in a diameter of 100-300nm holes accounts for total hole
The 15-45% of appearance.
2. the catalyst according to 1, it is characterised in that the pore volume of the carrier is 0.7-1.3 ml/g, specific surface
Product is 100-300 rice2/ gram, the pore volume in a diameter of 5-20nm holes accounts for the 35-50% of total pore volume, a diameter of 100-300nm holes
Pore volume accounts for the 20-40% of total pore volume.
3. the catalyst according to 1, it is characterised in that the active metal group on the basis of catalyst, in terms of oxide
The content for dividing ferrum is 5-70 weight %.
4. the catalyst according to 3, it is characterised in that the active metal group on the basis of catalyst, in terms of oxide
The content for dividing ferrum is 10-50 weight %.
5. the catalyst according to 4, it is characterised in that the active metal group on the basis of catalyst, in terms of oxide
The content for dividing ferrum is 12-30 weight %.
6. the catalyst according to 1, it is characterised in that in the catalyst containing selected from Cu, Mo, Ta, W, Zr, Ti,
The first adjuvant component of one or more in REO, Re, Mn, V or K, the first auxiliary agent on the basis of catalyst, in terms of oxide
The content of component is below 10 weight %.
7. the catalyst according to 6, it is characterised in that the first promoter metal component is in Ti, Zr, W or Mn
One or more, on the basis of catalyst, the content of the first adjuvant component counted with oxide is as below 6 weight %.
8. the catalyst according to 1 or 6, it is characterised in that in the catalyst containing selected from Ru, Rh, Pd, Os, Ir,
The second adjuvant component of one or more in Pt, Ag or Au, on the basis of catalyst, the second adjuvant component in terms of element contains
Amount is below 0.5 weight %.
9. the catalyst according to 8, it is characterised in that the one kind of second adjuvant component in Ru, Pt or Pd
Or it is several, on the basis of catalyst, the content of the second adjuvant component in terms of element is below 0.3 weight %.
10. according to 1 catalyst preparation method, including preparing carrier and supported active metals component on this carrier
Ferrum, wherein, the preparation of the carrier is included the hydrated alumina PA and PB containing boehmite with a kind of containing the thin water of plan
The modifier PC mixing of the hydrated alumina of aluminum stone, molding, drying roasting, wherein, the Mixing ratio by weight of described PA, PB and PC
For 20-60：20-50：The κ values of 5-50, PC are the κ=DI 0 to less than or equal to 0.92/DI1, DI1For PC hydration oxygen before modified
Change the sour peptization index of aluminum, DI2For the sour peptization index of the PC.
11. methods according to 10, it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50：35-
50：10-30；The k value of the PC is 0 to less than or equal to 0.6.
12. methods according to 10 or 11, it is characterised in that the hydrated alumina PA's containing boehmite
Pore volume is 0.75-1 ml/g, and specific surface is 200-450 rice2/ gram, most probable bore dia 3-10nm；It is described containing intending thin water aluminum
The pore volume of the hydrated alumina PB of stone is 0.9-1.4 ml/g, and specific surface is 100-350 rice2/ gram, most probable bore dia is more than
10 to less than or equal to 30nm.
13. methods according to 12, it is characterised in that the pore volume of the hydrated alumina PA containing boehmite
For 0.80-0.95 ml/g, specific surface is 200-400 rice2/ gram, most probable bore dia 5-10nm；It is described containing intending thin water aluminum
The pore volume of the hydrated alumina PB of stone is 0.95-1.3 ml/g, and specific surface is 120-300 rice2/ gram, most probable bore dia is big
In 10 to less than or equal to 25nm.
14. methods according to 10 or 11 any one, it is characterised in that particulate matters of the PC for 80-300 mesh.
15. methods according to 14, it is characterised in that particulate matters of the PC for 100-200 mesh.
16. methods according to 10, it is characterised in that the condition of the drying includes：Temperature is 40-350 DEG C, the time
For 1-24 hours, the condition of the roasting includes：Temperature is that the time is 1-8 hours more than 500 to less than or equal to 1200 DEG C.
17. methods according to 16, it is characterised in that the condition of the drying includes：Temperature is 100-200 DEG C, when
Between be 2-12 hours, the condition of the roasting includes：Temperature is that roasting time is 2-6 more than 800 to less than or equal to 1000 DEG C
Hour.
18. methods according to 10, it is characterised in that the hydrated alumina containing boehmite is modified as into PC's
One of method is, by the hydrated alumina molding containing boehmite, drying, to grind its all or part afterwards
Mill, screening, the condition of the drying include：Temperature is 40-350 DEG C, and the time is 1-24 hours；The two of method are to obtain method one
The article shaped roasting arrived, sintering temperature are that roasting time is 1-8 hours, afterwards which is complete more than 350 to less than or equal to 1400 DEG C
Portion or part are ground, sieve；The three of method are that the hydrated alumina containing boehmite is dodged dry, and it is big to dodge dry temperature
In 150 to less than or equal to 1400 DEG C, flash-off time is 0.05-1 hours；The four of method be by one of method, method two and with
One or more in the modifier that the three of method obtain are mixed to get.
19. methods according to 18, it is characterised in that the condition of the drying in methods described one includes：Temperature is
100-200 DEG C, the time is 2-12 hours；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is that 0.1-6 is little
When；The dry temperature of sudden strain of a muscle in the three of method is 200-1000 DEG C, and flash-off time is 0.1-0.5 hours.
20. methods according to 18, it is characterised in that the PC is changing for the hydrated alumina containing boehmite
The particulate matter of 80-300 mesh in property thing.
21. methods according to 20, it is characterised in that the PC is changing for the hydrated alumina containing boehmite
The particulate matter of 100-200 mesh in property thing.
22. methods according to 10, it is characterised in that the method in supported on carriers active metal component ferrum is
Infusion process, is counted by oxide and on the basis of catalyst, and described dipping makes the content of active metal component in the catalyst
For 5-70 weight %.
23. methods according to claim 22, it is characterised in that the active metal component is cobalt, with oxide
Count and on the basis of catalyst, it is 10-50 weight % that described dipping makes the content of active metal component in the catalyst.
24. methods according to 23, it is characterised in that counted by oxide and on the basis of catalyst, described leaching
It is 12-30 weight % that stain makes the content of active metal component in the catalyst.
25. methods according to 10, it is characterised in that methods described include introduce selected from Cu, Mo, Ta, W, Zr,
The step of one or more in Ti, REO, Re, Mn, V or K the first promoter metal component, in terms of oxide and with the catalysis
On the basis of agent, the introduction volume of the promoter metal component is less than 10 weight %.
26. methods according to 25, it is characterised in that the first promoter metal component is in Ti, Zr, W or Mn
One or more, counted by oxide and on the basis of the catalyst, the introduction volume of the first promoter metal component does not surpass
Cross 6 weight %.
27. catalyst according to claim 10 or 25, it is characterised in that methods described includes that introducing is selected from
The step of one or more in Ru, Rh, Pd, Os, Ir, Pt, Ag or Au the second promoter metal component, in terms of element and with described
On the basis of catalyst, the introduction volume of the second promoter metal component is less than 0.5 weight %.
28. catalyst according to claim 27, it is characterised in that the second promoter metal component selected from Ru,
One or more in Pt or Pd, are counted by element and on the basis of the catalyst, the introducing of the second promoter metal component
Amount is less than 0.3 weight %.
A kind of 29. Fischer-Tropsch synthesis methods, are included in carbon monoxide and the mixture of hydrogen under the conditions of Fischer-Tropsch synthesis
With catalyst haptoreaction, it is characterised in that the catalyst is urging described in aforementioned any one of claim 1-9 claim
Agent.
According to the catalyst that the present invention is provided, require that carrier therein can be made into various easily operated molding depending on difference
Thing, such as spherical, cellular, nest like, tablet or bar shaped（Herba Trifolii Pratentis, butterfly, cylinder etc.）.Molding can be entered according to a conventional method
The combination of a kind of method or several method OK, for example, in spin, tabletting and extruded moulding.In molding, such as extrusion into
Type, is to ensure that the molding is smoothed out, can add in described mixture water, extrusion aid and/or adhesive, containing or not
Containing expanding agent, then extrusion molding, it is dried afterwards and roasting.The extrusion aid, the species of peptizer and consumption are ability
Well known to field technique personnel, such as common extrusion aid can be selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol, poly- second
One or more in alcohol, the peptizer can be mineral acid and/or organic acid, and described expanding agent can be starch, conjunction
Into one or more in cellulose, polymeric alcohol and surfactant.Synthetic cellulose therein be preferably hydroxymethyl cellulose,
One or more in methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol are preferably poly- second two
One or more in alcohol, poly- propanol, polyvinyl alcohol, surfactant be preferably fat alcohol polyethylene ether, fatty alkanol amide and
Its derivant, molecular weight are one or more in the propylene alcohol copolymer and maleic acid copolymer of 200-10000.
In the present invention, sour peptization index D I refers to the hydrated alumina containing boehmite and containing the thin water of plan
The hydrated alumina modifier of aluminum stone is added after nitric acid, by peptization containing plan within certain response time by certain acid aluminum ratio
The hydrated alumina of boehmite is with Al2O3The percent of meter, DI=（1-W2/W1) × 100%, W1And W2Respectively containing the thin water of plan
Before the hydrated alumina of aluminum stone and acid reaction and with acid reaction after with Al2O3The weight of meter.
The measure of DI includes：(1) the calcination base of the hydrated alumina containing boehmite is determined（Also referred to as butt）Content
（Calcination base content referred to quantitative boehmite in 600 DEG C of roastings 4 hours, after its burning weight with burn before weight ratio, with
Percent is represented）, it is calculated as a；(2) the hydrated alumina W containing boehmite is weighed with analytical balance0Gram, W0Amount meet with
Al2O3The W of meter1For 6 grams（W1/a=W0）, weigh W gram of deionized water, W=40.0-W0, will weigh under stirring containing the thin water aluminum of plan
The hydrated alumina of stone and deionized water mix in adding beaker；(3) it is the dilute of 0.74N to pipette 20mL, concentration with 20mL pipets
The acid solution is added to step by salpeter solution（2）Beaker in, the lower reaction of stirring 8 minutes；(4) by step（3）It is reacted
Serosity is centrifuged in centrifuge, precipitate is inserted in the crucible weighed, afterwards, and which is little in 125 DEG C of dryings 4
When, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh and obtain calcination sample size W2Gram；（5）According to formula DI=(1-W2/W1)×
100% is calculated.
On the premise of it be enough to make final carrier meet application claims, the present invention is to the water containing boehmite
Close aluminium oxide PA and PB not specially require, can be the boehmite, or the thin water of plan of any prior art preparation
The mixture of aluminum stone and other hydrated aluminas, other hydrated aluminas are selected from a water aluminium oxide, gibbsite
And one or more in amorphous hydrated aluminium oxide.
In a detailed embodiment, the preferred pore volumes of hydrated alumina PA containing boehmite are 0.75-1
Ml/g, specific surface is 200-450 rice2/ gram, most probable bore dia 3-10nm, further preferred pore volume are 0.80-0.95 millis
Rise/gram, specific surface is 200-400 rice2/ gram, most probable bore dia 5-10nm；The hydrated alumina containing boehmite
The preferred pore volumes of PB are 0.9-1.4 ml/g, and specific surface is 100-350 rice2/ gram, most probable bore dia is more than 10 to being less than or equal to
30nm, further preferred pore volume are 0.95-1.3 ml/g, and specific surface is 120-300 rice2/ gram, most probable bore dia is more than 10
To less than or equal to 25nm.
In the present invention, the pore volume of the hydrated alumina containing boehmite, specific surface area and most can and aperture, be by institute
The hydrated alumina containing boehmite is stated after 600 DEG C of roastings 4 hours, is characterized by BET N2 adsorptions and is obtained.
In further preferred embodiment, characterized with X diffraction, the hydrated alumina PA containing boehmite
It is not less than 50% with the boehmite content in PB, more preferably not less than 60%.
Inventors of the present invention have surprisingly found that, the hydrated alumina containing boehmite is carried out being thermally treated resulting in changing
Property thing PC, relative to the original hydrated alumina containing boehmite, the peptization index of modifier PC changes, will
After this modifier and PA and PB mixed-formings, drying roasting, resulting carrier has obvious bimodal pore distribution.Especially
It is by the granule of 80-300 mesh therein, preferably after the granule of 100-200 mesh and PA and PB mixed-formings, drying roasting,
Resulting carrier it is bimodal in each unimodal pore size distribution especially concentrate.Here, the granule of the 80-300 mesh, preferably
The granule of 100-200 mesh refers to the modifier through sieve（The step of including broken or grinding if necessary）, its screening thing（Under sieve
Thing）Meet the granule of 80-300 mesh, the particulate matter of preferably 100-200 mesh accounts for the percent of total amount（By weight）Not less than 60%,
Further preferably it is not less than 70%.Here the hydrated alumina containing boehmite can be prepared by any prior art
The mixture of boehmite, or boehmite and other hydrated aluminas, other hydrated aluminas
One or more in a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide.In a preferred embodiment,
Modifiers of the PC for PA and/or PB.
In the present invention, during the Mixing ratio by weight of described PA, PB and PC refers to the mixture of described PA, PB and PC parts per hundred parts
The ratio of parts by weight shared by PA, PB and PC difference.Wherein, PA：PB：PC is preferably 20-60：20-50：5-50, further preferably
For 30-50：35-50：10-30.
In the present invention, described PC can be conveniently obtained by following method：
Hereinafter, the method for obtaining PC is illustrated by initiation material of the PA and PB.
(1) based on being dried to obtain PC, including by hydrated alumina PA and/or PB containing boehmite according to a conventional method
During molding prepares regular oxidation alumina supporter, the tailing of drying by-product, for example：In extruded moulding, bar shaped article shaped exists
The dry, tailing of integer process by-product（Traditionally it is referred to as being dried waste material）, the tailing is milled, is sieved and is obtained PC.
(2) obtained based on roasting, including by hydrated alumina PA and/or PB containing boehmite according to a conventional method into
During type prepares regular oxidation alumina supporter, the tailing of fired by-product（Traditionally it is referred to as roasting waste material）, for example, spin into
In type, the tailing is milled, sieves and obtain PC by the tailing of spheroidal particle by-product in roasting process；Or directly will
PA and/or PB dodge it is dry obtains, directly will PA and/or PB dodge dry when, flash-off time is preferably 0.05-1 hours, further preferably
For 0.1-0.5 hours.
(3) two or more in the modifier PC for being obtained based on preceding method are mixed to get.When being obtained using mixed method
When obtaining C, the mixed proportion of the modifier PC respectively obtained to aforementioned several method is not limited.
According to the catalyst that the present invention is provided, the content of active metal component ferrum therein is fischer-tropsch synthetic catalyst routine
Content, for example, is counted by oxide and on the basis of catalyst, and the content of the active metal component is 5～70 weight %, excellent
Elect 10～50 weight % as, be more preferably 12～30 weight %.
On the premise of it be enough to described active metal component is carried on the carrier, the present invention will be living to described
Property metal component is carried on the method on the carrier and is not particularly limited.For example, it may be enough to effective dose
Under conditions of active metal component is deposited on the carrier, by described carrier and containing effective dose group containing active metal
Point compound solution contact, such as by dipping, the method such as be co-precipitated, preferred infusion process is dried, roasting or not afterwards
Roasting.The method of the drying and be conventional method, for example, the method for heating, drying, when drying meanss be heat drying when, institute
Stating dry operating condition includes：Temperature be 80～350 DEG C, preferably 100～300 DEG C, the time be 1～24 hour, preferably 2
～12 hours.When the catalyst needs to carry out roasting, the temperature of the roasting is described containing active metal component to realize
For the purpose of compound is converted into its oxide, preferred sintering temperature is 200-700 DEG C, and roasting time is 1～6 hour, enters one
Walk preferred temperature and be preferably 250-500 DEG C, roasting time is 2～4 hours.
The compound containing active metal component preferably is selected from one or more in their soluble compound, such as contains
One or more in water-soluble salt of active metal component, complex.
Prior art research shows, individually or collectively introduce in fischer-tropsch synthetic catalyst one group selected from Cu, Mo, Ta, W,
One or more promoter metal components in Zr, Ti, REO, Re, Mn, V or K；Or one group of introducing selected from Ru, Rh, Pd, Os, Ir,
The other adjuvant component of one or more in Pt, Ag or Au, it is favourable to improving catalyst performance.
According to the present invention provide catalyst, in the catalyst containing selected from Cu, Mo, Ta, W, Zr, Ti, REO, Re,
One or more promoter metal components in Mn, V or K, preferably comprise one or more in Ti, Zr, W or Mn, with oxygen
Compound meter on the basis of the catalyst, the content of the promoter metal component are less than 10 weight %, and preferred content is less than
6 weight %.
When in the catalyst containing the one kind in the component such as Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K or
When two kinds, its introducing method can prepare the compound containing the auxiliary agent with the compound containing active metal component is contained
Contact with the carrier into after mixed solution；Can also be by the compound containing auxiliary agent individually prepare after solution with the carrier
Contact, is dried and roasting afterwards.When auxiliary agent does not introduce the carrier with active metal component, preferably first with containing auxiliary agent
Polymer solution is contacted with the carrier, is contacted with the solution of the compound containing active metal component after drying roasting again,
For example by methods, preferably infusion process such as ion exchange, dipping, co-precipitation.The sintering temperature is 200-700 DEG C, preferably
250-500 DEG C, roasting time is 2-8 hours, preferably 3-6 hours.
According to the catalyst that the present invention is provided, also containing selected from Ru, Rh, Pd, Os, Ir, Pt, Ag or Au in the catalyst
In the other adjuvant component of one or more, preferably comprise one or more in Ru, Pt or Pd, in terms of element simultaneously
On the basis of the catalyst, the content of the promoter metal component is less than 0.3 weight %, and preferred content is less than 0.15 weight
Amount %.
When in the catalyst containing one or more adjuvant components in Ru, Rh, Pd, Os, Ir, Pt, Ag or Au
When, its introducing method can be will containing the auxiliary agent compound with containing containing active metal component compound with or without
The compound of other adjuvant components（For example, containing the change selected from Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K adjuvant component
Compound）Contact with the carrier after being configured to mixed solution；Can also be and individually prepare the compound containing auxiliary agent after solution
Contact with the carrier, be dried afterwards and roasting.When auxiliary agent does not introduce the carrier with active metal component, preferably use first
Contact with the carrier containing auxiliary compound solution, after drying roasting again with the compound containing active metal component
Solution（With or without the compound of other adjuvant components）Contact, such as it is by methods such as ion exchange, dipping, co-precipitation, excellent
Select infusion process.The sintering temperature be 200-700 DEG C, preferably 250-500 DEG C, roasting time be 2-8 hours, preferably 3-6
Hour.
Catalyst is provided according to the present invention, was needed before for Fischer-Tropsch synthesis in presence of hydrogen, by active gold
Category carries out reduction activation, and reducing condition is：Reduction temperature is 100 DEG C to 800 DEG C, preferably 200 DEG C to 600 DEG C, it is further excellent
300 DEG C are elected as to 450 DEG C；Recovery time is 0.5-72 hours, and preferably 1-24 hours, more preferably 2-8 hours are described
Reduction can be carried out in pure hydrogen, also can be carried out in the gaseous mixture of hydrogen and noble gases, such as in hydrogen and nitrogen and/or argon
Gaseous mixture in carry out, Hydrogen Vapor Pressure is 0.1-4MPa, preferably 0.1-2MPa.
According to the Fischer-Tropsch synthesis method that the present invention is provided, the mixture by carbon monoxide and hydrogen and the catalyst
Catalytic condition：Preferable temperature is 160～280 DEG C, and more preferably 190～250 DEG C, pressure is preferably 1～8MPa,
The mol ratio of more preferably 1-5MPa, hydrogen and carbon monoxide is 0.4～2.5, preferably 1.5～2.5, further preferably
For 1.8～2.2, the when null-rate of gas is 200 hours-1～20000 hours-1, preferably 500 hours-1～12000 hours-1。
The fischer-tropsch synthetic catalyst that the present invention is provided makes catalyst using including using bimodal porous aluminum oxide as carrier
Performance is improved.For example, in catalyst in the case of active metal component content, preparation condition identical, with reference agent phase
Than the present invention provides the CO activity of conversion of catalyst and improves nearly 6%, and methane selectively reduces nearly 2%.
Specific embodiment
The present invention will be further described for example below, but should be therefore understands that being not limitation of the invention.
The boehmite for using below in an example includes：
PA-1：The dry glue powder of Chang Ling catalyst branch company production（Pore volume is 0.9 ml/g, and specific surface is 280 meters2/ gram,
Most probable bore dia 8.5nm.Butt is 73%, wherein boehmite content be 68%, gibbsite content be 5 weight %, surplus
For amorphous alumina, DI values 34.6）.
PA-2：The dry glue powder of the limited production of the neat cyclopentadienyl catalyst in Zibo（Pore volume is 0.9 ml/g, and specific surface is 290 meters2/
Gram, most probable bore dia 8.3nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 weight %,
Balance of amorphous alumina, DI values 33.2）.
PB-1：The dry glue powder of Chang Ling catalyst branch company production（Pore volume is 1.2 mls/g, and specific surface is 280 meters2/ gram,
Most probable bore dia 15.8nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 weight %, remaining
Measure as amorphous alumina, DI values 15.8）.
PB-2：The dry glue powder of Yantai Heng Hui Chemical Co., Ltd.s production（Pore volume is 1.1 mls/g, and specific surface is 260
Rice2/ gram, most probable bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 weights
Amount %, balance of amorphous alumina, DI values 17.2）.
Embodiment 1-10 illustrates PC of the present invention and preparation method thereof.
Embodiment 1
1000 grams of PA-1 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）10 milliliters of aqueous solution 1000
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar obtains dried strip in 120 DEG C of dryings 4 hours,
By dried strip shaping, sieve, length is less than into the dried strip material of 2mm（Commonly referred to as industrially drying bar waste material）Milled,
Sieve, take wherein 100～200 mesh sieves point, obtain the modifier PC-A1 of PA-1.The k value of PC-A1 is shown in Table 1.
Embodiment 2
1000 grams of PA-1 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）10 milliliters of aqueous solution 1000
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C of dryings 4 hours, 800 DEG C of roastings 4
Hour, carrier is obtained, carrier strip shaping is sieved, length is less than into the carrier strip material of 2mm（Commonly referred to as industrial carrier gives up
Material）Milled, sieved, taken wherein 100～200 mesh sieves point, obtain final product the modifier PC-A2 of PA-1.The k value of PC-A2 is shown in Table 1.
Embodiment 3
1000 grams of PA-2 are weighed, is dodged dry 6 minutes in 400 DEG C, is obtained the modifier PC-A3 of PA-2.The k value of PC-A3 is shown in Table
1。
Embodiment 4
The each 200 grams of uniform mixing of PC-A3 that the PC-A1 and embodiment 3 that embodiment 1 is obtained is obtained, obtain PA-1 and PA-
2 modifier PC-A4.The k value of PC-A4 is shown in Table 1.
Embodiment 5
1000 grams of PB-1 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）10 milliliters of aqueous solution 1440
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C of dryings 4 hours, 1200 DEG C of roastings 4
Hour, carrier is obtained, carrier strip shaping is sieved, length is less than into the carrier strip material of 2mm（Commonly referred to as industrial carrier gives up
Material）Milled, sieved, taken wherein 100～200 mesh sieves point, obtain final product the modifier PC-B1 of PB-1.The k value of PC-B1 is shown in Table 1.
Embodiment 6
1000 grams of PB-2 are weighed, is dodged dry 10 minutes in 650 DEG C, is obtained the modifier PC-B2 of PB-2.The k value of PC-B2 is shown in Table
1。
Embodiment 7
1000 grams of PB-2 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）10 milliliters of aqueous solution 1440
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar obtains dried strip in 120 DEG C of dryings 4 hours,
By dried strip shaping, sieve, length is less than into the dried strip material of 2mm（Commonly referred to as industrially drying bar waste material）Milled,
Sieve, take wherein 100～200 mesh sieves point, obtain the modifier PC-B3 of PB-2.The k value of PC-B3 is shown in Table 1.
Embodiment 8
The each 200 grams of uniform mixing of PC-B2 that the PC-B1 and embodiment 6 that embodiment 5 is obtained is obtained, obtain PB-1 and PB-
2 modifier PC-B4.The k value of PC-B4 is shown in Table 1.
Embodiment 9
150 grams of PC-B3 that the 100 grams of PC-A1 and embodiment 7 that embodiment 1 is obtained are obtained uniformly mix, obtain PA-1 and
The modifier PC-B5 of PB-2.The k value of PC-B5 is shown in Table 1.
Embodiment 10
The each 150 grams of uniform mixing of PC-B1 that the PC-A3 and embodiment 5 that embodiment 3 is obtained is obtained, obtain PA-2 and PB-
1 modifier PC-B6.The k value of PC-B6 is shown in Table 1.
Table 1
| Embodiment | Raw material | DI | k |
| 1 | PC-A1 | 10.0 | 0.29 |
| 2 | PC-A2 | 0.9 | 0.02 |
| 3 | PC-A3 | 3.6 | 0.11 |
| 4 | PC-A4 | 6.7 | 0.20 |
| 5 | PC-B1 | 0 | 0 |
| 6 | PC-B2 | 2.1 | 0.12 |
| 7 | PC-B3 | 5.3 | 0.31 |
| 8 | PC-B4 | 1.0 | 0.06 |
| 9 | PC-B5 | 7.0 | 0.29 |
| 10 | PC-B6 | 1.6 | 0.07 |
Bimodal hole carrier that the embodiment 11-18 explanation present invention is provided and preparation method thereof.The explanation of comparative example 1-5 is conventional to urge
Agent carrier and preparation method thereof.
Embodiment 11
Weigh PA-1 and PB-1 each 400 grams, after uniformly mixing with 2 obtained 200 grams of raw material PC-A2 of embodiment, addition contains
Nitric acid（Three factory's product of Tianjin chemical reagent）1300 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 900 DEG C of the article shaped is carried
Body Z1.The property of carrier Z1 is listed in table 2.
Embodiment 12
300 grams of PA-2,200 grams of PB-2 are weighed, after uniformly mixing with 6 obtained 500 grams of raw material PC-B2 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1300 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 900 DEG C of the article shaped is carried
Body Z2.The property of carrier Z2 is listed in table 2.
Embodiment 13
500 grams of PA-2,300 grams of PB-2 are weighed, after uniformly mixing with 8 obtained 200 grams of raw material PC-B4 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1300 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 950 DEG C of the article shaped is carried
Body Z3.The property of carrier Z3 is listed in table 2.
Comparative example 1
500 grams of PA-2,500 grams of PB-2 are weighed, after uniform mixing, three factory's product of the chemical reagent of Tianjin containing nitric acid is added）10 millis
1300 milliliters of the aqueous solution for rising, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is little in 120 DEG C of dryings 4
When, article shaped is obtained, by the roasting 3 hours of 900 DEG C of the article shaped, carrier DZ1 is obtained.The property of carrier DZ1 is listed in table 2.
Comparative example 2
400 grams of PA-1,600 grams of PB-1 are weighed, after uniform mixing, three factory's product of the chemical reagent of Tianjin containing nitric acid is added）10 millis
1300 milliliters of the aqueous solution for rising, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is little in 120 DEG C of dryings 4
When, article shaped is obtained, by the roasting 3 hours of 950 DEG C of the article shaped, carrier DZ2 is obtained.The property of carrier DZ2 is listed in table 2.
Embodiment 14
250 grams of PA-1,500 grams of PB-1 are weighed, after uniformly mixing with 9 obtained 250 grams of raw material PC-B5 of embodiment, is added
Containing nitric acid（Three factory's product of Tianjin chemical reagent）1300 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 1000 DEG C of the article shaped is obtained
Carrier Z4.The property of carrier Z4 is listed in table 2.
Embodiment 15
350 grams of PA-2,350 grams of PB-2 are weighed, after uniformly mixing with 10 obtained 300 grams of raw material PC-B6 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1440 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 1000 DEG C of the article shaped is obtained
Carrier Z5.The property of carrier Z5 is listed in table 2.
Embodiment 16
200 grams of PA-1,600 grams of PB-1 are weighed, after uniformly mixing with 5 obtained 200 grams of raw material PC-B1 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1440 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 850 DEG C of the article shaped is carried
Body Z6.The property of carrier Z6 is listed in table 2.
Embodiment 17
200 grams of PA-1,600 grams of PB-1 are weighed, after uniformly mixing with 4 obtained 200 grams of raw material PC-A4 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1440 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 850 DEG C of the article shaped is carried
Body Z7.The property of carrier Z76 is listed in table 2.
Embodiment 18
200 grams of PA-1,600 grams of PB-1 are weighed, after uniformly mixing with 2 obtained 200 grams of raw material PC-A2 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1440 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 850 DEG C of the article shaped is carried
Body Z8.The property of carrier Z8 is listed in table 2.
Comparative example 3
According to the method that patent CN1782031A embodiment 7 is provided, it is extruded into external diameter φ 1.4mm's on plunger type bar extruder
Butterfly bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 900 DEG C of the article shaped, obtains carrier DZ3.
The property of carrier DZ3 is listed in table 2.
Comparative example 4
According to the method that patent CN1120971A embodiment 1 is provided, it is extruded into external diameter φ 1.4mm's on plunger type bar extruder
Butterfly bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 1000 DEG C of the article shaped, obtains carrier DZ3.
The property of carrier DZ3 is listed in table 2.
Comparative example 5
200 grams of PA-1,800 grams of PB-2 are weighed, three factory's product of the chemical reagent of Tianjin containing nitric acid is added）10 milliliters of aqueous solution
1300 milliliters, the butterfly bar of external diameter φ 1.4mm is extruded on double screw banded extruder.Wet bar is obtained in 120 DEG C of dryings 4 hours
Type thing, by the roasting 3 hours of 1000 DEG C of the article shaped, obtains carrier DZ5.The property of carrier DZ5 is listed in table 2.
Table 2
Can be seen by the result of table 2, compared with conventional method, the alumina support tool prepared by the method provided by the present invention
There is obvious structure of double peak holes.
Embodiment 19-26
Illustrate to provide fischer-tropsch synthetic catalyst prepared by aluminium oxide shaping carrier by the present invention.
Z1, Z2, Z3, Z4, Z5, Z6, Z7 and Z8 carrier in embodiment is used into mixed containing ferric nitrate, copper nitrate and potassium nitrate
Close solution, carry out saturation dipping, be dried afterwards and roasting, respectively obtain catalyst C1, C2, C3, C4, C5, C6, C7 and
C8.Wherein, baking temperature is 120 DEG C, and drying time is 6 hours, and sintering temperature is 400 DEG C, roasting time 3 hours.The nitre
During the consumption of sour ferrum, copper nitrate and potassium nitrate makes final catalyst, Fe contents are 12.0 weight %, and Cu contents are 0.2 weight %,
K2O content is 0.1 weight %.
Comparative example 6-10
By mixed solution of DZ1, DZ2, DZ3, DZ4 and DZ5 carrier containing ferric nitrate, copper nitrate and potassium nitrate, satisfied
And dipping, it is dried afterwards and roasting, respectively obtains catalyst DC1, DC2, DC3, DC4 and DC5.Wherein, baking temperature is
120 DEG C, drying time is 6 hours, and sintering temperature is 400 DEG C, roasting time 3 hours.The ferric nitrate and copper nitrate and nitric acid
It is 12.0 weight % that the consumption of potassium makes Fe contents in final catalyst, and Cu contents are 0.2 weight %, K2O content is 0.1 weight
Amount %.
Embodiment 27-34
Illustrate that the present invention provides the application of catalyst and its effect.
Evaluate the Fischer-Tropsch synthesis of catalyst C1, C2, C3, C4, C5, C6, C7 and C8 in fixed bed reactors respectively
Performance.
Unstripped gas is constituted：H2/CO/N2=64%/32%/4% (hundred number of volume).Catalyst reduction reaction condition：Pressure
For normal pressure, heating rate is 5 DEG C/min, and hydrogen gas space velocity is 600h-1, reduction temperature is 400 DEG C, and the recovery time is 5 hours.
Reaction condition：Pressure 2.5MPa, 200 DEG C of temperature, synthesis gas (unstripped gas) air speed 2000h-1.Reaction carries out 24 hours
After take gas sample and carry out chromatography, wherein, COization charcoal percent conversion and methane selectively are listed in table 3.
Comparative example 11-15
Illustrate comparative catalyst's performance, according to the method same with embodiment 27-34 evaluate respectively catalyst DC1, DC2,
DC3、DC4、DC5.Wherein, COization charcoal percent conversion and methane selectively are listed in table 3.
Table 3
From table 3 it can be seen that being used as catalyst carrier using the bimodal porous aluminum oxide that the present invention is provided, expense is then prepared into
Tropsch synthesis catalyst, the catalyst have more preferable F- T synthesis performance, i.e., higher CO in the case of other condition identicals
Conversion ratio and C5+ hydrocarbon selectives, lower methane selectively and CO2 selectivitys.
Claims (28)
1. a kind of iron-base fischer-tropsch synthesis catalyst, containing alumina support and active metal component ferrum, wherein, the carrier has
Structure of double peak holes, is characterized with mercury injection method, and the pore volume of the carrier is 0.6-1.4 ml/g, and specific surface area is 80-400 rice2/
Gram, the pore volume in a diameter of 5-20nm holes accounts for the 30-60% of total pore volume, and the pore volume in a diameter of 100-300nm holes accounts for total pore volume
15-45%.
2. catalyst according to claim 1, it is characterised in that the pore volume of the carrier is 0.7-1.3 ml/g, than
Surface area is 100-300 rice2/ gram, the pore volume in a diameter of 5-20nm holes accounts for the 35-50% of total pore volume, a diameter of 100-300nm
The pore volume in hole accounts for the 20-40% of total pore volume.
3. the catalyst according to claim 1, it is characterised in that on the basis of catalyst, the activity gold in terms of oxide
The content of category component of iron is 5-70 weight %.
4. catalyst according to claim 3, it is characterised in that on the basis of catalyst, the activity gold in terms of oxide
The content of category component of iron is 10-50 weight %.
5. catalyst according to claim 4, it is characterised in that on the basis of catalyst, the activity gold in terms of oxide
The content of category component of iron is 12-30 weight %.
6. catalyst according to claim 1, it is characterised in that in the catalyst containing selected from Cu, Mo, Ta, W, Zr,
The first adjuvant component of one or more in Ti, REO, Re, Mn, V or K, on the basis of catalyst, first in terms of oxide
The content of adjuvant component is below 10 weight %.
7. catalyst according to claim 6, it is characterised in that the first promoter metal component be selected from Ti, Zr, W or
One or more in Mn, on the basis of catalyst, the content of the first adjuvant component counted with oxide is as below 6 weight %.
8. the catalyst according to claim 1 or 6, it is characterised in that in the catalyst containing selected from Ru, Rh, Pd,
The second adjuvant component of one or more in Os, Ir, Pt, Ag or Au, the second auxiliary agent group on the basis of catalyst, in terms of element
The content divided is below 0.5 weight %.
9. catalyst according to claim 8, it is characterised in that second adjuvant component is in Ru, Pt or Pd
One or more, on the basis of catalyst, the content of the second adjuvant component in terms of element is below 0.3 weight %.
10. the preparation method of catalyst according to claim 1, including preparing carrier and supported active metals on this carrier
Component of iron, wherein, the preparation of the carrier is included the hydrated alumina PA and PB containing boehmite with a kind of containing plan
The modifier PC mixing of the hydrated alumina of boehmite, molding, drying roasting, it is wherein, described containing boehmite
The pore volume of hydrated alumina PA is 0.75-1 ml/g, and specific surface is 200-450 rice2/ gram, most probable bore dia 3-10nm；Institute
The pore volume for stating the hydrated alumina PB containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice2/ gram, most
Can several bore dias more than 10 to less than or equal to 30nm, the Mixing ratio by weight of described PA, PB and PC is 20-60：20-50：5-50, PC
κ values be the κ=DI 0 to less than or equal to 0.92/DI1, DI1For the sour peptization index of PC hydrated aluminas before modified, DI2
For the sour peptization index of the PC.
11. methods according to claim 10, it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50：
35-50：10-30；The κ values of the PC are 0 to less than or equal to 0.6.
12. methods according to claim 10 or 11, it is characterised in that the hydrated alumina containing boehmite
The pore volume of PA is 0.80-0.95 ml/g, and specific surface is 200-400 rice2/ gram, most probable bore dia 5-10nm；It is described containing
The pore volume of the hydrated alumina PB of boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice2/ gram, most probable
Bore dia is more than 10 to less than or equal to 25nm.
13. methods according to claim 10 or 11 any one, it is characterised in that granules of the PC for 80-300 mesh
Thing.
14. methods according to claim 13, it is characterised in that particulate matters of the PC for 100-200 mesh.
15. methods according to claim 10, it is characterised in that the condition of the drying includes：Temperature is 40-350 DEG C,
Time is 1-24 hours, and the condition of the roasting includes：Temperature is that the time is that 1-8 is little more than 500 to less than or equal to 1200 DEG C
When.
16. methods according to claim 15, it is characterised in that the condition of the drying includes：Temperature is 100-200
DEG C, the time is 2-12 hours, and the condition of the roasting includes：Temperature is that to less than or equal to 1000 DEG C, roasting time is more than 800
2-6 hours.
17. methods according to claim 10, it is characterised in that the hydrated alumina containing boehmite is modified as
One of method of PC is, by the hydrated alumina molding containing boehmite, drying, to enter its all or part afterwards
Row grinding, screening, the condition of the drying include：Temperature is 40-350 DEG C, and the time is 1-24 hours；The two of method are by method
One of the article shaped roasting that obtains, sintering temperature is that roasting time is 1-8 hours, afterwards more than 350 to less than or equal to 1400 DEG C
Its all or part is ground, is sieved；The three of method are that the hydrated alumina containing boehmite is dodged dry, dodge dry temperature
Degree is that flash-off time is 0.05-1 hours more than 150 to less than or equal to 1400 DEG C；The four of method be by one of method, method it
Two and method three modifiers for obtaining in several be mixed to get.
18. methods according to claim 17, it is characterised in that the condition of the drying in one of methods described includes：Temperature
Spend for 100-200 DEG C, the time is 2-12 hours；The dry temperature of sudden strain of a muscle in the three of method is 200-1000 DEG C, and flash-off time is 0.1-
0.5 hour.
19. methods according to claim 17, it is characterised in that the PC is the hydrated alumina containing boehmite
Modifier in 80-300 mesh particulate matter.
20. methods according to claim 19, it is characterised in that the PC is the hydrated alumina containing boehmite
Modifier in 100-200 mesh particulate matter.
21. methods according to claim 10, it is characterised in that the side in supported on carriers active metal component ferrum
Method is infusion process, is counted by oxide and on the basis of catalyst, and described dipping makes active metal component in the catalyst
Content is 5-70 weight %.
22. methods according to claim 21, it is characterised in that counted by oxide and on the basis of catalyst, it is described
It is 10-50 weight % that dipping makes the content of active metal component in the catalyst.
23. methods according to claim 22, it is characterised in that counted by oxide and on the basis of catalyst, it is described
Dipping make active metal component in the catalyst content be 12-30 weight %.
24. methods according to claim 10, it is characterised in that methods described include introduce selected from Cu, Mo, Ta, W,
The step of one or more in Zr, Ti, REO, Re, Mn, V or K the first promoter metal component, urge in terms of oxide and with described
On the basis of agent, the introduction volume of the promoter metal component is less than 10 weight %.
25. methods according to claim 24, it is characterised in that the first promoter metal component be selected from Ti, Zr, W or
One or more in Mn, are counted by oxide and on the basis of the catalyst, the introduction volume of the first promoter metal component
Less than 6 weight %.
26. methods according to claim 10 or 24, it is characterised in that methods described include introduce selected from Ru, Rh,
The step of one or more in Pd, Os, Ir, Pt, Ag or Au the second promoter metal component, in terms of element and with the catalyst
On the basis of, the introduction volume of the second promoter metal component is less than 0.5 weight %.
27. methods according to claim 26, it is characterised in that the second promoter metal component is selected from Ru, Pt or Pd
In one or more, counted by element and on the basis of the catalyst, the introduction volume of the second promoter metal component does not surpass
Cross 0.3 weight %.
A kind of 28. Fischer-Tropsch synthesis methods, be included under the conditions of Fischer-Tropsch synthesis by the mixture of carbon monoxide and hydrogen with urge
Agent haptoreaction, it is characterised in that the catalyst is the catalyst described in aforementioned any one of claim 1-9.
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| CN102441393A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst by taking modified alumina as carrier and application thereof |
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| CN102441393A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst by taking modified alumina as carrier and application thereof |
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