CN104437669B

CN104437669B - A kind of fischer-tropsch synthetic catalyst and preparation thereof and application

Info

Publication number: CN104437669B
Application number: CN201310439473.7A
Authority: CN
Inventors: 夏国富; 孙霞; 孙淑玲; 侯朝鹏; 吴玉; 晋超; 吴昊; 李明丰
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-09-24
Filing date: 2013-09-24
Publication date: 2016-10-26
Anticipated expiration: 2033-09-24
Also published as: CN104437669A

Abstract

A kind of fischer-tropsch synthetic catalyst and preparation thereof and application, this catalyst contains carrier and active metal component, wherein, described carrier is a kind of aluminium oxide with bimodal hole, characterizing with mercury injection method, the pore volume of described carrier is 0.9 1.2 mls/g, and specific surface area is 50 300 meters²/ gram, the pore volume in a diameter of 10 30nm holes accounts for the 55 80% of total pore volume, and the pore volume in a diameter of 300 500nm holes accounts for the 10 35% of total pore volume.Compared with prior art, the catalyst that the present invention provides has more preferable F-T synthesis performance.

Description

A kind of fischer-tropsch synthetic catalyst and preparation thereof and application

Technical field

The present invention relates to fischer-tropsch synthetic catalyst and preparation thereof and application.

Background technology

Nineteen twenty-three, Fischer and Tropsch is found that CO and H₂The method of mixture Synthin product (F-T synthesis).In recent years, along with being becoming tight the day of petroleum resources, crude oil price soaring, to fuel The progressively harsh and coal of requirement and being continuously increased of natural gas proved reserves, make F-T synthesize this field Studying the most active, many companies are researched and developed in F-T synthesis.Good F-T synthesis catalytic Agent, it should to CO and H₂There is adsorption activity, the CO of absorption is had hydrogenization, contribute to chain and increase, gentle Ground promotes hydrogenation, the most should not hydrogenate too strong, Water gas shift/WGS simultaneously and too much and form carbon non-activated compound Deng.The first step of F-T synthesis is CO and H₂Chemisorbed, in terms of structural chemistry viewpoint, there is 3d and 4f key With the transition elements of energy level, mostly it is used as the active component of F-T synthetic catalyst.Wherein about Ni, The research of Fe, Co, Ru is more.Too strong due to hydrogenation activity except Ni, make chain growth probability too big, mainly Outside methanation, the active component of uncomfortable cooperation synthesis macromolecule wax hydrocarbon catalyst, its excess-three kind metal is urged Agent all can be used for F-T synthesis.And have commercial application value is Co and Fe catalyst, wherein due to Co F-T synthesizing activity high, reaction condition is gentle, and water gas shift reaction is few, stable performance, and the life-span is more Long, therefore Co catalyst has been carried out widely studying in research and application by people.Co for F-T Catalyst, the DNAcarrier free oxide of early application, such as pure cobalt/cobalt oxide, cobalt-chromated oxide and cobalt-zinc oxygen Compound etc.；Found later to add thorium oxide and magnesium oxide, the activity of catalyst can be increased；The most carrier loaded Co catalyst be research and the main flow of commercial Application.For F-T synthesis Co catalyst, researcher is selected It is modified by multiple auxiliary agent, improves its catalytic performance with expectation.

Disclosing a kind of method for preparing catalyst and using method in CN89109859 and CN93106465, this is urged Agent includes carrying the cobalt of catalysis live vol on the alumina support and selected from platinum, iridium, rhodium and mixture thereof Second metal also sensitive to load capacity.Metal oxide promoters can be added.

CN01810769.9 and CN01810773 discloses a kind of method for preparing catalyst and using method, and this is urged Agent includes the cobalt of catalysis live vol, and its content is 5gCo/100g-70gCo/100g carrier, it is also possible to add Enter Pd and Pt, as having the adulterant strengthening Co reducing power.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of performance to obtain modification on the basis of existing technology Fischer-tropsch synthetic catalyst and the preparation method and application of this catalyst.

Inventor studies discovery, prepares F-T synthetic catalyst when using a kind of carrier with structure of double peak holes Time, the F-T synthetic reaction performance of catalyst, such as C₅ ⁺Selectivity substantially improved.

The content that the present invention relates to includes:

1. a fischer-tropsch synthetic catalyst, containing carrier and active metal component, wherein, described carrier is one Kind there is the aluminium oxide in bimodal hole, characterize with mercury injection method, the pore volume of described carrier be 0.9-1.2 milliliter/ Gram, specific surface area is 50-300 rice²/ gram, the pore volume in a diameter of 10-30nm hole accounts for the 55-of total pore volume 80%, the pore volume in a diameter of 300-500nm hole accounts for the 10-35% of total pore volume.

2. according to the catalyst described in 1, it is characterised in that the pore volume of described carrier is 0.95-1.15 milliliter / gram, specific surface area is 80-200 rice²/ gram, the pore volume in a diameter of 10-30nm hole accounts for the 60-of total pore volume 75%, the pore volume in a diameter of 300-500nm hole accounts for the 15-30% of total pore volume.

3. according to the catalyst described in 1, it is characterised in that described active metal component is cobalt, with catalyst On the basis of, the content of the active metal component counted with oxide is for 5-70 weight %.

4. the work according to the catalyst described in 3, it is characterised in that on the basis of catalyst, in terms of oxide The content of property metal component is 10-50 weight %.

5. the work according to the catalyst described in 4, it is characterised in that on the basis of catalyst, in terms of oxide The content of property metal component is 12-30 weight %.

6. according to the catalyst described in 1, it is characterised in that in described catalyst containing selected from Cu, Mo, One or more in Ta, W, Zr, Ti, REO, Re, Mn, V or K the first adjuvant component, with catalysis On the basis of agent, the content of the first adjuvant component in terms of oxide is below 10 weight %.

7. according to the catalyst described in 6, it is characterised in that described first promoter metal component selected from Ti, One or more in Zr, W or Mn, on the basis of catalyst, the first adjuvant component in terms of oxide Content is below 6 weight %.

8. according to the catalyst described in 1 or 6, it is characterised in that in described catalyst containing selected from Ru, One or more in Rh, Pd, Os, Ir, Pt, Ag or Au the second adjuvant component, with catalyst as base Standard, the content of the second adjuvant component in terms of element is below 0.5 weight %.

9. according to the catalyst described in 8, it is characterised in that described second adjuvant component selected from Ru, Pt or One or more in Pd, on the basis of catalyst, the content of the second adjuvant component in terms of element is 0.3 Below weight %.

10. according to the preparation method of catalyst described in 1, including preparing carrier supported active on this carrier Metal component, wherein, the preparation method of described carrier includes the hydrated alumina P1 containing boehmite Modifier P2 mixing with P1, molding, dry and roasting, wherein, the weight mixing of described P1 and P2 It is 0 to less than or equal to 0.9 than the κ value being 20-95:5-80, P2, described κ=DI₂/DI₁, DI₁For containing There are the sour peptization index of the hydrated alumina P1 of boehmite, DI₂For the hydration oxygen containing boehmite Change the sour peptization index of the modifier P2 of aluminum P1.

11. according to the method described in 10, it is characterised in that the Mixing ratio by weight of described P1 and P2 is 70- The k value of 95:5-30, P2 is 0 to less than or equal to 0.6.

12. according to the method described in 10 or 11, it is characterised in that the described hydration containing boehmite The pore volume of aluminium oxide P1 is 0.9-1.4 ml/g, and specific surface is 100-350 rice²/ gram, most probable hole is straight Footpath 8-30nm.

13. according to the method described in 12, it is characterised in that the described hydrated alumina containing boehmite The pore volume of P1 is 0.95-1.3 ml/g, and specific surface is 120-300 rice²/ gram, most probable bore dia 10- 25nm。

14. according to the method described in 10 or 11, it is characterised in that described P2 is the granule of 80-300 mesh Thing.

15. according to the method described in 14, it is characterised in that described P2 is the particulate matter of 100-200 mesh.

16. according to the method described in 10, it is characterised in that described dry condition includes: temperature is 40- 350 DEG C, the time is 1-24 hour, and the condition of described roasting includes: temperature is to being less than or equal to more than 500 1200 DEG C, the time is 1-8 hour.

17. according to the method described in 10, it is characterised in that described dry condition includes: temperature is 100- 200 DEG C, the time is 2-12 hour, and the condition of described roasting includes: temperature is to being less than or equal to more than 800 1000 DEG C, roasting time is 2-6 hour.

18. according to the method described in 10, it is characterised in that be by institute by one of P1 method being modified as P2 State the hydrated alumina P1 molding containing boehmite, be dried, afterwards it is completely or partially ground Mill, screening, obtaining powder body thing is P2, and described dry condition includes: temperature is 40-350 DEG C, the time For 1-24 hour；The two of method are article shaped roastings method one obtained, and sintering temperature is more than 350 To less than or equal to 1400 DEG C, roasting time is 1-8 hour, it is completely or partially ground afterwards, sieves Point, obtaining powder body thing is P2；The three of method are to dodge the hydrated alumina P1 containing boehmite to do, Dodging dry temperature is that flash-off time is 0.05-1 hour, obtains powder body more than 150 to less than or equal to 1400 DEG C Thing is P2；The four of method are by one of method, the two of method and the modifier that obtains with the three of method Kind or several be mixed to get.

19. according to the method described in 18, it is characterised in that the condition being dried in described method one includes: Temperature is 100-200 DEG C, and the time is 2-12 hour；Sintering temperature in the two of method is 500- 1200 DEG C, roasting time is 0.1-6 hour；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, dodges dry Time is 0.1-0.5 hour.

20. according to the method described in 18 or 19, it is characterised in that described P2 is 80-in P1 modifier The particulate matter of 300 mesh.

21. according to the method described in 20, it is characterised in that described P2 is 100-200 mesh in P1 modifier Particulate matter.

22. according to the method described in 10, it is characterised in that described at supported on carriers active metal component Method is infusion process, counts and on the basis of catalyst by oxide, and described dipping makes to live in described catalyst The content of property metal component is 5-70 weight %.

23. methods according to claim 22, it is characterised in that described active metal component is cobalt, Counting and on the basis of catalyst by oxide, described dipping makes containing of active metal component in described catalyst Amount is 10-50 weight %.

24. according to the method described in 23, it is characterised in that count and on the basis of catalyst by oxide, Described dipping makes the content of active metal component in described catalyst be 12-30 weight %.

25. according to the method described in 10, it is characterised in that described method include introduce selected from Cu, One or more in Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K the first auxiliary agent gold Belong to the step of component, count and on the basis of described catalyst by oxide, described promoter metal component Introduction volume is less than 10 weight %.

26. according to the method described in 25, it is characterised in that described first promoter metal component is selected from One or more in Ti, Zr, W or Mn, count and on the basis of described catalyst by oxide, The introduction volume of described first promoter metal component is less than 6 weight %.

27. according to the catalyst described in claim 10 or 25, it is characterised in that wrap in described method Include one or more second auxiliary agents introduced in Ru, Rh, Pd, Os, Ir, Pt, Ag or Au The step of metal component, counts and on the basis of described catalyst by element, described second promoter metal group The introduction volume divided is less than 0.5 weight %.

28. catalyst according to claim 27, it is characterised in that described second promoter metal One or more in Ru, Pt or Pd of component, count with element and with described catalyst as base Standard, the introduction volume of described second promoter metal component is less than 0.3 weight %.

29. 1 kinds of Fischer-Tropsch synthesis methods, be included in carbon monoxide and hydrogen under the conditions of Fischer-Tropsch synthesis is mixed Compound and catalyst haptoreaction, it is characterised in that described catalyst is urging described in aforementioned any one of 1-9 Agent.

Depending on difference, the catalyst provided according to the present invention, requires that carrier therein can be made into various easily operated Article shaped, the most spherical, cellular, nest like, tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder Deng).Molding can be carried out according to a conventional method, such as, a kind of method in spin, tabletting and extruded moulding or The combination of several method.When molding, such as extruded moulding, for ensureing that described molding is smoothed out, can To add water, extrusion aid and/or adhesive in described mixture, with or without expanding agent, then squeeze Go out molding, be dried afterwards and roasting.Described extrusion aid, the kind of peptizer and consumption are this area Well known to technical staff, the most common extrusion aid can be selected from sesbania powder, methylcellulose, starch, One or more in polyvinyl alcohol, PVOH, described peptizer can be mineral acid and/or organic acid, Described expanding agent can be the one in starch, synthetic cellulose, polymeric alcohol and surfactant or several Kind.Synthetic cellulose therein is preferably hydroxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyl One or more in fiber fat alcohol polyethylene ether, polymeric alcohol is preferably Polyethylene Glycol, poly-propanol, poly-second One or more in enol, surfactant preferably fat alcohol polyethylene ether, fatty alkanol amide and spread out One or several in the propenyl copolymer biological, molecular weight is 200-10000 and maleic acid copolymer Kind.

Wherein, sour peptization index D I in the preparation of described carrier refers to the aqua oxidation containing boehmite After aluminum (including its modifier) adds nitric acid by certain acid aluminum ratio, by peptization within certain response time Hydrated alumina containing boehmite is with Al₂O₃The percent of meter, DI=(1-W₂/W₁) × 100%, W₁With W₂Before respectively intending thin water aluminum and acid reaction and with acid reaction after with Al₂O₃The weight of meter.

The mensuration of DI includes: (1) measure the calcination base content (calcination of the hydrated alumina containing boehmite Base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours, weight weight front with burning after its burning Ratio), be calculated as a；(2) weigh the hydrated alumina W containing boehmite with analytical balance₀Gram, W₀'s Amount meets with Al₂O₃The W of meter₁It is 6 grams of (W₁/a=W₀), weigh deionized water W gram, W=40.0-W₀, stir Mix and mix the lower hydrated alumina containing boehmite weighed and deionized water are added in beaker；(3) use 20mL pipet pipettes 20mL, concentration is the dilute nitric acid solution of 0.74N, and this acid solution is joined step (2) in beaker, the lower reaction of stirring 8 minutes；(4) by step (3) reacted serosity in centrifuge It is centrifuged separating, precipitate is inserted in the crucible weighed, afterwards, it is dried 4 in 125 DEG C little Time, 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 being enough to make final carrier meet application claims, the present invention to described containing intend thin water aluminum The hydrated alumina of stone does not specially require, and can be the boehmite prepared of any prior art, it is possible to Being boehmite and the mixture of other hydrated alumina, other hydrated alumina described is selected from one One or more in water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide.In the present invention, contain There are the pore volume of the hydrated alumina of boehmite, specific surface area and most probable pore size, are containing plan by described The hydrated alumina of boehmite, after 600 DEG C of roastings 4 hours, is characterized by BET N2 adsorption and obtains.

In a preferred embodiment, the pore volume of the described hydrated alumina P1 containing boehmite is 0.9-1.4 ml/g, specific surface is 100-350 rice²/ gram, most probable bore dia 8-30nm, further The pore volume of the preferably described hydrated alumina P1 containing boehmite is 0.95-1.3 ml/g, compares table Face is 120-300 rice²/ gram, most probable bore dia 10-25nm.Wherein, characterize with X diffraction, described contain There is in the hydrated alumina of boehmite boehmite content not less than 50%, the least In 60%.

Inventors of the present invention have surprisingly found that, the hydrated alumina P1 containing boehmite is carried out heat Processing modified, the peptization index of its modifier changes, by this modifier with the most thermally treated After P1 mixed-forming, dry also roasting, obtained carrier has obvious bimodal pore distribution.Particularly exist By the granule of 80-300 mesh therein, the granule of preferably 100-200 mesh mixes with the most thermally treated part Molding, be dried and roasting after, obtained carrier bimodal in each unimodal pore size distribution concentrate especially. Here, the granule of described 80-300 mesh, the granule of preferably 100-200 mesh refers to that described modifier is through sieving (including step that is broken or that grind if desired), its screening thing (siftage) meets 80-300 purpose Grain, the particulate matter of preferably 100-200 mesh accounts for the percent (by weight) of total amount and is not less than 60%, enters one Step is preferably not less than 70%.

In being embodied as, described P2 conveniently can be obtained by following method:

(1) based on being dried to obtain P2, including by the hydrated alumina P1 containing boehmite according to a conventional method During regular oxidation alumina supporter is prepared in molding, the tailing of drying by-product, such as: in extruded moulding, Bar shaped article shaped is at dry, the tailing (being referred to as traditionally being dried waste material) of integer process by-product, by this tail Material is milled, and sieves and obtains P2.

(2) obtain based on roasting, become according to a conventional method including by the hydrated alumina P1 containing boehmite During regular oxidation alumina supporter prepared by type, the tailing (being referred to as roasting waste material traditionally) of fired by-product, Such as, in roller forming, spheroidal particle is the tailing of by-product in roasting process, is ground by this tailing Mill, sieves and obtains P2；Or directly P1 is dodged dry obtaining, when directly dodging dry by P1, flash-off time Preferably 0.05-1 hour, more preferably 0.1-0.5 hour.

(3) two or more be mixed to get in the modifier P2 obtained based on preceding method.When using mixing When method obtains P2, the mixed proportion of the modifier P2 respectively obtaining aforementioned several method does not limit.

The catalyst provided according to the present invention, wherein, described active metal component is preferably cobalt, active metal The content of component is fischer-tropsch synthetic catalyst customary amount, such as, count with oxide and with catalyst as base Standard, the content of described active metal component is 5～70 weight %, preferably 10～50 weight %, more It is preferably 12～30 weight %.

On the premise of being enough to be carried on described carrier described active metal component, the present invention is to described The method on described carrier that active metal component is carried on be not particularly limited.For example, it may be Be enough to by effective dose active metal component be deposited on described carrier under conditions of, by described carrier Contact with the solution of the compound containing active metal component containing effective dose, as by dipping, co-precipitation etc. Method, preferably infusion process, be dried, roasting or not roasting afterwards.Described dry method and be conventional Method, such as, the method for heating, drying, when drying means is heat drying, described dry operation bar Part includes: temperature is 80～350 DEG C, preferably 100～300 DEG C, and the time is 1～24 hour, is preferably 2～12 hours.When described catalyst needs to carry out roasting, the temperature of described roasting is described containing living to realize For the purpose of the compound of property metal component is converted into its oxide, preferred sintering temperature is 200-700 DEG C, Roasting time is 1～6 hour, and further preferred temperature is preferably 250-500 DEG C, and roasting time is 2～4 hours.

The described compound containing active metal component preferably is selected from the one in their soluble compound or several Kind, such as one or more in the water-soluble salt containing active metal component, complex.

Prior art research shows, individually or collectively introduces one group and be selected from fischer-tropsch synthetic catalyst One or more auxiliary agents in Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K Metal component；Or one group of one introduced in Ru, Rh, Pd, Os, Ir, Pt, Ag or Au Or several other adjuvant components, favourable to improving catalyst performance.

According to the present invention provide catalyst, in described catalyst containing selected from Cu, Mo, Ta, One or more promoter metal components in W, Zr, Ti, REO, Re, Mn, V or K, preferably Containing one or more in Ti, Zr, W or Mn, in terms of oxide and with described catalyst it is Benchmark, the content of described promoter metal component is less than 10 weight %, and preferred content is less than 6 weight %。

When in described catalyst containing selected from Cu, Mo, Ta, W, Zr, Ti, REO, Re, During one or both in the components such as Mn, V or K, its introducing method can be by containing described auxiliary agent Compound connect with described carrier after being configured to mixed solution containing compound containing active metal component Touch；Can also is that and contact with described carrier, afterwards after the compound containing auxiliary agent is individually prepared solution It is dried and roasting.When auxiliary agent does not introduce described carrier with active metal component, first with containing Auxiliary compound solution contacts with described carrier, after drying roasting again with containing active metal component The solution contact of compound, such as exchange by ion, impregnate, the method such as co-precipitation, preferably soak Stain method.Described sintering temperature is 200-700 DEG C, preferably 250-500 DEG C, and roasting time is that 2-8 is little Time, preferably 3-6 hour.

According to the present invention provide catalyst, in described catalyst possibly together with selected from Ru, Rh, Pd, The other adjuvant component of one or more in Os, Ir, Pt, Ag or Au, preferably comprises and is selected from One or more in Ru, Pt or Pd, count and on the basis of described catalyst by element, described in help The content of agent metal component is less than 0.3 weight %, and preferred content is less than 0.15 weight %.

When described catalyst contains in Ru, Rh, Pd, Os, Ir, Pt, Ag or Au Kind or during several adjuvant component, its introducing method can be by the compound containing described auxiliary agent with contain Compound containing active metal component (such as, contains choosing with or without the compound of other adjuvant components Chemical combination from Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K adjuvant component Thing) be configured to mixed solution after contact with described carrier；Can also is that the compound list containing auxiliary agent Solely contact with described carrier after preparation solution, be dried afterwards and roasting.When auxiliary agent and active metal component When not introducing described carrier, first contact with described carrier with containing auxiliary compound solution, warp Be dried and after roasting again with containing active metal component the solution of compound (with or without other auxiliary agents The compound of component) contact, such as exchange by ion, impregnate, the method such as co-precipitation, preferably soak Stain method.Described sintering temperature is 200-700 DEG C, preferably 250-500 DEG C, and roasting time is that 2-8 is little Time, preferably 3-6 hour.

There is provided catalyst according to the present invention, needing in presence of hydrogen before Fischer-Tropsch synthesis, will Active metal carries out reduction activation, and reducing condition is: reduction temperature is 100 DEG C to 800 DEG C, is preferably 200 DEG C to 600 DEG C, more preferably 300 DEG C to 450 DEG C；Recovery time is 0.5-72 hour, preferably For 1-24 hour, more preferably 2-8 hour, described reduction can be carried out in pure hydrogen, it is possible to The gaseous mixture of hydrogen and noble gas is carried out, as carried out in hydrogen with the gaseous mixture of nitrogen and/or argon, Hydrogen Vapor Pressure is 0.1-4MPa, preferably 0.1-2MPa.

According to the present invention provide Fischer-Tropsch synthesis method, described by the mixture of carbon monoxide and hydrogen with described The catalytic condition of catalyst: preferable temperature is 160～280 DEG C, more preferably 190～ 250 DEG C, pressure is preferably 1～8MPa, more preferably 1-5MPa, hydrogen and carbon monoxide mole Ratio is 0.4～2.5, preferably 1.5～2.5, more preferably 1.8～2.2, and the time null-rate of gas It it is 200 hours^-1～20000 hours^-1, preferably 500 hours^-1～12000 hours^-1。

The fischer-tropsch synthetic catalyst that the present invention provides uses and includes using bimodal porous aluminum oxide as carrier, makes to urge The performance of agent is improved.Such as, active metal component content, preparation condition at catalyst are identical In the case of, compared with reference agent, the present invention provides the CO activity of conversion of catalyst to improve nearly 6%, methane Selectivity reduces nearly 2%.

Detailed description of the invention

The present invention will be further described for example below, but should be therefore understands that be not the limit to the present invention Fixed.

Bimodal hole carrier that the embodiment 1-13 explanation present invention provides and preparation method thereof.The explanation of comparative example 1-2 Conventional catalyst carrier and preparation method thereof.

The boehmite used below in an example includes:

(pore volume is 1.2 mls/g to the dry glue powder that P1-1: Chang Ling catalyst branch company produces, and specific surface is 280 meters²/ gram, most probable bore dia 15.8nm.Butt is 73%, and wherein boehmite content is 68%, gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 15.8).

(pore volume is 1.1 mls/g to the dry glue powder that P1-2: Yantai Heng Hui Chemical Co., Ltd. produces, specific surface It it is 260 meters²/ gram, most probable bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 17.2).

Modifier P2 and the preparation side thereof of the described P1 of carrier of the present invention is prepared in the explanation of embodiment 1-5 Method.

Embodiment 1

Weigh 1000 grams of P1-1, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) Aqueous solution 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C it is dried 4 hours, obtains dried strip, by dried strip shaping, sieve, by length less than the dried strip of 2mm Material (commonly referred to as industrially drying bar waste material) is milled, and sieves, takes wherein 100～200 mesh sieve Point, obtain the modifier P2A of P1-1.The k value of P2A is shown in Table 1.

Embodiment 2

Weigh 1000 grams of P1-1, dodge dry 6 minutes in 240 DEG C, obtain the modifier P2B of P1-1.P2B K value be shown in Table 1.

Embodiment 3

The each 200 grams of uniform mixing of P2B that P2A embodiment 1 obtained and embodiment 2 obtain, obtain The modifier P2C of P1-1.The k value of P2C is shown in Table 1.

Embodiment 4

Weigh 1000 grams of P1-2, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) Aqueous solution 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C it is dried 4 hours, 1200 DEG C of roastings 4 hours, obtains carrier, by carrier strip shaping, sieve, by length Carrier strip material (commonly referred to as industry carrier waste material) less than 2mm is milled, and sieves, takes wherein 100～200 mesh sieves divide, and obtain the modifier P2D of P1-2.The k value of P2D is shown in Table 1.

Embodiment 5

Weigh 1000 grams of P1-2, dodge dry 10 minutes in 650 DEG C, obtain the modifier P2E of P1-2.P2E K value be shown in Table 1.

Table 1

Embodiment	Raw material	k
			1	P2A	0.5
2	P2B	0.4
			3	P2C	0.4
4	P2D	0
			5	P2E	0.3

The preparation method of carriers for catalysts of the present invention is prepared in the explanation of embodiment 6-13.The explanation of comparative example 1-2 The preparation method of conventional catalyst carrier.

Embodiment 6

Weighing 800 grams of P1-1, after the 200 grams of raw material P2A prepared with embodiment 1 uniformly mix, addition contains The aqueous solution 1440 milliliters of 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), at double screw banded extruder On be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, should 900 DEG C of roastings of article shaped 3 hours, obtain carrier Z1.The character of carrier Z1 is listed in table 2.

Embodiment 7

Weighing 200 grams of P1-1, after the 800 grams of raw material P2B prepared with embodiment 2 uniformly mix, addition contains Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth 900 DEG C of roastings of type thing 3 hours, obtain carrier Z2.The character of carrier Z2 is listed in table 2.

Embodiment 8

Weighing 500 grams of P1-1, after the 500 grams of raw material P2C prepared with embodiment 3 uniformly mix, addition contains Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth 950 DEG C of roastings of type thing 3 hours, obtain carrier Z3.The character of carrier Z3 is listed in table 2.

Comparative example 1

Weigh 1000 grams of P1-1, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution of 10 milliliters 1440 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried in 120 DEG C 4 hours, obtain article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ1.Carrier DZ1 Character be listed in table 2.

Embodiment 9

Weighing 800 grams of P1-2, after the 200 grams of raw material P2D prepared with embodiment 4 uniformly mix, addition contains The aqueous solution 1440 milliliters of 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), at double screw banded extruder On be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, should 1000 DEG C of roastings of article shaped 3 hours, obtain carrier Z4.The character of carrier Z4 is listed in table 2.

Embodiment 10

Weighing 900 grams of P1-1, after the 100 grams of raw material P2E prepared with embodiment 5 uniformly mix, addition contains Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth 1000 DEG C of roastings of type thing 3 hours, obtain carrier Z5.The character of carrier Z5 is listed in table 2.

Embodiment 11

Weighing 850 grams of P1-2, after the 150 grams of raw material P2C prepared with embodiment 3 uniformly mix, addition contains Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth 850 DEG C of roastings of type thing 3 hours, obtain carrier Z6.The character of carrier Z6 is listed in table 2.

Comparative example 2

Weigh 1000 grams of P1-2, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution of 10 milliliters 1440 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried in 120 DEG C 4 hours, obtain article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ2.Carrier The character of DZ2 is listed in table 2.

Embodiment 12

Weighing 900 grams of P1-2, after the 100 grams of raw material P2D prepared with embodiment 4 uniformly mix, addition contains Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth 1000 DEG C of roastings of type thing 3 hours, obtain carrier Z7.The character of carrier Z7 is listed in table 2.

Embodiment 13

Weighing 850 grams of P1-2, after the 150 grams of raw material P2E prepared with embodiment 5 uniformly mix, addition contains Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth 900 DEG C of roastings of type thing 3 hours, obtain carrier Z8.The character of carrier Z8 is listed in table 2.

Table 2

By the result of table 2 it will be seen that compared with conventional method, provider's method of the present invention the oxidation prepared Alumina supporter has obvious structure of double peak holes.

Embodiment 14～21 illustrates the fischer-tropsch synthetic catalyst being provided aluminium oxide shaping carrier to prepare by the present invention.

Z1, Z2, Z3, Z4, Z5, Z6, Z7 and Z8 carrier is molten with the mixing containing cobalt nitrate and platinum chloride ammonia Liquid, carries out saturated dipping, is dried afterwards and roasting, 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 consumption of described cobalt nitrate and platinum chloride ammonia makes cobalt oxide in final catalyst contain Amount is 15 weight %, and platinum content is 0.1 weight %.

Comparative example 3～4

By DZ1, DZ2 carrier with containing cobalt nitrate and the mixed solution of platinum chloride ammonia, carry out saturated dipping, afterwards It is dried and roasting, obtains catalyst CC1, CC2.Wherein, baking temperature is 120 DEG C, drying time Being 6 hours, sintering temperature is 400 DEG C, roasting time 3 hours.Described cobalt nitrate and the consumption of platinum chloride ammonia Making cobalt oxide content in final catalyst is 15 weight %, and platinum content is 0.1 weight %.

The embodiment 22-29 explanation present invention provides application and the effect thereof of catalyst.

The expense of catalyst C1, C2, C3, C4, C5, C6, C7 and C8 is evaluated respectively in fixed bed reactors Torr synthetic reaction performance.

Unstripped gas forms: H₂/CO/N₂=64%/32%/4% (volume hundred number).Catalyst reduction reaction bar Part: pressure is normal pressure, heating rate is 5 DEG C/min, and hydrogen gas space velocity is 600h^-1, reduction temperature is 400 DEG C, the recovery time is 5 hours.

Reaction condition: pressure 2.5MPa, temperature 200 DEG C, synthesis gas (unstripped gas) air speed 2000h-1.Reaction Taking gas sample after carrying out 24 hours and carry out chromatography, wherein, CO conversion ratio and methane selectively are listed in table 3。

Comparative example 5-6 explanation comparative catalyst's performance

Catalyst CC1, CC2 is evaluated respectively according to method similarly to Example 13.Wherein, CO conversion ratio and Methane selectively is listed in table 3.

Table 3

From table 3 it can be seen that the bimodal porous aluminum oxide using the present invention to provide is used as catalyst carrier, then Being prepared as fischer-tropsch synthetic catalyst, this catalyst has more preferable Fischer-Tropsch in the case of other condition is identical and closes Become performance, the most higher CO conversion ratio, lower methane selectively.

Claims

1. a fischer-tropsch synthetic catalyst, containing carrier and active metal component, wherein, described carrier For a kind of aluminium oxide with bimodal hole, characterizing with mercury injection method, the pore volume of described carrier is 0.9-1.2 Ml/g, specific surface area is 50-300 rice²/ gram, the pore volume in a diameter of 10-30nm hole accounts for total hole The 55-80% held, the pore volume in a diameter of 300-500nm hole accounts for the 10-35% of total pore volume.

Catalyst the most according to claim 1, it is characterised in that the pore volume of described carrier is 0.95-1.15 ml/g, specific surface area is 80-200 rice²/ gram, the hole in a diameter of 10-30nm hole Volume accounts for the 60-75% of total pore volume, and the pore volume in a diameter of 300-500nm hole accounts for the 15-of total pore volume 30%.

Catalyst the most according to claim 1, it is characterised in that described active metal component is Cobalt, on the basis of catalyst, the content of the active metal component counted with oxide is for 5-70 weight Amount %.

Catalyst the most according to claim 3, it is characterised in that on the basis of catalyst, with The content of the active metal component of oxide meter is 10-50 weight %.

Catalyst the most according to claim 4, it is characterised in that on the basis of catalyst, with The content of the active metal component of oxide meter is 12-30 weight %.

Catalyst the most according to claim 1, it is characterised in that containing choosing in described catalyst One or more in Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K first help Agent component, on the basis of catalyst, the content of the first adjuvant component in terms of oxide is 10 weight % Below.

Catalyst the most according to claim 6, it is characterised in that described first promoter metal group It is selected from one or more in Ti, Zr, W or Mn, on the basis of catalyst, in terms of oxide The content of the first adjuvant component is below 6 weight %.

8. according to the catalyst described in claim 1 or 6, it is characterised in that described catalyst contains There is the second auxiliary agent group of one or more in Ru, Rh, Pd, Os, Ir, Pt, Ag or Au Point, on the basis of catalyst, the content of the second adjuvant component in terms of element 0.5 weight % with Under.

Catalyst the most according to claim 8, it is characterised in that described second adjuvant component choosing One or more in Ru, Pt or Pd, the second auxiliary agent on the basis of catalyst, in terms of element The content of component is below 0.3 weight %.

10. the preparation method of catalyst described in claim 1, including preparing carrier and bearing on this carrier Carrying active metal component, wherein, the preparation method of described carrier includes the water containing boehmite Close the modifier P2 mixing of aluminium oxide P1 and P1, molding, be dried and roasting, wherein, described P1 It is 0 to less than or equal to 0.9 with the κ value that Mixing ratio by weight is 20-95:5-80, P2 of P2, described κ=DI₂/DI₁, DI₁For the sour peptization index of the hydrated alumina P1 containing boehmite, DI₂For The sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite.

11. methods according to claim 10, it is characterised in that the weight of described P1 and P2 Mixing ratio be the κ value of 70-95:5-30, P2 be 0 to less than or equal to 0.6.

12. according to the method described in claim 10 or 11, it is characterised in that described containing intending thin water The pore volume of the hydrated alumina P1 of aluminum stone is 0.9-1.4 ml/g, and specific surface area is 100-350 rice²/ gram, most probable bore dia 8-30nm.

13. methods according to claim 12, it is characterised in that described containing boehmite The pore volume of hydrated alumina P1 be 0.95-1.3 ml/g, specific surface area is 120-300 rice²/ Gram, most probable bore dia 10-25nm.

14. according to the method described in claim 10 or 11, it is characterised in that described P2 is 80- The particulate matter of 300 mesh.

15. methods according to claim 14, it is characterised in that described P2 is 100-200 mesh Particulate matter.

16. methods according to claim 10, it is characterised in that described dry condition bag Including: temperature is 40-350 DEG C, the time is 1-24 hour, and the condition of described roasting includes: temperature is More than 500 to less than or equal to 1200 DEG C, the time is 1-8 hour.

17. methods according to claim 10, it is characterised in that described dry condition bag Including: temperature is 100-200 DEG C, the time is 2-12 hour, and the condition of described roasting includes: temperature is More than 800 to less than or equal to 1000 DEG C, roasting time is 2-6 hour.

18. methods according to claim 10, it is characterised in that P1 is modified as the side of P2 One of method is by described hydrated alumina P1 molding containing boehmite, is dried, afterwards that it is complete Portion or part are ground, sieve, and obtaining powder body thing is P2, and described dry condition includes: temperature For 40-350 DEG C, the time is 1-24 hour；The two of method are article shaped roastings method one obtained Burning, sintering temperature is that roasting time is 1-8 hour, afterwards more than 350 to less than or equal to 1400 DEG C It being completely or partially ground, sieve, obtaining powder body thing is P2；The three of method are by containing intending The hydrated alumina P1 of boehmite dodges dry, and dodging dry temperature is to being less than or equal to more than 150 1400 DEG C, flash-off time is 0.05-1 hour, and obtaining powder body thing is P2；The four of method are by method One of, the two of method and the modifier that obtains with the three of method in one or more be mixed to get.

19. methods according to claim 18, it is characterised in that being dried in described method one Condition include: temperature is 100-200 DEG C, and the time is 2-12 hour；The dry temperature of sudden strain of a muscle in the three of method Degree is for 200-1000 DEG C, and flash-off time is 0.1-0.5 hour.

20. according to the method described in claim 18 or 19, it is characterised in that described P2 is that P1 changes The particulate matter of 80-300 mesh in property thing.

21. methods according to claim 20, it is characterised in that described P2 is P1 modifier The particulate matter of middle 100-200 mesh.

22. methods according to claim 10, it is characterised in that described alive at supported on carriers The method of property metal component is infusion process, counts and on the basis of catalyst by oxide, described dipping Making the content of active metal component in described catalyst is 5-70 weight %.

23. methods according to claim 22, it is characterised in that described active metal component is Cobalt, counts and on the basis of catalyst by oxide, and described dipping makes active metal in described catalyst The content of component is 10-50 weight %.

24. methods according to claim 23, it is characterised in that in terms of oxide and with catalysis On the basis of agent, described dipping makes the content of active metal component in described catalyst be 12-30 weight Amount %.

25. methods according to claim 10, it is characterised in that described method includes drawing Enter the one in Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K Or the step of several first promoter metal component, count with oxide and with described catalyst as base Standard, the introduction volume of described promoter metal component is less than 10 weight %.

26. methods according to claim 25, it is characterised in that described first promoter metal One or more in Ti, Zr, W or Mn of component, urge in terms of oxide and with described On the basis of agent, the introduction volume of described first promoter metal component is less than 6 weight %.

27. according to the method described in claim 10 or 25, it is characterised in that in described method Including one or more introduced in Ru, Rh, Pd, Os, Ir, Pt, Ag or Au the The step of two promoter metal components, counts and on the basis of described catalyst by element, described second The introduction volume of promoter metal component is less than 0.5 weight %.

28. methods according to claim 27, it is characterised in that described second promoter metal One or more in Ru, Pt or Pd of component, in terms of element and with described catalyst be Benchmark, the introduction volume of described second promoter metal component is less than 0.3 weight %.

29. 1 kinds of Fischer-Tropsch synthesis methods, are included in carbon monoxide and hydrogen under the conditions of Fischer-Tropsch synthesis Mixture and catalyst haptoreaction, it is characterised in that described catalyst is that claim 1-9 is appointed One described catalyst.