CN104437479B - A kind of ruthenio fischer-tropsch synthetic catalyst and preparation thereof and application - Google Patents
A kind of ruthenio fischer-tropsch synthetic catalyst and preparation thereof and application Download PDFInfo
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Abstract
A kind of ruthenio fischer-tropsch synthetic catalyst and preparation thereof and application, containing alumina support and active metal component ruthenium, wherein, described carrier has structure of double peak holes, characterizes with mercury injection method, and the pore volume of described carrier is 0.6 1.4 mls/g, and specific surface area is 80 400 meters2/ 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 the 15 45% of total pore volume.Compared with prior art, the catalyst that the present invention provides has more preferable F-T synthesis performance.
Description
Technical field
The present invention relates to a kind of fischer-tropsch synthetic catalyst and preparation and application thereof, more specifically to a kind of ruthenium
Base fischer-tropsch synthetic catalyst and preparation and application thereof.
Background technology
Nineteen twenty-three, Fischer and Tropsch is found that the mixture Synthin product of CO and H2
Method.The active component of fischer-tropsch synthetic catalyst is mainly main with Fe, Co and Ru, and its activity height is the most suitable
Sequence is Ru > Co > Fe, chain growth probability order substantially Ru > Co > Fe.
Literature research shows, Ru base catalyst can maintain in higher water partial pressure and oxygenatedchemicals atmosphere
Higher activity, thus be possibly used in biomass synthesis gas conversion reaction.With molecular sieve as carrier, literary composition
Offer [Phys.Chem.C, 2008,112:9706] and have studied Ru catalysis molecular sieve carried for SBA-15
Agent, compared with the factor such as Ru particle size, F-T is synthesized by the confinement effect of SBA-15 molecular sieve pore passage
The impact of products distribution is bigger；Also researcher [Chem Cat Chem, 2010,2:1030] is had to be prepared for
Ru/meso-ZSM5 Fischer-Tropsch catalyst, this catalyst has high C5-11 selectivity；Changed by alkali
Property and hole optimize, on 3%Ru/meso-beta catalyst, the selectivity of the C5-11 of F-T synthetic reaction can
Reach 77.2% [the 13rd the youth of the nation catalysis academic meeting paper collection, 2011,89].With CNT it is
Carrier, document [Angew.Chem., Int Ed, 2009,48:2565] is prepared for Ru/CNT catalysis
Agent, this catalyst has high C10-20 selectivity, under suitable acidity and Ru particle diameter, C10-20 hydrocarbon
Selectivity reaches 65%.
Active metal metal component Ru is loaded on carrier, Ru base FT synthetic catalyst can be obtained.But carry
The difference of volume property, the performance of FT synthetic catalyst is the biggest by difference.
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 ruthenio fischer-tropsch synthetic catalyst, containing alumina support and active metal component ruthenium, wherein,
Described carrier has structure of double peak holes, with mercury injection method characterize, the pore volume of described carrier be 0.6-1.4 milliliter/
Gram, specific surface area is 80-400 rice2/ gram, the pore volume in a diameter of 5-20nm hole accounts for total pore volume
30-60%, the pore volume in a diameter of 100-300nm hole accounts for the 15-45% of total pore volume.
2. according to the catalyst described in 1, it is characterised in that the pore volume of described carrier be 0.7-1.3 milliliter/
Gram, specific surface area is 100-300 rice2/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 35-of total pore volume
50%, the pore volume in a diameter of 100-300nm hole accounts for the 20-40% of total pore volume.
3. the work according to the catalyst described in 1, it is characterised in that on the basis of catalyst, in terms of oxide
The content of property metal component ruthenium is 0.5-30 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 ruthenium is 1-20 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 ruthenium is 2-10 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 Rh,
One or more in Pd, Os, Ir, Pt, Ag or Au the second adjuvant component, on the basis of catalyst,
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 is in Pt or Pd
One or more, on the basis of catalyst, the content of the second adjuvant component in terms of element is in 0.3 weight
Below %.
10. according to the preparation method of catalyst described in 1, including preparing carrier supported active on this carrier
Metal component ruthenium, wherein, the preparation of described carrier includes the hydrated alumina PA containing boehmite
Mix with the modifier PC of PB with a kind of hydrated alumina containing boehmite, molding, be dried and roast
Burning, wherein, the Mixing ratio by weight of described PA, PB and PC is the κ of 20-60:20-50:5-50, PC
Value is 0 to less than or equal to 0.9, described κ=DI2/DI1, DI1Sour glue for PC hydrated alumina before modified
Molten index, DI2Sour peptization index for described PC.
11. according to the method described in 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 described PC 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 PA is 0.75-1 ml/g, and specific surface is 200-450 rice2/ gram, most probable hole is straight
Footpath 3-10nm；The pore volume of the described hydrated alumina PB containing boehmite is 0.9-1.4 ml/g,
Specific surface is 100-350 rice2/ gram, most probable bore dia is more than 10 to less than or equal to 30nm.
13. according to the method described in 12, it is characterised in that the described 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；The pore volume of the described hydrated alumina PB containing boehmite is 0.95-1.3 ml/g, than
Surface is 120-300 rice2/ gram, most probable bore dia is more than 10 to less than or equal to 25nm.
14. according to the method described in 10 or 11 any one, it is characterised in that described PC is 80-300
Purpose particulate matter.
15. according to the method described in 14, it is characterised in that described PC 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 16, 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 the hydrated alumina containing boehmite is changed
Property be that one of the method for PC is by described hydrated alumina molding containing boehmite, is dried, afterwards
It being completely or partially ground, sieve, described dry condition includes: temperature is 40-350 DEG C, time
Between be 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；The three of method are to dodge dry by the hydrated alumina containing boehmite, dodge dry temperature be more than 150 to
Less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour；The four of method be by one of method, method it
Two and the modifier that obtains with the three of method in one or more 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, it is characterised in that described PC is the hydration containing boehmite
The particulate matter of 80-300 mesh in the modifier of aluminium oxide.
21. according to the method described in 20, it is characterised in that described PC is the hydration containing boehmite
The particulate matter of 100-200 mesh in the modifier of aluminium oxide.
22. according to the method described in 10, it is characterised in that described at supported on carriers active metal component ruthenium
Method be infusion process, count and on the basis of catalyst by oxide, described dipping makes in described catalyst
The content of active metal component is 0.5-30 weight %.
23. method according to claim 22, it is characterised in that in terms of oxide and with catalyst be
Benchmark, described dipping makes the content of active metal component in described catalyst be 1-20 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 2-10 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 promoter metal introduced in Rh, Pd, Os, Ir, Pt, Ag or Au
The step of component, counts and on the basis of described catalyst by element, described second promoter metal component
Introduction volume 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 Pt or Pd of component, count and on the basis of described catalyst by element, institute
State the introduction volume of the second promoter metal component 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 aforementioned any one of claim 1-9
Catalyst described in claim.
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.
In the present invention, described acid peptization index D I refers to the hydrated alumina containing boehmite and contains
After the hydrated alumina modifier having boehmite adds nitric acid by certain acid aluminum ratio, when certain reaction
In by the hydrated alumina containing boehmite of peptization with Al2O3The percent of meter, DI=(1-W2/W1)
× 100%, W1And W2Before being respectively hydrated alumina and the acid reaction containing boehmite and with acid reaction after
With Al2O3The weight of meter.
The mensuration of DI includes: the calcination base (1) measuring the hydrated alumina containing boehmite is (the most dry
Base) (calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours content, after it burns
Weight weight ratio front with burning, is expressed as a percentage), it is calculated as a；(2) weigh containing intending thin with analytical balance
The hydrated alumina W of diaspore0Gram, W0Amount meet with Al2O3The W of meter1It is 6 grams of (W1/a=W0), claim
Remove ionized water W gram, W=40.0-W0, under stirring by the hydrated alumina containing boehmite that weighs and
Deionized water adds in beaker and mixes；With 20mL pipet pipette 20mL, concentration is dilute nitre of 0.74N
Acid solution, joins in the beaker of step (2) by this acid solution, the lower reaction of stirring 8 minutes；(4) will step
Suddenly (3) reacted serosity is centrifuged separating in centrifuge, and precipitate is inserted the crucible weighed
In, afterwards, it is dried 4 hours in 125 DEG C, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh
To 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
Hydrated alumina PA and PB of stone does not specially require, and can be plan thin water aluminum prepared by any prior art
Stone, it is also possible to be boehmite and the mixture of other hydrated alumina, other aqua oxidation described
One or more in a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide of aluminum.
In a detailed description of the invention, the described preferred pore volume of hydrated alumina PA containing boehmite
For 0.75-1 ml/g, specific surface is 200-450 rice2/ gram, most probable bore dia 3-10nm, further
Preferably pore volume is 0.80-0.95 ml/g, and specific surface is 200-400 rice2/ gram, most probable bore dia 5-
10nm；The described preferred pore volume of hydrated alumina PB containing boehmite is 0.9-1.4 ml/g, than
Surface is 100-350 rice2/ gram, most probable bore dia more than 10 to less than or equal to 30nm, further preferably
Pore volume 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.
In the present invention, the pore volume of the hydrated alumina containing boehmite, specific surface area and can and hole
Footpath, is by the described hydrated alumina containing boehmite after 600 DEG C of roastings 4 hours, by BET nitrogen
Absorption representation obtains.
In further preferred embodiment, characterize with X diffraction, the described hydration containing boehmite
Boehmite content in aluminium oxide PA and PB is not less than 50%, more preferably not less than 60%.
Inventors of the present invention have surprisingly found that, the hydrated alumina containing boehmite is carried out heat treatment
Obtain modifier PC, relative to the original hydrated alumina containing boehmite, the glue of modifier PC
Molten index changes, after by this modifier and PA and PB mixed-forming, dry also roasting, and gained
To carrier there is obvious bimodal pore distribution.Particularly at the granule by 80-300 mesh therein, preferably
The granule of 100-200 mesh and PA and PB mixed-forming, it is dried and after roasting, obtained carrier bimodal
In each unimodal pore size distribution concentrate especially.Here, the granule of described 80-300 mesh, preferably 100-200
Purpose granule refers to that described modifier (includes step that is broken or that grind) if desired through sieving, and it sieves thing
(siftage) meets the granule of 80-300 mesh, and the particulate matter of preferably 100-200 mesh accounts for the percent of total amount
(by weight) not less than 60%, further preferably not less than 70%.Here containing boehmite
Hydrated alumina can be boehmite prepared by any prior art, it is also possible to be boehmite and its
The mixture of his hydrated alumina, described other hydrated alumina selected from a water aluminium oxide, three water oxidation
One or more in aluminum and amorphous hydrated aluminium oxide.In a preferred embodiment, described PC is PA
And/or the modifier of PB.
In the present invention, described PA, PB refer to the most described PA, PB and PC with the Mixing ratio by weight of PC
Mixture in the ratio of PA, PB and PC respectively shared parts by weight.Wherein, PA:PB:PC is preferably
20-60:20-50:5-50, more preferably 30-50:35-50:10-30.
In the present invention, described PC conveniently can be obtained by following method:
Hereinafter, the method illustrating to obtain PC with described PA and PB for initiation material.
(1) based on being dried to obtain PC, including by hydrated alumina PA and/or PB containing boehmite by
During regular oxidation alumina supporter is prepared in conventional method molding, the tailing of drying by-product, such as: in extrusion
In molding, bar shaped article shaped (is referred to as being dried giving up at tailing dry, integer process by-product traditionally
Material), this tailing is milled, sieves and obtain PC.
(2) obtain based on roasting, including by hydrated alumina PA and/or PB containing boehmite by often
During regular oxidation alumina supporter is prepared in rule method molding, the tailing of fired by-product (is referred to as roasting traditionally
Waste material), such as, in roller forming, spheroidal particle is the tailing of by-product in roasting process, by this tailing
Mill, sieve and obtain PC；Or directly PA and/or PB is dodged dry obtaining, directly by PA and
/ or time PB dodges dry, flash-off time is preferably 0.05-1 hour, more preferably 0.1-0.5 hour.
(3) two or more be mixed to get in the modifier PC obtained based on preceding method.Mixed when using
When conjunction method obtains C, the mixed proportion of the modifier PC respectively obtaining aforementioned several method does not limit
System.
The catalyst provided according to the present invention, counts and on the basis of catalyst by oxide, described activity gold
The content belonging to component is 0.5～30 weight %, and preferably 1～20 weight % are more preferably 2～10 weights
Amount %.
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
Cu, Mo, Ta, W, Zr, Ti, REO(rare earth), one or more in Re, Mn, V or K
Promoter metal component；Or one group of one introduced in 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, W,
Zr, Ti, REO(rare earth), one or more promoter metal components in Re, Mn, V or K, excellent
Choosing is containing one or more in Ti, Zr, W or Mn, in terms of oxide and with described catalyst
On the basis of, the content of described promoter metal component is less than 10 weight %, and preferred content is less than 6 weights
Amount %.
When described catalyst contains selected from Cu, Mo, Ta, W, Zr, Ti, REO(rare earth),
During one or both in the components such as Re, Mn, V or K, its introducing method can be by containing described
The compound of auxiliary agent with containing compound containing active metal component be configured to after mixed solution with described load
Body contacts；Can also is that and contact with described carrier after the compound containing auxiliary agent is individually prepared solution,
It is dried afterwards and roasting.When auxiliary agent does not introduce described carrier with active metal component, first use
Contact with described carrier containing auxiliary compound solution, after drying roasting again with containing active metal group
Point the solution contact of compound, such as exchange by ion, impregnate, the method such as co-precipitation, excellent
Select infusion process.Described sintering temperature is 200-700 DEG C, preferably 250-500 DEG C, and roasting time is
2-8 hour, preferably 3-6 hour.
According to the present invention provide catalyst, in described catalyst possibly together with selected from Rh, Pd, Os,
The other adjuvant component of one or more in Ir, Pt, Ag or Au, preferably comprise selected from Pt or
One or more in Pd, count and on the basis of described catalyst by element, described promoter metal component
Content less than 0.3 weight %, preferred content is less than 0.15 weight %.
When in described catalyst containing in Rh, Pd, Os, Ir, Pt, Ag or Au one or
During several adjuvant component, its introducing method can be to be lived with containing containing by the compound containing described auxiliary agent
Property metal component compound with or without the compound of other adjuvant components (such as, containing being selected from
The compound of Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K adjuvant component)
Contact with described carrier after being configured to mixed solution；Can also is that and the compound containing auxiliary agent is individually joined
Contact with described carrier after solution processed, be dried afterwards and roasting.When auxiliary agent does not draw with active metal component
When entering described carrier, first contact with described carrier with containing auxiliary compound solution, drying
And after roasting again with containing active metal component the solution of compound (with or without other adjuvant components
Compound) contact, such as exchange by ion, impregnate, the method such as co-precipitation, preferably impregnate
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%, and methane selects
Selecting property 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.
The boehmite used below in an example includes:
(pore volume is 0.9 ml/g to the dry glue powder that PA-1: Chang Ling catalyst branch company produces, and specific surface is
280 meters2/ gram, most probable bore dia 8.5nm.Butt is 73%, and wherein boehmite content is 68%,
Gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 34.6).
(pore volume is 0.9 ml/g to the dry glue powder of PA-2: Zibo limited production of neat cyclopentadienyl catalyst, and specific surface is
290 meters2/ gram, most probable bore dia 8.3nm.Butt is 73%, and wherein boehmite content is 68%,
Gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 33.2).
(pore volume is 1.2 mls/g to the dry glue powder that PB-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 PB-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).
Embodiment 1-10 illustrates PC of the present invention and preparation method thereof.
Embodiment 1
Weigh 1000 grams of PA-1, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product)
Aqueous solution 1000 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 PC-A1 of PA-1.The k value of PC-A1 is shown in Table 1.
Embodiment 2
Weigh 1000 grams of PA-1, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product)
Aqueous solution 1000 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, 800 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 PC-A2 of PA-1.The k value of PC-A2 is shown in Table 1.
Embodiment 3
Weigh 1000 grams of PA-2, dodge dry 6 minutes in 400 DEG C, obtain the modifier PC-A3 of PA-2.PC-
The k value of A3 is shown in Table 1.
Embodiment 4
The each 200 grams of uniform mixing of PC-A3 that PC-A1 embodiment 1 obtained and embodiment 3 obtain,
Modifier PC-A4 to PA-1 and PA-2.The k value of PC-A4 is shown in Table 1.
Embodiment 5
Weigh 1000 grams of PB-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, 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 PC-B1 of PB-1.The k value of PC-B1 is shown in Table 1.
Embodiment 6
Weigh 1000 grams of PB-2, dodge dry 10 minutes in 650 DEG C, obtain the modifier PC-B2 of PB-2.
The k value of PC-B2 is shown in Table 1.
Embodiment 7
Weigh 1000 grams of PB-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, 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 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 PC-B1 embodiment 5 obtained and embodiment 6 obtain,
Modifier PC-B4 to PB-1 and PB-2.The k value of PC-B4 is shown in Table 1.
Embodiment 9
150 grams of PC-B3 that 100 grams of PC-A1 embodiment 1 obtained and embodiment 7 obtain uniformly mix
Close, obtain the modifier PC-B5 of PA-1 and 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 PC-A3 embodiment 3 obtained and embodiment 5 obtain,
Modifier PC-B6 to PA-2 and PB-1.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 provides and preparation method thereof.Comparative example 1-5 is said
Bright conventional catalyst carrier and preparation method thereof.
Embodiment 11
Weighing each 400 grams of PA-1 and PB-1, the 200 grams of raw material PC-A2 prepared with embodiment 2 uniformly mix
After conjunction, add the aqueous solution 1300 milliliters containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product),
The butterfly bar of external diameter φ 1.4mm it is extruded on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, obtains
Article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier Z1.The character of carrier Z1 is listed in table
2。
Embodiment 12
Weigh 300 grams of PA-2,200 grams of PB-2, uniform with 500 grams of raw material PC-B2 that embodiment 6 prepares
After mixing, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution 1300 milliliters of 10 milliliters,
The butterfly bar of external diameter φ 1.4mm it is extruded on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, obtains
Article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier Z2.The character of carrier Z2 is listed in table
2。
Embodiment 13
Weigh 500 grams of PA-2,300 grams of PB-2, uniform with 200 grams of raw material PC-B4 that embodiment 8 prepares
After mixing, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution 1300 milliliters of 10 milliliters,
The butterfly bar of external diameter φ 1.4mm it is extruded on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, obtains
Article shaped, by 950 DEG C of roastings of this article shaped 3 hours, obtains carrier Z3.The character of carrier Z3 is listed in table
2。
Comparative example 1
Weigh 500 grams of PA-2,500 grams of PB-2, uniformly add chemical reagent three factory Han nitric acid Tianjin after mixing
Product) aqueous solution 1300 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly of external diameter φ 1.4mm
Shape bar.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by little for the 900 DEG C of roastings 3 of this article shaped
Time, obtain carrier DZ1.The character of carrier DZ1 is listed in table 2.
Comparative example 2
Weigh 400 grams of PA-1,600 grams of PB-1, uniformly add chemical reagent three factory Han nitric acid Tianjin after mixing
Product) aqueous solution 1300 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly of external diameter φ 1.4mm
Shape bar.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by little for the 950 DEG C of roastings 3 of this article shaped
Time, obtain carrier DZ2.The character of carrier DZ2 is listed in table 2.
Embodiment 14
Weigh 250 grams of PA-1,500 grams of PB-1, uniform with 250 grams of raw material PC-B5 that embodiment 9 prepares
After mixing, add the aqueous solution 1300 milliliters containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product),
Double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C,
To article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier Z4.The character of carrier Z4 is listed in
Table 2.
Embodiment 15
Weigh 350 grams of PA-2,350 grams of PB-2, equal with 300 grams of raw material PC-B6 that embodiment 10 prepares
After even mixing, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution 1440 milliliters of 10 milliliters,
Double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C,
To article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier Z5.The character of carrier Z5 is listed in
Table 2.
Embodiment 16
Weigh 200 grams of PA-1,600 grams of PB-1, uniform with 200 grams of raw material PC-B1 that embodiment 5 prepares
After mixing, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution 1440 milliliters of 10 milliliters,
The butterfly bar of external diameter φ 1.4mm it is extruded on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, obtains
Article shaped, by 850 DEG C of roastings of this article shaped 3 hours, obtains carrier Z6.The character of carrier Z6 is listed in table
2。
Embodiment 17
Weigh 200 grams of PA-1,600 grams of PB-1, uniform with 200 grams of raw material PC-A4 that embodiment 4 prepares
After mixing, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution 1440 milliliters of 10 milliliters,
The butterfly bar of external diameter φ 1.4mm it is extruded on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, obtains
Article shaped, by 850 DEG C of roastings of this article shaped 3 hours, obtains carrier Z7.The character of carrier Z76 is listed in table
2。
Embodiment 18
Weigh 200 grams of PA-1,600 grams of PB-1, uniform with 200 grams of raw material PC-A2 that embodiment 2 prepares
After mixing, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution 1440 milliliters of 10 milliliters,
The butterfly bar of external diameter φ 1.4mm it is extruded on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, obtains
Article shaped, by 850 DEG C of roastings of this article shaped 3 hours, obtains carrier Z8.The character of carrier Z8 is listed in table
2。
Comparative example 3
The method provided according to patent CN1782031A embodiment 7, is extruded into external diameter on plunger type bar extruder
The butterfly bar of φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 900 DEG C
Roasting 3 hours, obtains carrier DZ3.The character of carrier DZ3 is listed in table 2.
Comparative example 4
The method provided according to patent CN1120971A embodiment 1, is extruded into external diameter on plunger type bar extruder
The butterfly bar of φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 1000
DEG C roasting 3 hours, obtains carrier DZ3.The character of carrier DZ3 is listed in table 2.
Comparative example 5
Weigh 200 grams of PA-1,800 grams of PB-2, add the product in nitric acid Tianjin chemical reagent three factory) 10
The aqueous solution 1300 milliliters of milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar
It is dried 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier
DZ5.The character of carrier DZ5 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 19-26
The fischer-tropsch synthetic catalyst being provided aluminium oxide shaping carrier to prepare by the present invention is described.
By Z1, Z2, Z3, Z4, Z5, Z6, Z7 and Z8 carrier in embodiment with containing nitrosyl nitrate
Ruthenium and the mixed solution of zirconium nitrate, carry out saturated dipping, be dried afterwards and roasting, respectively obtain catalysis
Agent C1, C2, C3, C4, C5, C6, C7 and C8.Wherein, baking temperature is 120 DEG C, and drying time is
6 hours, sintering temperature was 400 DEG C, roasting time 3 hours.Described nitrosyl nitrate ruthenium and zirconium nitrate
Consumption make Ru content in final catalyst be 4.5 weight %, Zr content is 5.0 weight %.
Comparative example 6-10
By DZ1, DZ2, DZ3, DZ4 and DZ5 carrier mixed solution containing nitrosyl nitrate ruthenium and zirconium nitrate,
Carry out saturated dipping, be dried afterwards and roasting, respectively obtain catalyst DC1, DC2, DC3, DC4 and
DC5.Wherein, baking temperature is 120 DEG C, and drying time is 6 hours, and sintering temperature is 400 DEG C, roasting
3 hours time.The consumption of described nitrosyl nitrate ruthenium and zirconium nitrate makes the Ru content in final catalyst be
4.5 weight %, Zr content is 5.0 weight %.
Embodiment 27-34
Illustrate that the 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
Take gas sample after carrying out 24 hours and carry out chromatography, wherein, COization charcoal percent conversion and methane selectively row
In table 3.
Comparative example 11-15
Comparative catalyst's performance is described, evaluates catalyst respectively according to the method as embodiment 27-34
DC1、DC2、DC3、DC4、DC5.Wherein, COization charcoal percent conversion and methane selectively are listed in table 3.
Table 3
| Embodiment | Sample ID | CO conversion ratio, % | Methane selectively, % | C5+ hydrocarbon selective, % |
| 17 | C1 | 33.5 | 1.62 | 94.3 |
| 18 | C2 | 34.2 | 1.87 | 95.1 |
| 19 | C3 | 35.6 | 1.56 | 95.3 |
| 20 | C4 | 34.6 | 1.71 | 96.1 |
| 21 | C5 | 34.1 | 1.76 | 94.8 |
| 22 | C6 | 33.9 | 1.69 | 95.2 |
| 23 | C7 | 35.2 | 1.73 | 95.7 |
| 24 | C8 | 35.1 | 1.74 | 95.6 |
| Comparative example 11 | DC1 | 27.1 | 3.12 | 87.4 |
| Comparative example 12 | DC2 | 26.4 | 2.98 | 87.9 |
| Comparative example 13 | DC3 | 25.6 | 2.67 | 88.2 |
| Comparative example 14 | DC4 | 26.8 | 2.81 | 88.4 |
| Comparative example 15 | DC5 | 25.3 | 2.79 | 88.4 |
From table 3 it can be seen that the bimodal porous aluminum oxide using the present invention to provide is used as catalyst carrier, system
Standby one-tenth ruthenio fischer-tropsch synthetic catalyst, this catalyst has more preferable expense in the case of other condition is identical
Torr synthesis performance, the most higher CO conversion ratio and C5+ hydrocarbon selective, lower methane selectively.
Claims (29)
1. a ruthenio fischer-tropsch synthetic catalyst, containing alumina support and active metal component ruthenium, its
In, described carrier has structure of double peak holes, characterizes with mercury injection method, and the pore volume of described carrier is 0.6-
1.4 mls/g, specific surface area is 80-400 rice2/ gram, the pore volume in a diameter of 5-20nm hole accounts for always
The 30-60% of pore volume, the pore volume in a diameter of 100-300nm hole accounts for the 15-45% of total pore volume.
Catalyst the most according to claim 1, it is characterised in that the pore volume of described carrier is
0.7-1.3 ml/g, specific surface area is 100-300 rice2/ gram, the hole body in a diameter of 5-20nm hole
The long-pending 35-50% accounting for total pore volume, the pore volume in a diameter of 100-300nm hole accounts for the 20-of total pore volume
40%.
Catalyst the most according to claim 1, it is characterised in that on the basis of catalyst, with
The content of the active metal component ruthenium of oxide meter is 0.5-30 weight %.
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 ruthenium of oxide meter is 1-20 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 ruthenium of oxide meter is 2-10 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 adjuvant component choosing
One or more in Ti, Zr, W or Mn, on the basis of catalyst, first in terms of oxide
The content of 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 adjuvant component of one or more in Rh, Pd, Os, Ir, Pt, Ag or Au, with
On the basis of catalyst, the content of the second adjuvant component in terms of element is below 0.5 weight %.
Catalyst the most according to claim 8, it is characterised in that described second adjuvant component choosing
One or more in Pt or Pd, the second adjuvant component on the basis of catalyst, in terms of element
Content below 0.3 weight %.
The most according to claim 1, the preparation method of catalyst, including preparing carrier and in this load
Supported active metals component ruthenium on body, wherein, the preparation of described carrier includes containing boehmite
The modifier PC of hydrated alumina PA and PB and a kind of hydrated alumina containing boehmite mix
Conjunction, molding, dry and roasting, wherein, the Mixing ratio by weight of described PA, PB and PC is 20-
The κ value of 60:20-50:5-50, PC is 0 to less than or equal to 0.9, described κ=DI2/DI1, DI1For
The sour peptization index of PC hydrated alumina before modified, DI2Sour peptization index for described PC.
11. methods according to claim 10, it is characterised in that described PA, PB and PC's
Mixing ratio by weight is 30-50:35-50:10-30；The κ value of described PC is 0 to being 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 PA of aluminum stone is 0.75-1 ml/g, and specific surface area is 200-450 rice2/
Gram, most probable bore dia 3-10nm；The pore volume of the described hydrated alumina PB containing boehmite
For 0.9-1.4 ml/g, specific surface area is 100-350 rice2/ gram, most probable bore dia is more than 10
To less than or equal to 30nm.
13. methods according to claim 12, it is characterised in that described containing boehmite
The pore volume of hydrated alumina PA be 0.80-0.95 ml/g, specific surface area is 200-400 rice2/
Gram, most probable bore dia 5-10nm；The pore volume of the described hydrated alumina PB containing boehmite
For 0.95-1.3 ml/g, specific surface area is 120-300 rice2/ gram, most probable bore dia is more than 10
To less than or equal to 25nm.
14. according to the method described in claim 10 or 11 any one, it is characterised in that described
PC is the particulate matter of 80-300 mesh.
15. methods according to claim 14, it is characterised in that described PC 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 16, 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 by containing boehmite
One of hydrated alumina method being modified as PC is to be become by the described hydrated alumina containing boehmite
Type, be dried, afterwards it is completely or partially ground, sieves, described dry condition includes:
Temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are the molding one of method obtained
Thing roasting, sintering temperature is that roasting time is 1-8 hour more than 350 to less than or equal to 1400 DEG C,
Afterwards it is completely or partially ground, sieves；The three of method are by the water containing boehmite
Closing aluminium oxide and dodge dry, dodging dry temperature is that flash-off time is more than 150 to less than or equal to 1400 DEG C
0.05-1 hour；The four of method are by three modifiers obtained of one of method, the two of method and method
In several be mixed to get.
19. methods according to claim 18, it is characterised in that doing in one of described method
Dry condition includes: temperature is 100-200 DEG C, and the time is 2-12 hour；Sudden strain of a muscle in the three of method is done
Temperature is 200-1000 DEG C, and flash-off time is 0.1-0.5 hour.
20. methods according to claim 18, it is characterised in that described PC is for containing intending thin water
The particulate matter of 80-300 mesh in the modifier of the hydrated alumina of aluminum stone.
21. methods according to claim 20, it is characterised in that described PC is for containing intending thin water
The particulate matter of 100-200 mesh in the modifier of the hydrated alumina of aluminum stone.
22. methods according to claim 10, it is characterised in that described alive at supported on carriers
The method of property metal component ruthenium is infusion process, counts and on the basis of catalyst by oxide, described leaching
Stain makes the content of active metal component in described catalyst be 0.5-30 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 1-20 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 2-10 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 adjuvant component, count and on the basis of described catalyst by oxide, institute
State the introduction volume of promoter metal component less than 10 weight %.
26. methods according to claim 25, it is characterised in that described first adjuvant component
One or more in Ti, Zr, W or Mn, in terms of oxide and with described catalyst
On the basis of, the introduction volume of described first adjuvant 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
Second help including one or more introduced in Rh, Pd, Os, Ir, Pt, Ag or Au
The step of agent metal component, counts and on the basis of described catalyst by element, described second auxiliary agent
The introduction volume of 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 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, are included in carbon monoxide and hydrogen under the conditions of Fischer-Tropsch synthesis
The mixture of gas and catalyst haptoreaction, it is characterised in that described catalyst is aforementioned claim
Catalyst described in any one of 1-9.
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| CN1249208A (en) * | 1998-09-28 | 2000-04-05 | 中国石油化工集团公司 | Macroporous alumina carrier and preparing process thereof |
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| CN1727063A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Method for preparing alumina supporter in structure of double peak holes |
| CN101214454A (en) * | 2007-12-28 | 2008-07-09 | 上海第二工业大学 | Preparation method of macroporous aluminum oxide with diplopore distribution |
| CN102030351A (en) * | 2009-09-24 | 2011-04-27 | 中国石油化工股份有限公司 | Macroporous aluminum oxide with bimodal pore distribution and preparation method thereof |
| CN102861617A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Preparation method of double-hole-structure alumina supporter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1120971A (en) * | 1994-10-19 | 1996-04-24 | 中国石油化工总公司抚顺石油化工研究院 | Prepn of alumina supporter |
| CN1249208A (en) * | 1998-09-28 | 2000-04-05 | 中国石油化工集团公司 | Macroporous alumina carrier and preparing process thereof |
| CN1488441A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
| CN1727063A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Method for preparing alumina supporter in structure of double peak holes |
| CN101214454A (en) * | 2007-12-28 | 2008-07-09 | 上海第二工业大学 | Preparation method of macroporous aluminum oxide with diplopore distribution |
| CN102030351A (en) * | 2009-09-24 | 2011-04-27 | 中国石油化工股份有限公司 | Macroporous aluminum oxide with bimodal pore distribution and preparation method thereof |
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