CN104437479A - Ruthenium-based Fischer-Tropsch synthesis catalyst and preparation and application thereof - Google Patents
Ruthenium-based Fischer-Tropsch synthesis catalyst and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a ruthenium-based Fischer-Tropsch synthesis catalyst and preparation and application thereof. The catalyst contains an aluminum oxide carrier and an active metal component ruthenium, wherein the carrier has a bimodal pore structure, characterized by a mercury intrusion method, the carrier has the pore volume of 0.6-1.4ml/g and the specific surface area of 80-400m<2>/g, the volume of pores with the diameter of 5-20nm accounts for 30-60% the total pore volume, and the volume of pores with the diameter of 100-300nm accounts for 15-45% the total pore volume. Compared with the prior art, the catalyst provided by the invention has better Fischer-Tropsch synthesis performance.
Description
Technical field
The present invention relates to 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 has found the method for the mixture Synthin product of CO and H2.The active component of fischer-tropsch synthetic catalyst is mainly main with Fe, Co and Ru, and its active sequence is Ru>Co>Fe, and chain growth probability order is roughly Ru>Co>Fe.
Literature research shows, Ru is catalyst based can maintain higher activity, thus likely in biomass synthesis gas conversion reaction in higher water partial pressure and oxygenatedchemicals atmosphere.Take molecular sieve as carrier, document [Phys.Chem.C, 2008,112:9706] have studied the molecular sieve carried Ru catalyst of SBA-15, compared with the factors such as Ru particle size, the impact that the confinement effect of SBA-15 molecular sieve pore passage distributes on F-T synthetic product is larger; Also have researcher [Chem Cat Chem, 2010,2:1030] to prepare Ru/meso-ZSM5 Fischer-Tropsch catalyst, it is selective that this catalyst has high C5-11; Optimized by alkali modification and hole, on 3%Ru/meso-beta catalyst, the selective of C5-11 of F-T synthetic reaction reaches 77.2% [the 13 the youth of the nation catalysis academic meeting paper collection, 2011,89].Take CNT as carrier, Ru/CNT catalyst prepared by document [Angew.Chem., Int Ed, 2009,48:2565], and it is selective that this catalyst has high C10-20, and under suitable acidity and Ru particle diameter, C10-20 hydrocarbon-selective reaches 65%.
Active metal metal component Ru is loaded on carrier, Ru base FT synthetic catalyst can be obtained.But the difference of support, the performance of FT synthetic catalyst is very large by difference.
Prior art research shows, in fischer-tropsch synthetic catalyst respectively or common introduce one group and be selected from Cu, Mo, Ta, W, Zr, Ti, REO(rare earth), one or more promoter metal components in Re, Mn, V or K; Or one group is introduced the other adjuvant component of one or more be selected from Rh, Pd, Os, Ir, Pt, Ag or Au, favourable to improving catalyst performance.
According to catalyst provided by the invention, containing being selected from Cu, Mo, Ta, W, Zr, Ti, REO(rare earth in described catalyst), one or more promoter metal components in Re, Mn, V or K, preferably containing be selected from Ti, Zr, W or Mn one or more, with oxide basis and with described catalyst for benchmark, the content of described promoter metal component is no more than 10 % by weight, and preferred content is no more than 6 % by weight.
When in described catalyst containing being selected from Cu, Mo, Ta, W, Zr, Ti, REO(rare earth), one or both in the component such as Re, Mn, V or K time, its introducing method can be by the compound containing described auxiliary agent be mixed with containing the compound containing active metal component after mixed solution with described carrier contact; Can also be by after independent for the compound containing auxiliary agent obtain solution with described carrier contact, dry afterwards and roasting.When auxiliary agent and active metal component do not introduce described carrier, preferably first with containing auxiliary compound solution and described carrier contact, drying and after roasting again with containing active metal component the solution of compound contact, such as by methods such as ion-exchange, dipping, co-precipitation, preferred infusion process.Described sintering temperature is 200-700 DEG C, and be preferably 250-500 DEG C, roasting time is 2-8 hour, is preferably 3-6 hour.
According to catalyst provided by the invention, also containing the other adjuvant component of one or more be selected from Rh, Pd, Os, Ir, Pt, Ag or Au in described catalyst, preferably containing be selected from Pt or Pd one or more, in element and with described catalyst for benchmark, the content of described promoter metal component is no more than 0.3 % by weight, and preferred content is no more than 0.15 % by weight.
When in described catalyst containing one or more adjuvant components be selected from Rh, Pd, Os, Ir, Pt, Ag or Au time, its introducing method can be by the compound containing described auxiliary agent with containing containing active metal component compound containing or not containing the compound (such as, containing the compound being selected from Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K adjuvant component) of other adjuvant components be mixed with after mixed solution with described carrier contact; Can also be by after independent for the compound containing auxiliary agent obtain solution with described carrier contact, dry afterwards and roasting.When auxiliary agent and active metal component do not introduce described carrier, preferably first with containing auxiliary compound solution and described carrier contact, drying and after roasting again with containing active metal component compound solution (containing or not containing the compound of other adjuvant components) contact, such as by methods such as ion-exchange, dipping, co-precipitation, preferred infusion process.Described sintering temperature is 200-700 DEG C, and be preferably 250-500 DEG C, roasting time is 2-8 hour, is preferably 3-6 hour.
According to the invention provides catalyst, needed in presence of hydrogen before for Fischer-Tropsch synthesis, active metal is carried out reduction activation, reducing condition is: reduction temperature is 100 DEG C to 800 DEG C, be preferably 200 DEG C to 600 DEG C, more preferably 300 DEG C to 450 DEG C; Recovery time is 0.5-72 hour, be preferably 1-24 hour, more preferably 2-8 hour, described reduction can be carried out in pure hydrogen, also can carry out in the gaseous mixture of hydrogen and inert gas, as carried out in the gaseous mixture of hydrogen and nitrogen and/or argon gas, Hydrogen Vapor Pressure is 0.1-4MPa, is preferably 0.1-2MPa.
According to Fischer-Tropsch synthesis method provided by the invention, the described condition that the mixture of carbon monoxide and hydrogen and described catalyst exposure are reacted: preferable temperature is 160 ~ 280 DEG C, more preferably 190 ~ 250 DEG C, pressure is preferably 1 ~ 8MPa, more preferably 1-5MPa, the mol ratio of hydrogen and carbon monoxide is 0.4 ~ 2.5, is preferably 1.5 ~ 2.5, more preferably 1.8 ~ 2.2, the space-time speed of gas is 200 hours
-1~ 20000 hours
-1, be preferably 500 hours
-1~ 12000 hours
-1.
Fischer-tropsch synthetic catalyst provided by the invention adopts to comprise and uses bimodal porous aluminum oxide as carrier, and the performance of catalyst is improved.Such as, when the active metal component content of catalyst, preparation condition are identical, compared with reference agent, the CO activity of conversion that the invention provides catalyst improves nearly 6%, and methane selectively reduces nearly 2%.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of performance to obtain the fischer-tropsch synthetic catalyst of modification and the preparation method and application of this catalyst on the basis of existing technology.
Inventor studies discovery, when adopting a kind of carrier with structure of double peak holes to prepare F-T synthetic catalyst, and the F-T synthetic reaction performance of catalyst, such as C
5 +selectively obviously to improve.
The content that the present invention relates to comprises:
1. a ruthenium base fischer-tropsch synthetic catalyst, containing alumina support and active metal component ruthenium, wherein, described carrier has structure of double peak holes, and characterize with mercury injection method, the pore volume of described carrier is 0.6-1.4 ml/g, and specific area is 80-400 rice
2/ gram, diameter is the 30-60% that the pore volume in 5-20nm hole accounts for total pore volume, and diameter is the 15-45% that the pore volume in 100-300nm hole accounts for total pore volume.
2. the catalyst according to 1, is characterized in that, the pore volume of described carrier is 0.7-1.3 ml/g, and specific area is 100-300 rice
2/ gram, diameter is the 35-50% that the pore volume in 5-20nm hole accounts for total pore volume, and diameter is the 20-40% that the pore volume in 100-300nm hole accounts for total pore volume.
3. the catalyst according to 1, is characterized in that, take catalyst as benchmark, with the content of the active metal component ruthenium of oxide basis for 0.5-30 % by weight.
4. the catalyst according to 3, is characterized in that, take catalyst as benchmark, with the content of the active metal component ruthenium of oxide basis for 1-20 % by weight.
5. the catalyst according to 4, is characterized in that, take catalyst as benchmark, with the content of the active metal component ruthenium of oxide basis for 2-10 % by weight.
6. the catalyst according to 1, it is characterized in that, containing one or more first adjuvant components be selected from Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K in described catalyst, taking catalyst as benchmark, is less than 10 % by weight with the content of the first adjuvant component of oxide basis.
7. the catalyst according to 6, is characterized in that, described first promoter metal component is selected from one or more in Ti, Zr, W or Mn, and taking catalyst as benchmark, is less than 6 % by weight with the content of the first adjuvant component of oxide basis.
8. the catalyst according to 1 or 6, it is characterized in that, containing one or more second adjuvant components be selected from Rh, Pd, Os, Ir, Pt, Ag or Au in described catalyst, take catalyst as benchmark, in the content of the second adjuvant component of element below 0.5 % by weight.
9. the catalyst according to 8, is characterized in that, described second adjuvant component is selected from one or more in Pt or Pd, take catalyst as benchmark, in the content of the second adjuvant component of element below 0.3 % by weight.
10. the preparation method of catalyst according to 1, comprise and prepare carrier and supported active metals component ruthenium on this carrier, wherein, the preparation of described carrier comprise hydrated alumina PA and PB containing boehmite mix with a kind of modifier PC of the hydrated alumina containing boehmite, shaping, dry also roasting, wherein, to be the κ value of 20-60:20-50:5-50, PC be for the Mixing ratio by weight of described PA, PB and PC 0 to being less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1for the sour peptization index of PC hydrated alumina before modified, DI
2for the sour peptization index of described PC.
11. methods according to 10, it is characterized 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 being less than or equal to 0.6.
12. methods according to 10 or 11, is characterized in that, the pore volume of the described hydrated alumina PA containing boehmite is 0.75-1 ml/g, and specific surface is 200-450 rice
2/ gram, most probable bore dia 3-10nm; The pore volume of the described hydrated alumina PB containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, most probable bore dia is greater than 10 to being less than or equal to 30nm.
13. methods according to 12, is characterized in that, the pore volume of the described hydrated alumina PA containing boehmite is 0.80-0.95 ml/g, and specific surface is 200-400 rice
2/ 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, and specific surface is 120-300 rice
2/ gram, most probable bore dia is greater than 10 to being less than or equal to 25nm.
14. methods according to 10 or 11 any one, it is characterized in that, described PC is 80-300 object particle.
15. methods according to 14, it is characterized in that, described PC is 100-200 object particle.
16. methods according to 10, it is characterized in that, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour, and the condition of described roasting comprises: temperature is for being greater than 500 to being less than or equal to 1200 DEG C, and the time is 1-8 hour.
17. methods according to 16, it is characterized in that, the condition of described drying comprises: temperature is 100-200 DEG C, and the time is 2-12 hour, and the condition of described roasting comprises: temperature is for being greater than 800 to being less than or equal to 1000 DEG C, and roasting time is for being 2-6 hour.
18. methods according to 10, it is characterized in that, by shaping, dry for the described hydrated alumina containing boehmite by one of hydrated alumina method being modified as PC containing boehmite, afterwards its all or part of carrying out is ground, sieves, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour; Two of method is article shaped roastings method one obtained, and sintering temperature is for being greater than 350 to being less than or equal to 1400 DEG C, and roasting time is 1-8 hour, afterwards its all or part of carrying out is ground, is sieved; Three of method is dodged by the hydrated alumina containing boehmite to do, and dodge dry temperature for being greater than 150 to being less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour; Four of method is mixed to get one or more in two and the modifier that obtains with three of method of one of method, method.
19. methods according to 18, it is characterized in that, the condition of the drying in described method one comprises: temperature is 100-200 DEG C, and the time is 2-12 hour; Method two in sintering temperature be 500-1200 DEG C, roasting time is 0.1-6 hour; Method three in sudden strain of a muscle to do temperature be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.
20. methods according to 18, is characterized in that, described PC is 80-300 object particle in the modifier of hydrated alumina containing boehmite.
21. methods according to 20, is characterized in that, described PC is 100-200 object particle in the modifier of hydrated alumina containing boehmite.
22. methods according to 10, it is characterized in that, the described method at supported on carriers active metal component ruthenium is infusion process, is benchmark with oxide basis and with catalyst, and described dipping makes the content of active metal component in described catalyst be 0.5-30 % by weight.
23. methods according to claim 22, is characterized in that, are benchmark with oxide basis and with catalyst, and described dipping makes the content of active metal component in described catalyst be 1-20 % by weight.
24. methods according to 23, is characterized in that, with oxide basis and with catalyst for benchmark, described dipping makes the content of active metal component in described catalyst be 2-10 % by weight.
25. methods according to 10, it is characterized in that, described method comprises the step introducing one or more the first promoter metal components be selected from Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K, with oxide basis and with described catalyst for benchmark, the introduction volume of described promoter metal component is no more than 10 % by weight.
26. methods according to 25, it is characterized in that, described first promoter metal component is selected from one or more in Ti, Zr, W or Mn, and with oxide basis and with described catalyst for benchmark, the introduction volume of described first promoter metal component is no more than 6 % by weight.
27. catalyst according to claim 10 or 25, it is characterized in that, described method comprises the step introducing one or more the second promoter metal components be selected from Rh, Pd, Os, Ir, Pt, Ag or Au, in element and with described catalyst for benchmark, the introduction volume of described second promoter metal component is no more than 0.5 % by weight.
28. catalyst according to claim 27, is characterized in that, described second promoter metal component is selected from one or more in Pt or Pd, and in element and with described catalyst for benchmark, the introduction volume of described second promoter metal component is no more than 0.3 % by weight.
29. 1 kinds of Fischer-Tropsch synthesis methods, be included under Fischer-Tropsch synthesis condition and the mixture of carbon monoxide and hydrogen and catalyst exposure reacted, it is characterized in that, described catalyst is the catalyst described in aforementioned any one of claim 1-9 claim.
According to catalyst provided by the invention, require that carrier wherein can be made into the various article shaped being easy to operate depending on different, such as spherical, cellular, nest like, tablet or bar shaped (clover, butterfly, cylindrical etc.).Shapingly can to carry out according to a conventional method, such as, a kind of method in spin, compressing tablet and extruded moulding or the combination of several method.When shaping, such as extruded moulding, for ensureing described shapingly to carry out smoothly, can add in described mixture water, extrusion aid and/or adhesive, containing or not containing expanding agent, then extrusion molding, carry out drying and roasting afterwards.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, such as common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH, described peptizing agent can be inorganic acid and/or organic acid, and described expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and surfactant.Synthetic cellulose is wherein preferably one or more in CMC, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in polyethylene glycol, poly-propyl alcohol, polyvinyl alcohol, one or more in the propenyl copolymer that surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight is 200-10000 and maleic acid copolymer.
In the present invention, after described sour peptization index D I refers to that hydrated alumina containing boehmite and the hydrated alumina modifier containing boehmite add nitric acid by certain sour aluminum ratio, within certain reaction time by the hydrated alumina containing boehmite of peptization with Al
2o
3the percentage of meter, DI=(1-W
2/ W
1) × 100%, W
1and W
2before being respectively hydrated alumina containing boehmite and acid reaction and with acid reaction after with Al
2o
3the weight of meter.
The mensuration of DI comprises: (calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours calcination base (also referred to as the butt) content of hydrated alumina (1) measuring containing boehmite, its ratio burning rear weight and burn front weight, be expressed as a percentage), count a; (2) take the hydrated alumina W containing boehmite with assay balance
0gram, W
0amount meet with Al
2o
3the W of meter
1be 6 grams of (W
1/ a=W
0), take deionized water W gram, W=40.0-W
0, under stirring, the hydrated alumina containing boehmite taken and deionized water are added in beaker and mix; With 20mL pipette pipette 20mL, concentration is the dilute nitric acid solution of 0.74N, is joined by this acid solution in the beaker of step (2), stirs lower reaction 8 minutes; (4) step (3) reacted slurries are carried out centrifugation in centrifuges, inserted by sediment in the crucible of having weighed, afterwards, by it in 125 DEG C of dryings 4 hours, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh and obtain calcination sample size W
2gram; (5) according to formula DI=(1-W
2/ W
1) × 100% calculates.
Under being enough to make final carrier meet the prerequisite of application claims, the present invention does not specially require described hydrated alumina PA and PB containing boehmite, it can be boehmite prepared by any prior art, also can be the mixture of boehmite and other hydrated alumina, other hydrated alumina described be selected from one or more in a Water oxidize aluminium, gibbsite and amorphous hydrated aluminium oxide.
In a detailed description of the invention, the described preferred pore volume of hydrated alumina PA containing boehmite is 0.75-1 ml/g, and specific surface is 200-450 rice
2/ gram, most probable bore dia 3-10nm, preferably pore volume is 0.80-0.95 ml/g further, and specific surface is 200-400 rice
2/ 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, and specific surface is 100-350 rice
2/ gram, most probable bore dia is greater than 10 to being less than or equal to 30nm, and preferably pore volume is 0.95-1.3 ml/g further, and specific surface is 120-300 rice
2/ gram, most probable bore dia is greater than 10 to being less than or equal to 25nm.
In the present invention, the pore volume of the hydrated alumina containing boehmite, specific area and can and aperture, be that the described hydrated alumina containing boehmite after 4 hours in 600 DEG C of roastings, is characterized by BET N2 adsorption and obtains.
In further preferred embodiment, characterize with X diffraction, the boehmite content in described hydrated alumina PA and PB containing boehmite is not less than 50%, is more preferably not less than 60%.
The present inventor is surprised to find, hydrated alumina containing boehmite is heat-treated and obtains modifier PC, relative to the original hydrated alumina containing boehmite, the peptization index of modifier PC changes, by this modifier and PA and PB mixed-forming, dry and after roasting, the carrier obtained has obvious bimodal pore distribution.Particularly by 80-300 object particle wherein, preferred 100-200 object particle and PA and PB mixed-forming, dry and after roasting, the carrier obtained bimodal in each unimodal pore size distribution concentrated especially.Here, described 80-300 object particle, preferred 100-200 object particle refers to that described modifier is through sieve (step comprising fragmentation or grinding if desired), its screening thing (screenings) meets 80-300 object particle, the percentage (by weight) that preferred 100-200 object particle accounts for total amount is not less than 60%, is preferably not less than 70% further.Here the hydrated alumina containing boehmite can be boehmite prepared by any prior art, also can be the mixture of boehmite and other hydrated alumina, other hydrated alumina described be selected from one or more in a Water oxidize aluminium, gibbsite and amorphous hydrated aluminium oxide.In a preferred embodiment, described PC is the modifier of PA and/or PB.
In the present invention, the Mixing ratio by weight of described PA, PB and PC refers to the ratio of the shared parts by weight of PA, PB and PC difference in the mixture of every hundred parts of described PA, PB and PC.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:
Below, the method for PC is obtained with described PA and PB for initiation material illustrates.
(1) obtain PC based on drying, comprise and prepare in regular oxidation alumina supporter process by hydrated alumina PA and/or PB containing boehmite is shaping according to a conventional method, the tailing of drying by-product, such as: in extruded moulding, bar shaped article shaped is at tailing (being called dry waste material traditionally) that is dry, integer process by-product, this tailing is milled, sieves and obtain PC.
(2) obtain based on roasting, comprise and prepare in regular oxidation alumina supporter process by hydrated alumina PA and/or PB containing boehmite is shaping according to a conventional method, through the tailing (being called roasting waste material traditionally) of roasting by-product, such as, in roller forming, the tailing of spheric granules by-product in roasting process, mills this tailing, sieves and obtain PC; Or directly PA and/or PB is dodged dry obtaining, when directly dodging dry by PA and/or PB, 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.When adopting mixed method to obtain C, the mixed proportion of the modifier PC that aforementioned several method obtains respectively is not limited.
According to catalyst provided by the invention, with oxide basis and with catalyst for benchmark, the content of described active metal component is 0.5 ~ 30 % by weight, be preferably 1 ~ 20 % by weight, be more preferably 2 ~ 10 % by weight.
Be enough under the prerequisite being carried on described carrier by described active metal component, the present invention is not particularly limited the described method be carried on described carrier by active metal component.Such as, can be enough to by effective dose active metal component be deposited on described carrier condition under, the solution of described carrier with the compound containing active metal component containing effective dose is contacted, as passed through the methods such as dipping, co-precipitation, preferred infusion process, carries out drying, roasting or not roasting afterwards.The method of described drying and be conventional method, such as, the method for heating, drying, when drying means is heat drying, the operating condition of described drying comprises: temperature is 80 ~ 350 DEG C, is preferably 100 ~ 300 DEG C, time is 1 ~ 24 hour, is preferably 2 ~ 12 hours.When described catalyst needs to carry out roasting, the temperature of described roasting is to realize the described converting compounds containing active metal component for for the purpose of its oxide, preferred sintering temperature is 200-700 DEG C, roasting time is 1 ~ 6 hour, preferred temperature is preferably 250-500 DEG C further, and roasting time is 2 ~ 4 hours.
One or more preferably in their soluble compound of the described compound containing active metal component, as containing one or more in water-soluble salt of active metal component, complex compound.
Detailed description of the invention
The present invention will be further described for example below, but therefore should not be interpreted as limitation of the invention.
The boehmite used below in an example comprises:
PA-1: (pore volume is 0.9 ml/g to the dry glue powder that Chang Ling catalyst branch company produces, and specific surface is 280 meters
2/ gram, most probable bore dia 8.5nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 34.6).
PA-2: (pore volume is 0.9 ml/g to the dry glue powder of the limited production of the neat cyclopentadienyl catalyst in Zibo, and specific surface is 290 meters
2/ gram, most probable bore dia 8.3nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 33.2).
PB-1: (pore volume is 1.2 mls/g to the dry glue powder that Chang Ling catalyst branch company produces, and specific surface is 280 meters
2/ gram, most probable bore dia 15.8nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 15.8).
PB-2: (pore volume is 1.1 mls/g to the dry glue powder that Yantai Heng Hui Chemical Co., Ltd. produces, and specific surface is 260 meters
2/ gram, most probable bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 % by 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
Take 1000 grams of PA-1, add the aqueous solution 1000 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and obtain dried strip, by dried strip shaping, sieve, the dried strip material (being commonly referred to as industrially drying bar waste material) length being less than 2mm is milled, and sieves, gets wherein 100 ~ 200 mesh sieves and divide, obtain the modifier PC-A1 of PA-1.The k value of PC-A1 is in table 1.
Embodiment 2
Take 1000 grams of PA-1, add the aqueous solution 1000 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and 800 DEG C of roastings 4 hours, obtain carrier, by carrier strip shaping, sieve, the carrier strip material (being commonly referred to as industrial carrier waste material) length being less than 2mm is milled, sieve, get wherein 100 ~ 200 mesh sieves and divide, obtain the modifier PC-A2 of PA-1.The k value of PC-A2 is in table 1.
Embodiment 3
Take 1000 grams of PA-2, dodge dry 6 minutes in 400 DEG C, obtain the modifier PC-A3 of PA-2.The k value of PC-A3 is in table 1.
Embodiment 4
The each 200 grams of Homogeneous phase mixing of the PC-A3 that the PC-A1 obtain embodiment 1 and embodiment 3 obtain, obtain the modifier PC-A4 of PA-1 and PA-2.The k value of PC-A4 is in table 1.
Embodiment 5
Take 1000 grams of PB-1, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and 1200 DEG C of roastings 4 hours, obtain carrier, by carrier strip shaping, sieve, the carrier strip material (being commonly referred to as industrial carrier waste material) length being less than 2mm is milled, sieve, get wherein 100 ~ 200 mesh sieves and divide, obtain the modifier PC-B1 of PB-1.The k value of PC-B1 is in table 1.
Embodiment 6
Take 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 in table 1.
Embodiment 7
Take 1000 grams of PB-2, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and obtain dried strip, by dried strip shaping, sieve, the dried strip material (being commonly referred to as industrially drying bar waste material) length being less than 2mm is milled, and sieves, gets wherein 100 ~ 200 mesh sieves and divide, obtain the modifier PC-B3 of PB-2.The k value of PC-B3 is in table 1.
Embodiment 8
The each 200 grams of Homogeneous phase mixing of the PC-B2 that the PC-B1 obtain embodiment 5 and embodiment 6 obtain, obtain the modifier PC-B4 of PB-1 and PB-2.The k value of PC-B4 is in table 1.
Embodiment 9
150 grams of PC-B3 Homogeneous phase mixing that 100 grams of PC-A1 embodiment 1 obtained and embodiment 7 obtain, obtain the modifier PC-B5 of PA-1 and PB-2.The k value of PC-B5 is in table 1.
Embodiment 10
The each 150 grams of Homogeneous phase mixing of the PC-B1 that the PC-A3 obtain embodiment 3 and embodiment 5 obtain, obtain the modifier PC-B6 of PA-2 and PB-1.The k value of PC-B6 is 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 |
Embodiment 11-18 illustrates bimodal hole provided by the invention carrier and preparation method thereof.Comparative example 1-5 illustrates conventional catalyst carrier and preparation method thereof.
Embodiment 11
Take each 400 grams of PA-1 and PB-1, after 200 grams of raw material PC-A2 Homogeneous phase mixing that embodiment 2 is obtained, add the aqueous solution 1300 milliliters containing 10 milliliters, 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, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier Z1.The character of carrier Z1 lists in table 2.
Embodiment 12
Take 300 grams of PA-2,200 grams of PB-2, after 500 grams of raw material PC-B2 Homogeneous phase mixing that embodiment 6 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1300 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier Z2.The character of carrier Z2 lists in table 2.
Embodiment 13
Take 500 grams of PA-2,300 grams of PB-2, after 200 grams of raw material PC-B4 Homogeneous phase mixing that embodiment 8 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1300 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 950 DEG C of roastings 3 hours, obtains carrier Z3.The character of carrier Z3 lists in table 2.
Comparative example 1
Take 500 grams of PA-2,500 grams of PB-2, add after Homogeneous phase mixing containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1300 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier DZ1.The character of carrier DZ1 lists in table 2.
Comparative example 2
Take 400 grams of PA-1,600 grams of PB-1, add after Homogeneous phase mixing containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1300 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 950 DEG C of roastings 3 hours, obtains carrier DZ2.The character of carrier DZ2 lists in table 2.
Embodiment 14
Take 250 grams of PA-1,500 grams of PB-1, after 250 grams of raw material PC-B5 Homogeneous phase mixing that embodiment 9 is obtained, add the aqueous solution 1300 milliliters containing 10 milliliters, 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, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier Z4.The character of carrier Z4 lists in table 2.
Embodiment 15
Take 350 grams of PA-2,350 grams of PB-2, after 300 grams of raw material PC-B6 Homogeneous phase mixing that embodiment 10 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 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, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier Z5.The character of carrier Z5 lists in table 2.
Embodiment 16
Take 200 grams of PA-1,600 grams of PB-1, after 200 grams of raw material PC-B1 Homogeneous phase mixing that embodiment 5 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 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, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 850 DEG C of roastings 3 hours, obtains carrier Z6.The character of carrier Z6 lists in table 2.
Embodiment 17
Take 200 grams of PA-1,600 grams of PB-1, after 200 grams of raw material PC-A4 Homogeneous phase mixing that embodiment 4 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 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, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 850 DEG C of roastings 3 hours, obtains carrier Z7.The character of carrier Z76 lists in table 2.
Embodiment 18
Take 200 grams of PA-1,600 grams of PB-1, after 200 grams of raw material PC-A2 Homogeneous phase mixing that embodiment 2 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 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, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 850 DEG C of roastings 3 hours, obtains carrier Z8.The character of carrier Z8 lists in table 2.
Comparative example 3
According to the method that patent CN1782031A embodiment 7 provides, plunger type bar extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier DZ3.The character of carrier DZ3 lists in table 2.
Comparative example 4
According to the method that patent CN1120971A embodiment 1 provides, plunger type bar extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier DZ3.The character of carrier DZ3 lists in table 2.
Comparative example 5
Take 200 grams of PA-1,800 grams of PB-2, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1300 milliliters of 10 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier DZ5.The character of carrier DZ5 lists in table 2.
Table 2
Can be seen by the result of table 2, compared with conventional method, the alumina support prepared by the method for the invention provides has obvious structure of double peak holes.
Embodiment 19-26
Illustrate by the fischer-tropsch synthetic catalyst that the invention provides aluminium oxide shaping carrier and prepare.
By the mixed solution of Z1, Z2, Z3, Z4, Z5, Z6, Z7 and Z8 carrier in embodiment containing nitrosyl nitrate ruthenium and zirconium nitrate; carry out saturated dipping; carry out drying and roasting afterwards, obtain catalyst C1, C2, C3, C4, C5, C6, C7 and C8 respectively.Wherein, baking temperature is 120 DEG C, and drying time is 6 hours, and sintering temperature is 400 DEG C, roasting time 3 hours.It is 5.0 % by weight that the consumption of described nitrosyl nitrate ruthenium and zirconium nitrate makes Ru content in final catalyst be 4.5 % by weight, Zr content.
Comparative example 6-10
By the mixed solution of DZ1, DZ2, DZ3, DZ4 and DZ5 carrier containing nitrosyl nitrate ruthenium and zirconium nitrate, carry out saturated dipping, carry out drying and roasting afterwards, obtain catalyst DC1, DC2, DC3, DC4 and DC5 respectively.Wherein, baking temperature is 120 DEG C, and drying time is 6 hours, and sintering temperature is 400 DEG C, roasting time 3 hours.It is 5.0 % by weight that the consumption of described nitrosyl nitrate ruthenium and zirconium nitrate makes Ru content in final catalyst be 4.5 % by weight, Zr content.
Embodiment 27-34
The application and effect thereof that the invention provides catalyst are described.
The Fischer-Tropsch synthesis performance of difference evaluate catalysts C1, C2, C3, C4, C5, C6, C7 and C8 in fixed bed reactors.
Unstripped gas forms: H
2/ CO/N
2=64%/32%/4% (volume hundred number).Catalyst reduction reaction condition: 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, and the recovery time is 5 hours.
Reaction condition: pressure 2.5MPa, temperature 200 DEG C, synthesis gas (unstripped gas) air speed 2000h
-1.Get gas sample after reaction carries out 24 hours and carry out chromatography, wherein, COization charcoal percent conversion and methane selectively list in table 3.
Comparative example 11-15
Comparative catalyst's performance is described, according to the method same with embodiment 27-34 evaluate catalysts DC1, DC2, DC3, DC4, DC5 respectively.Wherein, COization charcoal percent conversion and methane selectively list 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 |
As can be seen from Table 3, bimodal porous aluminum oxide provided by the invention is adopted to be used as catalyst carrier, be prepared into ruthenium base fischer-tropsch synthetic catalyst, this catalyst has better F-T synthesis performance when other condition is identical, namely higher CO conversion ratio and C5+ hydrocarbon selective, lower methane selectively.
Claims (29)
1. a ruthenium base fischer-tropsch synthetic catalyst, containing alumina support and active metal component ruthenium, wherein, described carrier has structure of double peak holes, and characterize with mercury injection method, the pore volume of described carrier is 0.6-1.4 ml/g, and specific area is 80-400 rice
2/ gram, diameter is the 30-60% that the pore volume in 5-20nm hole accounts for total pore volume, and diameter is the 15-45% that the pore volume in 100-300nm hole accounts for total pore volume.
2. the catalyst according to 1, is characterized in that, the pore volume of described carrier is 0.7-1.3 ml/g, and specific area is 100-300 rice
2/ gram, diameter is the 35-50% that the pore volume in 5-20nm hole accounts for total pore volume, and diameter is the 20-40% that the pore volume in 100-300nm hole accounts for total pore volume.
3. the catalyst according to 1, is characterized in that, take catalyst as benchmark, with the content of the active metal component ruthenium of oxide basis for 0.5-30 % by weight.
4. the catalyst according to 3, is characterized in that, take catalyst as benchmark, with the content of the active metal component ruthenium of oxide basis for 1-20 % by weight.
5. the catalyst according to 4, is characterized in that, take catalyst as benchmark, with the content of the active metal component ruthenium of oxide basis for 2-10 % by weight.
6. the catalyst according to 1, it is characterized in that, containing one or more first adjuvant components be selected from Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K in described catalyst, taking catalyst as benchmark, is less than 10 % by weight with the content of the first adjuvant component of oxide basis.
7. the catalyst according to 6, is characterized in that, described first promoter metal component is selected from one or more in Ti, Zr, W or Mn, and taking catalyst as benchmark, is less than 6 % by weight with the content of the first adjuvant component of oxide basis.
8. the catalyst according to 1 or 6, it is characterized in that, containing one or more second adjuvant components be selected from Rh, Pd, Os, Ir, Pt, Ag or Au in described catalyst, take catalyst as benchmark, in the content of the second adjuvant component of element below 0.5 % by weight.
9. the catalyst according to 8, is characterized in that, described second adjuvant component is selected from one or more in Pt or Pd, take catalyst as benchmark, in the content of the second adjuvant component of element below 0.3 % by weight.
10. the preparation method of catalyst according to 1, comprise and prepare carrier and supported active metals component ruthenium on this carrier, wherein, the preparation of described carrier comprise hydrated alumina PA and PB containing boehmite mix with a kind of modifier PC of the hydrated alumina containing boehmite, shaping, dry also roasting, wherein, to be the κ value of 20-60:20-50:5-50, PC be for the Mixing ratio by weight of described PA, PB and PC 0 to being less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1for the sour peptization index of PC hydrated alumina before modified, DI
2for the sour peptization index of described PC.
11. methods according to 10, it is characterized 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 being less than or equal to 0.6.
12. methods according to 10 or 11, is characterized in that, the pore volume of the described hydrated alumina PA containing boehmite is 0.75-1 ml/g, and specific surface is 200-450 rice
2/ gram, most probable bore dia 3-10nm; The pore volume of the described hydrated alumina PB containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, most probable bore dia is greater than 10 to being less than or equal to 30nm.
13. methods according to 12, is characterized in that, the pore volume of the described hydrated alumina PA containing boehmite is 0.80-0.95 ml/g, and specific surface is 200-400 rice
2/ 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, and specific surface is 120-300 rice
2/ gram, most probable bore dia is greater than 10 to being less than or equal to 25nm.
14. methods according to 10 or 11 any one, it is characterized in that, described PC is 80-300 object particle.
15. methods according to 14, it is characterized in that, described PC is 100-200 object particle.
16. methods according to 10, it is characterized in that, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour, and the condition of described roasting comprises: temperature is for being greater than 500 to being less than or equal to 1200 DEG C, and the time is 1-8 hour.
17. methods according to 16, it is characterized in that, the condition of described drying comprises: temperature is 100-200 DEG C, and the time is 2-12 hour, and the condition of described roasting comprises: temperature is for being greater than 800 to being less than or equal to 1000 DEG C, and roasting time is for being 2-6 hour.
18. methods according to 10, it is characterized in that, by shaping, dry for the described hydrated alumina containing boehmite by one of hydrated alumina method being modified as PC containing boehmite, afterwards its all or part of carrying out is ground, sieves, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour; Two of method is article shaped roastings method one obtained, and sintering temperature is for being greater than 350 to being less than or equal to 1400 DEG C, and roasting time is 1-8 hour, afterwards its all or part of carrying out is ground, is sieved; Three of method is dodged by the hydrated alumina containing boehmite to do, and dodge dry temperature for being greater than 150 to being less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour; Four of method is mixed to get one or more in two and the modifier that obtains with three of method of one of method, method.
19. methods according to 18, it is characterized in that, the condition of the drying in described method one comprises: temperature is 100-200 DEG C, and the time is 2-12 hour; Method two in sintering temperature be 500-1200 DEG C, roasting time is 0.1-6 hour; Method three in sudden strain of a muscle to do temperature be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.
20. methods according to 18, is characterized in that, described PC is 80-300 object particle in the modifier of hydrated alumina containing boehmite.
21. methods according to 20, is characterized in that, described PC is 100-200 object particle in the modifier of hydrated alumina containing boehmite.
22. methods according to 10, it is characterized in that, the described method at supported on carriers active metal component ruthenium is infusion process, is benchmark with oxide basis and with catalyst, and described dipping makes the content of active metal component in described catalyst be 0.5-30 % by weight.
23. methods according to claim 22, is characterized in that, described active metal component is cobalt, are benchmark with oxide basis and with catalyst, and described dipping makes the content of active metal component in described catalyst be 1-20 % by weight.
24. methods according to 23, is characterized in that, with oxide basis and with catalyst for benchmark, described dipping makes the content of active metal component in described catalyst be 2-10 % by weight.
25. methods according to 10, it is characterized in that, described method comprises the step introducing one or more the first promoter metal components be selected from Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K, with oxide basis and with described catalyst for benchmark, the introduction volume of described promoter metal component is no more than 10 % by weight.
26. methods according to 25, it is characterized in that, described first promoter metal component is selected from one or more in Ti, Zr, W or Mn, and with oxide basis and with described catalyst for benchmark, the introduction volume of described first promoter metal component is no more than 6 % by weight.
27. catalyst according to claim 10 or 25, it is characterized in that, described method comprises the step introducing one or more the second promoter metal components be selected from Rh, Pd, Os, Ir, Pt, Ag or Au, in element and with described catalyst for benchmark, the introduction volume of described second promoter metal component is no more than 0.5 % by weight.
28. catalyst according to claim 27, is characterized in that, described second promoter metal component is selected from one or more in Pt or Pd, and in element and with described catalyst for benchmark, the introduction volume of described second promoter metal component is no more than 0.3 % by weight.
29. 1 kinds of Fischer-Tropsch synthesis methods, be included under Fischer-Tropsch synthesis condition and the mixture of carbon monoxide and hydrogen and catalyst exposure reacted, it is characterized in that, described catalyst is the catalyst described in aforementioned any one of 1-9.
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Citations (7)
| 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 |
| 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 |
-
2013
- 2013-09-24 CN CN201310439132.XA patent/CN104437479B/en active Active
Patent Citations (7)
| 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 |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582708A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Supported catalyst, application of supported catalyst and Fischer-Tropsch synthesis reaction method |
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