CN104437669A - Fischer-Tropsch synthesis catalyst and preparation and application thereof - Google Patents
Fischer-Tropsch synthesis catalyst and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a Fischer-Tropsch synthesis catalyst and preparation and application thereof. The catalyst contains a carrier and an active metal component, wherein the carrier is aluminum oxide with bimodal pores, characterized by a mercury intrusion method, the carrier has the pore volume of 0.9-1.2ml/g and the specific surface area of 50-300m<2>/g, the volume of pores with the diameter of 10-30nm accounts for 55-80% the total pore volume, and the volume of pores with the diameter of 300-500nm accounts for 10-35% the total pore volume. Compared with the prior art, the catalyst provided by the invention has better Fischer-Tropsch synthesis performance.
Description
Technical field
The present invention relates to fischer-tropsch synthetic catalyst and Synthesis and applications thereof.
Background technology
Nineteen twenty-three, Fischer and Tropsch has found CO and H
2the method (F-T synthesis) of mixture Synthin product.In recent years; along with being becoming tight the day of petroleum resources, soaring, the continuous increase to the progressively harsh of demanded fuel and coal and natural gas proved reserves of crude oil price; make F-T synthesize the research in this field very active, many companies research and develop in F-T synthesis.Good F-T synthetic catalyst, should to CO and H
2have adsorption activity, have hydrogenization to the CO of absorption, contribute to chain growth, leniently promote hydrogenation, do not answer again that hydrogenation is excessively strong simultaneously, Water gas shift/WGS too much and formation carbon non-activated compound etc.The first step of F-T synthesis is CO and H
2chemisorbed, from structural chemistry viewpoint, there is the transition elements of 3d and 4f key and energy level, be mostly used as the active component of F-T synthetic catalyst.Research wherein about Ni, Fe, Co, Ru is more.Except Ni is too strong due to hydrogenation activity, make chain growth probability too large, be mainly used in methanation, outside the active component of uncomfortable cooperation synthesis macromolecule wax hydrocarbon catalyst, its excess-three kind metallic catalyst all can be used for F-T synthesis.And what have commercial application value is Co and Fe catalyst, the F-T synthesizing activity wherein due to Co is high, and reaction condition is gentle, water gas shift reaction is few, stable performance, the life-span is longer, and therefore people have carried out studying widely to Co catalyst on investigation and application.For the Co catalyst of F-T, the DNAcarrier free oxide of early application, as pure cobalt/cobalt oxide, cobalt-chromated oxide and cobalt-zinc oxide etc.; Found afterwards to add thorium oxide and magnesia, the activity of catalyst can be increased; Co catalyst carrier loaded is at present the main flow of research and commercial Application.Use Co catalyst for F-T synthesis, researcher has selected multiple auxiliary agent to modify it, to expect to improve its catalytic performance.
Disclose a kind of method for preparing catalyst and using method in CN89109859 and CN93106465, this catalyst comprise the catalytic activity amount on the alumina support of carrying cobalt and be selected from platinum, iridium, rhodium, and composition thereof second metal also responsive to load capacity.Metal oxide promoters can be added.
CN01810769.9 and CN01810773 discloses a kind of method for preparing catalyst and using method, this catalyst includes the cobalt of catalytic activity amount, its content is 5gCo/100g-70gCo/100g carrier, also can add Pd and Pt, as having the adulterant strengthening Co reducing power.
Prior art research shows, in fischer-tropsch synthetic catalyst, introduce one group of one or more promoter metal component be selected from Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K respectively or jointly; Or one group is introduced the other adjuvant component of one or more be selected from Ru, Rh, Pd, Os, Ir, Pt, Ag or Au, favourable to improving catalyst performance.
According to catalyst provided by the invention, containing one or more the promoter metal components be selected from Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K in described catalyst, 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 be selected from the components such as Cu, Mo, Ta, W, Zr, Ti, REO, Re, Mn, V or K one or both 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 Ru, Rh, Pd, Os, Ir, Pt, Ag or Au in described catalyst, preferably containing be selected from Ru, 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 Ru, 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 fischer-tropsch synthetic catalyst, containing carrier and active metal component, wherein, described carrier is a kind of aluminium oxide with bimodal hole, and characterize with mercury injection method, the pore volume of described carrier is 0.9-1.2 ml/g, and specific area is 50-300 rice
2/ gram, diameter is the 55-80% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume.
2. the catalyst according to 1, is characterized in that, the pore volume of described carrier is 0.95-1.15 ml/g, and specific area is 80-200 rice
2/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.
3. the catalyst according to 1, is characterized in that, described active metal component is cobalt, take catalyst as benchmark, with the content of the active metal component of oxide basis for 5-70 % by weight.
4. the catalyst according to 3, is characterized in that, take catalyst as benchmark, with the content of the active metal component of oxide basis for 10-50 % by weight.
5. the catalyst according to 4, is characterized in that, take catalyst as benchmark, with the content of the active metal component of oxide basis for 12-30 % 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 Ru, 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 Ru, 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 on this carrier, wherein, the preparation method of described carrier comprises the modifier P2 of hydrated alumina P1 and P1 containing boehmite mixing, shaping, dry also roasting, wherein, to be the κ value of 20-95:5-80, P2 be for the Mixing ratio by weight of described P1 and P2 0 to being less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1for the sour peptization index of the hydrated alumina P1 containing boehmite, DI
2for the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite.
11. methods according to 10, is characterized in that, to be the k value of 70-95:5-30, P2 be for the Mixing ratio by weight of described P1 and P2 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 P1 containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, most probable bore dia 8-30nm.
13. methods according to 12, is characterized in that, the pore volume of the described hydrated alumina P1 containing boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, most probable bore dia 10-25nm.
14. methods according to 10 or 11, it is characterized in that, described P2 is 80-300 object particle.
15. methods according to 14, it is characterized in that, described P2 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 10, 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 2-6 hour.
18. methods according to 10, it is characterized in that, by shaping, dry for the described hydrated alumina P1 containing boehmite by one of P1 method being modified as P2, afterwards its all or part of carrying out is ground, sieves, obtaining powder thing is P2, 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, and afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2; Three of method is dodged by the hydrated alumina P1 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, and obtaining powder thing is P2; 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 or 19, it is characterized in that, described P2 is 80-300 object particle in P1 modifier.
21. methods according to 20, it is characterized in that, described P2 is 100-200 object particle in P1 modifier.
22. methods according to 10, it is characterized in that, the described method at supported on carriers active metal component 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 5-70 % 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 10-50 % 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 12-30 % 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 Ru, 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, it is characterized in that, described second promoter metal component is selected from one or more in Ru, 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.
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 also 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.
Wherein, after the sour peptization index D I in the preparation of described carrier refers to that the hydrated alumina (comprising its modifier) containing boehmite adds 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
2be respectively intend thin water aluminium and acid reaction front and with acid reaction after with Al
2o
3the weight of meter.
The mensuration of DI comprises: the (1) calcination base content (calcination base content refers to by quantitative boehmite in 600 DEG C of roastings 4 hours, its ratio burning rear weight and burn front weight) of the hydrated alumina of mensuration containing boehmite, counts 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 the described hydrated alumina 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 the present invention, the pore volume of the hydrated alumina containing boehmite, specific area and most probable pore size are that the described hydrated alumina containing boehmite after 4 hours in 600 DEG C of roastings, is characterized by BET N2 adsorption and obtained.
In a preferred embodiment, the pore volume of the described hydrated alumina P1 containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, most probable bore dia 8-30nm, preferably the pore volume of the described hydrated alumina P1 containing boehmite is 0.95-1.3 ml/g further, and specific surface is 120-300 rice
2/ gram, most probable bore dia 10-25nm.Wherein, characterize with X diffraction, in the described hydrated alumina containing boehmite, boehmite content is not less than 50%, is more preferably not less than 60%.
The present inventor is surprised to find, hydrated alumina P1 containing boehmite is heat-treated modified, the peptization index of its modifier changes, by this modifier with without heat treated P1 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 with without heat treated part 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.
In concrete enforcement, described P2 conveniently can be obtained by following method:
(1) obtain P2 based on drying, comprise and prepare in regular oxidation alumina supporter process by the hydrated alumina P1 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 P2.
(2) obtain based on roasting, comprise and prepare in regular oxidation alumina supporter process by the hydrated alumina P1 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 P2; Or directly P1 is dodged dry obtaining, when directly dodging dry by P1, 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 P2 obtained based on preceding method.When adopting mixed method to obtain P2, the mixed proportion of the modifier P2 that aforementioned several method obtains respectively is not limited.
According to catalyst provided by the invention, wherein, described active metal component is preferably cobalt, the content of active metal component is fischer-tropsch synthetic catalyst customary amount, such as, with oxide basis and with catalyst for benchmark, the content of described active metal component is 5 ~ 70 % by weight, be preferably 10 ~ 50 % by weight, be more preferably 12 ~ 30 % 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.
Embodiment 1-13 illustrates bimodal hole provided by the invention carrier and preparation method thereof.Comparative example 1-2 illustrates conventional catalyst carrier and preparation method thereof.
The boehmite used below in an example comprises:
P1-1: (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).
P1-2: (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 1-5 illustrates modifier P2 of the described P1 of preparation carrier of the present invention and preparation method thereof.
Embodiment 1
Take 1000 grams of P1-1, 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 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 P2A of P1-1.The k value of P2A is in table 1.
Embodiment 2
Take 1000 grams of P1-1, dodge dry 6 minutes in 240 DEG C, obtain the modifier P2B of P1-1.The k value of P2B is in table 1.
Embodiment 3
The each 200 grams of Homogeneous phase mixing of the P2B that the P2A obtain embodiment 1 and embodiment 2 obtain, obtain the modifier P2C of P1-1.The k value of P2C is in table 1.
Embodiment 4
Take 1000 grams of P1-2, 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 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 P2D of P1-2.The k value of P2D is in table 1.
Embodiment 5
Take 1000 grams of P1-2, dodge dry 10 minutes in 650 DEG C, obtain the modifier P2E of P1-2.The k value of P2E is in table 1.
Table 1
| Embodiment | Raw material | k |
| 1 | P2A | 0.5 |
| 2 | P2B | 0.4 |
| 3 | P2C | 0.4 |
| 4 | P2D | 0 |
| 5 | P2E | 0.3 |
Embodiment 6-13 illustrates the preparation method of preparation carriers for catalysts of the present invention.Comparative example 1-2 illustrates the preparation method of conventional catalyst carrier.
Embodiment 6
Take 800 grams of P1-1, after 200 grams of raw material P2A Homogeneous phase mixing that embodiment 1 is obtained, add the aqueous solution 1440 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 7
Take 200 grams of P1-1, after 800 grams of raw material P2B 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 900 DEG C of roastings 3 hours, obtains carrier Z2.The character of carrier Z2 lists in table 2.
Embodiment 8
Take 500 grams of P1-1, after 500 grams of raw material P2C Homogeneous phase mixing that embodiment 3 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 950 DEG C of roastings 3 hours, obtains carrier Z3.The character of carrier Z3 lists in table 2.
Comparative example 1
Take 1000 grams of P1-1, 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 900 DEG C of roastings 3 hours, obtains carrier DZ1.The character of carrier DZ1 lists in table 2.
Embodiment 9
Take 800 grams of P1-2, after 200 grams of raw material P2D Homogeneous phase mixing that embodiment 4 is obtained, add the aqueous solution 1440 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 10
Take 900 grams of P1-1, after 100 grams of raw material P2E 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 1000 DEG C of roastings 3 hours, obtains carrier Z5.The character of carrier Z5 lists in table 2.
Embodiment 11
Take 850 grams of P1-2, after 150 grams of raw material P2C Homogeneous phase mixing that embodiment 3 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.
Comparative example 2
Take 1000 grams of P1-2, 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 DZ2.The character of carrier DZ2 lists in table 2.
Embodiment 12
Take 900 grams of P1-2, after 100 grams of raw material P2D 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 1000 DEG C of roastings 3 hours, obtains carrier Z7.The character of carrier Z7 lists in table 2.
Embodiment 13
Take 850 grams of P1-2, after 150 grams of raw material P2E 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 900 DEG C of roastings 3 hours, obtains carrier Z8.The character of carrier Z8 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 14 ~ 21 illustrates 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 containing cobalt nitrate and platinum chloride ammonia, carry out saturated dipping, carry out drying and roasting afterwards, obtain catalyst C1, C2, C3, C4, C5, C6, C7 and C8.Wherein, baking temperature is 120 DEG C, and drying time is 6 hours, and sintering temperature is 400 DEG C, roasting time 3 hours.The consumption of described cobalt nitrate and platinum chloride ammonia makes cobalt oxide content in final catalyst be 15 % by weight, and platinum content is 0.1 % by weight.
Comparative example 3 ~ 4
By the mixed solution of DZ1, DZ2 carrier containing cobalt nitrate and platinum chloride ammonia, carry out saturated dipping, carry out drying and roasting afterwards, obtain catalyst CC1, CC2.Wherein, baking temperature is 120 DEG C, and drying time is 6 hours, and sintering temperature is 400 DEG C, roasting time 3 hours.The consumption of described cobalt nitrate and platinum chloride ammonia makes cobalt oxide content in final catalyst be 15 % by weight, and platinum content is 0.1 % by weight.
Embodiment 22-29 illustrates the application and the effect thereof that the invention provides catalyst.
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, CO conversion ratio and methane selectively list in table 3.
Comparative example 5-6 illustrates comparative catalyst's performance
According to evaluate catalysts CC1, the CC2 respectively of method similarly to Example 13.Wherein, CO conversion ratio and methane selectively list in table 3.
Table 3
As can be seen from Table 3, adopt bimodal porous aluminum oxide provided by the invention to be used as catalyst carrier, be then prepared into fischer-tropsch synthetic catalyst, this catalyst has better F-T synthesis performance when other condition is identical, namely higher CO conversion ratio, lower methane selectively.
Claims (29)
1. a fischer-tropsch synthetic catalyst, containing carrier and active metal component, wherein, described carrier is a kind of aluminium oxide with bimodal hole, and characterize with mercury injection method, the pore volume of described carrier is 0.9-1.2 ml/g, and specific area is 50-300 rice
2/ gram, diameter is the 55-80% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume.
2. the catalyst according to 1, is characterized in that, the pore volume of described carrier is 0.95-1.15 ml/g, and specific area is 80-200 rice
2/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.
3. the catalyst according to 1, is characterized in that, described active metal component is cobalt, take catalyst as benchmark, with the content of the active metal component of oxide basis for 5-70 % by weight.
4. the catalyst according to 3, is characterized in that, take catalyst as benchmark, with the content of the active metal component of oxide basis for 10-50 % by weight.
5. the catalyst according to 4, is characterized in that, take catalyst as benchmark, with the content of the active metal component of oxide basis for 12-30 % 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 Ru, 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 Ru, 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 on this carrier, wherein, the preparation method of described carrier comprises the modifier P2 of hydrated alumina P1 and P1 containing boehmite mixing, shaping, dry also roasting, wherein, to be the κ value of 20-95:5-80, P2 be for the Mixing ratio by weight of described P1 and P2 0 to being less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1for the sour peptization index of the hydrated alumina P1 containing boehmite, DI
2for the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite.
11. methods according to 10, is characterized in that, to be the k value of 70-95:5-30, P2 be for the Mixing ratio by weight of described P1 and P2 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 P1 containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, most probable bore dia 8-30nm.
13. methods according to 12, is characterized in that, the pore volume of the described hydrated alumina P1 containing boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, most probable bore dia 10-25nm.
14. methods according to 10 or 11, it is characterized in that, described P2 is 80-300 object particle.
15. methods according to 14, it is characterized in that, described P2 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 10, 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 2-6 hour.
18. methods according to 10, it is characterized in that, by shaping, dry for the described hydrated alumina P1 containing boehmite by one of P1 method being modified as P2, afterwards its all or part of carrying out is ground, sieves, obtaining powder thing is P2, 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, and afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2; Three of method is dodged by the hydrated alumina P1 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, and obtaining powder thing is P2; 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 or 19, it is characterized in that, described P2 is 80-300 object particle in P1 modifier.
21. methods according to 20, it is characterized in that, described P2 is 100-200 object particle in P1 modifier.
22. methods according to 10, it is characterized in that, the described method at supported on carriers active metal component 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 5-70 % 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 10-50 % 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 12-30 % 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 Ru, 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, it is characterized in that, described second promoter metal component is selected from one or more in Ru, 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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|---|---|---|---|---|
| CN1045710A (en) * | 1988-12-28 | 1990-10-03 | 斯塔特石油公司 | Hydrocarbon synthetic supported catalyst |
| JP2004503360A (en) * | 2000-06-12 | 2004-02-05 | サソール テクノロジー（プロプライエタリー）リミテッド | Cobalt catalyst |
| 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 |
| CN102908971A (en) * | 2011-08-04 | 2013-02-06 | 中国石油化工股份有限公司 | Titanium-containing silicon oxide-aluminum oxide forming composition and preparation method thereof |
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2013
- 2013-09-24 CN CN201310439473.7A patent/CN104437669B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045710A (en) * | 1988-12-28 | 1990-10-03 | 斯塔特石油公司 | Hydrocarbon synthetic supported catalyst |
| JP2004503360A (en) * | 2000-06-12 | 2004-02-05 | サソール テクノロジー（プロプライエタリー）リミテッド | Cobalt catalyst |
| 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 |
| CN102908971A (en) * | 2011-08-04 | 2013-02-06 | 中国石油化工股份有限公司 | Titanium-containing silicon oxide-aluminum oxide forming composition and preparation method thereof |
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