CN102233282B - A kind of Fischer-Tropsch synthesis catalyst with silica-alumina as carrier and its application - Google Patents
A kind of Fischer-Tropsch synthesis catalyst with silica-alumina as carrier and its application Download PDFInfo
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Abstract
The invention provides a Fischer-Tropsch synthesis catalyst taking silicon oxide-aluminum oxide as a carrier and application thereof. The catalyst contains the silicon oxide-aluminum oxide carrier and active metal components, and is characterized in that the volume of pores with the diameter of 100-200angstroms in the carrier accounts for over 50% of the total pore volume. Compared with the existing catalyst, the Fischer-Tropsch synthesis catalyst provided by the invention has the advantages of high activity and high C<5+>hydrocarbon selectivity.
Description
Invention field
The invention relates to a kind of fischer-tropsch synthetic catalyst and application thereof, more specifically to a kind of fischer-tropsch synthetic catalyst and application thereof take silica-alumina as carrier.
Background technology
Nineteen twenty-three, Fischer and the Tropsch of Germany have found CO and H
2The method of mixture Synthin product.20th century the '30s, Fischer-Tropsch (FT or F-T) is synthetic at first in German Industrial, the U.S., France, the former Soviet Union and China etc. have also set up similar artificial oil factory subsequently, relatively high because of this route artificial oil cost after World War II, benefit can not be closed one after another with oil competition, only have South Africa according to the Fischer-Tropsch synthetic technology of the national conditions Development of Coal liquefaction of the national rich coal resources fischer-tropsch synthesis process of company (Sasol) at present still at development and improvement constantly.Twentieth century seventies, Holland Shell company began the synthetic research of Fischer-Tropsch, the Co catalysts of their development in 1993 in Malaysia's operation of founding the factory.In recent years; along with day being becoming tight of petroleum resources, crude oil price soaring, to the continuous increase of progressively harshness and coal and the natural gas proved reserves of demanded fuel; make the research in FT synthetic this field very active, many companies research and develop on Fischer-Tropsch is synthetic.
Carrier is very complicated on the impact of Co catalysts in the Fischer-Tropsch building-up process, and offshore company also differs from one another in the preparation of the selection of catalyst carrier and catalyst.SiO
2Surface area is high, is the carrier of commonly using, in the world take the research and development of Shell company as main and industrialization.Al
2O
3Wearability good, mechanical strength is high, is applicable to starch attitude bed operation, in the world take the research and development of Sasol, Gulf/Chevron and Statoil company as main.TiO
2The oxide that often needs other as carrier is (as SiO
2, Al
2O
3And ZrO
2) come modification, in the world take the research and development of Exxon-Mobil company as main.
Also there is the researcher to work aspect carrier at molecular sieve.Molecular sieve is during as carrier, its surface acidity is strong and the aperture is less, reactant is difficult for diffusion and shifts out in the duct, make the time of staying longer, the product hydro carbons is easily hydrocracking and form lower carbon number hydrocarbons during this period, and the secondary response such as isomerization and aromatisation (Appl.Catal.A, 1999 easily occur product alkene, 186,145-168).Anderson etc. (J.Am.Chem.Soc., 1949,71,183-188) think reactant molecule H
2There are differences (H with CO at the catalyst duct inner diffusing rate that is full of liquid product
2Diffusion velocity faster than CO), make H in less duct, duct
2/ CO is higher, and hydrocarbon (product) distributes must be partial to lower carbon number hydrocarbons, and the chain growth factor can corresponding reducing.In recent years, mesoporous molecular sieve is obtained researcher's attention as the carrier of Fischer-Tropsch synthesis Co catalysts.These mesoporous molecular sieves comprise SCMM-1 and SCMM-2 (Appl.Surf.Sci., 1998,130-132,845-850), HMS (catalysis journal; 2000,21,221-224), SBA-15 (J.Catal.; 2002,206,230-241), MCM-41 (J.Catal.; 2002,206,230-241), HMS-2 (chemical journal; 2001,59 (11), 1870-1877), MSU-1 (SCI; 2002,23 (9), 1748-1752) etc.Wei etc. (New J.Chem., 2001,26,20-23) take aluminosilicate with central hole structure as carrier, investigated the synthetic performance of Co catalyst Fischer-Tropsch with paste state bed reactor, result shows that catalyst has stability preferably, hydrocarbon distributes and comparatively concentrates and with C
10-C
20Hydro carbons is main, but the conversion ratio of CO is lower, and methane content is higher.(the J.Catal. such as Panpranot, 2002,211, point out when 530-539) having studied the synthetic performance of normal pressure Fischer-Tropsch of Co/Ru/MCM-41, its reactivity is higher than the Co catalysts take silica gel as carrier, and it is former because MCM-41 has more superior cobalt dispersibility.
Also there is the researcher to work aspect carrier at activated carbon.Patent CN01136889 discloses a kind of for be mainly the catalyst of diesel oil distillate section alkane by the synthesis gas preparation, is comprised of active component, auxiliary agent and carrier three parts.Main active component is metallic cobalt, and first kind auxiliary element is from IVB family metallic element, and as Ti, Zr or IIIB family metallic element, as La, Ce etc., the second auxiliary element is from group VIII metallic element such as Rh, Ru, Pt etc.Carrier is selected almond active carbon, cocoanut active charcoal, oil palm active carbon or coal activated carbon, and the specific area of active carbon is in the 200-2000 meters squared per gram, and pore volume is 0.5-2.0 ml/g, and pore-size distribution is
Metallic cobalt accounts for 4-50% in total catalyst weight, the first auxiliary element accounts for 0.0-20.0% in total catalyst weight, and the second auxiliary element accounts for 0.01-5.0%.This catalyst can be used for directly being prepared by Fischer-Tropsch synthesis by synthesis gas the cleaning liquid fluid fuels such as high-quality diesel oil.
To traditional silica and alumina support, many researchers have also carried out unremitting effort in recent years, seek the relation of support and catalyst performance.Aspect silica, and Saib etc. (Catalysis Today, 2002,71,395-402) studied pore to Co/SiO
2The impact of the synthetic performance of the structure of (20 % by weight) catalyst and Fischer-Tropsch, show: pore size affects cobalt species grain size, cobalt reduction degree and cobalt decentralization; When the aperture was about 10nm, the catalyst reaction activity was the highest, and during hydrocarbon distributes, methane content is minimum, C
5+Hydrocarbon is the highest.Oldly build firm grade (the catalysis journal, 2000,21 (2): be 169-171) studies show that of 2.84,6.67,7.44,9.42 nanometer silica gels to the aperture, along with the increase in aperture, although that the conversion ratio of CO changes is little, chain growth probability increases and C
5+The selective raising.Patent CN200380105506 discloses a kind of catalyst that uses in Fischer-Tropsch synthesis, it comprises the cobalt that is carried on aluminium oxide, and wherein the particle mean size of this catalyst is in the 20-100 micrometer range; The specific area of the catalyst granules of dipping and roasting is greater than 80 meters squared per gram; The mean pore size of dipping and the catalyst of roasting is at least
(9 nanometer); With the pore volume of dipping and the catalyst of roasting greater than 0.35 ml/g.
As known from the above, carrier is many-sided to the performance impact of Co catalyst, it is all influential to the interaction between grain size, metal and the carrier of catalyst cobalt species, and the institutional framework of carrier and surface acid alkalescence matter also affect the performance of catalyst, and finally have influence on the Fischer-Tropsch synthesis performance of catalyst.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, and a kind of new, fischer-tropsch synthetic catalyst and application thereof that performance obtains further modification are provided.
The invention provides a kind of fischer-tropsch synthetic catalyst, this catalyst contains carrier and active metal component, and described carrier is selected from silica-alumina, it is characterized in that, the bore dia in described carrier exists
The pore volume percentage that accounts for total pore volume be more than 50%.
The present invention also provides a kind of Fischer-Tropsch synthesis method, is included under the Fischer-Tropsch synthesis condition, will contain hydrogen and contact with catalyst with CO gas, and wherein, described catalyst is aforementioned catalyst provided by the invention.
Compare with existing catalyst, fischer-tropsch synthetic catalyst of the present invention has high activity and C
5+Hydrocarbon selective.
The specific embodiment
According to catalyst provided by the invention, wherein the bore dia in preferred described carrier exists
The percentage that the pore volume in hole accounts for total pore volume is 50-90%, more preferably 50-80%.
Satisfying bore dia at described carrier exists
The pore volume percentage that accounts for total pore volume be more than 50%, be preferably 50-90%, more preferably under the prerequisite of 50-80%, the present invention is not particularly limited the source of described carrier, they can be commercially available commodity, also can adopt any one existing method preparation.
One preferred embodiment in, described silica-alumina carrier is obtained through roasting by the composition of boehmite and silicon-containing compound, wherein, boehmite described in the composition of described boehmite and silicon-containing compound comprises the boehmite P1 of at least a 1.1≤n≤2.5; n=D (031)/D (120) wherein, the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression boehmite crystal grain, described 031 peak refers to that 2 θ in XRD spectra are the peak of 34-43 °, described 120 peaks refer to that 2 θ in XRD spectra are the peak of 23-33 °, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of diffraction maximum, 2 θ are the position of diffraction maximum.For different diffraction maximums, the value that B and 2 θ all get peak correspondingly, for example, and when calculating D (031), D (031)=K λ/(Bcos θ), wherein B is the half-peak breadth of 031 diffraction maximum, 2 θ are the position of 031 diffraction maximum; When calculating D (120), D (120)=K λ/(Bcos θ), wherein B is the half-peak breadth of 120 diffraction maximums, 2 θ are the position of 120 diffraction maximums.
Described silicon-containing compound, it can be organic silicon-containing compound, as one or more in esters of silicon acis, silanol, silicon ether, silicone and silicone oil, can be also inorganic silicon-containing compound, for example be selected from a kind of in silica gel (hydrated SiO 2), Ludox, silicic acid, waterglass, amorphous aluminum silicide, zeolite molecular sieve.Preferred silica gel, silicic acid and the Ludox that adopts in inorganic silicon-containing compound.
Composition according to boehmite provided by the invention and silicon-containing compound, wherein, content to described boehmite and silicon-containing compound is not particularly limited, in oxide, the content of preferred boehmite is the 65-99 % by weight, more preferably the 75-97 % by weight, be more preferably the 80-95 % by weight, the content of silicon-containing compound is the 1-35 % by weight, and more preferably the 3-25 % by weight, be more preferably the 5-20 % by weight.
The preparation method of the boehmite P1 of described 1.1≤n≤2.5 comprises: aluminum contained compound solution is contacted with acid or alkali carry out precipitation reaction, perhaps organic aluminum contained compound is contacted the reaction that is hydrolyzed with water, obtain hydrated alumina; Carry out hydrated alumina obtained above aging, wherein, described aluminum contained compound solution and acid or alkali contact or described organic aluminum contained compound and water contact and hydrated alumina aging in any one process carry out under the grain growth conditioning agent exists, described grain growth conditioning agent is for can regulate the material of the speed of growth of crystal grain on different crystal faces.
As long as although make hydrolysis or precipitation reaction and aging in one of arbitrary process carry out realizing purpose of the present invention under the grain growth conditioning agent exists, but under preferable case, described hydrolysis and ageing process or described precipitation reaction and ageing process are all carried out under the grain growth conditioning agent exists, and can make like this n of gained boehmite in preferred 1.2≤n≤2.2 scopes.
Wherein, there is no particular limitation to the consumption of grain growth conditioning agent, in selective hydrolysis reaction, the consumption of grain growth conditioning agent is the 0.5-10 % by weight of organic aluminum contained compound weight to be hydrolyzed, more preferably 1-8.5 % by weight, further preferred 5-8.5 % by weight; In described precipitation reaction, the consumption of grain growth conditioning agent is the inorganic 0.5-10 % by weight that contains al reactant weight, more preferably 1-8.5 % by weight, further preferred 5-8.5 % by weight; In described ageing process, the consumption of grain growth conditioning agent can be preferably the 1-8.5 % by weight for the 0.5-10 % by weight of hydrated alumina weight, further preferred 5-8.5 % by weight.Unless stated otherwise, in the present invention, the consumption of described grain growth conditioning agent respectively in organic aluminum contained compound, inorganic aluminum contained compound and the hydrated alumina weight of corresponding aluminium oxide calculate as benchmark.Be also, in aluminium oxide, in described precipitation reaction, the consumption of described grain growth conditioning agent is the 0.5-10 % by weight of inorganic aluminum contained compound weight, in described hydrolysis, the consumption of described grain growth conditioning agent is the 0.5-10 % by weight of organic aluminum contained compound weight, and in described ageing process, the consumption of described grain growth conditioning agent is the 0.5-10 % by weight of hydrated alumina weight.
In the present invention, described grain growth conditioning agent can be the various materials that can regulate the speed of growth of crystal grain on different crystal faces, particularly can regulate crystal grain at the material of the speed of growth of 120 crystal faces and 031 crystal face, be preferably alditol and carboxylate thereof, be specifically as follows one or more in D-sorbite, glucose, gluconic acid, gluconate, ribitol, ribonic acid, ribose hydrochlorate.Described gluconate and ribose hydrochlorate can be their soluble-salt separately, for example, can be one or more in sylvite, sodium salt and lithium salts.
In boehmite preparation process of the present invention, the mode that adds to described grain growth conditioning agent is not particularly limited, the grain growth conditioning agent can be added separately, also can be in advance the grain growth conditioning agent be mixed with wherein one or more raw materials, and then the raw material that will contain the grain growth conditioning agent reacts.
Wherein, described inorganic aluminum contained compound solution can be various aluminum salt solutions and/or aluminate solution, and described aluminum salt solution can be various aluminum salt solutions, can be for example one or more the aqueous solution in aluminum sulfate, aluminium chloride, aluminum nitrate.Because price is low, preferably sulfuric acid aluminium, liquor alumini chloridi.Aluminium salt can use separately also and can use after two kinds or more of mixing.Described aluminate solution is aluminate solution arbitrarily, as sodium aluminate solution and/or potassium aluminate.Because its acquisition is easy and price is low, preferred sodium aluminate solution.Aluminate solution also can be used alone or as a mixture.
Concentration to described aluminum salt solution and/or aluminate solution is not particularly limited, and preferably counts the 0.2-1.1 mol/L with aluminium oxide.
Described acid can be various Bronsted acids or be acid oxide in aqueous medium, for example, can be one or more in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, oxalic acid, preferred Bronsted acid be selected from one or more in nitric acid, sulfuric acid, hydrochloric acid.Described carbonic acid can original position produce by pass into carbon dioxide in aluminum salt solution and/or aluminate solution.Concentration to described acid solution is not particularly limited, preferred H
+Concentration be the 0.2-2 mol/L.
Described aqueous slkali can be hydrolyzed for hydroxide or in aqueous medium the salt that makes the aqueous solution be alkalescence, and preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, potassium hydroxide; Preferred salt is selected from one or more in sodium metaaluminate, potassium metaaluminate, carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, potash.Concentration to described aqueous slkali is not particularly limited, preferred OH
-Concentration be the 0.2-4 mol/L.When during as alkali, when calculating the consumption of described grain growth conditioning agent, also considering the amount of corresponding aluminium oxide in sodium metaaluminate and/or potassium metaaluminate with sodium metaaluminate and/or potassium metaaluminate.
Described organic aluminum contained compound can be various can the reaction with steeping in water for reconstitution unboiled water solution, one or more in the aluminum alkoxide of generation aqua oxidation aluminum precipitation can be for example one or more in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and isooctanol aluminium.Described organic aluminum contained compound and water consumption ratio are not particularly limited, and the preferred water yield is greater than the required amount of stoichiometry.
In boehmite preparation process of the present invention, the described condition of precipitation reaction that makes is not particularly limited, preferred pH value is 3-11, more preferably 6-10; Temperature can be 30-90 ℃, is preferably 40-80 ℃.
Wherein, it is conventionally known to one of skill in the art making the method for aluminum precipitation by the control of consumption to alkali in reactant or acid.
Condition to described hydrolysis is not particularly limited, as long as water contacts with aluminum alkoxide, hydrolysis generation hydrated alumina occurs, and the concrete condition that hydrolysis occurs is conventionally known to one of skill in the art.
Wherein, can add the compound of crystal grain growth regulating effect in hydrolysis or precipitation reaction obtain slurries that the slurries of hydrated alumina or filter cake after filtering add the water preparation again, also can add aqueous slkali or acid solution suitably to regulate the pH value to 7-10, then carry out aging at suitable temperature.Then separate, washing, drying.
Described acid solution or aqueous slkali can be with above-described identical or different.
Described aging temperature is preferably 35-98 ℃, and ageing time is preferably 0.2-6 hour.
According to method provided by the invention, the described known technology that is separated into this area is as the method for filtration or centrifugation or evaporation.
In boehmite preparation process of the present invention, also comprise the washing and the dry step that often comprise in preparation boehmite process after aging, described washing and dry method are preparation boehmite conventional process.For example, can use oven dry, forced air drying or spray-dired method.Generally speaking, baking temperature can be 100-350 ℃, is preferably 120-300 ℃.
According to the preparation method of boehmite of the present invention, a preferred embodiment comprises the following steps:
(1) will contain the aluminum contained compound solution of grain growth conditioning agent and aqueous slkali or acid solution and stream or batch (-type) and join and carry out precipitation reaction in reaction vessel, obtain the hydrated alumina slurries; Perhaps add the reaction that is hydrolyzed of grain growth conditioning agent and aluminum alkoxide in deionized water, obtain the hydrated alumina slurries;
(2) filter cake after the hydrated alumina dope filtration that step (1) is obtained adds in the aluminium oxide slurries that water making beating obtains again again, adds the grain growth conditioning agent, after regulating pH and being 7-10, in 35-98 ℃ of aging 0.2-6 hour; The hydrated alumina slurries that also above-mentioned steps (1) can be obtained are without filtering in the existence of grain growth conditioning agent or being under 7-10 at pH not, in 35-98 ℃ of aging 0.2-6 hour;
(3) product that filter, washing step (2) obtains;
(4) product that obtains of drying steps (3) obtains the boehmite of 1.1≤n provided by the invention≤2.5.
Composition according to boehmite provided by the invention and silicon-containing compound, wherein can also comprise the boehmite P2 except the boehmite of 1.1≤n≤2.5, described P2 is the boehmite of n＜1.1, preferred P2 is the boehmite of 0.8＜n＜1.1, and further preferred P2 is the boehmite of 0.85≤n≤1.05.When described composition contained P2, in oxide and take the boehmite total amount as benchmark, the content of described P2 was not more than 70 % by weight, further preferably was not more than 50 % by weight, more preferably was not more than 30 % by weight.
Described composition can adopt any prior art that described boehmite and described silicon-containing compound are mixed to get.Wherein, described mixing can be the simple accumulation that described boehmite and described silicon-containing compound are placed in a place, can be also to adopt any one prior art, for example, can directly boehmite be mixed by the mode that stirs with silicon-containing compound in mixer, grinder, can boehmite, silicon-containing compound and water be mixed being enough under the condition of pulp, filter afterwards, dry or moist method mixes.When adopting any one prior art to mix, those skilled in the art optionally can control the uniformity that described mixing should reach, to this present invention to being not particularly limited.
During the consumption of each component makes final composition in described mixed process, in oxide, the content of preferred boehmite is the 65-99 % by weight, 75-97 % by weight more preferably, be more preferably 80-95% weight, the content of silicon-containing compound is the 1-35 % by weight, and more preferably the 3-25 % by weight, be more preferably the 5-20 % by weight.Said composition obtains silica-alumina provided by the invention through roasting.
According to silica-alumina provided by the present invention, wherein, described method of roasting and condition can be that this area prepares examples of such carriers customary way and condition.Preferred roasting condition comprises: temperature 400-900 ℃ is carried out, and further preferred 500-750 ℃, roasting time is 1-12 hour, more preferably 2-8 hour.
Described silica-alumina carrier optionally can be made into the article shaped of convenient operation arbitrarily, as spherical, compressing tablet and bar shaped.Described moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.
In one embodiment, described silica-alumina carrier is the extruded moulding thing, and its preparation method comprises:
(1) the boehmite P1 of described 1.1≤n≤2.5, the boehmite P2 that contains or do not contain n＜1.1, silicon-containing compound and water are mixed being enough under the condition of pulp, filter afterwards, dry or moist, obtain described composition;
(2) with the extrusion molding on banded extruder of step (1) resulting composition;
(3) step (2) gained extrusion molding thing is dry and roasting.
Wherein, be to guarantee carrying out smoothly of extruded moulding, comprise in step (2) step of introducing appropriate water, peptizing agent (as in being selected from nitric acid, acetic acid and citric acid one or more), extrusion aid (as being one or more in sesbania powder, cellulose) in the described composition and mixing.Described drying is conventional method, carries out drying as adopting baking oven, mesh-belt kiln, converter and fluid bed, when adopting heating means to carry out drying, preferred baking temperature is 50-200 ℃, 0.3-12 hour drying time, further preferred baking temperature is 60-150 ℃, and be 0.5-8 hour drying time.The method of described roasting and condition are conventional method and the condition that the catalyst carrier preparation is adopted, as adopt mesh-belt kiln, vertical heater, horizontal chamber furnace (oven) and converter to carry out roasting, the condition of described roasting is preferably, at the roasting temperature 1-12 of 400-900 ℃ hour, further preferably 500-750 ℃ roasting temperature 2-8 hour.
In another embodiment, described silica-alumina is the extruded moulding thing, and its preparation method comprises:
(1) on kneading machine or grinder, the boehmite P1 of described 1.1≤n≤2.5, the boehmite P2 that contains or do not contain n＜1.1 are mixed with silicon-containing compound, obtain described composition;
(2) with the extrusion molding on banded extruder of step (1) resulting composition;
(3) step (2) gained extrusion molding thing is dry and roasting.
Wherein, be to guarantee carrying out smoothly of extruded moulding, comprise in step (1) and introduce appropriate water, peptizing agent (as in being selected from nitric acid, acetic acid and citric acid one or more), extrusion aid (as being one or more in sesbania powder, cellulose).Described drying is conventional method, carries out drying as adopting baking oven, mesh-belt kiln, converter and fluid bed, when adopting heating means to carry out drying, preferred baking temperature is 50-200 ℃, 0.3-12 hour drying time, further preferred baking temperature is 60-150 ℃, and be 0.5-8 hour drying time.The method of described roasting and condition are conventional method and the condition that the catalyst carrier preparation is adopted, as adopt mesh-belt kiln, vertical heater, horizontal chamber furnace (oven) and converter to carry out roasting, the condition of described roasting is preferably, at the roasting temperature 1-12 of 400-900 ℃ hour, further preferably 500-750 ℃ roasting temperature 2-8 hour.
Silica-alumina carrier according to the preceding method preparation has following physico-chemical property: pore volume is 0.5-1.1 ml/g, and specific surface is the 100-400 meters squared per gram, and the most probable bore dia is
Bore dia
The pore volume percentage that accounts for total pore volume be more than 50%; Further preferred in preferred embodiment, the pore volume of described silica-alumina carrier is 0.55-0.90 ml/g, and specific surface is the 150-350 meters squared per gram, and the most probable bore dia is
Bore dia
The pore volume percentage that accounts for total pore volume be 50-90%, more preferred
The percentage that the pore volume in hole accounts for total pore volume is 50-80%
According to catalyst provided by the present invention, the kind of wherein said active metal component and content are usual kind and the content that fischer-tropsch synthetic catalyst adopts.For example described active metal component can be iron or cobalt and their combination; Take catalyst as benchmark, the content of described active metal component can be the 2-40 % by weight, is preferably the 5-30 % by weight in oxide.
Under the prerequisite that is enough to described active metal component is carried on described carrier, the present invention is not particularly limited the method that described active metal component is carried on described carrier.For example, can be enough to effective dose active metal component be deposited under condition on described carrier, the solution of described carrier with the compound that contains active metal component that contains effective dose is contacted, as passing through the methods such as dipping, co-precipitation, preferred infusion process is carried out drying, roasting or not roasting afterwards.The condition of described drying for the habitual condition of this type of catalyst of preparation, is 80-350 ℃ as baking temperature, is preferably 100-300 ℃, and be 1-24 hour drying time, is preferably 2-12 hour.When described catalyst need to carry out roasting, described temperature was preferably 100-700 ℃, and roasting time is 1-6 hour, and further preferred temperature is preferably 200-500 ℃, and roasting time is 2-4 hour.
One or more in described their soluble compound of compound that contains active metal component, as contain water-soluble salt of active metal component, one or more in complex compound.
According to catalyst provided by the invention, can also contain any material that does not affect the catalytic performance that the invention provides catalyst and maybe can improve the material of the catalytic performance of catalyst provided by the invention.As introducing one or both in the components such as Ru, Re, Pt and Pd, in element and take catalyst as benchmark, the introducing amount of above-mentioned auxiliary agent is the 0.001-25 % by weight, is preferably the 0.01-10 % by weight.
During one or both components in containing components such as being selected from Ru, Re, Pt and Pd in described catalyst, its introducing method can be the compound that will contain described auxiliary agent and contact with described alumina support after the compound that contains active metal component is mixed with mixed solution; Can also be to contact with described alumina support after the independent obtain solution of the compound that contains auxiliary agent and roasting.When auxiliary agent and active metal component are introduced described alumina support respectively, preferably at first auxiliary compound solution contacts with described alumina support and roasting with containing, afterwards again with contain 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 250-600 ℃, is preferably 300-500 ℃, roasting time is 2-8 hour, is preferably 3-6 hour.
According to the Fischer-Tropsch synthesis method that the present invention also provides, the popular response condition that wherein said Fischer-Tropsch synthesis condition is Fischer-Tropsch synthesis.For example, according to the conventional method in this area, at first with catalyst reduction, suitable reduction temperature is 100-800 ℃, and preferred 200-600 ℃, more preferably 250-550 ℃, the suitable recovery time is 0.5-72 hour, preferred 1-24 hour.Heating rate is 0.01-20 ℃/minute, preferred 0.1-10 ℃/minute.Reduction is carried out under reducing medium exists, and described reducing medium can be H
2, CO, or with the H of nitrogen or inert gas dilution
2, CO etc., the gaseous mixture of preferred hydrogen and hydrogen and inert gas, when reducing medium was the gaseous mixture of hydrogen and inert gas, the content of hydrogen preferably was not less than 0.5 volume % in mixture, more preferably was not less than 2 volume %.The space-time speed of reducing gas be 200-10000 mark liters/gram catalyst/hour, be preferably 500-8000 mark liter/gram catalyst/hour.Described reduction can be carried out also can carrying out in original position in reactor outside reactor.
Described reaction condition comprises: reaction temperature is 120-350 ℃, preferred 160-280 ℃, be particularly preferably 190-250 ℃, and reaction pressure is the 0.5-15 MPa, is preferably the 1-8 MPa, is particularly preferably the 1-5 MPa.Describedly contain that in hydrogen and CO gas mist, the mol ratio of hydrogen and carbon monoxide is 0.4-3, be preferably 1.5-2.5, more preferably 1.8-2.2.The space-time speed of gaseous mixture be 200-10000 mark liters/gram catalyst/hour, be preferably 500-10000 mark liter/gram catalyst/hour.
Described contact can be carried out in the reactor of any type, for example fixed bed reactors, slurry attitude bed tank reactor, fluidized-bed reactor or bubbling bed reactor and corresponding scheme.Obviously, the granular size of catalyst changes according to the reaction scheme of their employings.Given reaction scheme is selected most suitable catalyst granules granularity, relate to reactant and the product diffusion problem in catalyst granules, beds and reaction medium, this belongs to those skilled in the art's general knowledge.
The present invention will be further described for following example.
Agents useful for same in example except specifying, is chemically pure reagent.
In example of the present invention, the n value of all boehmites all adopts XRD method to measure.The XRD test is carried out on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44 kilovolts, 40 milliamperes, sweep speed is 2 °/minute.According to the Scherrer formula: (D is crystallite dimension to D=K λ/(Bcos θ), λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) calculation of parameter at ° peak goes out (120) take 2 θ as 23-33 respectively grain size is D (031) as D (120), the calculation of parameter at ° peak goes out (031) take 2 θ as 34-43 grain size, and by formula n=D (031)/D (120) calculates the n value.
The preparation method of the boehmite P2 of boehmite P1, the n of the 1.1≤n that uses in the embodiment of the present invention≤2.5＜1.1 and originate as follows:
P1-1 (comprising P1-1a and P1-1b), adopt following method preparation:
In the retort of 2 liters and stream add 600 ml concns be 96 gram aluminium oxide/liter, wherein contain the aluminum sulfate solution of 3.6 gram ribitol and ammonia spirit that concentration is 8 % by weight carries out precipitation reaction, reaction temperature is 40 ℃, reaction time is 10 minutes, it is 7 that the flow of control ammonia spirit makes the pH of reaction system, after precipitation reaction finishes, adding proper ammonia to make the pH value of slurries in slurries is 8.5, slurries filtered after under 55 ℃ aging 60 minutes, filter cake washs 2 times with the deionized water making beating, and drying does not obtain hydrated alumina P1-1a; Through 120 ℃ of dryings 24 hours, obtain hydrated alumina P1-1b.XRD characterizes and shows that P1-1a and P1-1b have structure of similar to thin diaspore.
Characterizing through XRD the n value that calculates P1-1a and P1-1b lists in table 1.
P1-2, adopt following method preparation:
To contain 210 gram aluminium oxide/liter, the causticity coefficient is 1.62 high concentration NaAlO
2Solution and deionized water are mixed with Al
2O
3Concentration is 5 liters of the solution of 40 grams per liters, then adds gluconic acid sodium salt 16.3 grams to obtain containing the NaAlO of gluconic acid sodium salt
2Then solution be transferred in the plastic reactor of cumulative volume 8L, and the reactor ratio of height to diameter is 8, bottom band CO
2Gas distributor.Controlling solution temperature is 25 ± 5 ℃, passes into the CO of concentration 90 volume % from reactor bottom
2Gas carries out the plastic reaction, and the plastic temperature is controlled at 20-40 ℃, regulates CO
2Gas flow is 15 ± 2 liter/mins of clocks, makes reaction end pH value reach 8.0-8.5 in 4-6 minute, namely stops ventilation, finishes the plastic reaction.With the gained slurries be heated to 70 ℃ aging 4 hours, then filter with vacuum filter, to be filtered complete after, replenish on filter cake and added 20 liters of deionized waters (temperature 70 C) flush cake approximately 30 minutes.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying with being pumped into spray dryer, obtain hydrated alumina P1-2.XRD characterizes demonstration, and P1-2 has structure of similar to thin diaspore, characterizes through XRD the n value that calculates P1-2 and lists in table 1.
P1-3, adopt following method preparation:
In the retort of 2 liters and stream add 1000 ml concns be 48 gram aluminium oxide/liter aluminum trichloride solution and 300 milliliters contain 200 gram aluminium oxide/liter, the causticity coefficient is 1.58, D-sorbite content is 1.82 grams per liters sodium aluminate solution carries out precipitation reaction, reaction temperature is during 80 ℃, conditioned reaction logistics capacity make and the pH value is 4.0, reaction time 15 minutes; Adding concentration in the gained slurries is the weak aqua ammonia adjusting slurries pH to 10.0 of 5 % by weight, and be warming up to 80 ℃, aging 3 hours, then filter with vacuum filter, to be filtered complete after, replenish on filter cake and added 20 liters of deionized waters (80 ℃ of temperature) flush cake approximately 30 minutes.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying with being pumped into spray dryer, control the spray dryer outlet temperature 100-110 ℃ of scope, approximately 2 minutes dry materials time, obtain hydrated alumina P1-3 after drying.Adopt XRD to characterize, P1-3 has structure of similar to thin diaspore.The n value that adopts XRD method to calculate P1-3 is listed in table 1.
P2-1 (comprising P2-1a and P2-1b), adopt following method preparation:
Method according to P1-1 prepares boehmite, and different is, the aluminum sulfate solution that contains ribitol by concentration be 96 gram aluminium oxide/liter aluminum sulfate solution replace, be also not contain ribitol in aluminum sulfate solution.Filtration product not drying obtains hydrated alumina P2-1a; Drying obtains hydrated alumina P2-1b.XRD characterizes demonstration, and P2-1a and P2-1b have structure of similar to thin diaspore, characterizes through XRD the n value and the degree of crystallinity that calculate P2-1a and P2-1b and lists in table 1.
P2-2 is the business boehmite SB powder that German Condea company aluminium alcoholates Hydrolyze method is produced, and the n value that adopts the XRD characterizing method to calculate the P2-2 powder is listed in table 1.
P2-3 is the business boehmite SD powder of Shandong Aluminium Industrial Corp's production.XRD characterizes and shows that P2-3 has structure of similar to thin diaspore, characterizes through XRD the n value that calculates P2-3 and lists in table 1.
P1-1a and P2-1a sample all carry out the XRD test again after 12 hours through 120 ℃ of dryings, obtain the n value.
Repeatedly prepare according to the method described above, to obtain enough for the boehmite raw material in example.
From the results shown in Table 1, boehmite P1-1a, P1-1b, P1-2 and P1-3 have the feature of 1.1≤n≤2.5; The n of boehmite P2-1a, P2-1b, P2-2 and P2-3＜1.1.In addition, take the degree of crystallinity of the business SB powder of Condea company as 100%, adopt the degree of crystallinity of boehmite of method preparation provided by the invention in the 60-80% scope.
Table 1
Embodiment 1～5 explanation described composition provided by the invention, silica-alumina carrier and preparation method thereof.
Embodiment 1
(1) composition of boehmite provided by the invention and silicon-containing compound and preparation thereof:
At room temperature the 1600 gram synthetic boehmite P1-1a (butt 22%) in laboratory are added 3000 ml water making beating, stir after 30 minutes, (Silica Gel955, U.S. Davison Chemical company product contains SiO under agitation to add business silica gel
299.8 % by weight) 62 grams continue to stir after 150 minutes, filtered, and filter cake 120 ℃ of dryings 10 hours, is obtained composition Z H-1 of the present invention (butt 77%).Adopt x-ray fluorescence method to record the composition of ZH-1, in oxide and with butt, silica content is 15 % by weight, and alumina content is 85 % by weight.
(2) silica-alumina provided by the invention and preparation thereof:
420 gram ZH-1 are mixed with sesbania powder 4 grams, afterwards with this mixture and 13.5 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 530 ml waters mix, and on double screw banded extruder kneading, be extruded into the butterfly bar of 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina Z-1 through 120 ℃ of dryings.The silica content of Z-1, specific area, pore volume and pore size distribution data are listed in table 2.
Embodiment 2
(1) composition of boehmite provided by the invention and silicon-containing compound and preparation thereof:
First 400 synthetic boehmite P1-1b (butt 70%) and the Ludox in gram laboratory (are contained SiO
230 % by weight, the production of Beijing flying dragon horse company) after 295 grams, sesbania powder 11 grams mix, again with 8.2 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, Shantou west) and 310 milliliters of mixing of water, afterwards this mixture is continued kneading on double screw banded extruder, obtain composition Z H-2 of the present invention.ZH-2 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-2, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 24 % by weight, and alumina content is 76 % by weight.
(2) silica-alumina provided by the invention and preparation thereof:
Continue whole aforementioned ZH-2 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina Z-2 through 120 ℃ of dryings.The silica content of Z-2, specific area, pore volume and pore size distribution data are listed in table 2.
Embodiment 3
(1) composition of boehmite provided by the invention and silicon-containing compound and preparation thereof:
First (Beijing chemical reagents corporation contains SiO for the boehmite P1-2 (butt 69%) that 450 gram laboratories are synthetic and ethyl orthosilicate
228 % by weight are analyzed pure) 46 grams, 12.5 gram sesbania powder mix, then with this mixture and 8.2 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, Shantou west), 400 ml waters mix, and continue afterwards kneading equal on double screw banded extruder, obtain composition Z H-3 of the present invention.ZH-3 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-3, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 4 % by weight, and alumina content is 96 % by weight.
(2) silica-alumina provided by the invention and preparation thereof:
Continue whole aforementioned ZH-3 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina Z-3 through 120 ℃ of dryings.The silica content of Z-3, specific area, pore volume and pore size distribution data are listed in table 2.
Embodiment 4
(1) composition of boehmite provided by the invention and silicon-containing compound and preparation thereof:
First (Siral 40, contain SiO for the boehmite P1-3 (butt 71%) that 400 gram laboratories are synthetic and amorphous aluminum silicide
240% weight, Germany Condea company product) 304 grams, sesbania powder 19 grams mix, again with this mixture and 12 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 413 ml waters mix, after kneading on double screw banded extruder is even, obtain composition Z H-4 of the present invention afterwards.ZH-4 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-4, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 30 % by weight, and alumina content is 70 % by weight.
(2) silica-alumina provided by the invention and preparation thereof:
Continue whole aforementioned ZH-4 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina Z-4 through 120 ℃ of dryings.The silica content of Z-4, specific area, pore volume and pore size distribution data are listed in table 2.
Embodiment 5
(1) composition of boehmite provided by the invention and silicon-containing compound and preparation thereof:
First 300 synthetic boehmite P1-3 (butt 71%), business boehmite (Shandong Aluminium Industrial Corp produces, butt 67% weight, n value 1.02) 212 grams, the Ludox in gram laboratory (are contained SiO
230% weight, the production of Beijing flying dragon horse company) 131 grams, sesbania powder 13 grams mix, again with 11 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 210 ml waters mix, after continuation kneading on double screw banded extruder is even, obtain composition Z H-5 of the present invention afterwards.ZH-5 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-5, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 10 % by weight, and alumina content is 90 % by weight.
(2) silica-alumina provided by the invention and preparation thereof:
Whole aforementioned ZH-5 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina Z-5 through 120 ℃ of dryings.The silica content of Z-5, specific area, pore volume and pore size distribution data are listed in table 2.The aluminium oxide that is provided by P1-3 accounts in carrier all 60 % by weight of alumina contents.
Comparative Examples 1-5 explanation reference composition, silica-alumina and preparation method thereof.
Comparative Examples 1
(1) reference composition and preparation thereof
At room temperature the 1600 gram synthetic boehmite P2-1a (butt 21%) in laboratory are added 3000 ml water making beating, stir after 30 minutes, (Silica Gel955, U.S. Davison Chemical company product contains SiO under agitation to add business silica gel
299.8 % by weight) 60 grams continue to stir after 150 minutes, filtered, and filter cake 120 ℃ of dryings 10 hours, is obtained composition CZH-1 of the present invention (butt 78%).Adopt x-ray fluorescence method to record the composition of CZH-1, in oxide and with butt, silica content is 15 % by weight, and alumina content is 85 % by weight.
(2) reference silica-alumina and preparation thereof
420 gram CZH-1 are mixed with sesbania powder 4.2 grams, afterwards with this mixture and 13.5 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 530 ml waters mix, on double screw banded extruder kneading, be extruded into the butterfly bar of 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CZ-1 through 120 ℃ of dryings.The silica content of CZ-1, specific area, pore volume and pore size distribution data are listed in table 2.
Comparative Examples 2
(1) reference composition and preparation thereof:
First the 400 gram synthetic boehmite P2-1b (butt 68%) in laboratory (are contained SiO with Ludox
230% weight, the production of Beijing flying dragon horse company) 287 grams, sesbania powder 11.3 grams mix, again with this mixture and 8.8 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 313 ml waters mix, continue afterwards kneading on double screw banded extruder, obtain reference silica-alumina CZH-2.CZH-2 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-2, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 24 % by weight, and alumina content is 76 % by weight.
(2) reference silica-alumina and preparation thereof:
Whole aforementioned CZH-2 are continued to be extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CZ-2 through 120 ℃ of dryings.The silica content of CZ-2, specific area, pore volume and pore size distribution data are listed in table 2.
Comparative Examples 3
(1) reference composition and preparation thereof:
First (Beijing chemical reagents corporation contains SiO with 450 gram business boehmite P2-2 (the SB powder that German Condea company produces, butt 75%) and ethyl orthosilicate
228% weight is analyzed pure) 49.5 grams, 9 gram sesbania powder mix, then this mixture is mixed with 9 milliliters of nitric acid, 390 ml waters, continue afterwards kneading on double screw banded extruder, obtain reference composition CZH-3.CZH-3 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-3, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 4 % by weight, and alumina content is 96 % by weight.
(2) reference silica-alumina and preparation thereof:
Continue whole aforementioned CZH-3 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CZ-3 through 120 ℃ of dryings.The silica content of CZ-3, specific area, pore volume and pore size distribution data are listed in table 2.
Comparative Examples 4
(1) reference composition and preparation thereof:
First (Siral 40, contain SiO for the boehmite P2-3 (butt 68%) that 400 gram laboratories are synthetic and amorphous aluminum silicide
240% weight, Germany Condea company product) 291 grams, sesbania powder 18.7 grams mix, again with this mixture and 12 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 446 ml waters mix, continue afterwards kneading on double screw banded extruder, obtain reference composition CZH-4.CZH-4 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-4, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 30 % by weight, and alumina content is 70 % by weight.
(2) reference silica-alumina and preparation thereof:
Continue whole aforementioned CZH-4 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CZ-4 through 120 ℃ of dryings.The silica content of CZ-4, specific area, pore volume and pore size distribution data are listed in table 2.
Comparative Examples 5
(1) reference composition and preparation thereof:
First (Shandong Aluminium Industrial Corp produces with 300 synthetic boehmite P2-3 (butt 68%), the business boehmites in gram laboratory, butt 67% weight, n value 1.02) 202 grams, Ludox (contain SiO230% weight, the production of Beijing flying dragon horse company) 126 grams, sesbania powder 13 grams mix, again this mixture is mixed with 11 milliliters of nitric acid, 265 ml waters, continue afterwards kneading on double screw banded extruder, obtain reference composition CZH-5.CZH-5 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-5, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 10 % by weight, and alumina content is 90 % by weight.
(2) reference silica-alumina and preparation thereof:
Continue on double screw banded extruder to say that whole aforementioned CZH-5 are extruded into the butterfly bar of 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CZ-5 through 120 ℃ of dryings.The silica content of CZ-5, specific area, pore volume and pore size distribution data are listed in table 2.The aluminium oxide that is provided by P2-3 accounts in carrier all 60 % by weight of alumina contents.
PV in table 2 (10-20)/PV is always the pore volume of 10-20 nanometer shared ratio in total pore volume for bore dia.
Table 2
As can be seen from Table 2, the invention provides that silica-alumina PV (10-20)/the PV total value is all greater than 50%, and the PV of Comparative Examples silica-alumina (10-20)/PV is all below 50%.Therefore, silica-alumina of the present invention not only have larger can several apertures, and have more concentrated pore size distribution.
Embodiment 6～10 explanation catalyst provided by the invention and preparations thereof.
Embodiment 6～10
Take respectively Z1, Z2, Z3, Z4, each 20 grams of Z5 carrier, the cabaltous nitrate hexahydrate of 13.74 grams is got in weighing, 2.24 gram platinum chloride ammonia solutions (concentration is 1.07 gram platinum/100 gram solution).Be mixed with required solution, equal-volume total immersion stain carrier then, then baking 4 hours under 120 ℃ in baking oven, the 450 ℃ of roastings in Muffle furnace that continue 3 hours.Obtain catalyst C1, C2, C3, C4 and C5.In oxide and take catalyst as benchmark, in catalyst, cobalt oxide content is 15.0 % by weight, and in element and take catalyst as benchmark, platinum content is 0.1 % by weight (being calculated value).
Comparative Examples 6～10 reference catalyst and preparation thereof.
Comparative Examples 6～10
Take respectively each 20 grams of CZ1, CZ2, CZ3, CZ4 and CZ5 carrier, the cabaltous nitrate hexahydrate of 13.74 grams is got in weighing, 2.24 gram g platinum chloride ammonia solutions (concentration is 1.07 gram platinum/100 gram solution).Be mixed with required solution, equal-volume total immersion stain carrier then, then baking 4 hours under 120 ℃ in baking oven, the 450 ℃ of roastings in Muffle furnace that continue 3 hours.Obtain catalyst CC1, CC2, CC3, CC4 and CC5.In oxide and take catalyst as benchmark, in catalyst, cobalt oxide content is 15.0 % by weight, and in element and take catalyst as benchmark, platinum content is 0.1 % by weight (being calculated value).
Embodiment 11-15 explanation the invention provides catalyst in Fischer-Tropsch is synthetic application and effect thereof.
In fixed bed reactors, adopt catalyst C1, C2, C3, C4 and C5 to carry out Fischer-Tropsch synthesis.
Unstripped gas forms: H
2/ CO/N
2=64%/32%/4% (volume hundred umbers).
The catalyst reduction reaction condition: pressure is normal pressure, and heating rate is 5 ℃/minute, and hydrogen gas space velocity is 600 hours
-1, reduction temperature is 400 ℃, the recovery time is 5 hours.
Reaction condition: pressure 2.5 MPas, 200 ℃ of temperature, synthesis gas (unstripped gas) air speed 2000 hours
-1
Reaction is carried out getting the gas sample after 24 hours and is carried out chromatography, and wherein, CO conversion ratio and methane selectively are listed in table 3.
Comparative Examples 11-15 explanation reference catalyst in Fischer-Tropsch is synthetic application and effect thereof.
Adopt and embodiment 11 the same terms, adopt catalyst CC1, CC2, CC3, CC4 and CC5 to carry out Fischer-Tropsch synthesis.Wherein, CO conversion ratio and methane selectively are listed in table 3.
Table 3
As can be seen from Table 3, adopt the aluminium oxide-silicon oxide of method provided by the invention preparation as catalyst carrier, the fischer-tropsch synthetic catalyst that is prepared into has better Fischer-Tropsch synthetic performance, i.e. higher activity and a C in the situation that other condition is identical
5+Selectively and lower methane selectively.
Claims (17)
1. fischer-tropsch synthetic catalyst take silica one aluminium oxide as carrier, this catalyst contains carrier and active metal component, and described carrier is selected from silica-alumina, it is characterized in that, and the bore dia in described carrier exists
The percentage that the pore volume in hole accounts for total pore volume is more than 50%, described silica-alumina is obtained through roasting by the composition of a kind of boehmite and silicon-containing compound, wherein, the boehmite described in the composition of described boehmite and silicon-containing compound comprises the boehmite P1 of at least a 1.1≤n≤2.5; n=D (031)/D (120) wherein, the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression boehmite crystal grain, described 031 peak refers to that 2 θ in XRD spectra are the peak of 34-43 °, described 120 peaks refer to that 2 θ in XRD spectra are the peak of 23-33 °, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of diffraction maximum, 2 θ are the position of diffraction maximum.
2. catalyst according to claim 1, is characterized in that, the bore dia in described silica-alumina exists
The percentage that the pore volume in hole accounts for total pore volume is 50-90%.
3. catalyst according to claim 2, is characterized in that, the bore dia in described silica-alumina exists
The percentage that the pore volume in hole accounts for total pore volume is 50-80%.
4. catalyst according to claim 1, is characterized in that, described P1 is the boehmite of 1.2≤n≤2.2.
5. catalyst according to claim 1, is characterized in that, in oxide, in the composition of described boehmite and silicon-containing compound, the content of boehmite is the 65-99 % by weight, and the content of silicon-containing compound is the 1-35 % by weight.
6. catalyst according to claim 5, is characterized in that, in oxide, in the composition of described boehmite and silicon-containing compound, the content of boehmite is the 75-97 % by weight, and the content of silicon-containing compound is the 3-25 % by weight.
7. catalyst according to claim 6, is characterized in that, in oxide, in the composition of described boehmite and silicon-containing compound, the content of boehmite is the 80-95 % by weight, and the content of silicon-containing compound is the 5-20 % by weight.
8. catalyst according to claim 1, is characterized in that, described silicon-containing compound is selected from one or more in organic silicon-containing compound.
9. catalyst according to claim 8, described silicon-containing compound is selected from one or more in esters of silicon acis, silanol, silicon ether, silicone, silicone oil.
10. catalyst according to claim 1, is characterized in that, described silicon-containing compound is selected from one or more in inorganic silicon-containing compound.
11. catalyst according to claim 10 is characterized in that, described inorganic silicon-containing compound is selected from one or more in hydrated SiO 2, Ludox, silicic acid, waterglass.
12. catalyst according to claim 1 is characterized in that, described active metal component chosen from Fe or cobalt and their combination, and take catalyst as benchmark, the content of described active metal component is the 2-40 % by weight.
13. catalyst according to claim 12 is characterized in that, the content of described active metal component is the 5-30 % by weight.
14. catalyst according to claim 1 is characterized in that, comprises also in described boehmite that P2 is the boehmite of n＜1.1, in oxide and take the boehmite total amount as benchmark, the content of described P2 is not more than 70 % by weight.
15. catalyst according to claim 14 is characterized in that, described in oxide and take the boehmite total amount as benchmark, the content of described P2 is not more than 50 % by weight.
16. catalyst according to claim 15 is characterized in that, described in oxide and take the boehmite total amount as benchmark, the content of described P2 is not more than 30 % by weight.
17. a Fischer-Tropsch synthesis method is included under the Fischer-Tropsch synthesis condition, will contain hydrogen and contact with catalyst with CO gas, wherein, described catalyst is the described catalyst of 1-16 any one claim.
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| CN104624192B (en) * | 2015-01-23 | 2017-04-12 | 武汉凯迪工程技术研究总院有限公司 | Cobalt-based fischer-tropsch synthesis catalyst and preparation method and application |
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| CN107803206B (en) * | 2016-09-08 | 2020-11-13 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst regeneration method and application thereof |
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| 朱洪法.催化剂载体制备及应用技术.《催化剂载体制备及应用技术》.石油工业出版社,2002,第514页. * |
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