CN102233268A - Fischer-Tropsch synthesis catalyst and application thereof - Google Patents
Fischer-Tropsch synthesis catalyst and application thereof Download PDFInfo
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Abstract
The invention discloses a Fischer-Tropsch synthesis catalyst and application thereof. The catalyst contains carriers and active metal components and is characterized by being prepared by roasting pseudo-boehmite which contains transition metal addition components, wherein based on oxides and the dry basis of the pseudo-boehmite, the content of the transition metal addition components in the pseudo-boehmite is 0.05 to 20 weight percent; the pseudo-boehmite comprises at least one kinds of pseudo-boehmite P1 of which n is more than or equal to 1.1 and less than or equal to 2.5; n is equal to D(031)/D(120); the D(031) means the size of crystal grains on a crystal surface represented by a 031 peak in an X ray diffraction (XRD) spectrogram of pseudo-boehmite crystal grains; the D(120) means the size of crystal grains on a crystal surface represented by a 120 peak in the XRD spectrogram of the pseudo-boehmite crystal grains; the 031 peak means a peak of which 2 theta is 34 to 43 DEG in the XRD spectrogram; the 120 peak means a peak of which the 2 theta is 23 to 33 DEG in the XRD spectrogram; the D is equal to K lambda/(B cosine theta); the K is a Scherrer constant; the lambda is the diffraction wavelength of a target material; the B is the half peak width of a diffraction peak; and the 2 theta is the position of the diffraction peak.
Description
Invention field
The present invention relates to a kind of fischer-tropsch synthetic catalyst and application thereof, is the fischer-tropsch synthetic catalyst and the application thereof of carrier more specifically to a kind of aluminium oxide with the component that contains transition metal.
Background technology
Nineteen twenty-three, Fischer and Tropsch have found CO and H
2The method of mixture Synthin product.20th century the '30s, F-T synthetic (Fischer-Tropsch is synthetic) is at first in German Industrialization, the back U.S., France, the former Soviet Union and China etc. have also set up similar artificial oil factory, of a high price because of this route after World War II, benefit can not be closed one after another with oil competition, have only the F-T synthetic technology of South Africa according to the national conditions development coal system oil of national rich coal resources, the F-T synthesis technique of Sasol company is still in development and perfect constantly at present.Twentieth century seventies, Holland Shell company began the synthetic research of F-T, 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 the coal and the natural gas proved reserves of demanded fuel; make the research in synthetic this field of F-T very active, many companies research and develop on F-T is synthetic.
Good F-T synthetic catalyst should be to CO and H
2Adsorption activity is arranged, the CO of absorption is had hydrogenization, help chain growth, leniently promote hydrogenation, do not answer again simultaneously that hydrogenation is strong excessively, Water gas shift/WGS too much and form nonactive carbonization thing etc.The synthetic first step of F-T is CO and H
2Chemisorbed, from the structural chemistry viewpoint, have the transition elements of 3d and 4f key and energy level, be used as the active component of F-T synthetic catalyst mostly.Wherein more about the research of Ni, Fe, Co, Ru.Remove Ni because hydrogenation activity is too strong, make the chain growth probability too big, be mainly used in methanation, be not suitable for doing outside the active component of synthetic macromolecule wax hydrocarbon catalyst, it is synthetic that its excess-three kind metallic catalyst all can be used for F-T.And what have commercial application value is Co and Fe catalyst, wherein because the F-T synthesizing activity height of Co, and the reaction condition gentleness, water gas shift reaction is few, stable performance, the life-span is longer, so people have carried out research widely to the Co catalyst in research and application.
Be used for the Co catalyst of F-T, use DNAcarrier free oxide in early days, as pure cobalt/cobalt oxide, cobalt-chromated oxide and cobalt-zinc oxide etc.; Found afterwards to add thorium oxide and magnesia, and can increase activity of such catalysts; Carrier loaded Co catalyst is the main flow of research and commercial Application at present.Use Co catalyst, researcher to select for use multiple auxiliary agent that it is modified for F-T is synthetic, improve its catalytic performance with expectation.
A kind of method for preparing catalyst and using method are disclosed among the patent CN89109859 and 93106465, this catalyst comprise the cobalt of the catalytic activity amount that is loaded on the alumina support and be selected from platinum, iridium, rhodium, and composition thereof second metal also responsive to load capacity.Can add metal oxide promoters.
Patent CN01810769.9 and 01810773 discloses a kind of method for preparing catalyst and using method, this catalyst includes the cobalt of catalytic activity amount, its content is the 5gCo/100g-70gCo/100g carrier, also can add Pd and Pt, as having the adulterant that strengthens the Co reducing power.
Patent CN01118173 discloses a kind of F-T synthetic catalyst, loaded catalyst for the Ln-Co base, wherein LnO represents one or more alkali metal, alkaline-earth metal, transition metal or rare earth oxide, and described oxide and Co with respect to the loading of carrier are: Co:1.0-20% weight, LnO:0.1-20% weight.Wherein Ln represents La, Ce, Mg, Mn, Zr, Ni, K.
Patent CN200680022459 discloses the method for a kind of catalyst and this catalyst of preparation, and this catalyst comprises that 5-75wt% loads on the cobalt on the oxidation carrier, and this oxidation carrier comprises the lithium of aluminium and 0.01-20wt%.The F-T that this catalyst can be used for hydrocarbon synthesizes.
A kind of method for preparing catalyst and using method are disclosed among the patent CN88107330 and 91104473, this catalyst includes the cobalt of catalytic activity amount, its content can and have the rhenium of catalyst activity amount up to 60% (weight), its content is about the 0.5-50% (weight) of catalyst cobalt content, and cobalt and rhenium all are stated from the aluminium oxide.Also can add alkaline components in the catalyst as auxiliary agent.
Summary of the invention
The technical problem to be solved in the present invention is the Fischer-Tropsch synthesis method that provides a kind of performance to obtain the fischer-tropsch synthetic catalyst of modification on the basis of existing technology and use this catalyst.
The invention provides a kind of fischer-tropsch synthetic catalyst, described catalyst contains carrier and active metal component, it is characterized in that, described carrier is obtained through roasting by a kind of boehmite that contains transition metal component, in oxide and with the butt of described boehmite is benchmark, the content of transition metal component is 0.05-20 weight % in the described boehmite, and described boehmite comprises the boehmite P1 of at least a 1.1≤n≤2.5; Wherein, n=D (031)/D (120), 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 is meant that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks are meant that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of diffraction maximum, and 2 θ are the position of diffraction maximum.
The present invention further provides a kind of Fischer-Tropsch synthesis method, be included under the Fischer-Tropsch synthesis condition, it is characterized in that described catalyst is aforementioned catalyst provided by the invention the mixture and the catalyst haptoreaction of carbon monoxide and hydrogen.
Fischer-tropsch synthetic catalyst provided by the invention adopts the carrier that comprises that at least a boehmite P1 that contains 1.1≤n≤2.5 of transition metal interpolation component prepares, and the performance of catalyst is improved.
For example, under the identical situation of activity of such catalysts metal component content, preparation condition, compare with the reference agent, the CO activity of conversion that the invention provides catalyst improves can reach 4-8%, and methane selectively reduces 2-3%.
The specific embodiment
According to catalyst provided by the invention, wherein, the described boehmite that contains transition metal interpolation component, in oxide and with the butt of described boehmite is benchmark, described transition metal adds components contents can be selected between 0.05-20 weight %, and preferred content is 0.1-10 weight %.Butt described here is meant described boehmite percentage of the ratio of weight before the weight of 600 ℃ of roastings after 4 hours and the roasting under air atmosphere.
According to described boehmite provided by the invention, to look finally aluminium oxide application target difference, the content of transition metal component, kind can be different.For example, gama-alumina is to the conversion of Alpha-alumina phase when improving high-temperature roasting, improve the heat endurance of gama-alumina, described boehmite preferably contains and is selected from lanthanide series metal, IVB family metal (for example Zr), VB family metal (for example Ta), group vib metal (for example W), VIIB family metal (for example Mn), one or more transition metal component in the IIB family metal (for example Zn), wherein, in oxide and described boehmite butt is several, the content of described transition metal component can be selected between 0.05-20 weight %, and preferred content is 0.1-10 weight %.
For improving the activity of F-T synthetic catalyst, preferably contain in the described boehmite and be selected from VB family metal (for example Ta), group vib metal (Mo for example, W), IB family metal (for example Cu), VIII family metal (Ru for example, Re) one or more transition metal component in, wherein, in oxide and described boehmite butt is several, and the content of described transition metal component can be selected between 0.05-20 weight %, and preferred content is 0.1-10 weight %.
Selectivity for the C5+ that improves the F-T synthetic catalyst, preferably contain in the described boehmite and be selected from IVB family metal (Ti for example, Zr), one or more transition metal component in VIII family metal (for example Ru) and the rare earth metal, wherein, in oxide and described boehmite butt is several, the content of described transition metal component can be selected between 0.05-20 weight %, and preferred content is 0.1-10 weight %.
For improving the regenerability of Co base F-T synthetic catalyst, preferably contain in the described boehmite and be selected from IVB family metal (for example Hf), VIII family metal (Ru for example, Re) and one or more transition metal component in the rare earth metal, wherein, in oxide and described boehmite butt is several, the content of described transition metal component can be selected between 0.05-20 weight %, and preferred content is 0.1-10 weight %.
Under the prerequisite that is enough to make the content of described interpolation component in described boehmite to meet the demands, the present invention is not particularly limited the introducing method that described transition metal adds component.For example, can be in the process of the boehmite P1 for preparing described 1.1≤n≤2.5, to introduce to contain the method introducing that transition metal adds the compound of component, also can be the boehmite P1 that at first prepares described 1.1≤n≤2.5, afterwards its method with the compound that contains transition metal interpolation component be introduced.Wherein, the described compound that contains transition metal component can be their salt, oxide or acid (comprising as molybdic acid wolframic acid etc.), preferred water soluble compound wherein.
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; The above-mentioned hydrated alumina that obtains is worn out, 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 in the presence of the grain growth conditioning agent, carry out, 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 in the presence of the grain growth conditioning agent, carry out realizing purpose of the present invention, but under the preferable case, described hydrolysis and ageing process or described precipitation reaction and ageing process are all carried out in the presence of the grain growth conditioning agent, and the n that can make the gained boehmite like this is in preferred 1.2≤n≤2.2 scopes.
Wherein, there is no particular limitation to the consumption of grain growth conditioning agent, the consumption of grain growth conditioning agent is the 0.5-10 weight % that treats organic aluminum contained compound weight of hydrolysis in the selective hydrolysis reaction, 1-8.5 weight % more preferably, further preferred 5-8.5 weight %; The consumption of grain growth conditioning agent is the inorganic 0.5-10 weight % that contains al reactant weight in the described precipitation reaction, 1-8.5 weight % more preferably, further preferred 5-8.5 weight %; In the described ageing process, the consumption of grain growth conditioning agent can be preferably 1-8.5 weight % for the 0.5-10 weight % of hydrated alumina weight, further preferred 5-8.5 weight %.Unless stated otherwise, among the present invention, the consumption of described grain growth conditioning agent is that benchmark calculates with the weight of aluminium oxide corresponding in organic aluminum contained compound, inorganic aluminum contained compound and the hydrated alumina respectively.Also be, in aluminium oxide, in the described precipitation reaction, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of inorganic aluminum contained compound weight, in the described hydrolysis, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of organic aluminum contained compound weight, and in the described ageing process, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of hydrated alumina weight.
Among 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 the material of crystal grain in the speed of growth of 120 crystal faces and 031 crystal face, be preferably alditol and carboxylate thereof, be specifically as follows in D-sorbite, glucose, gluconic acid, gluconate, ribitol, ribonic acid, the ribose hydrochlorate one or more.Described gluconate and ribose hydrochlorate can be their soluble-salt separately, for example, can be in sylvite, sodium salt and the lithium salts one or more.
In boehmite preparation process of the present invention, adding mode 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, for example can be one or more the aqueous solution in aluminum sulfate, aluminium chloride, the aluminum nitrate.Because price is low, preferably sulfuric acid aluminium, liquor alumini chloridi.Aluminium salt can use separately also and can use two kinds or more of mixing back.Described aluminate solution is an 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 with aluminium oxide.
Described acid can be various Bronsted acids or be acid oxide in aqueous medium, for example, can be in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetate, citric acid, the oxalic acid one or more, preferred Bronsted acid be selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid.Described carbonic acid can original position produces by feed 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.
Described aqueous slkali can for hydroxide or in aqueous medium hydrolysis make the aqueous solution be the salt of alkalescence, preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, the 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, the potash.Concentration to described aqueous slkali is not particularly limited, preferred OH
-Concentration be the 0.2-4 mol.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 the potassium metaaluminate with sodium metaaluminate and/or potassium metaaluminate.
Described organic aluminum contained compound can be various can with water generation hydrolysis, producing in the aluminum alkoxide of aqua oxidation aluminum precipitation one or more, for example can be in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and the isooctanol aluminium one or more.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 the reactant or acid.
Condition to described hydrolysis is not particularly limited, as long as water contacts with aluminum alkoxide hydrolysis generation hydrated alumina takes place, and the condition that hydrolysis specifically takes place is conventionally known to one of skill in the art.
Wherein, can in hydrolysis or precipitation reaction obtain slurries that the slurries of hydrated alumina or filter cake after filtering add the water preparation again, add the compound of crystal grain growth regulating effect, also can add aqueous slkali or acid solution and suitably regulate the pH value, under suitable temperature, wear out then to 7-10.Separate then, 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, after aging, also comprise the washing and the dry step that often comprise in the preparation boehmite process, 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, an embodiment preferred may further comprise the 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 the reaction vessel, obtain the hydrated alumina slurries; Perhaps in deionized water, add the reaction that is hydrolyzed of grain growth conditioning agent and aluminum alkoxide, obtain the hydrated alumina slurries;
(2) filter cake behind 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; Also the hydrated alumina slurries that above-mentioned steps (1) can be obtained without filter the grain growth conditioning agent exist or not in the presence of be under the 7-10 at pH, 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.
When introducing in the process of boehmite P1 of preparation described 1.1≤n≤2.5 when containing transition metal and adding the compound of component, containing transistion metal compound can introduce in above-mentioned step (1), (2), (3) or (4) any one or several steps.
According to catalyst provided by the invention, wherein, described boehmite optionally can also comprise the boehmite P2 except that 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 contains P2, be benchmark with the boehmite total amount, the content of described P2 is not more than 70 weight %, further preferably is not more than 50 weight %, more preferably is not more than 30 weight %.Described P2 is 0.8＜n
2＜1.1 boehmite can be to be selected from the boehmite that commercially available commodity also can adopt any one prior art for preparing.
The boehmite that contains transition metal interpolation component of the present invention obtains the aluminium oxide that containing metal of the present invention adds component through roasting, and the method for described roasting is conventional method and condition.For example, when described purpose aluminium oxide was gama-alumina, described roasting condition comprised: sintering temperature is 350-950 ℃, is preferably 450-900 ℃, and roasting time is 1-12 hour, is preferably 2-8 hour.
According to catalyst provided by the invention, wherein said active metal component is the usual active metal component in the FT synthetic catalyst.For example, select the cobalt and/or the ferrous metal component of group VIII.The content of described metal component is customary amount, in oxide and with catalyst be benchmark, the content of preferred active metal component is 5～70 weight %, more preferably 10～50 weight % more are preferably 12～30 weight %.
According to catalyst provided by the invention, optionally can be made into and be convenient to the article shaped of operating 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.
Catalyst provided by the invention can adopt the conventional method preparation, for example, when the invention provides catalyst and be bar shaped catalyst, its preparation method comprises: (1) with describedly contain boehmite P1 (containing or do not contain P2) extruded moulding that transition metal adds component, dry and roasting prepares described carrier; Wherein, when extrusion molding, can add entry, extrusion aid and/or adhesive, extrusion molding then to described containing in the boehmite that transition metal adds component; The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, and for example common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, the poly-ethanol; The temperature of described drying can be 100-200 ℃, is preferably 120-150 ℃; Sintering temperature is 350-950 ℃, is preferably 450-900 ℃, and roasting time is 1-12 hour, is preferably 2-8 hour; (2) adopt the method for dipping in described carrier, to introduce active metal component, dry and roasting; Wherein, the temperature of described drying can be 100-200 ℃, is preferably 120-150 ℃.The temperature of roasting can be 400-650 ℃, is preferably 450-600 ℃, and roasting time is 1-15 hour, is preferably 3-10 hour.Described dipping method is a conventional method, and for example preparation contains the solution of the compound of described active metal component, afterwards by the method dipping that soaks or spray, dry and roasting.The described compound that contains active metal component is selected from one or more in these their soluble compounds, for example, can be in the nitrate, acetate, carbonate, chloride, soluble complexes of these metals one or more.
Be selected from one or more adjuvant components in Cu, Mo, Ta, W, Ru, Zr, Ti, REO, Re, Hf, Ce, Mn, V and the noble metal, described noble metal wherein is selected from one or more among Pt, Pd, Rh, the Ir, further preferred noble metal is Pt, is the adjuvant component that is usually used in fischer-tropsch synthetic catalyst known in the art.According to catalyst of the present invention, optionally can choose wantonly to contain and be selected from the above-mentioned adjuvant component one or more.Except that noble metal, in oxide and with catalyst be benchmark, the content of described adjuvant component preferably below 30 weight %, more preferably below the 20 weight %, more is preferably below the 15 weight %.When adjuvant component is selected from noble metal, in metal and with catalyst be benchmark, the content of described adjuvant component is preferably below 10 weight %, more preferably below the 1 weight %.
When also containing described adjuvant component in the described catalyst, also be included in the step that catalyst is introduced described adjuvant component in the described Preparation of catalysts method.According to the conventional method of preparation FT synthetic catalyst, described adjuvant component can be before the supported active metal component, introduce afterwards or simultaneously.For example, with the solution that contains described adjuvant component compound before the carried metal component, afterwards or simultaneously the method for dipping is introduced.
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 a Fischer-Tropsch synthesis.For example, according to the conventional method in this area, at first with catalyst reduction, suitable reducing condition comprises: reduction temperature is 100 ℃ to 800 ℃, is preferably 200 ℃ to 600 ℃, more preferably 300 ℃ to 450 ℃; 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 in the gaseous mixture of hydrogen and inert gas, carry out, as carrying 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 FT synthetic method provided by the invention, described mixture and the catalytic condition of described catalyst with carbon monoxide and hydrogen: preferred temperature is 160～280 ℃, more preferably 190～250 ℃, pressure is preferably 1～8MPa, 1-5MPa more preferably, 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 200～10000h
-1, be preferably 500～4000h
-1
To the present invention be described by example below.Agents useful for same in the example except that specifying, is chemically pure reagent.
Embodiment 1-6 explanation the invention provides described boehmite, aluminium oxide and preparation method thereof.
Embodiment 1
(1) contains the boehmite of transition metal
In one 2 liters retort and stream add 600 ml concns be 96 gram aluminium oxide/liter, wherein contain 3.6 gram ribitol and 0.7 gram ammonium metatungstate ((NH
4) 6H
2W
120
40XH
2O, WO
3Weight content be about 88%) aluminum nitrate solution and the concentration ammonia spirit that is 8 weight % carry 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 ammoniacal liquor in slurries, to make the pH value of slurries be 8.5, slurries filtered after under 55 ℃ aging 60 minutes, filter cake washs 2 times with the deionized water making beating, filter cake was through 120 ℃ of dryings 24 hours, obtain hydrated alumina P1-1, adopt XRD to characterize, P1-1 has structure of similar to thin diaspore.
XRD measures 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 a crystallite dimension to D=K λ/(Bcos θ), λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) be that grain size that the calculation of parameter at 23-33 ° of peak goes out (120) is D (120), is that the grain size that the calculation of parameter at 34-43 ° of peak goes out (031) is D (031) with 2 θ with 2 θ respectively, and calculate n=D (031)/D (120), characterize the n value that calculates P1-1 through XRD and list in the table 1.
(2) containing metal adds the aluminium oxide of component
The mixed solution of 3 gram nitric acid and 120 gram deionized waters is mixed with 200 gram P1-1, on the twin-screw banded extruder, mix to pinch afterwards and be plastic, and be extruded into the clover shape bar of 1.2 millimeters of ф, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 4 hours, obtain carrier Z1, carrier Z1 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Comparative Examples 1-5 reference boehmite, aluminium oxide and preparation method thereof.
Comparative Examples 1
(1) contains the boehmite of transition metal
Method according to embodiment 1-(1) prepares boehmite, and different is, the aluminum nitrate solution that contains ribitol by concentration be 96 gram aluminium oxide/liter aluminum nitrate solution replace, also be not contain ribitol in the aluminum nitrate solution, obtain hydrated alumina P2-1.Method according to embodiment 1 adopts XRD to characterize, and P2-1 has structure of similar to thin diaspore, characterizes the n value that calculates P2-1 through XRD and lists in the table 1.
(2) containing metal adds the aluminium oxide of component
Method according to embodiment 1-(2) adopts P2-1 to prepare aluminium oxide, obtains support C Z1, and support C Z1 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Embodiment 2
(1) contains the boehmite of transition metal
In one 2 liters retort and stream add 800 ml concns be 60 gram aluminium oxide/liter, gluconic acid content be 3.9 grams per liters and contain 10.4 gram ammonium metatungstate ((NH
4) 6H
2W
12O
40XH
2O, WO
3Weight content be about 88%) aluminum nitrate solution and 300 milliliters contain 200 the gram aluminium oxide/liter, the causticity coefficient is that 1.58 sodium aluminate solution carries out precipitation reaction, reaction temperature is 55 ℃, during the conditioned reaction logistics capacity makes and the pH value be 7.0, reaction stops after 15 minutes and filters, the gained solid is pulled an oar with deionized water, adding concentration then in the gained slurries is the sodium bicarbonate solution of 150 grams per liters, regulate slurries pH to 9.0, and be warming up to 65 ℃, aging 5 hours, filter with vacuum filter then, behind to be filtered the finishing, on filter cake, replenished adding 20 liters of deionized waters (65 ℃ of temperature) flush cake about 30 minutes.Filter cake obtains hydrated alumina P1-2 through 120 ℃ of dryings 24 hours.Method according to embodiment 1 adopts XRD to characterize, and P1-2 has structure of similar to thin diaspore, characterizes the n value that calculates P1-2 through XRD and lists in the table 1.
(2) containing metal adds the aluminium oxide of component
Method according to embodiment 1-(2) adopts P1-2 to prepare aluminium oxide, obtains carrier Z2, and carrier Z2 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Comparative Examples 2
(1) contains the boehmite of transition metal
Method according to embodiment 2-(1) prepares boehmite, and different is, the aluminum nitrate solution that contains glucose change into concentration be 60 gram aluminium oxide/liter aluminum nitrate solution, obtain hydrated alumina P2-2.Method according to embodiment 1 adopts XRD to characterize, and P2-2 has structure of similar to thin diaspore, characterizes the n value that calculates P2-2 through XRD and lists in the table 1.
(2) containing metal adds the aluminium oxide of component
Method according to embodiment 1-(2) adopts P2-2 to prepare aluminium oxide, obtains support C Z2, and support C Z2 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Embodiment 3
(1) contains the boehmite of transition metal
In 2.5 liters of there-necked flasks of band stirring and reflux condensing tube, adding the ribonic acid sodium content is azeotropic mixture (water content is 15 weight %) 1000 grams of isopropyl alcohol-water of 0.5 weight %, be heated to 90 ℃, slowly be added dropwise in flask by separatory funnel 500 gram fusing aluminium isopropoxides, after the back flow reaction 24 hours, steam the dehydration isopropyl alcohol, divide then to add for 3 times to contain 3.3 gram ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) 1.5 liters of the deionized waters of ribonic acid sodium content 0.5 weight %, 90 ℃ aging 4 hours, in aging, steam aqueous isopropanol, after the hydrated alumina after aging filters,, obtain hydrated alumina P1-3 through 120 ℃ of dryings 24 hours.Method according to embodiment 1 adopts XRD to characterize, and P1-3 has structure of similar to thin diaspore, characterizes the n value that calculates P1-3 through XRD and lists in the table 1.
(2) containing metal adds the aluminium oxide of component
Method according to embodiment 1-(2) adopts P1-3 to prepare aluminium oxide, obtains carrier Z3, and carrier Z3 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Comparative Examples 3
(1) contains the boehmite of transition metal
Method according to embodiment 3-(1) prepares boehmite, and different is, does not add ribonic acid sodium in azeotropic mixture of isopropyl alcohol-water (water content is 15 weight %) and the deionized water, obtains hydrated alumina P2-3.Method according to embodiment 1 adopts XRD to characterize, and P2-3 has structure of similar to thin diaspore, characterizes the n value that calculates P2-3 through XRD and lists in the table 1.
(2) containing metal adds the aluminium oxide of component
Method according to embodiment 1-(2) adopts P2-3 to prepare aluminium oxide, obtains support C Z3, and support C Z3 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Embodiment 4
(1) contains the boehmite of transition metal
In 2.5 liters of there-necked flasks of band stirring and reflux condensing tube, adding the ribonic acid sodium content is azeotropic mixture (water content is 15 weight %) 1000 grams of isopropyl alcohol-water of 0.5 weight %, be heated to 85 ℃, slowly be added dropwise in flask by separatory funnel 500 gram fusing aluminium isopropoxides, after the back flow reaction 24 hours, steam the dehydration isopropyl alcohol, divide then to add for 3 times to contain 2.8 gram manganese nitrates (with Mn (NO
3)
2The solution form add) and 3.2 restrain zirconium nitrate (Zr (NO
3)
45H
2O) 1.5 liters of the deionized waters of ribonic acid sodium content 0.5 weight %, 85 ℃ aging 4 hours, in aging, steam aqueous isopropanol, after the hydrated alumina after aging filters,, obtain hydrated alumina P1-4 through 120 ℃ of dryings 24 hours.Method according to embodiment 1 adopts XRD to characterize, and P1-4 has structure of similar to thin diaspore, characterizes the n value that calculates P1-4 through XRD and lists in the table 1.
(2) containing metal adds the aluminium oxide of component
Method according to embodiment 1-(2) adopts P1-4 to prepare aluminium oxide, obtains carrier Z4, and carrier Z4 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Comparative Examples 4
(1) contains the boehmite of transition metal
Method according to embodiment 4-(1) prepares boehmite, and different is, does not add ribonic acid sodium in azeotropic mixture of isopropyl alcohol-water (water content is 15 weight %) and the deionized water, obtains hydrated alumina P2-4.Method according to embodiment 1 adopts XRD to characterize, and P2-4 has structure of similar to thin diaspore, characterizes the n value that calculates P2-4 through XRD and lists in the table 1.
(2) containing metal adds the aluminium oxide of component
Method according to embodiment 1-(2) adopts P2-4 to prepare aluminium oxide, obtains support C Z4, and support C Z4 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Embodiment 5
(1) contains the boehmite of transition metal
In 2 liters of there-necked flasks of band stirring and reflux condensing tube, azeotropic mixture (water content is 15 weight %) 1000 grams that add isopropyl alcohol-water, be heated to 60 ℃, slowly be added dropwise in flask by separatory funnel 500 gram fusing aluminium isopropoxides, after the back flow reaction 20 hours, steam the dehydration isopropyl alcohol, divide then to add for 3 times to contain 7.3 gram lanthanum nitrate (La (NO
3)
36H
2O) 1.5 liters of the deionized waters of ribonic acid content 7 weight %, 60 ℃ aging 6 hours, aging pH value is 8, steams aqueous isopropanol in aging, after the hydrated alumina filtration after aging, through 120 ℃ of dryings 24 hours, obtains hydrated alumina P1-4.Method according to embodiment 1 adopts XRD to characterize, and P1-5 has structure of similar to thin diaspore, characterizes the n value that calculates P1-5 through XRD and lists in the table 1.
(2) containing metal adds the aluminium oxide of component
Method according to embodiment 1-(2) adopts P1-5 to prepare aluminium oxide, obtains carrier Z5, and carrier Z5 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Comparative Examples 5
(1) boehmite
Get the commercial boehmite product SB powder that Sasol company sells, be numbered P2-5, according to the method employing XRD sign of embodiment 1, P2-5 has structure of similar to thin diaspore, characterizes the n value that calculates P2-5 through XRD and lists in the table 1.Adopt the method for dipping that lanthanum nitrate is introduced.
(2) aluminium oxide
Method according to embodiment 1-(2) adopts P2-5 to prepare aluminium oxide, obtains support C Z5, and support C Z5 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Comparative Examples 6
1) boehmite
Get the commercial boehmite product SD powder that mountain aluminium company of Chalco joint-stock company sells, be numbered P2-6, according to the method employing XRD sign of embodiment 1, P2-6 has structure of similar to thin diaspore, characterizes the n value that calculates this SD powder through XRD and lists in the table 1.Adopt the method for dipping that lanthanum nitrate is introduced.
(2) aluminium oxide
Method according to embodiment 1-(2) adopts P2-6 to prepare aluminium oxide, obtains support C Z6, and support C Z6 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Embodiment 6
(1) contains the boehmite of transition metal
According to embodiment 1, in one 2 liters retort and stream add 600 ml concns be 96 gram aluminium oxide/liter, wherein contain 3.6 gram ribitol and 0.7 gram ammonium metatungstate ((NH
4) 6H
2W
12O
40XH
2O, WO
3Weight content be about 88%) aluminum nitrate solution and the concentration ammonia spirit that is 8 weight % carry 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 ammoniacal liquor in slurries, to make the pH value of slurries be 8.5, and slurries obtain filter cake in 55 ℃ of filtrations after aging 60 minutes down.
Method according to Comparative Examples 1-(1) prepares boehmite, obtains filter cake.
Get two kinds of filter cakes according to 85: 15 ratio of mass fraction and mix, with deionized water making beating washing 2 times, filter cake obtains hydrated alumina P1-6 through 120 ℃ of dryings 24 hours, adopts XRD to characterize, and P1-6 has structure of similar to thin diaspore.Characterizing the n value that calculates P1-6 through XRD lists in the table 1.
(2) containing metal adds the aluminium oxide of component
The mixed solution of 3 gram nitric acid and 120 gram deionized waters is mixed with 200 gram P1-6, on the twin-screw banded extruder, mix to pinch afterwards and be plastic, and be extruded into the clover shape bar of 1.2 millimeters of ф, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 4 hours, obtain carrier Z6, carrier Z6 is characterized by gama-alumina through XRD.Adopt fluorescence spectrometry to add the content of metal component, adopt BET determination of nitrogen adsorption pore volume, specific area and can several apertures, the results are shown in table 2.
Table 1
* the commercial SB powder with Condea company is a benchmark, records the degree of crystallinity of each sample.
Table 2
Embodiment 7～12 explanations are by the fischer-tropsch synthetic catalyst that the invention provides the preparation of aluminium oxide shaping carrier.
Z1, Z2, Z3, Z4, Z5 and Z6 carrier with the mixed solution that contains cobalt nitrate and ruthenic chloride, are carried out saturated dipping, carry out drying and roasting afterwards, obtain catalyst C1, C2, C3, C4, C5 and C6.Wherein, baking temperature is 120 ℃, and be 4 hours drying time, and sintering temperature is 400 ℃, roasting time 3 hours.The consumption of described cobalt nitrate and ruthenic chloride makes that cobalt oxide content is 15 weight % in the final catalyst, and ruthenium content is 0.1%.
Comparative Examples 7～12
CZ1, CZ2, CZ3, CZ4, CZ5 and CZ6 carrier with the mixed solution that contains cobalt nitrate and ruthenic chloride, are carried out saturated dipping, carry out drying and roasting afterwards, obtain catalyst CC1, CC2, CC3, CC4, CC5 and CC6.Wherein, baking temperature is 120 ℃, and be 6 hours drying time, and sintering temperature is 400 ℃, roasting time 3 hours.The consumption of described cobalt nitrate and ruthenic chloride makes that cobalt oxide content is 15 weight % in the final catalyst, and ruthenium content is 0.1 weight %.
Embodiment 13-18 explanation the invention provides Application of Catalyst and effect thereof.
The Fischer-Tropsch synthesis performance of difference evaluate catalysts C1, C2, C3, C4, C5 and C6 in fixed bed reactors.
Unstripped gas is formed: 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 600h
-1, reduction temperature is 400 ℃, the recovery time is 5 hours.
Reaction condition: pressure 2.5MPa, 200 ℃ of temperature, synthesis gas (unstripped gas) air speed 2000h
-1
Reaction is carried out getting the gas sample after 24 hours and is carried out chromatography, and wherein, the conversion ratio and the methane selectively of COization carbon are listed in table 3.
Comparative Examples 13-18 explanation comparative catalyst performance
According to method difference evaluate catalysts CC1, CC2, CC3, CC4, CC5 and CC6 similarly to Example 13.Wherein, the conversion ratio of COization carbon and methane selectively are listed in table 3.
Table 2
| The embodiment numbering | The sample title | The CO conversion ratio, % | Methane selectively, % |
| 13 | C1 | 40.4％ | 7.4％ |
| Comparative Examples 13 | CC1 | 33.1％ | 10.5％ |
| 14 | C2 | 38.9％ | 6.9％ |
| Comparative Examples 14 | CC2 | 34.5％ | 9.8％ |
| 15 | C3 | 39.2％ | 7.0％ |
| Comparative Examples 15 | CC3 | 35.4％ | 10.1％ |
| 16 | C4 | 42.0％ | 6.2％ |
| Comparative Examples 16 | CC4 | 36.9％ | 8.9％ |
| 17 | C5 | 41.2％ | 7.5％ |
| Comparative Examples 17 | CC5 | 36.0％ | 9.8％ |
| Comparative Examples 18 | CC6 | 29.5％ | 11％ |
| 18 | C6 | 38.5％ | 7.8％ |
As can be seen from Table 2, adopt the aluminium oxide that makes after the boehmite roasting provided by the invention as catalyst carrier, be prepared into the FT synthetic catalyst then, this catalyst has the synthetic performance of better FT under the identical situation of other condition, promptly higher CO conversion ratio, lower methane selectively.
Claims (16)
1. fischer-tropsch synthetic catalyst, contain carrier and active metal component, it is characterized in that, described carrier is obtained through roasting by a kind of boehmite that contains transition metal interpolation component, in oxide and with the butt of described boehmite is benchmark, transition metal interpolation components contents is 0.05-20 weight % in the described boehmite, and described boehmite comprises the boehmite P1 of at least a 1.1≤n≤2.5; Wherein, n=D (031)/D (120), 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 is meant that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks are meant that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of diffraction maximum, and 2 θ are the position of diffraction maximum.
2. catalyst according to claim 1 is characterized in that, described P1 is 1.2≤n
1≤ 2.2 boehmite; In oxide and with the butt of described boehmite is benchmark, transition metal interpolation components contents is 0.1-10 weight % in the described boehmite, and described transition metal interpolation component is selected from one or more in IB, IIB, IVB, VB, VIB, VIIB, VIII family or the rare earth metal component.
3. catalyst according to claim 1 and 2 is characterized in that, described transition metal interpolation component is selected from one or more among Zr, Ta, Mo, W, Mn, Ta, Zn, Cu, Ru, Re, the Hf.
4. catalyst according to claim 1 is characterized in that, the condition of described roasting comprises: sintering temperature is 350-950 ℃, and roasting time is 1-12 hour.
5. catalyst according to claim 4 is characterized in that, described roasting condition comprises: sintering temperature is 450-900 ℃, and roasting time is 2-8 hour.
6. catalyst according to claim 1 is characterized in that, described active metal component is selected from cobalt and/or ferrous metal component, in oxide and with catalyst be benchmark, the content of described active metal component is 5～70 weight %.
7. catalyst according to claim 6 is characterized in that, described active metal component is selected from cobalt and/or ferrous metal component, in oxide and with catalyst be benchmark, the content of described active metal component is 10～50 weight %.
8. catalyst according to claim 7 is characterized in that, described active metal component is selected from cobalt and/or ferrous metal component, in oxide and with catalyst be benchmark, the content of described active metal component is 12～30 weight %.
9. catalyst according to claim 1 is characterized in that, described boehmite comprises the boehmite P2 of 0.8＜n＜1.1, is benchmark with described boehmite total amount, and the content of described P2 is not more than 50 weight %.
10. catalyst according to claim 9 is characterized in that, described P2 is the boehmite of 0.85≤n≤1.05, is benchmark with described boehmite total amount, and the content of described P2 is not more than 30 weight %.
11. catalyst according to claim 1, it is characterized in that, contain one or more adjuvant components that are selected among Cu, Mo, Ta, W, Ru, Zr, Ti, REO, Re, Hf, Ce, Mn, the V in the described catalyst, in oxide and with catalyst be benchmark, the content of described adjuvant component is no more than 30 weight %.
12. catalyst according to claim 11 is characterized in that, in oxide and with catalyst be benchmark, the content of described adjuvant component is no more than 20 weight %.
13. catalyst according to claim 12 is characterized in that, in oxide and with catalyst be benchmark, the content of described adjuvant component is no more than 15 weight %.
14. catalyst according to claim 1, it is characterized in that, contain one or more precious metal additive components that are selected among Pt, Pd, Rh, the Ir in the described catalyst, in metal and with catalyst be benchmark, the content of described adjuvant component is no more than 1 weight %.
15. catalyst according to claim 14 is characterized in that, described precious metal additive component is Pt.
16. a Fischer-Tropsch synthesis method is included under the Fischer-Tropsch synthesis condition the mixture and the catalyst haptoreaction of carbon monoxide and hydrogen, it is characterized in that described catalyst is the described catalyst of each claim of aforementioned claim 1-15.
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| US20070004810A1 (en) * | 2005-06-30 | 2007-01-04 | Yong Wang | Novel catalyst and fischer-tropsch synthesis process using same |
| CN1896190A (en) * | 2005-07-15 | 2007-01-17 | 中国石油化工股份有限公司 | Hydrogenation modified catalyst of Fischer-Tropsch synthetic oil and its production |
| CN1981927A (en) * | 2005-12-14 | 2007-06-20 | 中国石油化工股份有限公司 | Cobalt-based Fischer-Tropasch synthetic catalyst and its production |
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| CN1206037A (en) * | 1997-07-22 | 1999-01-27 | 中国石油化工总公司 | Residuum hydrogenating and metal-eliminating catalyst |
| US20070004810A1 (en) * | 2005-06-30 | 2007-01-04 | Yong Wang | Novel catalyst and fischer-tropsch synthesis process using same |
| CN1896190A (en) * | 2005-07-15 | 2007-01-17 | 中国石油化工股份有限公司 | Hydrogenation modified catalyst of Fischer-Tropsch synthetic oil and its production |
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