CN102233268B - 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, the fischer-tropsch synthetic catalyst and the application thereof that are carrier more specifically to a kind of aluminium oxide of take containing the component of 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 Industrial, the rear 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, only have the F-T synthetic technology of South Africa according to the national conditions Development of Coal liquefaction of national rich coal resources, at present the F-T synthesis technique of Sasol company is still at development and improvement constantly.Twentieth century seventies, Holland Shell company started 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 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 to hydrogenization, contribute to chain growth, leniently promote hydrogenation, do not answer again that hydrogenation is excessively strong simultaneously, Water gas shift/WGS too much and formation carbon non-activated compound etc.The synthetic first step of F-T is CO and H
2chemisorbed, from the structural chemistry viewpoint, there is the transition elements of 3d and 4f key and energy level, mostly be used as the active component of F-T synthetic catalyst.Wherein more about the research of Ni, Fe, Co, Ru.Except Ni, because hydrogenation activity is too strong, make chain growth probability too large, be mainly used in methanation, outside the active component of the synthetic macromolecule wax hydrocarbon catalyst of uncomfortable cooperation, 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 the F-T synthesizing activity due to Co is high, the reaction condition gentleness, water gas shift reaction is few, stable performance, the life-span is longer, so people have carried out research widely in research and application to the Co catalyst.
For the Co catalyst of F-T, the DNAcarrier free oxide of early application, as pure cobalt/cobalt oxide, cobalt-chromated oxide and cobalt-zinc oxide etc.; Found afterwards to add thorium oxide and magnesia, and can increase the activity of catalyst; Carrier loaded Co catalyst is the main flow of research and commercial Application at present.For F-T is synthetic, use Co catalyst, researcher to select multiple auxiliary agent to be modified it, with expectation, improve its catalytic performance.
A kind of method for preparing catalyst and using method are disclosed in patent CN89109859 and 93106465, this catalyst comprise the cobalt of the catalytic activity amount be loaded on alumina support and be selected from platinum, iridium, rhodium, and composition thereof to load capacity responsive the second metal also.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 a kind of method of catalyst and this catalyst of preparation, and this catalyst comprises that 5-75wt% loads on the cobalt on 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 in 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 aluminium oxide.In catalyst, also can add alkaline components 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 on the basis of existing technology a kind of performance to obtain the fischer-tropsch synthetic catalyst of modification and apply 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 containing transition metal component, in oxide and take the butt of described boehmite as benchmark, in described boehmite, the content of transition metal component is the 0.05-20 % by weight, and described boehmite comprises the boehmite P1 of at least one 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 refers to the peak that in XRD spectra, 2 θ are 34-43 °, described 120 peaks refer to the peak that in XRD spectra, 2 θ are 23-33 °, D=K λ/(Bcos θ), K is the Scherrer constant, the diffraction wavelength that λ is the target shaped material, the half-peak breadth that B is diffraction maximum, the position that 2 θ are diffraction maximum.
The present invention further provides a kind of Fischer-Tropsch synthesis method, be included under the Fischer-Tropsch synthesis condition the mixture of carbon monoxide and hydrogen and catalyst haptoreaction, it is characterized in that, described catalyst is aforementioned catalyst provided by the invention.
Fischer-tropsch synthetic catalyst provided by the invention adopts the carrier that comprises prepared by least one boehmite P1 that contains 1.1≤n of transition metal interpolation component≤2.5, and the performance of catalyst is improved.
For example, in the situation that active metal component content, the preparation condition of catalyst are identical, with the reference agent, compare, 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 adds component containing transition metal, in oxide and take the butt of described boehmite as benchmark, described transition metal adds the content of component can be selected between the 0.05-20 % by weight, and preferred content is the 0.1-10 % by weight.Butt described here refers to described boehmite percentage of the ratio of weight before the weight of 600 ℃ of roastings after 4 hours and roasting under air atmosphere.
According to described boehmite provided by the invention, depending on finally, to 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), for example, one or more transition metal component in IIB family metal (Zn), wherein, take oxide described boehmite butt as several, the content of described transition metal component can be selected between the 0.05-20 % by weight, preferred content is the 0.1-10 % by weight.
For improving the activity of F-T synthetic catalyst, preferably contain in 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, take oxide described boehmite butt as several, the content of described transition metal component can be selected between the 0.05-20 % by weight, and preferred content is the 0.1-10 % by weight.
Selective for the C5+ that improves the F-T synthetic catalyst, preferably contain in described boehmite and be selected from IVB family metal (Ti for example, Zr), for example, one or more transition metal component in VIII family metal (Ru) and rare earth metal, wherein, take oxide described boehmite butt as several, the content of described transition metal component can be selected between the 0.05-20 % by weight, and preferred content is the 0.1-10 % by weight.
For improving the regenerability of Co base F-T synthetic catalyst, preferably contain in 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 rare earth metal, wherein, take oxide described boehmite butt as several, the content of described transition metal component can be selected between the 0.05-20 % by weight, and preferred content is the 0.1-10 % by weight.
Be enough under the prerequisite that the content of described interpolation component in described boehmite is met the demands, the introducing method that the present invention adds component to described transition metal is not particularly limited.For example, can be to introduce the method introducing of adding the compound of component containing transition metal in the process of the boehmite P1 for preparing described 1.1≤n≤2.5, can be also the boehmite P1 that at first prepares described 1.1≤n≤2.5, by it, the method with the compound of adding component containing transition metal be introduced afterwards.Wherein, the described compound containing 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 and carries out precipitation reaction with acid or alkali, or organic aluminum contained compound is contacted to the reaction that is hydrolyzed with water, obtain hydrated alumina; By hydrated alumina obtained above, undertaken 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 under the grain growth conditioning agent exists, carry out, described grain growth conditioning agent is for regulating 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 under the grain growth conditioning agent exists, carry out realizing purpose of the present invention, 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 the n that can make like this gained boehmite is in preferred 1.2≤n≤2.2 scopes.
Wherein, to the consumption of grain growth conditioning agent, there is no particular limitation, the 0.5-10 % by weight that in selective hydrolysis reaction, the consumption of grain growth conditioning agent is organic aluminum contained compound weight to be hydrolyzed, 1-8.5 % by weight more preferably, 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 containing 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 be take respectively the weight of corresponding aluminium oxide in organic aluminum contained compound, inorganic aluminum contained compound and hydrated alumina and is calculated as benchmark.Be also, in aluminium oxide, in described precipitation reaction, the 0.5-10 % by weight that the consumption of described grain growth conditioning agent is inorganic aluminum contained compound weight, in described hydrolysis, the 0.5-10 % by weight that the consumption of described grain growth conditioning agent is organic aluminum contained compound weight, in described ageing process, the 0.5-10 % by weight that the consumption of described grain growth conditioning agent is 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 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 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 in advance the grain growth conditioning agent be mixed with one or more raw materials wherein, and then the raw material that will contain the grain growth conditioning agent is reacted.
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 be used 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 it obtains easy and price is low, preferably 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 with aluminium oxide, counts the 0.2-1.1 mol/L.
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 aluminum salt solution and/or aluminate solution, passing into carbon dioxide.Concentration to described acid solution is not particularly limited, preferably H
+concentration be the 0.2-2 mol/L.
Described aqueous slkali can be hydrolyzed and make the aqueous solution be alkaline salt for hydroxide or in aqueous medium, 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, preferably OH
-concentration be the 0.2-4 mol/L.When usining sodium metaaluminate and/or potassium metaaluminate during as alkali, while calculating the consumption of described grain growth conditioning agent, also consider the amount of corresponding aluminium oxide in sodium metaaluminate and/or potassium metaaluminate.
Described organic aluminum contained compound can be various can with water generation hydrolysis, 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 preferably the 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, preferably the 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 obtain the slurries of hydrated alumina or filter cake after filtering in hydrolysis or precipitation reaction and add the compound of crystal grain growth regulating effect in again adding slurries prepared by water, 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 separated, 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, as the method for filtration or centrifugation or evaporation.
In boehmite preparation process of the present invention, also comprise after aging and prepare the washing that often comprises in the boehmite process and dry step, described washing and dry method are for preparing the 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 join in reaction vessel and carry out precipitation reaction containing the aluminum contained compound solution of grain growth conditioning agent and aqueous slkali or acid solution stream or batch (-type), 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 after the hydrated alumina slurries that step (1) obtained filter adds in the aluminium oxide slurries that the 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 filter, washing step (2) obtained;
(4) product that drying steps (3) obtains, obtain the boehmite of 1.1≤n provided by the invention≤2.5.
Introduce in the process of boehmite P1 in preparation described 1.1≤n≤2.5 while containing transition metal, adding the compound of component, can introduce in above-mentioned step (1), (2), (3) or (4) any one or several step containing transistion metal compound.
According to catalyst provided by the invention, wherein, described boehmite optionally can also comprise the boehmite P2 except the boehmite of 1.1≤n≤2.5, the boehmite that described P2 is n<1.1, the boehmite that preferably P2 is 0.8<n<1.1, the boehmite that further preferably P2 is 0.85≤n≤1.05.When described composition contains P2, take the boehmite total amount as benchmark, the content of described P2 is not more than 70 % by weight, further preferably is not more than 50 % by weight, more preferably is not more than 30 % by 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 to prepare.
The boehmite that adds component containing transition metal of the present invention obtains through roasting the aluminium oxide that containing metal of the present invention adds component, and the method for described roasting is conventional method and condition.For example, when described purpose aluminium oxide is gama-alumina, described roasting condition comprises: 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 cobalt and/or the ferrous metal component of group VIII.The content of described metal component is customary amount, in oxide and take catalyst as benchmark, the content of preferred active metal component is 5～70 % by weight, more preferably 10～50 % by weight, more be preferably 12～30 % by weight.
According to catalyst provided by the invention, 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, as the methods such as compressing tablet, spin, extrusion all can.
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) by described containing transition metal add component boehmite P1 (containing or containing P2) extruded moulding, dry and roasting prepare described carrier; Wherein, when extrusion molding, can in the described boehmite containing transition metal interpolation component, add water, extrusion aid and/or adhesive, then extrusion molding; 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, PVOH; 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 to introduce active metal component in described carrier, 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 conventional method, and for example preparation is containing 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 containing active metal component is selected from one or more in these their soluble compounds, for example, can be one or more in the nitrate, acetate, carbonate, chloride, soluble complexes of these metals.
Be selected from one or more adjuvant components in Cu, Mo, Ta, W, Ru, Zr, Ti, REO, Re, Hf, Ce, Mn, V and noble metal, described noble metal wherein is selected from one or more in Pt, Pd, Rh, 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 optionally contain one or more that are selected from above-mentioned adjuvant component.Except noble metal, in oxide and take catalyst as benchmark, the content of described adjuvant component preferably, below 30 % by weight, more preferably, below 20 % by weight, more is preferably below 15 % by weight.When adjuvant component is selected from noble metal, in metal and take catalyst as benchmark, the content of described adjuvant component is preferably below 10 % by weight, more preferably below 1 % by weight.
While in described catalyst, also containing described adjuvant component, also be included in the step that catalyst is introduced described adjuvant component in the preparation method of described catalyst.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 containing the solution of described adjuvant component compound before the carried metal component, afterwards or simultaneously the method for dipping is introduced.
The Fischer-Tropsch synthesis method also provided according to the present invention, 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 by 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, 2-8 hour more preferably, described reduction can be carried out in pure hydrogen, also can in the gaseous mixture of hydrogen and inert gas, carry out, as carried out in the gaseous mixture at 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 by the mixture of carbon monoxide and hydrogen and the catalytic condition of described catalyst: preferably 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.
Below will the present invention be described by example.Agents useful for same in example, except special instruction, be chemically pure reagent.
Embodiment 1-6 explanation the invention provides described boehmite, aluminium oxide and preparation method thereof.
Embodiment 1
(1) contain the boehmite of transition metal
In the retort of 2 liters and stream add 600 ml concns be 96 gram aluminium oxide/liter, wherein containing 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 concentration be 8 % by weight ammonia spirit 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, in slurries, adding ammoniacal liquor to make the pH value of slurries is 8.5, slurries filter after aging 60 minutes under 55 ℃, deionized water making beating washing 2 times for filter cake, 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 crystallite dimension to D=K λ/(Bcos θ), the diffraction wavelength that λ is the target shaped material, the half-peak breadth that B is corrected diffraction maximum, the position that 2 θ are diffraction maximum) take respectively calculation of parameter that 2 θ are 23-33 ° of peak, to go out the grain size that calculation of parameter that the grain size of (120) is 34-43 ° of peak as D (120), 2 θ of take goes out (031) be D (031), and calculate n=D (031)/D (120), characterize through XRD the n value that calculates P1-1 and list in 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 double screw banded extruder, kneading is plastic afterwards, 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) contain the boehmite of transition metal
Method according to embodiment 1-(1) prepares boehmite, different, containing the aluminum nitrate solution of ribitol by concentration be 96 gram aluminium oxide/liter aluminum nitrate solution replace, be also in aluminum nitrate solution containing ribitol, 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 through XRD the n value that calculates P2-1 and lists in 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) contain the boehmite of transition metal
In the retort of 2 liters and stream add 800 ml concns be 60 gram aluminium oxide/liter, gluconic acid content be 3.9 grams per liters and containing 10.4 gram ammonium metatungstate ((NH
4) 6H
2w
12o
40xH
2o, WO
3weight content be about 88%) aluminum nitrate solution and 300 milliliters containing 200 gram aluminium oxide/liter, the sodium aluminate solution that the causticity coefficient is 1.58 carries out precipitation reaction, reaction temperature is 55 ℃, during the conditioned reaction logistics capacity makes, with the pH value, be 7.0, reaction stops after 15 minutes and filters, the gained solid is pulled an oar by deionized water, then add the sodium bicarbonate solution that concentration is 150 grams per liters in the gained slurries, regulate slurries pH to 9.0, and be warming up to 65 ℃, aging 5 hours, then with vacuum filter, filtered, to be filtered complete after, supplement and add 20 liters of deionized waters (65 ℃ of temperature) flush cake approximately 30 minutes on filter cake.Filter cake, through 120 ℃ of dryings 24 hours, obtains hydrated alumina P1-2.Method according to embodiment 1 adopts XRD to characterize, 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.
(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) contain the boehmite of transition metal
Method according to embodiment 2-(1) prepares boehmite, different, containing the aluminum nitrate solution of 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 through XRD the n value that calculates P2-2 and lists in 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) contain the boehmite of transition metal
In 2.5 liters of there-necked flasks of band stirring and reflux condensing tube, azeotropic mixture (water content is 15 % by weight) 1000 grams that add the isopropanol-water that the ribonic acid sodium content is 0.5 % by weight, be heated to 90 ℃, by 500 gram fusing aluminium isopropoxides, by separatory funnel, slowly be added dropwise in flask, after back flow reaction 24 hours, steam the dehydration isopropyl alcohol, then divide and add for 3 times containing 3.3 gram ammonium molybdate ((NH
4)
6mo
7o
244H
21.5 liters of the deionized waters of ribonic acid sodium content 0.5 % by weight O), 90 ℃ aging 4 hours, steam aqueous isopropanol in aging, after the hydrated alumina after aging filters, through 120 ℃ of dryings 24 hours, obtain hydrated alumina P1-3.Method according to embodiment 1 adopts XRD to characterize, and P1-3 has structure of similar to thin diaspore, characterizes through XRD the n value that calculates P1-3 and lists in 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) contain the boehmite of transition metal
Method according to embodiment 3-(1) prepares boehmite, different, in the azeotropic mixture of isopropanol-water (water content is 15 % by weight) and deionized water, does not add ribonic acid sodium, 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 through XRD the n value that calculates P2-3 and lists in 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) contain the boehmite of transition metal
In 2.5 liters of there-necked flasks of band stirring and reflux condensing tube, azeotropic mixture (water content is 15 % by weight) 1000 grams that add the isopropanol-water that the ribonic acid sodium content is 0.5 % by weight, be heated to 85 ℃, by 500 gram fusing aluminium isopropoxides, by separatory funnel, slowly be added dropwise in flask, after back flow reaction 24 hours, steam the dehydration isopropyl alcohol, then divide and add for 3 times containing 2.8 gram manganese nitrates (with Mn (NO
3)
2the solution form add) and 3.2 gram zirconium nitrate (Zr (NO
3)
45H
21.5 liters of the deionized waters of ribonic acid sodium content 0.5 % by weight O), 85 ℃ aging 4 hours, steam aqueous isopropanol in aging, after the hydrated alumina after aging filters, through 120 ℃ of dryings 24 hours, obtain hydrated alumina P1-4.Method according to embodiment 1 adopts XRD to characterize, and P1-4 has structure of similar to thin diaspore, characterizes through XRD the n value that calculates P1-4 and lists in 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) contain the boehmite of transition metal
Method according to embodiment 4-(1) prepares boehmite, different, in the azeotropic mixture of isopropanol-water (water content is 15 % by weight) and deionized water, does not add ribonic acid sodium, 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 through XRD the n value that calculates P2-4 and lists in 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) contain 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 % by weight) 1000 grams that add isopropanol-water, be heated to 60 ℃, by 500 gram fusing aluminium isopropoxides, by separatory funnel, slowly be added dropwise in flask, after back flow reaction 20 hours, steam the dehydration isopropyl alcohol, then divide and add for 3 times containing 7.3 gram lanthanum nitrate (La (NO
3)
36H
21.5 liters of the deionized waters of ribonic acid content 7 % by weight O), 60 ℃ aging 6 hours, aging pH value is 8, steams aqueous isopropanol in aging, after the hydrated alumina after aging filters, 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 through XRD the n value that calculates P1-5 and lists in 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 business 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 through XRD the n value that calculates P2-5 and lists in 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 business 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 through XRD the n value that calculates this SD powder and lists in 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) contain the boehmite of transition metal
According to embodiment 1, in the retort of 2 liters and stream add 600 ml concns be 96 gram aluminium oxide/liter, wherein containing 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 concentration be 8 % by weight ammonia spirit 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, in slurries, adding ammoniacal liquor to make the pH value of slurries is 8.5, and slurries filter after aging 60 minutes under 55 ℃, obtain filter cake.
Method according to Comparative Examples 1-(1) prepares boehmite, obtains filter cake.
Get two kinds of filter cakes according to the mass fraction ratio of 85: 15 and mix, with deionized water making beating washing 2 times, filter cake, through 120 ℃ of dryings 24 hours, obtains hydrated alumina P1-6, adopts XRD to characterize, and P1-6 has structure of similar to thin diaspore.Characterizing through XRD the n value that calculates P1-6 lists in 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 double screw banded extruder, kneading is plastic afterwards, 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 business SB powder of Condea company of take is benchmark, records the degree of crystallinity of each sample.
Table 2
Embodiment 7～12 illustrates the fischer-tropsch synthetic catalyst prepared by the invention provides the aluminium oxide shaping carrier.
By the mixed solution containing cobalt nitrate and ruthenic chloride for Z1, Z2, Z3, Z4, Z5 and Z6 carrier, carry out saturated dipping, carry out afterwards drying and roasting, 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.It is 15 % by weight that the consumption of described cobalt nitrate and ruthenic chloride makes cobalt oxide content in final catalyst, and ruthenium content is 0.1%.
Comparative Examples 7～12
By the mixed solution containing cobalt nitrate and ruthenic chloride for CZ1, CZ2, CZ3, CZ4, CZ5 and CZ6 carrier, carry out saturated dipping, carry out afterwards drying and roasting, 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.It is 15 % by weight that the consumption of described cobalt nitrate and ruthenic chloride makes cobalt oxide content in final catalyst, and ruthenium content is 0.1 % by weight.
Embodiment 13-18 explanation the invention provides application and the effect thereof of catalyst.
The Fischer-Tropsch synthesis performance of difference evaluate catalysts C1, C2, C3, C4, C5 and C6 in fixed bed reactors.
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 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, 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 made after boehmite roasting provided by the invention as catalyst carrier, then be prepared into the FT synthetic catalyst, this catalyst has a synthetic performance of better FT in the situation that other condition is identical, i.e. higher CO conversion ratio, lower methane selectively.
Claims (16)
1. a 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 containing transition metal interpolation component, in oxide and take the butt of described boehmite as benchmark, in described boehmite, the content of transition metal interpolation component is the 0.05-20 % by weight, and described boehmite comprises the boehmite P1 of at least one 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 refers to the peak that in XRD spectra, 2 θ are 34-43 °, described 120 peaks refer to the peak that in XRD spectra, 2 θ are 23-33 °, D=K λ/(Bcos θ), K is the Scherrer constant, the diffraction wavelength that λ is the target shaped material, the half-peak breadth that B is diffraction maximum, the position that 2 θ are diffraction maximum.
2. catalyst according to claim 1, is characterized in that, the boehmite that described P1 is 1.2≤n≤2.2; In oxide and take the butt of described boehmite as benchmark, in described boehmite, the content of transition metal interpolation component is the 0.1-10 % by weight, and described transition metal adds component and is selected from one or more in IB, IIB, IVB, VB, VIB, VIIB, VIII family or rare earth metal component.
3. catalyst according to claim 1 and 2, is characterized in that, described transition metal adds component and is selected from one or more in Zr, Ta, Mo, W, Mn, Zn, Cu, Ru, Re, 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 take catalyst as benchmark, the content of described active metal component is 5～70 % by 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 take catalyst as benchmark, the content of described active metal component is 10～50 % by 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 take catalyst as benchmark, the content of described active metal component is 12～30 % by weight.
9. catalyst according to claim 1, is characterized in that, described boehmite comprises the boehmite P2 of 0.8<n<1.1, and the described boehmite total amount of take is benchmark, and the content of described P2 is not more than 50 % by weight.
10. catalyst according to claim 9, is characterized in that, the boehmite that described P2 is 0.85≤n≤1.05, and the described boehmite total amount of take is benchmark, the content of described P2 is not more than 30 % by weight.
11. catalyst according to claim 1, it is characterized in that, contain one or more adjuvant components that are selected from Cu, Mo, Ta, W, Ru, Zr, Ti, REO, Re, Hf, Ce, Mn, V in described catalyst, in oxide and take catalyst as benchmark, the content of described adjuvant component is no more than 30 % by weight.
12. catalyst according to claim 11, is characterized in that, in oxide and take catalyst as benchmark, the content of described adjuvant component is no more than 20 % by weight.
13. catalyst according to claim 12, is characterized in that, in oxide and take catalyst as benchmark, the content of described adjuvant component is no more than 15 % by weight.
14. catalyst according to claim 1, it is characterized in that, contain one or more precious metal additive components that are selected from Pt, Pd, Rh, Ir in described catalyst, in metal and take catalyst as benchmark, the content of described adjuvant component is no more than 1 % by weight.
15. catalyst according to claim 14, is characterized in that, described precious metal additive component is Pt.
16. a Fischer-Tropsch synthesis method, be included under the Fischer-Tropsch synthesis condition the mixture of carbon monoxide and hydrogen and catalyst haptoreaction, it is characterized in that, described catalyst is the described catalyst of aforementioned claim 1-15 any one claim.
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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 |
| 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 |
| 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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