CN102233273B - Fischer-Tropsch synthesis catalyst and application thereof - Google Patents
Fischer-Tropsch synthesis catalyst and application thereof Download PDFInfo
- Publication number
- CN102233273B CN102233273B CN 201010160486 CN201010160486A CN102233273B CN 102233273 B CN102233273 B CN 102233273B CN 201010160486 CN201010160486 CN 201010160486 CN 201010160486 A CN201010160486 A CN 201010160486A CN 102233273 B CN102233273 B CN 102233273B
- Authority
- CN
- China
- Prior art keywords
- boehmite
- catalyst
- weight
- component
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a Fischer-Tropsch synthesis catalyst and application thereof. The catalyst contains a carrier and active metal ingredients, wherein the carrier is obtained by roasting pseudo-boehmite containing alkali metal and/or alkaline-earth metal adding ingredients; based on oxides and dry basis of the pseudo-boehmite, the content of the alkali metal and/or alkaline-earth metal adding ingredients in the pseudo-boehmite is 0.05-20 percent by weight, and the pseudo-boehmite comprises at least one pseudo-boehmite P1 (n is more than or equal to 1.0 and less than or equal to 2.5); and n is D(031)/ D(120), the D(031) expresses the grain size of a crystal face represented by the peak 031 in an X-ray diffraction (XRD) spectrogram of pseudo-boehmite grains, the D(120) expresses the grain size of a crystal face represented by the peak 120 in the XRD spectrogram of the pseudo-boehmite grains, the peak 031 means that 2 theta is a peak of 34-43 degrees in the XRD spectrogram, the peak 120 means that 2 theta is a peak of 23-33 degrees in the XRD spectrogram, D=K lambda/(B cosine theta), K is a Scherrer constant, lambda is diffraction wavelength of a target material, B is half peak width of a diffraction peak, and 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, more specifically to fischer-tropsch synthetic catalyst and the application thereof of a kind of aluminium oxide take alkali metal containing and/or alkaline earth metal component as carrier.
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 South Africa according to the F-T synthetic technology of 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 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 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 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 excessively strong, 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, have 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.Because hydrogenation activity is too strong, make chain growth probability too large except Ni, be mainly used in methanation, outside the active component of uncomfortable cooperation synthetic high polymer 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, and wherein because the F-T synthesizing activity of Co is high, reaction condition is gentle, water gas shift reaction is few, stable performance, the life-span is longer, so people have carried out widely research to the Co catalyst in research and application.
Be used for the Co catalyst of F-T, the DNAcarrier free oxide of early application is such 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.Use Co catalyst, researcher to select 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 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 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 on the basis of existing technology a kind of performance to obtain the fischer-tropsch synthetic catalyst of modification 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 the boehmite that a kind of alkali metal containing and/or alkaline-earth metal add component, in oxide and take the butt of described boehmite as benchmark, the content of alkali metal and/or alkaline-earth metal interpolation component is the 0.05-20 % by 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 refers to that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks refer to 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 shaped 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 mixture and the catalyst haptoreaction of carbon monoxide and hydrogen, it is characterized in that, described catalyst is aforementioned catalyst provided by the invention.
Fischer-tropsch synthetic catalyst provided by the invention adopts and comprises that at least a alkali metal containing and/or alkaline-earth metal add the carrier of the boehmite P1 preparation of 1.1≤n of component≤2.5, improve the performance of catalyst.
For example, in the identical situation of active metal component content, the preparation condition of catalyst, compare with the reference agent, the CO activity of conversion that the invention provides catalyst improves can reach 6%, and methane selectively reduces by 2%.
The specific embodiment
According to catalyst provided by the invention, wherein, described alkali metal containing and/or alkaline-earth metal add the boehmite of component, in oxide and take the butt of described boehmite as benchmark, described alkali metal and/or alkaline-earth metal add the content of component can be selected between the 0.05-20 % by weight, and preferred content is the 0.1-10 % by weight.Described alkali metal is one or both in Li, K preferably, and described alkaline-earth metal is one or more in Mg, Ca, Sr and Ba preferably.Described P1 is preferably the boehmite of 1.2≤n≤2.2.Butt described here refers to described boehmite percentage of the ratio of weight before the weight of 600 ℃ of roastings after 4 hours and the roasting under air atmosphere.
Add the boehmite of component according to containing metal provided by the invention, depending on finally different to the aluminium oxide application target, the metal that is selected from alkali metal and/or alkaline-earth metal adds the content of 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, contain in the preferred described boehmite and be selected from IIA family metal (Ca for example, Ba) interpolation metal component, wherein, take oxide and described boehmite butt as several, described 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.
For improving the activity of fischer-tropsch synthetic catalyst, contain in the preferred described boehmite and be selected from IA family metal (Li for example, K,), IIA family metal (Mg for example, Sr) one or more in, wherein, take oxide and described boehmite butt as several, described 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.
According to described boehmite provided by the invention, be enough to make described metal to add under the prerequisite that the content of component in described boehmite meets the demands, the introducing method that described metal is added component is not particularly limited.For example, can be in the process of the boehmite P1 for preparing described 1.1≤n≤2.5, to introduce the method introducing that containing metal adds the compound of component, also can be the boehmite P1 that at first prepares described 1.1≤n≤2.5, afterwards itself and containing metal be added the method introducing of the compound of component.Wherein, the compound that described containing metal adds component can be their salt, oxide or alkali, 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; Hydrated alumina obtained above 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, can make like this n of gained boehmite in preferred 1.2≤n≤2.2 scopes.
Wherein, there is no particular limitation to the consumption of grain growth conditioning agent, the consumption of grain growth conditioning agent is the 0.5-10 % by weight of organic aluminum contained compound weight to be hydrolyzed, more preferably 1-8.5 % by weight, further preferred 5-8.5 % by weight in the selective hydrolysis reaction; The consumption of grain growth conditioning agent is the inorganic 0.5-10 % by weight that contains al reactant weight in the described precipitation reaction, more preferably 1-8.5 % by weight, further preferred 5-8.5 % by weight; In the 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, among the present invention, the consumption of described grain growth conditioning agent respectively in organic aluminum contained compound, inorganic aluminum contained compound and the hydrated alumina weight of corresponding aluminium oxide calculate as benchmark.Also be, in aluminium oxide, in the described precipitation reaction, the consumption of described grain growth conditioning agent is the 0.5-10 % by weight of inorganic aluminum contained compound weight, in the described hydrolysis, the consumption of described grain growth conditioning agent is the 0.5-10 % by weight of organic aluminum contained compound weight, and in the described ageing process, the consumption of described grain growth conditioning agent is the 0.5-10 % by 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 crystal grain at the material of the speed of growth of 120 crystal faces and 031 crystal face, be preferably alditol and carboxylate thereof, be specifically as follows 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 after the two kinds or more of mixing.Described aluminate solution is aluminate solution arbitrarily, such as sodium aluminate solution and/or potassium aluminate.Because its acquisition is easy and price is low, preferred sodium aluminate solution.Aluminate solution also can be used alone or as a mixture.
Concentration to described aluminum salt solution and/or aluminate solution is not particularly limited, and preferably counts the 0.2-1.1 mol/L with aluminium oxide.
Described acid can be various Bronsted acids or be acid oxide in aqueous medium, for example, can be one or more in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, the oxalic acid, preferred Bronsted acid be selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid.Described carbonic acid can original position produce by pass into carbon dioxide in aluminum salt solution and/or aluminate solution.Concentration to described acid solution is not particularly limited, preferred H
+Concentration be the 0.2-2 mol/L.
Described aqueous slkali can be hydrolyzed for hydroxide or in aqueous medium the salt that makes the aqueous solution be alkalescence, and preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, 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/L.When during as alkali, when calculating the consumption of described grain growth conditioning agent, also considering the amount of corresponding aluminium oxide in sodium metaaluminate and/or the potassium metaaluminate with sodium metaaluminate and/or potassium metaaluminate.
Described organic aluminum contained compound can be various can the reaction with steeping in water for reconstitution unboiled water solution, in the aluminum alkoxide of generation aqua oxidation aluminum precipitation one or more for example can be one or more in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and the isooctanol aluminium.Described organic aluminum contained compound and water consumption ratio are not particularly limited, and the preferred water yield is greater than the required amount of stoichiometry.
In boehmite preparation process of the present invention, the described condition of precipitation reaction that makes is not particularly limited, preferred pH value is 3-11, more preferably 6-10; Temperature can be 30-90 ℃, is preferably 40-80 ℃.
Wherein, it is conventionally known to one of skill in the art making the method for aluminum precipitation by the control of consumption to alkali in the 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 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 to 7-10, then under suitable temperature, wear out.Then separate, washing, drying.
Described acid solution or aqueous slkali can be with above-described identical or different.
Described aging temperature is preferably 35-98 ℃, and ageing time is preferably 0.2-6 hour.
According to method provided by the invention, the described known technology that is separated into this area is such 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, a preferred embodiment 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; The hydrated alumina slurries that also 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 described metal add the compound of component in the process of boehmite P1 of preparation described 1.1≤n≤2.5, described containing metal adds the compound of component can be introduced in above-mentioned step (1), (2), (3) or (4) any one or several step.
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, described P2 is the boehmite of n＜1.1, preferred P2 is the boehmite of 0.8＜n＜1.1, and further preferred P2 is the boehmite of 0.85≤n≤1.05.When described composition contained P2, take described boehmite total amount as benchmark, the content of described P2 was not more than 70 % by weight, further preferably was not more than 50 % by weight, more preferably was not more than 30 % by weight.Described 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 preparation.
The boehmite that containing metal of the present invention adds component 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 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 are preferably 12～30 % by weight.
According to catalyst provided by the invention, optionally can be made into the arbitrarily article shaped of convenient operation, such as sphere, compressing tablet and bar shaped.Described moulding can be carried out according to a conventional method, all can such 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 described alkali metal containing and/or alkaline-earth metal add boehmite P1 (containing or the do not contain P2) extruded moulding of component, dry and roasting prepares described carrier; Wherein, when extrusion molding, can in the boehmite of described alkali metal containing and/or alkaline-earth metal interpolation component, add entry, 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, the 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 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 conventional method, and for example preparation contains the solution of the compound of described hydrogenation active metals component, afterwards by the method dipping that soaks or spray, dry and roasting.The described compound that contains the hydrogenation activity 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 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 and contain one or more that are selected from the 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.
When also containing described adjuvant component in the described catalyst, also be included in the step that catalyst is introduced described adjuvant component among 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 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 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
The below will illustrate the present invention by example.Agents useful for same in the example except specifying, is chemically pure reagent.
Embodiment 1-6 illustrates described boehmite provided by the invention, aluminium oxide and preparation method thereof.
Embodiment 1
(1) containing metal adds the boehmite of component
In one 2.5 liters retort and stream add 700 ml concns be 96 gram aluminium oxide/liter, wherein contain the aluminum nitrate solution of 3.6 gram ribitol and the ammonia spirit that concentration is 8 % by weight and 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 in slurries and containing concentration is that to make the pH value of slurries be 8.5 for the ammoniacal liquor of 10 % by weight potassium nitrate, slurries filter after 55 ℃ of lower wearing out 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 at SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44 do volt, and 40 milliamperes, sweep speed is 2 °/minute.According to the Scherrer formula: (D is crystallite dimension to D=K λ/(Bcos θ), λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) calculation of parameter at ° peak goes out (120) take 2 θ as 23-33 respectively grain size is D (031) as D (120), the calculation of parameter at ° peak goes out (031) take 2 θ as 34-43 grain size, and 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, kneading is plastic on double screw banded extruder afterwards, and be extruded into the column-shape strip of 1.1 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) containing metal adds the boehmite of component
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) containing metal adds the boehmite of component
In one 2.5 liters retort and stream add 800 ml concns be 70 gram aluminium oxide/liter, gluconic acid content be the aluminum nitrate solution of 3.9 grams per liters and 300 milliliters contain 200 gram aluminium oxide/liter, the causticity coefficient is that 1.58 sodium aluminate solution carries out precipitation reaction, reaction temperature is 55 ℃, the conditioned reaction logistics capacity so that in and the pH value be 7.0, reaction stops after 15 minutes and filters, the gained solid is pulled an oar with deionized water, then adding concentration in the gained slurries is the potassium bicarbonate solution of 250 grams per liters, regulate slurries pH to 9.0, and be warming up to 65 ℃, aging 5 hours, then filter with vacuum filter, to be filtered complete after, replenish to add 20 liters of deionized waters (65 ℃ of temperature) flush cake approximately 30 minutes at filter cake.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) containing metal adds the boehmite of component
Method according to embodiment 2-(2) prepares boehmite, and different is, the aluminum sulfate 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) containing metal adds the boehmite of component
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 % by weight) 1000 grams of the isopropanol-water of 0.5 % by 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, then divide add for 3 times contain concentration be 2.2 % by weight magnesium nitrates 1.5 liters of the deionized waters of ribonic acid sodium content 0.5 % by weight, 90 ℃ were worn out 4 hours, in aging, steam aqueous isopropanol, after 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 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) containing metal adds the boehmite of component
Method according to embodiment 3-(1) prepares boehmite, and different is, does not add ribonic acid sodium in the azeotropic mixture of isopropanol-water (water content is 15 % by 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) containing metal adds the boehmite of component
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 ℃, 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, then divide to add for 3 times and contain 1.5 liters of the deionized waters that concentration is ribonic acid content 7 % by weight of 12.8 % by weight strontium nitrates, 60 ℃ were worn out 6 hours, aging pH value is 8, steams aqueous isopropanol in aging, after the hydrated alumina after wearing out filters, through 120 ℃ of dryings 24 hours, obtain hydrated alumina 1-P4.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) boehmite
Get the commercial boehmite product SB powder that Sasol company sells, be numbered P2-4, according to the method employing XRD sign of embodiment 1, 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.Adopt the method for dipping that strontium nitrate is introduced.
(2) aluminium oxide
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) containing metal adds the boehmite of component
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 isopropanol-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, then divide to add for 3 times and contain 1.5 liters of the deionized waters that concentration is ribonic acid content 7 % by weight of 5.2 % by weight calcium nitrate and 3.1 % by weight lithium nitrates, 60 ℃ were worn out 6 hours, aging pH value is 8, steams aqueous isopropanol in aging, after the hydrated alumina after wearing out filters, through 120 ℃ of dryings 24 hours, obtain hydrated alumina P5.Method according to embodiment 1 adopts XRD to characterize, and P5 has structure of similar to thin diaspore, characterizes the n value that calculates P5 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 SD powder that mountain aluminium company of Chalco joint-stock 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 this SD powder through XRD and lists in the table 1.Adopt the method for dipping that lithium 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.
Embodiment 6
(1) containing metal adds the boehmite of component
According to embodiment 1, in one 2.5 liters retort and stream add 700 ml concns be 96 gram aluminium oxide/liter, wherein contain the aluminum nitrate solution of 3.6 gram ribitol and the ammonia spirit that concentration is 8 % by weight and 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 in slurries and containing concentration is that to make the pH value of slurries be 8.5 for the ammoniacal liquor of 10 % by weight potassium nitrate, slurries filter after 55 ℃ of lower wearing out 60 minutes, filter cake obtains filter cake with deionized water making beating washing 2 times.
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, kneading is plastic on double screw banded extruder 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.
(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.
Table 1
* take the commercial SB powder of Condea company as benchmark, record 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 platinum chloride ammonia, are carried 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 6 hours drying time, and sintering temperature is 400 ℃, roasting time 3 hours.The consumption of described cobalt nitrate and platinum chloride ammonia makes that cobalt oxide content is 15 % by weight in the final catalyst, and platinum content is 0.1 % by weight.
Comparative Examples 6～10
CZ1, CZ2, CZ3, CZ4, CZ5 carrier with the mixed solution that contains cobalt nitrate and platinum chloride ammonia, are carried out saturated dipping, carry out afterwards drying and roasting, obtain catalyst CC1, CC2, CC3, CC4 and CC5.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 platinum chloride ammonia makes that cobalt oxide content is 15 % by weight in the final catalyst, and platinum 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 11-15 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 3
| Embodiment | The sample title | The CO conversion ratio, % | Methane selectively, % |
| 13 | C1 | 38.7％ | 7.0％ |
| Comparative Examples 11 | CC1 | 32.1％ | 10.6％ |
| 14 | C2 | 41.2％ | 7.7％ |
| Comparative Examples 12 | CC2 | 35.5％ | 9.9％ |
| 15 | C3 | 39.4％ | 7.3％ |
| Comparative Examples 13 | CC3 | 34.4％ | 10.0％ |
| 16 | C4 | 40.0％ | 7.5％ |
| Comparative Examples 14 | CC4 | 37.0％ | 9.8％ |
| 17 | C5 | 38.9％ | 7.8％ |
| Comparative Examples 15 | CC5 | 31.0％ | 11.4％ |
| 18 | C6 | 37.0％ | 7.8％ |
As can be seen from Table 3, adopt the aluminium oxide that makes after the 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 (15)
1. fischer-tropsch synthetic catalyst, contain carrier and active metal component, described active metal component is selected from cobalt and/or ferrous metal component, it is characterized in that, described carrier is obtained through roasting by the boehmite that a kind of alkali metal containing and/or alkaline-earth metal add component, in oxide and take the butt of described boehmite as benchmark, the content of alkali metal and/or alkaline-earth metal interpolation component is the 0.05-20 % by 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 refers to that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks refer to 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 shaped 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 the boehmite of 1.2≤n≤2.2; Described alkali metal is selected from a kind of and combination among Li, the K, described alkaline-earth metal is selected from one or more among Mg, Ca, Sr and the Ba, in oxide and take the butt of described boehmite as benchmark, the content of alkali metal and/or alkaline earth metal component is the 1-10 % by weight in the described boehmite.
3. 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.
4. catalyst according to claim 3 is characterized in that, described roasting condition comprises: sintering temperature is 450-900 ℃, and roasting time is 2-8 hour.
5. catalyst according to claim 1 is characterized in that, described active metal component is selected from cobalt and/or ferrous metal component, and in oxide and take catalyst as benchmark, the content of described active metal component is 5～70 % by weight.
6. catalyst according to claim 5 is characterized in that, described active metal component is selected from cobalt and/or ferrous metal component, and in oxide and take catalyst as benchmark, the content of described active metal component is 10～50 % 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, and in oxide and take catalyst as benchmark, the content of described active metal component is 12～30 % by weight.
8. catalyst according to claim 1 is characterized in that, described boehmite comprises the boehmite P2 of 0.8＜n＜1.1, and take described boehmite total amount as benchmark, the content of described P2 is not more than 50 % by weight.
9. catalyst according to claim 8 is characterized in that, described P2 is the boehmite of 0.85≤n≤1.05, and take described boehmite total amount as benchmark, the content of described P2 is not more than 30 % by weight.
10. 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 take catalyst as benchmark, the content of described adjuvant component is below 30 % by weight.
11. catalyst according to claim 10 is characterized in that, in oxide and take catalyst as benchmark, the content of described adjuvant component is below 20 % 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 below 15 % by weight.
13. catalyst according to claim 1 is characterized in that, contains one or more adjuvant components that are selected among Pt, Pd, Rh, the Ir in the described catalyst, with metal and take catalyst as benchmark, the content of described adjuvant component is below 1 % by weight.
14. catalyst according to claim 13 is characterized in that, described adjuvant component is Pt.
15. a Fischer-Tropsch synthesis method is included under the Fischer-Tropsch synthesis condition 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 1-14.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010160486 CN102233273B (en) | 2010-04-30 | 2010-04-30 | Fischer-Tropsch synthesis catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010160486 CN102233273B (en) | 2010-04-30 | 2010-04-30 | Fischer-Tropsch synthesis catalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102233273A CN102233273A (en) | 2011-11-09 |
| CN102233273B true CN102233273B (en) | 2013-03-06 |
Family
ID=44884675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010160486 Active CN102233273B (en) | 2010-04-30 | 2010-04-30 | Fischer-Tropsch synthesis catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102233273B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109382081A (en) * | 2017-08-14 | 2019-02-26 | 中国石油化工股份有限公司 | Carrier and preparation method thereof and fischer-tropsch synthetic catalyst and Fischer-Tropsch synthesis method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070004810A1 (en) * | 2005-06-30 | 2007-01-04 | Yong Wang | Novel catalyst and fischer-tropsch synthesis process using same |
-
2010
- 2010-04-30 CN CN 201010160486 patent/CN102233273B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102233273A (en) | 2011-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5716669B2 (en) | Methanol synthesis catalyst | |
| CA2864680A1 (en) | Catalyst and method for the direct synthesis of dimethyl ether from synthesis gas | |
| WO2012040977A1 (en) | Catalyst for catalytically hydrogenating co2 to methanol and preparation thereof | |
| CN108722408B (en) | Catalyst for synthesizing ethylene glycol by dimethyl oxalate gas phase hydrogenation and preparation method thereof | |
| CN114405505B (en) | Platinum modified indium-based oxide catalyst and preparation method and application thereof | |
| CN102234124B (en) | Pseudoboehmite containing transition metal components and aluminum oxide prepared from same | |
| CN102234125B (en) | Pseudo-boehmite containing alkali metal and/or alkaline earth metal component, and alumina prepared from pseudo-boehmite | |
| CN100569365C (en) | Gaseous hydrocarbon low temperature insulation transformation catalyst and reaction process thereof | |
| CN105214672A (en) | A kind of preparation method of the catalyst for methanol that maximizes | |
| CN102233282B (en) | Fischer-Tropsch synthesis catalyst taking silicon oxide-aluminum oxide as carrier and application thereof | |
| CN103476492B (en) | For aldehyde being hydrogenated the promoted cu zn catalyst for alcohol | |
| CN101983765B (en) | Catalyst for preparing methyl alcohol by catalytic hydrogenation on assistant modified carbon dioxide and preparation method thereof | |
| CN102267710B (en) | Boracic pseudoboehmite and aluminum oxide prepared from same | |
| CN103787829A (en) | Method for preparing alcohol by carboxylic acid hydrogenation with cobalt silver catalyst | |
| CN112221509B (en) | Preparation method of high-stability methanol synthesis catalyst | |
| CN102233273B (en) | Fischer-Tropsch synthesis catalyst and application thereof | |
| JP2001070793A (en) | Dimethyl ether synthesis catalyst and synthesis method | |
| CN102233268B (en) | Fischer-Tropsch synthesis catalyst and application thereof | |
| CN102205241A (en) | Aromatic hydrogenated saturated catalyst and application thereof | |
| CN101722002A (en) | Composite catalyst used for synthesizing dimethyl ether with carbon dioxide and preparation method and application thereof | |
| CN102266760B (en) | Heavy-oil hydrogenating catalyst and application thereof | |
| CN112517017B (en) | Doped copper silicate nanotube catalyst for methyl acetate hydrogenation and preparation method and application thereof | |
| CN110935456A (en) | Preparation method of catalyst for synthesizing methanol | |
| CN100567171C (en) | A kind of method for preparing high specific surface area meso-porous nickelous oxide | |
| CN102233271B (en) | Fischer-Tropsch synthesis catalyst taking aluminum oxide as carrier and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |