CN102234125A - Pseudo-boehmite containing alkali metal and/or alkaline earth metal component, and alumina prepared from pseudo-boehmite - Google Patents
Pseudo-boehmite containing alkali metal and/or alkaline earth metal component, and alumina prepared from pseudo-boehmite Download PDFInfo
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Abstract
The invention relates to a pseudo-boehmite containing alkali metal and/or alkaline earth metal component and alumina prepared from pseudo-boehmite. The content of the alkali metal and/or alkaline earth metal component in pseudo-boehmite is 0.05 to 20 wt% by oxide with a dry basis of pseudo-boehmite a reference, and pseudo-boehmite is a P1 containing at least one type of pseudo-boehmite with n which is more than or equal to 1.1 and less than or equal to 2.5; wherein n is a ratio of D(031) to D(120), the D(031) represents a crystal grain size of a crystal face represented by a peak 031 in an XRD spectra of pseudo-boehmite crystal grains, the D(120) represents a crystal grain size of a crystal face represented by a peak 120 in the XRD spectra of the pseudo-boehmite crystal grains, the peak 031 is a peak at 2*theta of 34-43 DEG in the XRD spectra, the peak 120 is a peak at 2*theta of 23-33 DEG in the XRD spectra, D is a ratio of K*lambda to (B*cos theta), K is the Scherrer constant, lambda is a diffraction wavelength of a target type material, B is a half band width of a diffraction peak, and 2*theta is a position of the diffraction peak.
Description
Invention field
The invention relates to the pseudo-boehmite and the aluminum oxide prepared therefrom of the component of a kind of alkali metal containing and/or alkaline-earth metal.
Background technology
Aluminum oxide, particularly gama-alumina, because of it has better pore structure, specific surface and heat-resistant stability, the Chang Zuowei substrate material is used for Preparation of catalysts.The precursor of aluminum oxide is a hydrated aluminum oxide, and as pseudo-boehmite (or claiming quasi-crystalline boehmites), by the modification to hydrated aluminum oxide, people can carry out modulation to the character of aluminum oxide, make it satisfy some specific needs.
Summary of the invention
The technical problem to be solved in the present invention just provides a kind of new, improved alkali metal containing of performance and/or alkaline-earth metal adds the pseudo-boehmite and the aluminum oxide prepared therefrom of component.
The invention provides the pseudo-boehmite of the component of a kind of alkali metal containing and/or alkaline-earth metal, in oxide compound and with the butt of described pseudo-boehmite is benchmark, the content of basic metal and/or alkaline earth metal component is 0.05-20 weight % in the described pseudo-boehmite, and described pseudo-boehmite is the pseudo-boehmite P1 that comprises at least a 1.1≤n≤2.5; Wherein, n=D (031)/D (120), the grain-size of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression pseudo-boehmite crystal grain, the grain-size of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression pseudo-boehmite crystal grain, described 031 peak is meant that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks are meant that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target section bar material, B is the peak width at half height of diffraction peak, and 2 θ are the position of diffraction peak.
The present invention further provides the aluminum oxide that a kind of alkali metal containing and/or alkaline-earth metal add component, the aluminum oxide that described alkali metal containing and/or alkaline-earth metal add component is obtained through roasting by aforementioned pseudo-boehmite provided by the invention.
The pseudo-boehmite of alkali metal containing provided by the invention and/or alkaline-earth metal interpolation component comprises the pseudo-boehmite P1 of at least a 1.1≤n≤2.5.The pseudo-boehmite that this alkali metal containing and/or alkaline-earth metal add component obtains the improved aluminum oxide of a kind of performance through roasting.
For example, described pseudo-boehmite provided by the invention is obtained the gama-alumina of a kind of alkali metal containing and/or alkaline-earth metal interpolation component after 4 hours in 600 ℃ of roastings.Adopt this aluminum oxide as preparing carriers Fischer-Tropsch (F-T) synthetic catalyst, under the identical situation of activity of such catalysts metal component content, preparation condition, compare with the reference agent, the CO activity of conversion of catalyzer improves can reach 6%, and methane selectively reduces by 2%.
Embodiment
According to described pseudo-boehmite provided by the invention, in oxide compound and with the butt of described pseudo-boehmite is benchmark, described basic metal and/or alkaline-earth metal add components contents and are preferably 0.1-10 weight %, and described P1 is preferably the pseudo-boehmite of 1.2≤n≤2.2.Butt described here is meant described pseudo-boehmite percentage ratio of the ratio of weight before the weight of 600 ℃ of roastings after 4 hours and the roasting under air atmosphere.
Add the pseudo-boehmite of component according to containing metal provided by the invention, look finally aluminum oxide application target difference, the metal that is selected from basic metal and/or alkaline-earth metal adds components contents, kind can be different.
For example, gama-alumina is to the conversion of Alpha-alumina phase when improving high-temperature roasting, improve the thermostability of gama-alumina, contain in the preferred described pseudo-boehmite and be selected from IIA family metal (Ca for example, Ba) interpolation metal component wherein, is several in oxide compound and described pseudo-boehmite butt, described metal adds components contents can be selected between 0.05-20 weight %, and preferred content is 0.1-10 weight %.
For improving the activity of fischer-tropsch synthetic catalyst, contain in the preferred described pseudo-boehmite and be selected from IA family metal (Li for example, K,), IIA family metal (Mg for example, Sr) one or more in wherein, are several in oxide compound and described pseudo-boehmite butt, described metal adds components contents can be selected between 0.05-20 weight %, and preferred content is 0.1-10 weight %.
According to described pseudo-boehmite provided by the invention, be enough to make described metal to add under the prerequisite that the content of component in described pseudo-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 pseudo-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 pseudo-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 compound or alkali, preferred water-soluble cpds wherein.
According to described pseudo-boehmite provided by the invention, wherein, the preparation method of the pseudo-boehmite P1 of described 1.1≤n≤2.5 comprises: aluminum contained compound solution is contacted with acid or alkali carry out precipitin reaction, perhaps organic aluminum contained compound is contacted the reaction that is hydrolyzed with water, obtain hydrated aluminum oxide; The above-mentioned hydrated aluminum oxide that obtains is worn out, wherein, described aluminum contained compound solution and acid or alkali contact or described organic aluminum contained compound and water contact and hydrated aluminum oxide aging in any one process in the presence of the grain growing conditioning agent, carry out, described grain growing 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 reaction or precipitin reaction and aging in one of arbitrary process in the presence of the grain growing conditioning agent, carry out realizing purpose of the present invention, but under the preferable case, described hydrolysis reaction and weathering process or described precipitin reaction and weathering process are all carried out in the presence of the grain growing conditioning agent, and the n that can make the gained pseudo-boehmite like this is in preferred 1.2≤n≤2.2 scopes.
Wherein, there is no particular limitation to the consumption of grain growing conditioning agent, the consumption of grain growing conditioning agent is the 0.5-10 weight % that treats organic aluminum contained compound weight of hydrolysis in the selective hydrolysis reaction, 1-8.5 weight % more preferably, further preferred 5-8.5 weight %; The consumption of grain growing conditioning agent is the inorganic 0.5-10 weight % that contains al reactant weight in the described precipitin reaction, 1-8.5 weight % more preferably, further preferred 5-8.5 weight %; In the described weathering process, the consumption of grain growing conditioning agent can be preferably 1-8.5 weight % for the 0.5-10 weight % of hydrated aluminum oxide weight, further preferred 5-8.5 weight %.Unless stated otherwise, among the present invention, the consumption of described grain growing conditioning agent is that benchmark calculates with the weight of aluminum oxide corresponding in organic aluminum contained compound, inorganic aluminum contained compound and the hydrated aluminum oxide respectively.Also be, in aluminum oxide, in the described precipitin reaction, the consumption of described grain growing conditioning agent is the 0.5-10 weight % of inorganic aluminum contained compound weight, in the described hydrolysis reaction, the consumption of described grain growing conditioning agent is the 0.5-10 weight % of organic aluminum contained compound weight, and in the described weathering process, the consumption of described grain growing conditioning agent is the 0.5-10 weight % of hydrated aluminum oxide weight.
Among the present invention, described grain growing 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 polyhydric sugar-alcohol and carboxylate salt thereof, be specifically as follows in Sorbitol Powder, 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 pseudo-boehmite preparation process of the present invention, adding mode to described grain growing conditioning agent is not particularly limited, the grain growing conditioning agent can be added separately, also can be in advance the grain growing conditioning agent be mixed with wherein one or more raw materials, and then the raw material that will contain the grain growing 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 Tai-Ace S 150, aluminum chloride, the aluminum nitrate.Because price is low, preferably sulfuric acid aluminium, liquor alumini chloridi.Aluminium salt can use separately also and can use two kinds or more of mixing back.Described aluminate solution is an aluminate solution arbitrarily, as sodium aluminate solution and/or potassium aluminate.Because its acquisition is easy and price is low, preferred sodium aluminate solution.Aluminate solution also can be used alone or as a mixture.
Concentration to described aluminum salt solution and/or aluminate solution is not particularly limited, and preferably counts the 0.2-1.1 mol with aluminum oxide.
Described acid can be various protonic acids or be the tart oxide compound in water medium, for example, can be in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetate, citric acid, the oxalic acid one or more, preferred protonic acid be selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid.Described carbonic acid can original position produces by feed carbonic acid gas in aluminum salt solution and/or aluminate solution.Concentration to described acid solution is not particularly limited, preferred H
+Concentration be the 0.2-2 mol.
Described alkaline solution can for oxyhydroxide or in water medium hydrolysis make the aqueous solution be the salt of alkalescence, preferred oxyhydroxide is selected from one or more in ammoniacal liquor, sodium hydroxide, the potassium hydroxide; Preferred salt is selected from one or more in sodium metaaluminate, potassium metaaluminate, bicarbonate of ammonia, volatile salt, sodium bicarbonate, yellow soda ash, saleratus, the salt of wormwood.Concentration to described alkaline solution is not particularly limited, preferred OH
-Concentration be the 0.2-4 mol.When during as alkali, when calculating the consumption of described grain growing conditioning agent, also considering the amount of corresponding aluminum oxide in sodium metaaluminate and/or the potassium metaaluminate with sodium metaaluminate and/or potassium metaaluminate.
Described organic aluminum contained compound can be various can with water generation hydrolysis reaction, producing in the sedimentary aluminum alkoxide of hydrated aluminum oxide one or more, for example can be in aluminum isopropylate, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and the isooctyl alcohol aluminium one or more.Described organic aluminum contained compound and water consumption ratio are not particularly limited, and the preferred water yield is greater than the required amount of stoichiometry.
In pseudo-boehmite preparation process of the present invention, the described condition of precipitin 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 reaction is not particularly limited, as long as water contacts with aluminum alkoxide hydrolysis reaction generation hydrated aluminum oxide takes place, and the condition that hydrolysis specifically takes place is conventionally known to one of skill in the art.
Wherein, can in hydrolysis reaction or precipitin reaction obtain slurries that the slurries of hydrated aluminum oxide or filter cake after filtering add the water preparation again, add the compound of crystal grain growth regulating effect, also can add alkaline solution or acid solution and suitably regulate the pH value, under suitable temperature, wear out then to 7-10.Separate then, washing, drying.
Described acid solution or alkaline solution can be with above-described identical or different.
Described aged temperature is preferably 35-98 ℃, and digestion time is preferably 0.2-6 hour.
According to method provided by the invention, the described known technology that is separated into this area is as the method for filtration or centrifugation or evaporation.
In pseudo-boehmite preparation process of the present invention, after aging, also comprise the washing and the exsiccant step that often comprise in the preparation pseudo-boehmite process, described washing and exsiccant method are preparation pseudo-boehmite conventional process.For example, can use oven dry, forced air drying or spray-dired method.Generally speaking, drying temperature can be 100-350 ℃, is preferably 120-300 ℃.
According to the preparation method of pseudo-boehmite of the present invention, an embodiment preferred may further comprise the steps:
(1) will contain the aluminum contained compound solution of grain growing conditioning agent and alkaline solution or acid solution and stream or intermittent type and join and carry out precipitin reaction in the reaction vessel, obtain the hydrated aluminum oxide slurries; Perhaps in deionized water, add the reaction that is hydrolyzed of grain growing conditioning agent and aluminum alkoxide, obtain the hydrated aluminum oxide slurries;
(2) filter cake behind the hydrated aluminum oxide dope filtration that step (1) is obtained adds in the aluminum oxide slurries that water making beating obtains again again, adds the grain growing conditioning agent, after regulating pH and being 7-10, in 35-98 ℃ of aging 0.2-6 hour; Also the hydrated aluminum oxide slurries that above-mentioned steps (1) can be obtained without filter the grain growing 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 step (3) obtains the pseudo-boehmite of 1.1≤n provided by the invention≤2.5.
When introducing described metal add the compound of component in the process of pseudo-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 steps.
According to described pseudo-boehmite provided by the invention, optionally can also comprise the pseudo-boehmite P2 except that the pseudo-boehmite of 1.1≤n≤2.5, described P2 is the pseudo-boehmite of n＜1.1, preferred P2 is the pseudo-boehmite of 0.8＜n＜1.1, and further preferred P2 is the pseudo-boehmite of 0.85≤n≤1.05.When described composition contains P2, be benchmark with the pseudo-boehmite total amount, the content of described P2 is not more than 70 weight %, further preferably is not more than 50 weight %, more preferably is not more than 30 weight %.Described P2 is 0.8＜n
2＜1.1 pseudo-boehmite can be to be selected from the pseudo-boehmite that commercially available commodity also can adopt any one prior art for preparing.
Described pseudo-boehmite provided by the invention obtains the aluminum oxide that containing metal of the present invention adds component through roasting, and the method for described roasting is ordinary method and condition.For example, when described purpose aluminum oxide was gama-alumina, described roasting condition comprised: maturing temperature is 350-950 ℃, is preferably 450-900 ℃, and roasting time is 1-12 hour, is preferably 2-8 hour.
According to aluminum oxide provided by the invention, optionally can be made into and be convenient to the forming composition of operating arbitrarily, as spherical, compressing tablet and bar shaped.Described moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.
In one embodiment, described aluminum oxide forming composition preparation method comprises the pseudo-boehmite P1 of described 1.1≤n≤2.5 (comprising or do not comprise pseudo-boehmite P2), extrusion aid, peptizing agent and water is mixed, mixture is extrusion moulding on banded extruder, carries out drying and roasting afterwards.Wherein, the example of described peptizing agent can be to be selected from nitric acid, acetic acid and the citric acid one or more; The example of described extrusion aid can be to be selected from sesbania powder, the Mierocrystalline cellulose one or more.The kind of the consumption of described water and described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not repeat them here.Described drying is an ordinary method, carries out drying as adopting baking oven, mesh-belt kiln and fluidized-bed, when adopting heating means to carry out drying, preferred drying temperature is 50-200 ℃, 0.3-12 hour time of drying, further preferred drying temperature is 60-150 ℃, and be 0.5-8 hour time of drying.The method of described roasting and condition are conventional method and the condition that the support of the catalyst preparation is adopted, as adopt mesh-belt kiln, upright examination stove and converter to carry out roasting, the condition optimization of described roasting is, at 350-950 ℃ roasting temperature 1-12 hour, further preferably 450-900 ℃ roasting temperature 2-8 hour.
The aluminum oxide of containing metal interpolation component provided by the invention can be used as the matrix of various sorbent materials, support of the catalyst and catalyzer and uses.
To the present invention be described by example below.Agents useful for same in the example except that specifying, is chemically pure reagent.
Embodiment 1-6 illustrates described pseudo-boehmite provided by the invention, aluminum oxide and preparation method thereof.
Embodiment 1
(1) containing metal adds the pseudo-boehmite of component
In one 2.5 liters retort and stream add 700 ml concns be 96 gram aluminum oxide/liter, wherein contain the aluminum nitrate solution of 3.6 gram ribitol and the ammonia soln that concentration is 8 weight % and carry out precipitin reaction, temperature of reaction is 40 ℃, reaction times is 10 minutes, it is 7 that the flow of control ammonia soln makes the pH of reaction system, after precipitin 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 weight % saltpetre, slurries are in 55 ℃ of down aging 60 minutes after-filtration, filter cake washs 2 times with the deionized water making beating, filter cake was through 120 ℃ of dryings 24 hours, obtain hydrated aluminum oxide 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 velocity is 2 °/minute.According to the Scherrer formula: (D is a grain-size to D=K λ/(Bcos θ), λ is the diffraction wavelength of target section bar material, B is the peak width at half height of corrected diffraction peak, 2 θ are the position of diffraction peak) be that grain size that the calculation of parameter at 23-33 ° of peak goes out (120) is D (120), is that the grain size that the calculation of parameter at 34-43 ° of peak goes out (031) is D (031) with 2 θ with 2 θ respectively, and calculate n=D (031)/D (120), characterize the n value that calculates P1-1 through XRD and list in the table 1.
(2) containing metal adds the aluminum oxide of component
The mixing solutions of 3 gram nitric acid and 120 gram deionized waters is mixed with 200 gram P1-1, on the twin screw banded extruder, mix to pinch afterwards and be plastic, and be extruded into the 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 surface area and can several apertures, the results are shown in table 2.
Comparative Examples 1-5 reference pseudo-boehmite, aluminum oxide and preparation method thereof.
Comparative Examples 1
(1) containing metal adds the pseudo-boehmite of component
Method according to embodiment 1-(1) prepares pseudo-boehmite, and different is, the aluminum nitrate solution that contains ribitol by concentration be 96 gram aluminum oxide/liter aluminum nitrate solution replace, also be not contain ribitol in the aluminum nitrate solution, obtain hydrated aluminum oxide 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 aluminum oxide of component
Method according to embodiment 1-(2) adopts P2-1 to prepare aluminum 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 surface area and can several apertures, the results are shown in table 2.
Embodiment 2
(1) containing metal adds the pseudo-boehmite of component
In one 2.5 liters retort and stream add 800 ml concns be 70 gram aluminum oxide/liter, gluconic acid content be the aluminum nitrate solution of 3.9 grams per liters and 300 milliliters contain 200 gram aluminum oxide/liter, the causticity coefficient is that 1.58 sodium aluminate solution carries out precipitin reaction, temperature of reaction is 55 ℃, during the conditioned reaction logistics capacity makes and the pH value be 7.0, reaction stops 15 minutes after-filtration, the gained solid is pulled an oar with deionized water, adding concentration then 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, filter with vacuum filter then, behind to be filtered the finishing, on filter cake, replenished adding 20 liters of deionized waters (65 ℃ of temperature) flush cake about 30 minutes.Filter cake obtains hydrated aluminum oxide 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 aluminum oxide of component
Method according to embodiment 1-(2) adopts P1-2 to prepare aluminum 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 surface area and can several apertures, the results are shown in table 2.
Comparative Examples 2
(1) containing metal adds the pseudo-boehmite of component
Method according to embodiment 2-(2) prepares pseudo-boehmite, and different is, the alum liquor that contains glucose change into concentration be 60 gram aluminum oxide/liter aluminum nitrate solution, obtain hydrated aluminum oxide 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 aluminum oxide of component
Method according to embodiment 1-(2) adopts P2-2 to prepare aluminum 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 surface area and can several apertures, the results are shown in table 2.
Embodiment 3
(1) containing metal adds the pseudo-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 azeotrope (water content is 15 weight %) 1000 grams of Virahol-water of 0.5 weight %, be heated to 90 ℃, slowly be added dropwise in flask by separating funnel 500 gram fusing aluminium isopropoxides, after the back flow reaction 24 hours, steam the dehydration Virahol, divide then add for 3 times contain concentration be 2.2 weight % magnesium nitrates 1.5 liters of the deionized waters of ribonic acid sodium content 0.5 weight %, 90 ℃ were worn out 4 hours, steam aqueous isopropanol simultaneously at aged, after hydrated aluminum oxide after aging filters,, obtain hydrated aluminum oxide P1-3 through 120 ℃ of dryings 24 hours.Method according to embodiment 1 adopts XRD to characterize, and P1-3 has structure of similar to thin diaspore, characterizes the n value that calculates P1-3 through XRD and lists in the table 1.
(2) containing metal adds the aluminum oxide of component
Method according to embodiment 1-(2) adopts P1-3 to prepare aluminum 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 surface area and can several apertures, the results are shown in table 2.
Comparative Examples 3
(1) containing metal adds the pseudo-boehmite of component
Method according to embodiment 3-(1) prepares pseudo-boehmite, and different is, does not add ribonic acid sodium in azeotrope of Virahol-water (water content is 15 weight %) and the deionized water, obtains hydrated aluminum oxide 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 aluminum oxide of component
Method according to embodiment 1-(2) adopts P2-3 to prepare aluminum 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 surface area and can several apertures, the results are shown in table 2.
Embodiment 4
(1) containing metal adds the pseudo-boehmite of component
In 2 liters of there-necked flasks of band stirring and reflux condensing tube, azeotrope (water content is 15 weight %) 1000 grams that add Virahol-water, be heated to 60 ℃, slowly be added dropwise in flask by separating funnel 500 gram fusing aluminum isopropylates, after the back flow reaction 20 hours, steam the dehydration Virahol, divide then to add for 3 times and contain 1.5 liters of the deionized waters that concentration is the ribonic acid content 7 weight % of 12.8 weight % strontium nitrates, 60 ℃ were worn out 6 hours, aged pH value is 8, steams aqueous isopropanol simultaneously at aged, after the hydrated aluminum oxide after wearing out filters, through 120 ℃ of dryings 24 hours, obtain hydrated aluminum oxide 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 aluminum oxide of component
Method according to embodiment 1-(2) adopts P1-4 to prepare aluminum 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 surface area and can several apertures, the results are shown in table 2.
Comparative Examples 4
(1) pseudo-boehmite
Get the commercial pseudo-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) aluminum oxide
Method according to embodiment 1-(2) adopts P2-4 to prepare aluminum 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 surface area and can several apertures, the results are shown in table 2.
Embodiment 5
(1) containing metal adds the pseudo-boehmite of component
In 2.5 liters of there-necked flasks of band stirring and reflux condensing tube, azeotrope (water content is 15 weight %) 1000 grams that add Virahol-water, be heated to 60 ℃, slowly be added dropwise in flask by separating funnel 500 gram fusing aluminum isopropylates, after the back flow reaction 20 hours, steam the dehydration Virahol, divide then to add for 3 times and contain 1.5 liters of the deionized waters that concentration is the ribonic acid content 7 weight % of 5.2 weight % nitrocalcite and 3.1 weight % lithium nitrates, 60 ℃ were worn out 6 hours, aged pH value is 8, steams aqueous isopropanol simultaneously at aged, after the hydrated aluminum oxide after wearing out filters, through 120 ℃ of dryings 24 hours, obtain hydrated aluminum oxide 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 aluminum oxide of component
Method according to embodiment 1-(2) adopts P1-5 to prepare aluminum 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 surface area and can several apertures, the results are shown in table 2.
Comparative Examples 5
1) pseudo-boehmite
Get the commercial pseudo-boehmite product SD powder that mountain aluminium company of Chalco 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) aluminum oxide
Method according to embodiment 1-(2) adopts P2-5 to prepare aluminum 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 surface area and can several apertures, the results are shown in table 2.
Embodiment 6
(1) containing metal adds the pseudo-boehmite of component
According to embodiment 1, in one 2.5 liters retort and stream add 700 ml concns be 96 gram aluminum oxide/liter, wherein contain the aluminum nitrate solution of 3.6 gram ribitol and the ammonia soln that concentration is 8 weight % and carry out precipitin reaction, temperature of reaction is 40 ℃, reaction times is 10 minutes, it is 7 that the flow of control ammonia soln makes the pH of reaction system, after precipitin 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 weight % saltpetre, slurries are in 55 ℃ of down aging 60 minutes after-filtration, filter cake obtains filter cake with deionized water making beating washing 2 times.
Method according to Comparative Examples 1-(1) prepares pseudo-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 aluminum oxide 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 aluminum oxide of component
The mixing solutions of 3 gram nitric acid and 120 gram deionized waters is mixed with 200 gram P1-6, on the twin screw banded extruder, mix to pinch afterwards and be plastic, and be extruded into the trifolium 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 surface area and can several apertures, the results are shown in table 2.
(2) containing metal adds the aluminum oxide of component
Method according to embodiment 1-(2) adopts P2-1 to prepare aluminum 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 surface area and can several apertures, the results are shown in table 2.
Table 1
* the commercial SB powder with Condea company is a benchmark, records the degree of crystallinity of each sample.
Table 2
Embodiment 7～12 explanations are by the fischer-tropsch synthetic catalyst that the invention provides the preparation of aluminum oxide shaping carrier.
Z1, Z2, Z3, Z4, Z5 and Z6 carrier with the mixing solutions that contains Xiao Suangu and platinum chloride ammonia, are carried out saturated dipping, carry out drying and roasting afterwards, obtain catalyzer C1, C2, C3, C4, C5 and C6.Wherein, drying temperature is 120 ℃, and be 6 hours time of drying, and maturing temperature is 400 ℃, roasting time 3 hours.The consumption of described Xiao Suangu and platinum chloride ammonia makes that cobalt oxide content is 15 weight % in the final catalyzer, and platinum content is 0.1 weight %.
Comparative Examples 6～10
CZ1, CZ2, CZ3, CZ4, CZ5 carrier with the mixing solutions that contains Xiao Suangu and platinum chloride ammonia, are carried out saturated dipping, carry out drying and roasting afterwards, obtain catalyzer CC1, CC2, CC3, CC4 and CC5.Wherein, drying temperature is 120 ℃, and be 6 hours time of drying, and maturing temperature is 400 ℃, roasting time 3 hours.The consumption of described Xiao Suangu and platinum chloride ammonia makes that cobalt oxide content is 15 weight % in the final catalyzer, and platinum content is 0.1 weight %.
Embodiment 13-18 explanation the invention provides aluminum oxide and prepares Application of Catalyst and effect thereof.
The Fischer-Tropsch synthesis performance of difference evaluate catalysts C1, C2, C3, C4, C5 and C6 in fixed-bed reactor.
Unstripped gas is formed: H
2/ CO/N
2=64%/32%/4% (volume hundred umbers).
The catalyst reduction reaction conditions: pressure is normal pressure, and temperature rise rate is 5 ℃/minute, and hydrogen gas space velocity is 600h
-1, reduction temperature is 400 ℃, the recovery time is 5 hours.
Reaction conditions: pressure 2.5MPa, 200 ℃ of temperature, synthetic gas (unstripped gas) air speed 2000h
-1
Reaction is carried out getting the gas sample after 24 hours and is carried out stratographic analysis, and wherein, the transformation efficiency 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 transformation efficiency of COization carbon and methane selectively are listed in table 3.
Table 3
| Embodiment | The sample title | The CO transformation efficiency, % | Methane selectively, % |
| 7 | C1 | 38.7％ | 7.0％ |
| Comparative Examples 6 | CC1 | 32.1％ | 10.6％ |
| 8 | C2 | 41.2％ | 7.7％ |
| Comparative Examples 7 | CC2 | 35.5％ | 9.9％ |
| 9 | C3 | 39.4％ | 7.3％ |
| Comparative Examples 8 | CC3 | 34.4％ | 10.0％ |
| 10 | C4 | 40.0％ | 7.5％ |
| Comparative Examples 9 | CC4 | 37.0％ | 9.8％ |
| 11 | C5 | 38.9％ | 7.8％ |
| Comparative Examples 10 | CC5 | 31.0％ | 11.4％ |
| 12 | C6 | 37.0％ | 7.8％ |
As can be seen from Table 3, adopt the aluminum oxide that makes after the pseudo-boehmite roasting provided by the invention as support of the catalyst, be prepared into the FT synthetic catalyst then, this catalyzer has the synthetic performance of better FT under the identical situation of other condition, promptly higher CO transformation efficiency, lower methane selectively.
Claims (8)
1. the pseudo-boehmite of alkali metal containing and/or alkaline earth metal component, in oxide compound and with the butt of described pseudo-boehmite is benchmark, the content of basic metal and/or alkaline earth metal component is 0.05-20 weight % in the described pseudo-boehmite, and described pseudo-boehmite is the pseudo-boehmite P1 that comprises at least a 1.1≤n≤2.5; Wherein, n=D (031)/D (120), the grain-size of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression pseudo-boehmite crystal grain, the grain-size of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression pseudo-boehmite crystal grain, described 031 peak is meant that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks are meant that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target section bar material, B is the peak width at half height of diffraction peak, and 2 θ are the position of diffraction peak.
2. pseudo-boehmite according to claim 1 is characterized in that, described P1 is 1.2≤n
1≤ 2.2 pseudo-boehmite; Described basic metal is selected from Li, K and combination thereof, described alkaline-earth metal is selected from one or more among Mg, Ca, Sr and the Ba, in oxide compound and with the butt of described pseudo-boehmite is benchmark, and the content of basic metal and/or alkaline earth metal component is 1-10 weight % in the described pseudo-boehmite.
3. pseudo-boehmite according to claim 1 is characterized in that, described pseudo-boehmite comprises the pseudo-boehmite P2 of 0.8＜n＜1.1, is benchmark with described pseudo-boehmite total amount, and the content of described P2 is not more than 50 weight %.
4. composition according to claim 3 is characterized in that, described P2 is the pseudo-boehmite of 0.85≤n≤1.05, is benchmark with described pseudo-boehmite total amount, and the content of described P2 is not more than 30 weight %.
5. aluminum oxide, this aluminum oxide is obtained by the pseudo-boehmite roasting, it is characterized in that, and described pseudo-boehmite is the pseudo-boehmite of any described alkali metal containing and/or alkaline earth metal component among the claim 1-4.
6. aluminum oxide according to claim 5 is characterized in that, described aluminum oxide is a gama-alumina.
7. according to claim 5 or 6 described aluminum oxide, it is characterized in that described roasting condition comprises: maturing temperature is 350-950 ℃, and roasting time is 1-12 hour.
8. aluminum oxide according to claim 7 is characterized in that, described roasting condition comprises: maturing temperature is 450-900 ℃, and roasting time is 2-8 hour.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515230A (en) * | 2011-12-14 | 2012-06-27 | 德米特（苏州）电子环保材料有限公司 | Method for manufacturing aluminum oxide substrate polishing material for automobile painting surface |
| WO2018160934A1 (en) * | 2017-03-03 | 2018-09-07 | Exxonmobil Research And Engineering Company | High performance co2/h2o displacement desorption sorbents and methods of making same |
| CN112915999A (en) * | 2021-01-26 | 2021-06-08 | 北京石油化工学院 | Catalyst for degrading benzene series and ethyl acetate and preparation method and application thereof |
| CN113209956A (en) * | 2021-04-28 | 2021-08-06 | 杭州智华杰科技有限公司 | Method for improving high-temperature stability of alumina catalyst carrier |
| CN113559889A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Modified phosphorus-containing pseudo-boehmite, preparation method thereof, modified phosphorus-containing alumina and hydrogenation catalyst |
| US12030032B2 (en) | 2021-05-11 | 2024-07-09 | ExxonMobil Technology and Engineering Company | High performance CO2/H2O displacement desorption sorbents and methods of making same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001012551A2 (en) * | 1999-08-11 | 2001-02-22 | Akzo Nobel N.V. | Quasi-crystalline boehmites containing additives |
| CN1915486A (en) * | 2005-08-17 | 2007-02-21 | 中国石油化工股份有限公司 | Hydrated alumina with structure of similar to thin diaspore of containing additive |
-
2010
- 2010-04-30 CN CN 201010160489 patent/CN102234125B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001012551A2 (en) * | 1999-08-11 | 2001-02-22 | Akzo Nobel N.V. | Quasi-crystalline boehmites containing additives |
| CN1915486A (en) * | 2005-08-17 | 2007-02-21 | 中国石油化工股份有限公司 | Hydrated alumina with structure of similar to thin diaspore of containing additive |
Non-Patent Citations (1)
| Title |
|---|
| 高建峰等: "用偏铝酸钠直接制取高纯拟薄水铝石", 《催化学报》, vol. 24, no. 7, 31 July 2003 (2003-07-31), pages 505 - 508 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515230A (en) * | 2011-12-14 | 2012-06-27 | 德米特（苏州）电子环保材料有限公司 | Method for manufacturing aluminum oxide substrate polishing material for automobile painting surface |
| WO2018160934A1 (en) * | 2017-03-03 | 2018-09-07 | Exxonmobil Research And Engineering Company | High performance co2/h2o displacement desorption sorbents and methods of making same |
| CN113559889A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Modified phosphorus-containing pseudo-boehmite, preparation method thereof, modified phosphorus-containing alumina and hydrogenation catalyst |
| CN112915999A (en) * | 2021-01-26 | 2021-06-08 | 北京石油化工学院 | Catalyst for degrading benzene series and ethyl acetate and preparation method and application thereof |
| CN113209956A (en) * | 2021-04-28 | 2021-08-06 | 杭州智华杰科技有限公司 | Method for improving high-temperature stability of alumina catalyst carrier |
| US12030032B2 (en) | 2021-05-11 | 2024-07-09 | ExxonMobil Technology and Engineering Company | High performance CO2/H2O displacement desorption sorbents and methods of making same |
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