CN102275961B - Pseudoboehmite compound and alumina prepared from same - Google Patents
Pseudoboehmite compound and alumina prepared from same Download PDFInfo
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Abstract
The invention discloses a pseudoboehmite compound and alumina prepared from the same. The pseudoboehmite compound comprises at least two kinds of pseudoboehmite, namely, P1 and P2, and in terms of taking the total amount of the pseudoboehmite compound as a reference, the content of P2 accounts for more than 50wt%, wherein P1 is the pseudoboehmite with n1 not smaller than 1.1 and not more than 2.5, and P2 is the pseudoboehmite with n2 more than 0.8 and smaller than 1.1; n(1 or 2)=D(1 or 2)(031)/D(1 or 2)(120), wherein D(1 or 2)(031) represents the crystallite dimension of a crystal face represented by a peak (031) in an XRD (X-ray diffraction) spectrum of a P1/P2-pseudoboehmite crystallite, D(1 or 2)(120) represents the crystallite dimension of a crystal face represented by a peak (120) inthe XRD spectrum of the P1/P2-pseudoboehmite crystallite, D=Klambda/(Bcostheta), lambda refers to the diffraction wavelength of a target material, B refers to the peak width at half height of a corrected diffraction peak, and 2theta refers to the position of the diffraction peak. Compared with the prior art, the alumina prepared from the pseudoboehmite compound disclosed by the invention has an improved performance, and can be used as various adsorbents, catalyst carriers and matrixes.
Description
Technical field
The present invention is about a kind of pseudo-boehmite and the aluminum oxide that made by this pseudo-boehmite.
Background technology
Aluminum oxide, particularly gama-alumina, because it has pore structure, specific surface and heat-resistant stability preferably, the Chang Zuowei carrier is used for Preparation of catalysts.The precursor of aluminum oxide is hydrated aluminum oxide, and as pseudo-boehmite, its size of particles, pattern, degree of crystallinity etc. exert an influence to character such as the pore volume of alumina supporter, pore distribution, specific surface areas.
Pseudo-boehmite as the alumina supporter raw material is generally prepared by following method: (1) alkaline precipitation, i.e. acidifying aluminium salt and alkali neutralization.Be settled out monohydrate alumina with alkali from the acidifying aluminum salt solution, obtain the pseudo-boehmite product by processes such as aging, washing, dryings again, this method often is called as alkali precipitation (acid system), as in the ammoniacal liquor and the method for aluminum chloride; (2) acid precipitation method is namely in the aluminium salt of strong acid or strong acid and aluminate.Be settled out monohydrate alumina with acid from aluminate solution earlier, obtain the pseudo-boehmite product by processes such as aging, washing, dryings again, often be called as Acid precipitation (alkaline process), common method comprises the most at present: CO
2In the gas and in the method for sodium metaaluminate, Tai-Ace S 150 and the method for sodium metaaluminate; (3) aluminum alkoxide hydrolysis method generates monohydrate alumina with aluminum alkoxide and water generation hydrolysis reaction, obtains the pseudo-boehmite product through aging, filtration, drying again.Preparation process at pseudo-boehmite generally all is made up of processes such as crystal grain generation (neutralization precipitation or hydrolytic process), grain growing (weathering process), washing, dryings.Therefore, crystal grain generates, the processing condition of grain growing can exert an influence to quantity and the speed of growth that crystal grain generates, the preparation technology of various pseudo-boehmites has proposed processing condition separately, grain size, the degree of crystallinity of control product are to reach the purpose of physical propertiess such as control product pore volume and specific surface area.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of new pseudo-boehmite composition and the aluminum oxide that is prepared by said composition.
The invention provides a kind of pseudo-boehmite composition, it is characterized in that, said composition contains at least two kinds of pseudo-boehmite P1 and P2, is benchmark with the total amount of pseudo-boehmite composition, and the content of described P2 is more than the 50 weight %, and wherein, P1 is 1.1≤n
1≤ 2.5 pseudo-boehmite, P2 are 0.8＜n
2＜1.1 pseudo-boehmite; n
(1 or 2)=D
(1 or 2)(031)/D
(1 or 2)(120), described D
(1 or 2)(031) grain-size of the crystal face of (031) peak representative in the XRD spectra of expression P1 or P2 pseudo-boehmite crystal grain, D
(1 or 2)(120) grain-size of the place crystal face at (120) peak in the XRD spectra of expression P1 or P2 pseudo-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), λ is the diffraction wavelength of target section bar material, B is the peak width at half height of corrected diffraction peak, and 2 θ are the position of diffraction peak.
The present invention further provides a kind of aluminum oxide, this aluminum oxide is obtained through roasting by pseudo-boehmite, it is characterized in that, wherein said pseudo-boehmite is aforementioned pseudo-boehmite composition provided by the invention.
Compared with prior art, pseudo-boehmite composition properties provided by the invention improves.
For example, under identical reaction conditions, adopt the catalyzer the invention provides pseudo-boehmite preparation of compositions preparing carriers, its 4, the relative reference agent of 6-dimethyl Dibenzothiophene hydrodesulfurization activity can improve 7-38%.
Embodiment
According to pseudo-boehmite composition provided by the invention, be benchmark with the total amount of pseudo-boehmite composition, the content of described P2 is preferably more than the 60 weight %; Described P1 is preferably 1.2≤n
1≤ 2.2 pseudo-boehmite, P2 is preferably 0.85≤n
2≤ 1.05 pseudo-boehmite.
In a concrete embodiment, the weight ratio of P1 and P2 is 50 in the described composition: 50-5: 95, be preferably 40: 60-10: 90.
Described composition is mixed with P2 by P1 and obtains, described mixing can be the simple accumulation that described P1 and P2 are placed a place, can be to adopt any one prior art, for example can in stirrer, shredder, directly P1 be mixed by the mode that stirs with P2, also can be under the condition of pulp P1 to be mixed with P2 and water being enough to, afterwards after filtration, dry or moist.When adopting any one prior art to mix, those skilled in the art optionally can to described mix the homogeneity that should reach control, the present invention is not particularly limited this.
According to pseudo-boehmite composition provided by the invention, wherein, described P2 is 0.8＜n
2＜1.1 pseudo-boehmite can be the pseudo-boehmite that adopts any one prior art for preparing.
Described P1 is 1.1≤n
1The preparation method of≤2.5 pseudo-boehmite 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 any one 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, can make the n of gained P1 pseudo-boehmite like this
2At preferred 1.2≤n
1In≤2.2 scopes.
Wherein, there is no particular limitation to the consumption of grain growing conditioning agent, and the consumption of grain growing conditioning agent is the 0.5-10% that treats organic aluminum contained compound weight of hydrolysis in the selective hydrolysis reaction, more preferably 1-8.5%, further preferred 5-8.5%; The consumption of grain growing conditioning agent is the inorganic 0.5-10% that contains al reactant weight in the described precipitin reaction, more preferably 1-8.5%, further preferred 5-8.5%; In the described weathering process, the consumption of grain growing conditioning agent can be preferably 1-8.5% for the 0.5-10% of hydrated aluminum oxide weight, further preferred 5-8.5%.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% of inorganic aluminum contained compound weight, in the described hydrolysis reaction, the consumption of described grain growing conditioning agent is the 0.5-10% 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% 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 crystal grain at the material of the speed of growth of 120 crystal faces and 031 crystal face, preferred conditioning agent is poly-hydroxy sugar alcohol and carboxylate salt thereof, is 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 P1 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 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 acid oxide compound in water medium, for example, can be in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, 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, and the concentration of preferred H+ is 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 aluminum alkoxide of aqua oxidation aluminum precipitation 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 P1 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 to 7-10, under suitable temperature, wear out then.Separate then, washing, drying.
Described acid solution or alkaline solution can be with above-described identical or different.
Described aging 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 P1 pseudo-boehmite preparation process of the present invention, after aging, also comprise the washing and the dry step that often comprise in the preparation pseudo-boehmite process, described washing and dry 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 P1 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 are without filtering in the existence of grain growing conditioning agent or not, be under 7-10,35-98 ℃ at pH, aging 0.2-6 hour;
(3) product that filter, washing step (2) obtains;
(4) product that obtains of drying step (3) obtains P1 pseudo-boehmite provided by the invention.
According to aluminum oxide provided by the present invention, wherein, described roasting method and condition can be that this area prepares examples of such carriers customary way and condition.Preferred wherein said roasting condition comprises: temperature is 550～950 ℃, is preferably 600～850 ℃, 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.
One preferred embodiment in, described aluminum oxide is the bar shaped forming composition, its preparation method comprises:
(1) mixes at the pseudo-boehmite P2 and the water that are enough under the condition of pulp pseudo-boehmite P1, n＜1.1 of described 1.1≤n≤2.5, filter afterwards, dry or moist, obtain described composition;
(2) with the extrusion moulding on banded extruder of step (1) resulting composition;
(3) the dry and roasting with step (2) gained extrusion moulding thing.
Wherein, be to guarantee carrying out smoothly of extruded moulding, comprise the step of introducing an amount of water, peptizing agent (as be selected from nitric acid, acetic acid and the citric acid one or more), extrusion aid (as being in sesbania powder, the Mierocrystalline cellulose one or more) in the described composition and mixing in step (2).Described drying is 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 550-950 ℃ roasting temperature 1-12 hour, further preferably 600-850 ℃ roasting temperature 2-8 hour.
Another preferred embodiment in, described aluminum oxide is the bar shaped forming composition, its preparation method comprises:
(1) mixes at the pseudo-boehmite P2 of kneading machine with pseudo-boehmite P1, n＜1.1 of described 1.1≤n≤2.5, obtain described composition;
(2) with the extrusion moulding on banded extruder of step (1) resulting composition;
(3) the dry and roasting with step (2) gained extrusion moulding thing.
Wherein, be to guarantee carrying out smoothly of extruded moulding, comprise in step (1) and introduce an amount of water, peptizing agent (as be selected from nitric acid, acetic acid and the citric acid one or more), extrusion aid (as being in sesbania powder, the Mierocrystalline cellulose one or more).Described drying is 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 550-950 ℃ roasting temperature 1-12 hour, further preferably 600-850 ℃ roasting temperature 2-8 hour.
When extrusion moulding, 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.
Aluminum oxide provided by the invention can be used as the matrix of various sorbent materials, support of the catalyst and catalyzer and uses.
The following examples will the present invention is described further, but not thereby limiting the invention.
Agents useful for same in the example except specifying, is chemically pure reagent.Each component concentration all adopts x-ray fluorescence spectrometry except specifying in the catalyzer.
The n value of all pseudo-boehmites all adopts XRD method to measure in the example of the present invention.The XRD test is carried out at 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 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 by formula n=D (031)/D (120) calculates the n value.
The pseudo-boehmite P1 preparation method of employed 1.1≤n≤2.5 is as follows in the embodiment of the invention:
P1-1, adopt following method preparation:
In one 2 liters retort and stream add 600 ml concns be 96 gram aluminum oxide/liter, wherein contain the alum liquor 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 proper ammonia in slurries, to make the pH value of slurries be 8.5, 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.
Characterizing the n value that calculates P1-1 through XRD lists in the table 1.
P1-2, adopt following method preparation:
To contain 210 gram aluminum oxide/liter, the causticity coefficient is 1.62 high density NaAlO
2Solution and deionized water are mixed with Al
2O
3Concentration is 5 liters of the solution of 40 grams per liters, adds the NaAlO that Sunmorl N 60S 16.3 grams obtain containing Sunmorl N 60S then
2Solution is transferred in the one-tenth glue reactor of cumulative volume 8L then, and the reactor aspect ratio is 8, bottom band CO
2Gas distributor.The control solution temperature is 25 ± 5 ℃, feeds the CO of concentration 90 volume % from reactor bottom
2Gas becomes the glue reaction, becomes the control of glue temperature at 20-40 ℃, regulates CO
2Gas flow is 15 ± 2 liters/minute, makes reaction end pH value reach 8.0-8.5 in 4-6 minute, namely stops ventilation, finishes into the glue reaction.With aging 4 hours of gained slurries heat temperature raising to 70 ℃, filter with vacuum filter then, to be filtered intact after, replenish at filter cake and to add 20 liters of deionized waters (70 ℃ of temperature) flush cake about 30 minutes.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying with being pumped into spray-dryer, obtain hydrated aluminum oxide P1-2.XRD characterizes demonstration, 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.
P1-3, adopt following method preparation:
In one 2 liters retort and stream add 1000 ml concns be 48 gram aluminum oxide/liter aluminum trichloride solution and 300 milliliters contain 200 gram aluminum oxide/liter, the causticity coefficient is 1.58, Sorbitol Powder content is 1.82 grams per liters sodium aluminate solution carries out precipitin reaction, temperature of reaction is during 80 ℃, conditioned reaction logistics capacity make and the pH value is 4.0, reaction time 15 minutes; Adding concentration in the gained slurries is the weak ammonia adjusting slurries pH to 10.0 of 5 weight %, and be warming up to 80 ℃, aging 3 hours, filter with vacuum filter then, behind to be filtered the finishing, replenished adding 20 liters of deionized waters (80 ℃ of temperature) flush cake about 30 minutes at filter cake.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying with being pumped into spray-dryer, control spray-dryer temperature out about 2 minutes of dry materials time, obtains hydrated aluminum oxide P1-3 100-110 ℃ of scope after the drying.Adopt XRD to characterize, P1-3 has structure of similar to thin diaspore.The n value that adopts XRD method to calculate P1-3 is listed in the table 1.
The preparation method of the pseudo-boehmite P2 of employed n＜1.1 is as follows in the embodiment of the invention.
P2-1, adopt following method preparation:
Method according to P1-1 prepares pseudo-boehmite, and different is, the alum liquor that contains ribitol by concentration be 96 gram aluminum oxide/liter alum liquor replace, also be not contain ribitol in the alum liquor.Finally obtain hydrated aluminum oxide P2-1.XRD characterizes demonstration, and P2-1 has structure of similar to thin diaspore, and the n value that characterizes and calculate P2-1 through XRD is listed in the table 1.
Repeatedly prepare as stated above, to obtain enough for the pseudo-boehmite raw material that uses in the example.
P2-2 is the commercial pseudo-boehmite SB powder that German Condea company produces.
P2-3 is the commercial pseudo-boehmite SD powder that Shandong Aluminium Industrial Corp produces.Employing XRD characterizes and calculates the n value of P2-2 and P2-3 powder and lists in the table 1.
Table 1
Embodiment 1-6 illustrates pseudo-boehmite provided by the invention, aluminum oxide shaping carrier and preparation method thereof.
Embodiment 1
(1) pseudo-boehmite composition:
Take by weighing 350 gram pseudo-boehmite P1-1 and 650 gram pseudo-boehmite P2-3 kneading machine mixing 20 minutes, obtain the invention provides composition Z P-1.
(2) alumina supporter:
It is 1.6 millimeters cloverleaf pattern bar that ZP-1 is extruded into circumscribed circle diameter with banded extruder, 120 ℃ of dryings 6 hours.Get wherein 300 grams, at 850 ℃, calcination process is 2 hours under the blowing air condition, makes carrier S
1, wherein air flow quantity is 2 standard cubic meter/kilograms. hour.
Embodiment 2
(1) pseudo-boehmite composition:
Take by weighing 300 gram pseudo-boehmite P1-2 and 700 gram pseudo-boehmite P2-3 kneading machine mixing 15 minutes, obtain the invention provides composition Z P-2.
(2) alumina supporter:
It is 1.6 millimeters cloverleaf pattern bar that ZP-2 is extruded into circumscribed circle diameter with banded extruder, 120 ℃ of dryings 8 hours.Get wherein 300 grams, at 800 ℃, calcination process is 4 hours under the blowing air condition, makes carrier S
2, wherein air flow quantity is 1.5 standard cubic meter/kilograms. hour.
Embodiment 3
(1) pseudo-boehmite composition:
Take by weighing 250 gram pseudo-boehmite P1-3 and 750 gram pseudo-boehmite P2-2, add respectively in 3000 ml deionized water, continue to stir 15 minutes after being stirred to pulp, filter then, in 120 ℃ dry 6 hours down, obtain composition Z P-3 provided by the invention
(2) alumina supporter:
Getting composition Z P-3 600 gram, to be extruded into circumscribed circle diameter with banded extruder be 1.2 millimeters cloverleaf pattern bar, 120 ℃ of dryings 8 hours.Get wherein 300 grams, at 750 ℃, calcination process is 5 hours under the blowing air condition, makes carrier S
3, wherein air flow quantity is 1.5 standard cubic meter/kilograms. hour.
Embodiment 4
(1) pseudo-boehmite composition:
Take by weighing 150 gram pseudo-boehmite P1-1 and 850 gram pseudo-boehmite P2-3 kneading machine mixing 20 minutes, obtain the invention provides composition Z P-4.
(2) alumina supporter:
It is 1.4 millimeters cloverleaf pattern bar that ZP-4 is extruded into circumscribed circle diameter with banded extruder, 120 ℃ of dryings 4 hours.Get wherein 600 grams, at 700 ℃, calcination process is 6 hours under the blowing air condition, makes carrier S
4, wherein air flow quantity is 1.5 standard cubic meter/kilograms. hour.
Embodiment 5
(1) pseudo-boehmite composition:
Take by weighing 100 gram pseudo-boehmite P1-3 and 900 gram pseudo-boehmite P2-3 kneading machine mixing 20 minutes, obtain the invention provides composition Z P-5.
(2) alumina supporter:
It is 1.4 millimeters cloverleaf pattern bar that ZP-5 is extruded into circumscribed circle diameter with banded extruder, 120 ℃ of dryings 4 hours.Get wherein 600 grams, at 600 ℃, calcination process is 8 hours under the blowing air condition, makes carrier S
5, wherein air flow quantity is 1.5 standard cubic meter/kilograms. hour.
Embodiment 6
(1) pseudo-boehmite composition:
ZP-1 with embodiment 1.
(2) alumina supporter:
It is 1.6 millimeters cloverleaf pattern bar that ZP-1 is extruded into circumscribed circle diameter with banded extruder, 120 ℃ of dryings 6 hours.Get wherein 300 grams, at 600 ℃, calcination process is 5 hours under the blowing air condition, makes carrier S
6, wherein air flow quantity is 2 standard cubic meter/kilograms. hour.
Comparative Examples 1
(1) pseudo-boehmite composition:
Take by weighing 350 gram pseudo-boehmite P2-1 and 650 gram pseudo-boehmite P2-3 kneading machine mixing 20 minutes, obtain the invention provides composition DP-1.
(2) alumina supporter:
It is 1.6 millimeters cloverleaf pattern bar that DP-5 is extruded into circumscribed circle diameter with banded extruder, 120 ℃ of dryings 6 hours.Get wherein 600 grams, at 600 ℃, calcination process is 5 hours under the blowing air condition, makes carrier DS
1, wherein air flow quantity is 2 standard cubic meter/kilograms. hour.
Embodiment 7-12 explanation is by the catalyzer that the invention provides the preparation of aluminum oxide shaping carrier.
Embodiment 7
Take by weighing 100 gram carrier S
1, with 86 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 3.9 gram, nickelous nitrate 28.2 grams and ammonium metawolframate 57.8 grams 2 hours, 120 ℃ of dryings 5 hours were handled 4 hours, and were obtained catalyzer C for 180 ℃
1Catalyzer C
1Middle MoO
3, NiO and WO
3Weight content be respectively 1.8%, 4.1% and 27.6%.
Embodiment 8
Take by weighing 100 gram carrier S
2, 85 milliliters of the aqueous solution with containing 10.7 gram Neutral ammonium fluorides flooded 1 hour, 130 ℃ of dryings 5 hours, and 480 ℃ of roastings 3 hours get fluorine-containing carrier, wherein fluorine-containing 5.0 weight %.
Take by weighing above-mentioned fluorine-containing carrier 100 grams, with 85 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 4.9 grams, nickelous nitrate 23.4 grams, ammonium metawolframate 54.6 grams and phosphoric acid 7.8 grams 2 hours, 120 ℃ of dryings 5 hours were handled 4 hours for 200 ℃.Continuation is with the aqueous solution dipping of 55 milliliters of the aqueous solution that contain glycerol 7.2 gram 1.5 hours, and 165 ℃ of dryings 6 hours obtain catalyzer C
2Catalyzer C
2Middle MoO
3, NiO, WO
3, F, P
2O
5Be respectively 2.2%, 3.3%, 24.8%, 3.2%, 2.7% and 4.0% with the weight content of organic additive.
Embodiment 9
Take by weighing 100 gram carrier S
3, 84 milliliters of the aqueous solution with containing 13.0 gram Neutral ammonium fluorides flooded 1 hour, 120 ℃ of dryings 6 hours, and 400 ℃ of roastings 5 hours get fluorine-containing carrier, wherein fluorine-containing 6.0 weight %.
Take by weighing fluorine-containing carrier 100 grams of this kind, ammonium paramolybdate 3.4 restrains with containing, nickelous nitrate 19.4 restrains, ammonium metawolframate 63.9 restrains, phosphoric acid 5.3 restrains and the aqueous solution of ethylenediamine tetraacetic acid (EDTA) 10.0 grams flooded 1 hour for 84 milliliters, 120 ℃ of dryings 3 hours, 180 ℃ of dryings 4 hours obtain catalyzer C
3Catalyzer C
3Middle MoO
3, NiO, WO
3, F, P
2O
5Be respectively 1.5%, 2.6%, 28.2%, 3.6%, 1.8% and 5.4% with the weight content of organic additive.
Embodiment 10
Take by weighing 100 gram carrier S
4, 83 milliliters of the aqueous solution with containing 15.8 gram Neutral ammonium fluorides flooded 2 hours, 100 ℃ of dryings 7 hours, and 450 ℃ of roastings 3 hours get fluorine-containing carrier, and fluorine content is 7.2 weight %.
Take by weighing the fluorine-containing carrier of this kind 100 grams, with 82 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 4.9 grams, nickelous nitrate 23.9 grams, ammonium metawolframate 59.1 grams and citric acid 13.3 grams 1.5 hours, 120 ℃ of dryings 5 hours were handled 4 hours, and were obtained catalyzer C for 200 ℃
4Catalyzer C
4Middle MoO
3, NiO, WO
3, F and organic additive weight content be respectively 2.2%, 3.3%, 26.5%, 4.4% and 6.6%.
Embodiment 11
Take by weighing 100 gram carrier S
5, with 82 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 6.3 gram, nickelous nitrate 25.5 grams, ammonium metawolframate 62.0 grams, phosphatase 11 1.0 grams and citric acid 12.8 grams 1 hour, 120 ℃ of dryings 3 hours, 170 ℃ of dryings 6 hours obtain catalyzer C
5Catalyzer C
5Middle MoO
3, NiO, WO
3, P
2O
5Be respectively 2.6%, 3.3%, 25.8%, 3.4% and 5.9% with the weight content of organic additive.
Embodiment 12
Take by weighing S
6Carrier 100 gram flooded 1 hour for 86 milliliters with the aqueous solution that contains nickelous nitrate 15.5 grams and ammonium paramolybdate 32.2 grams, 120 ℃ of dryings 6 hours, and 450 ℃ of roastings 4 hours obtain catalyzer C
6C
6Middle NiO and MoO
3Weight content is respectively 3.0% and 20.0%.
Comparative Examples 2
Take by weighing DS
1Carrier 100 gram flooded 1 hour for 81 milliliters with the aqueous solution that contains nickelous nitrate 15.5 grams and ammonium paramolybdate 32.2 grams, 120 ℃ of dryings 6 hours, and 450 ℃ of roastings 4 hours obtain reference catalyst DC1.NiO and MoO among the DC1
3Weight content is respectively 3.0% and 20.0%.
Embodiment 13-18 explanation the invention provides Application of Catalyst and effect thereof.
The catalyst activity evaluation is carried out at the continuous flow high-pressure micro-device.Catalyzer carries out prevulcanized earlier to be handled.Cure conditions: vulcanized oil is the hexanaphthene that contains dithiocarbonic anhydride 5 weight %, 360 ℃ of curing temperatures, and the hydrogen dividing potential drop is 4.14MPa.Vulcanize after 3 hours, feeding contains the n-decane solution that 4,6-dimethyl Dibenzothiophene is 0.45 weight %, also contains a small amount of sulfur-bearing and nitrogenous compound in this reaction raw materials, and the catalyzer loading amount is 0.15g, and temperature of reaction is 300 ℃, and the hydrogen dividing potential drop is 4.14MPa.Reaction is carried out taking a sample after t hour, adopts gas-chromatography (GC) methods analyst 4 then, 6-dimethyl Dibenzothiophene residual concentration C
t4,6-dimethyl Dibenzothiophene hydrodesulfurization reaction is handled by first order reaction, and reaction rate constant is calculated by following method.
When at first calculating reacting time is t 4,6-dimethyl Dibenzothiophene desulfurization transformation efficiency x:
x＝(C
0-C
t)/C
0
C in the formula
0Be when beginning reaction 4,6-dimethyl Dibenzothiophene concentration (C
0Be 0.45%), C
tWhen being t (be sample time, for different catalysts, keep identical reaction times t) for the reaction times 4,6-dimethyl Dibenzothiophene concentration.
4,6-dimethyl Dibenzothiophene desulphurization reaction rate constant is:
k＝1/t.Ln(1/(1-x))
The relative hydrodesulfurization activity of catalyzer in the recently expression of the reaction rate constant on this catalyzer with reaction rate constant on the Comparative Examples catalyzer, the results are shown in Table 2 with 4,6-dimethyl Dibenzothiophene.
Comparative Examples 3
Application and the performance thereof of this Comparative Examples explanation reference catalyst.Adopt with embodiment 13 same procedure and estimate the DC1 catalyzer, measure its reaction rate constant k, and to define its relative hydrodesulfurization activity be 100%.The results are shown in table 2
By data declaration in the table 2, has higher hydrodesulfurization activity by catalyzer provided by the invention.
Table 2
| Example | Catalyzer | Relative hydrodesulfurization activity/the % of catalyzer |
| 13 | C 1 | 115 |
| 14 | C 2 | 135 |
| 15 | C 3 | 138 |
| 16 | C 4 | 128 |
| 17 | C 5 | 120 |
| 18 | C 6 | 107 |
| Contrast medium 3 | DC1 | 100 |
Claims (10)
1. a pseudo-boehmite composition is characterized in that, contains at least two kinds of pseudo-boehmite P1 and P2, is benchmark with the total amount of pseudo-boehmite composition, and the content of described P2 is greater than 60 weight %, and wherein, P1 is 1.1≤n
1≤ 2.5 pseudo-boehmite, P2 are 0.8＜n
2＜1.1 pseudo-boehmite; n
(1 or 2)=D
(1 or 2)(031)/D
(1 or 2)(120), described D
(1 or 2)(031) grain-size of the crystal face of (031) peak representative in the XRD spectra of expression P1 or P2 pseudo-boehmite crystal grain, D
(1 or 2)(120) grain-size of the place crystal face at (120) peak in the XRD spectra of expression P1 or P2 pseudo-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), λ is the diffraction wavelength of target section bar material, B is the peak width at half height of corrected diffraction peak, and 2 θ are the position of diffraction peak.
2. pseudo-boehmite composition according to claim 1 is characterized in that, is benchmark with the total amount of pseudo-boehmite composition, and the content of described P2 is more than the 65 weight %; Described P1 is 1.2≤n
1≤ 2.2 pseudo-boehmite, P2 are 0.85≤n
2≤ 1.05 pseudo-boehmite.
3. pseudo-boehmite composition according to claim 1 is characterized in that, the weight ratio of P1 and P2 is 35 in the described composition: 65-5: 95.
4. pseudo-boehmite composition according to claim 3 is characterized in that, the weight ratio of P1 and P2 is 35 in the described composition: 65-10: 90.
5. aluminum oxide, this aluminum oxide is obtained through roasting by pseudo-boehmite, it is characterized in that, and described pseudo-boehmite is any described pseudo-boehmite composition among the claim 1-4.
6. aluminum oxide according to claim 5 is characterized in that, described aluminum oxide is formed alumina.
7. aluminum oxide according to claim 6 is characterized in that, described formed alumina is bar shaped, and the preparation method of described bar shaped aluminum oxide comprises:
(1) mixes at the pseudo-boehmite P2 and the water that are enough under the condition of pulp pseudo-boehmite P1, n＜1.1 of described 1.1≤n≤2.5, filter afterwards, dry or moist, obtain described composition;
(2) with the extrusion moulding on banded extruder of step (1) resulting composition;
(3) the dry and roasting with step (2) gained extrusion moulding thing.
8. aluminum oxide according to claim 6 is characterized in that, described formed alumina is bar shaped, and the preparation method of described bar shaped aluminum oxide comprises:
(1) mixes at the pseudo-boehmite P2 of kneading machine with pseudo-boehmite P1, n＜1.1 of described 1.1≤n≤2.5, obtain described composition;
(2) with the extrusion moulding on banded extruder of step (1) resulting composition;
(3) the dry and roasting with step (2) gained extrusion moulding thing.
9. according to claim 5,7 or 8 described aluminum oxide, it is characterized in that described maturing temperature is 550-950 ℃, roasting time 1-12 hour.
10. aluminum oxide according to claim 9 is characterized in that, described maturing temperature is 600-850 ℃, roasting time 2-8 hour.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5334366A (en) * | 1993-01-07 | 1994-08-02 | Aluminum Company Of America | Transition alumina and method for its production |
| CN100999328A (en) * | 2006-01-10 | 2007-07-18 | 中国石油化工股份有限公司 | Pseudo thin allophane and its preparation method |
| CN101643228A (en) * | 2008-08-08 | 2010-02-10 | 中国科学院大连化学物理研究所 | Method for preparing alumina having mesoporous structure |
| CN102161492A (en) * | 2010-02-24 | 2011-08-24 | 中国石油化工股份有限公司 | Pseudo-boehmite composition and alumina prepared from same |
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2010
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5334366A (en) * | 1993-01-07 | 1994-08-02 | Aluminum Company Of America | Transition alumina and method for its production |
| CN100999328A (en) * | 2006-01-10 | 2007-07-18 | 中国石油化工股份有限公司 | Pseudo thin allophane and its preparation method |
| CN101643228A (en) * | 2008-08-08 | 2010-02-10 | 中国科学院大连化学物理研究所 | Method for preparing alumina having mesoporous structure |
| CN102161492A (en) * | 2010-02-24 | 2011-08-24 | 中国石油化工股份有限公司 | Pseudo-boehmite composition and alumina prepared from same |
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