CN1164494C - Prepn of gamma-alumina - Google Patents
Prepn of gamma-alumina Download PDFInfo
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- CN1164494C CN1164494C CNB021207720A CN02120772A CN1164494C CN 1164494 C CN1164494 C CN 1164494C CN B021207720 A CNB021207720 A CN B021207720A CN 02120772 A CN02120772 A CN 02120772A CN 1164494 C CN1164494 C CN 1164494C
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- boehmite
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Abstract
The present invention relates to a method for preparing gamma-alumina. The present invention comprises: a kind of pseudo boehmite is roasted, wherein the pseudo boehmite is prepared by the following method: sodium metaaluminate solution or sodium aluminate solution is in contact with gas containing carbon dioxide to generate peptized solution in an intermittent or continuous manner, the peptized solution is aged, the solid products are separated from the aged peptized solution, the solid products are washed and dried to obtain the pseudo-boehmite, the pH value at the peptizing end point or in the peptizing process is controlled within the range of 6 to 9.5, the peptizing reaction time or the residence time is less than 40 minutes, the peptizing reaction temperature is from 10 to 100 DEG C, alkaline matter is immediately added after the peptizing reaction to make the pH value of the slurry up to 9.5 to 11.5, or solid-liquid separation and washing are carried out immediately.
Description
The invention relates to a kind of preparation method of aluminum oxide, more specifically say so about prepare the method for gama-alumina from alkali-metal meta-aluminate or aluminate.
Sodium metaaluminate (or sodium aluminate)-carbon dioxide process is one of common method of preparation pseudo-boehmite and gama-alumina.Because this method can be in conjunction with aluminium manufacturer's industry practical situation, can be feedstock production pseudo-boehmite and gama-alumina with the sodium aluminate solution of bauxite production or sodium aluminate solution and CO 2 waste gas, be a kind of inexpensive method, thereby this method is used widely industrial.
In the prior art, the glue reaction (or claiming neutralization reaction) that becomes of sodium aluminate solution or sodium aluminate solution and carbonic acid gas can intermittently or be carried out continuously.Becoming in the glue reaction at intermittent type, is with CO
2Gas is passed in a large amount of sodium aluminate solution or sodium aluminate solution, becomes the endpoint pH of glue reaction all to be controlled at 9.5, and is best more than 10.In becoming the glue reaction continuously, sodium aluminate solution or sodium aluminate solution contact with certain speed separately with carbonic acid gas, become glue reaction pH value (process pH value) also to be controlled at 9.5, and be best more than 10.Be carried out to the glue reaction under this high pH value, can obtain the higher pseudo-boehmite of degree of crystallinity, but because its grain shape is solid spherical, intercrystalline is piled up closely, therefore the pore volume of the gama-alumina that generates after roasting is less, is generally less than 0.5 milliliter/gram.This has greatly limited its application in distillate hydrogenation, particularly heavy oil, residual oil hydrocatalyst.
For example, US 3,268, and 295 disclose a kind of preparation method of hydrated aluminum oxide, and this hydrated aluminum oxide contains the crystal water of 1.4～1.6 moles in every mole of aluminum oxide, average crystal grain size 20～40 dusts.The peak area at ℃ peak, 2 θ=28.1 is 40～90% of a boehmite respective peaks area in the x-ray diffraction spectra.This method comprises that (a) restrains Na with sodium content less than about 200
2CO
3Every liter sodium aluminate and approximate stoichiometric carbon dioxide reaction, preparation is substantially free of the amorphous hydroted alumina of crystalline hydrate aluminum oxide, the condition of reaction is 25～60 ℃ of temperature of reaction, 2～20 minutes reaction times, pH value 10～11 is settled out aluminium hydroxide by neutralization reaction rather than hydrolysis reaction basically.(b) from mother liquor, isolate precipitation, washing, and will precipitate with the water reslurry and make precipitation dispersion, make it to be in metamict.(c) below 100 ℃ and the precipitation 5～90 minutes in 8～9 times aging slurries of pH value, make amorphous hydroted alumina be transformed into crystallization shape hydrated aluminum oxide.
EP0,147,167A2 disclose a kind of continuously in and the aluminate solution method of producing alumina gel, this method comprises that (a) makes the reactor of sodium aluminate solution inflow with certain total causticity and certain aluminum oxide and causticity ratio.(b) solution in the reactor is kept certain temperature.(c) contact with this solution with a kind of neutralization reagent, make the pH value be reduced to preset value, described neutralization reagent is selected from gas that can be dissolved in described sodium aluminate solution and the liquid that is insoluble to described sodium aluminate solution.(d) from reactor, be continuously removed the alumina gel of generation, according to the ratio of causticity, aluminum oxide and causticity, temperature of reaction, the pH and the residence time, the speed of selecting to shift out makes alumina gel form specific modality.Point out that the 7th page of this application according to the desired product difference that obtains, the pH value of neutralization reaction can from 8.5 to 12, for example, can obtain dawsonite (dawsonite) when pH is 8.5～10.2.Can obtain gibbsite (gibbsite) when pH is about 12 the time.And work as pH is 10.4～10.7, will mainly obtain pseudo-boehmite.
CN85,100,161A discloses a kind of industrial sodium aluminate solution that utilizes in the alumina producing, changes into the processing method that glue is produced pseudo-boehmite through carbonic acid.This method is included in alumina concentration 70～130 grams per liters, add distilled water or deionized water dilution in the industrial sodium aluminate solution that temperature is 70～100 ℃ and be cooled to alumina concentration 20～60 grams per liters, 15～45 ℃ of temperature will be diluted cooled solution then and be purified after filtration and remove Al (OH)
3Residue feeds concentration again and is 30～45% carbon dioxide and carries out quick carbonic acid and change into glue, and carbonic acid changes into glue and is divided into and is interrupted and dual mode continuously, is adopting when being interrupted carbonic acid and changing into glue logical CO
2Gas velocity 2～8 gram CO
2/ gram Al
2O
3Hour, 10～30 minutes time.When adopting continuous carbonation to become glue, logical CO
2Gas velocity 1～6CO
2/ gram Al
2O
3Hour, carbonation is 30～90 minutes.Become the later slurries of glue then to be heated to 70～100 ℃, permanent aging 1～6 hour of temperature or elder generation directly carry out liquid-solid separation back and are worn out in washing process, distilled water that the solid usefulness temperature that separation obtains is 70～100 ℃ or deionized water wash 1～4 time, washings partly returns makes dilution industrial sodium aluminate solution usefulness, separate mother liquor and remain washings and send the alumina producing flow process back to, to wash good wet stock at last and dry routinely and the grinding mode processing, obtain the powdery pseudo-boehmite.According to the described one-tenth adhesive tape of this application part, its endpoint pH or process pH value also are controlled between 10.5～12.0.
When producing pseudo-boehmite with sodium metaaluminate (or sodium aluminate)-carbon dioxide process, why terminal point or process pH value are controlled at 10～12nd in the prior art, because in becoming the glue process, when terminal point or process pH value less than 10, particularly less than 9.5 o'clock, aluminium hydroxide that one-tenth glue process generates and sodium bicarbonate were had an effect and are generated dawsonite (NaAl (OH)
2CO
3), producing pseudo-boehmite with sodium metaaluminate-carbon dioxide process is example, becomes to have following reaction in the glue process:
Water insoluble because of dawsonite, in washing process, can not be removed, thereby sodium content is too high in the product that obtains, this has seriously influenced the character of product.
The purpose of this invention is to provide the method that a kind of new employing sodium metaaluminate or sodium aluminate-carbon dioxide process prepare gama-alumina, the pseudo-boehmite of this method preparation is fibrous, and high degree of crystallinity is arranged.Through the pore volume of the gama-alumina that roasting forms between 0.5～2.0 milliliter/gram.
The present inventor finds, be carried out in the process of glue reaction at sodium metaaluminate or sodium aluminate and carbonic acid gas, when the pH of terminal point or process value less than 9.5 the time, though can follow yellow soda ash and aluminium hydroxide effect to generate the reaction of dawsonite, but this reaction needed has time enough just can finish, this time generally needs 40 minutes or longer time, when gelatigenous pH value is lower than 9.5, be no more than 40 minutes as long as guarantee the time of low pH value, can obtain the pseudo-boehmite of essentially no dawsonite.Yet well-known, the aluminium hydroxide of generation need wear out, and the aged time adds the gelatigenous time generally greater than 0.5 hour, generally is certain to above 40 minutes.According to above-mentioned situation, the present inventor invents out the preparation method of gama-alumina as described below dexterously.
The preparation method of gama-alumina provided by the invention comprises a kind of pseudo-boehmite of roasting, wherein, described pseudo-boehmite adopts following method preparation: sodium metaaluminate or sodium aluminate solution are contacted with carbonated gas, intermittence or successive mode to become glue, the aging pseudo-boehmite that obtains, isolate solid product, washing is also dry.Wherein, described gelatigenous endpoint pH or process pH value are controlled in 6～9.5 the scope, become the time or the residence time of glue reaction to be less than 40 minutes, 10～100 ℃ of the temperature of one-tenth glue reaction, become the glue reaction to finish the back and add alkaline matter rapidly, make the pH value of slurries rise to 9.5 or more or carry out solid-liquid separation rapidly and also wash.
According to method provided by the invention, the concentration of described sodium metaaluminate or sodium aluminate solution can be arbitrarily, the concentration that may exist, for guaranteeing to prepare expeditiously pseudo-boehmite, preferred 5～120 gram aluminum oxide of the concentration of sodium metaaluminate or sodium aluminate solution/liter.
According to method provided by the invention, the content of carbonic acid gas can in very large range change in the described carbonated atmosphere, and general carbon dioxide content is preferably greater than 20 volume % greater than 5 volume %.
According to method provided by the invention, described one-tenth glue reaction can be step, when adopting this mode, at first sodium metaaluminate or sodium aluminate solution are placed one one-tenth glue jar, feed carbonated gas from the bottom of jar, temperature of reaction is controlled at 10～100 ℃, preferred 10～80 ℃, endpoint pH is controlled at 6.0～9.5, and preferred 6.5～9.3.The concentration and the flow of concentration, consumption and carbonated atmosphere by regulating sodium metaaluminate or sodium aluminate solution, the time that makes into the glue reaction is no more than 40 minutes, preferably is no more than 25 minutes.After becoming the glue reaction to finish, add alkaline matter rapidly, the pH value of slurries is risen to rapidly more than 9.5, between preferred 9.5～11.5, or carry out solid-liquid separation and washing rapidly.Under normal condition, wear out then, filter, wash and drying, obtain pseudo-boehmite.The pseudo-boehmite that roasting obtains obtains gama-alumina.
According to method provided by the invention, described one-tenth glue reaction also can be a successive.When adopting this one-tenth glue mode, at first in one one-tenth glue jar, add a certain amount of deionized water in advance or do not add deionized water, feed carbonated gas simultaneously from the bottom of jar and feed sodium metaaluminate or sodium aluminate solution from the top of jar, be controlled to 10～100 ℃ of glue temperature, preferred 10～80 ℃, control sodium metaaluminate or the concentration of sodium aluminate solution and the concentration and the flow velocity of speed and carbon dioxide containing gas, make into the glue process pH value 6～9.5, between preferred 6.5～9.3, and make the residence time be no more than 40 minutes, preferably be no more than 25 minutes.The slurries that become the glue process to generate are collected in the digestion tank continuously or discontinuously, adding alkaline matter continuously or discontinuously rises to more than 9.5 slurry pH value, between preferred 9.5～11.5, after collecting for some time, the slurries that become the glue reaction to generate are switched to another digestion tank, and pH value in first digestion tank worn out greater than 9.5 slurries, filter, washing and dry.Obtain pseudo-boehmite.The pseudo-boehmite that roasting obtains obtains gama-alumina.
Described alkaline matter is selected from one or more in multiple mineral alkali, organic bases and their aqueous solution.In the oxyhydroxide of wherein said mineral alkali preferred as alkali, meta-aluminate, carbonate, supercarbonate, volatile salt, ammoniacal liquor and their aqueous solution one or more.In described organic bases preferably water dissolubility amine, urea, pyridine and their aqueous solution one or more, in preferred water-soluble aliphatics amine, alkyl ammonium hydroxide, urea, pyridine and their aqueous solution one or more, particularly one or more in the various isomer of the various isomer of methylamine, ethamine, propylamine, propylene diamine, butylamine, amylamine, tetraethyl ammonium hydroxide, urea, pyridine and their aqueous solution.
The method of described solid-liquid separation can adopt the method for filtering method or centrifugation.It is the reactant carbonic acid hydrogen sodium that wherein can generate dawsonite in order to remove that solid-liquid separation is separated later washing, general be not less than 10 times deionized water wash at least once.
Described aging condition routinely is aging, and in general aging temperature is 5～100 ℃, and preferred 30～100 ℃, more preferred 50～100 ℃, digestion time is greater than 0.5 hour, preferred 1～8 hour.When adopting the method that adds alkaline matter adjusting pH value, the aged medium can be mother liquor or deionized water.Adopt when carrying out the method for solid-liquid separation rapidly, the aged medium generally is a deionized water.
Described washing after aging is carried out according to a conventional method, and the purpose of washing is the foreign ion of removing wherein, and the content that makes alkalimetal oxide wherein is less than 0.15 weight %.
Described drying conditions is conventional drying conditions, and the exsiccant temperature can be that room temperature to pseudo-boehmite changes below the brilliant temperature, preferred 100～200 ℃.
According to method provided by the invention, before described roasting pseudo-boehmite, pseudo-boehmite can first moulding or not moulding.Described moulding is carried out according to a conventional method, and as pseudo-boehmite can being mixed with suitable quantity of water, extrusion moulding perhaps mixes extrusion moulding then with pseudo-boehmite and an amount of extrusion aid and/or tackiness agent and suitable quantity of water.Described extrusion aid, peptizing agent can be this area kind and consumptions commonly used.
The condition of described roasting pseudo-boehmite is conventional roasting condition, as 500～900 ℃ of maturing temperatures, and preferred 550～850 ℃, roasting time 2～8 hours, preferred 3～6 hours.
Method provided by the invention has overcome the less shortcoming of gama-alumina pore volume of prior art sodium metaaluminate or sodium aluminate-carbon dioxide process preparation, can prepare the gama-alumina of 0.5～2.0 milliliter/mole of pore volume.
The gama-alumina of method preparation provided by the invention can be directly as various sorbent materials and various catalyzer, as the carrier or the matrix of catalyzer such as hydrotreatment, hydrocracking, catalytic cracking, reformation, isomerization, alkylation, disproportionation.
The gama-alumina of method preparation provided by the invention is especially suitable for use as heavy oil (comprising residual oil) and various distillate hydrogenation is handled or the carrier of hydrocracking catalyst.
The following examples will the present invention will be further described.
Example 1
Prepare gama-alumina by method provided by the invention.
Getting 1.5 liters of concentration is 10 gram Al
2O
3/ liter sodium aluminate solution, place one 2 liters one-tenth glue jar, 15 ℃ of initial temperatures feed carbonic acid gas and the Air mixing gas of carbon dioxide content 30 volume % from the bottom that becomes the glue jar, the flow of gas mixture is 1.8 meters
3/ hour, to react 3 minutes, the pH value drops to 6.5, and this moment, temperature of reaction was 22 ℃, stopped into the glue reaction, and adding concentration rapidly is 10 gram Al
2O
3/ liter the alkaline matter sodium aluminate solution, make slurry pH value in 4 minutes, rise to 9.8.Be warming up to 32 ℃, aging 4 hours of constant temperature.Filter, with 20 times of 90 ℃ of deionized water wash 2 times, 120 ℃ of oven dry must pseudo-boehmite N
1, get the pseudo-boehmite that obtains of part in 550 ℃ of roastings 5 hours, gama-alumina A
1Table 1 has provided N
1And A
1Physico-chemical property.Accompanying drawing 1 has provided pseudo-boehmite N among the CN1250746A
1Amplify 50,000 times transmission electron microscope photo.The pseudo-boehmite of seeing method preparation provided by the invention from its transmission electron microscope photo is fibrous.
Wherein, pseudo-boehmite content and alumina trihydrate content adopt thermogravimetric (TGA) method to measure (referring to volumes " commercial catalysts analytical test sign " such as Liu Xiyao, hydrocarbon industry press, 292,1990).Sodium oxide content adopts plasma emission spectrum (IPC) method, measures on the DS-4 type vacuum inductively coupled plasma quantorecorder that U.S. BAIRD company makes.Degree of crystallinity adopts x-ray diffraction method (XRD) to measure, and the degree of crystallinity of described pseudo-boehmite is relative crystallinity, is that the aluminium hydroxide that the German Condea company of SB produces is standard specimen with the trade mark, and the degree of crystallinity of the aluminum oxide that forms after the SB roasting is 100%.Specific surface, pore volume adopt cryogenic nitrogen absorption BET method to measure.Transmission electron microscope photo records on the JEM-2000FX II of NEC company type transmission electron microscope.
Example 2
Prepare gama-alumina by method provided by the invention.
Method by example 1 prepares pseudo-boehmite and gama-alumina, and different is to replace the alkaline matter sodium aluminate solution with alkaline matter sodium hydroxide, makes slurry pH value rise to 9.8 within 1 minute, gets pseudo-boehmite N
2With gama-alumina A
2Table 1 has provided N
2And A
2Physico-chemical property.
Example 3
Prepare gama-alumina by method provided by the invention.
Method by example 1 prepares pseudo-boehmite and gama-alumina, and different is to replace the alkaline matter sodium metaaluminate with alkaline matter potassium hydroxide, makes slurry pH value rise to 9.8 at 3 minutes, gets pseudo-boehmite N
3With gama-alumina A
3Table 1 has provided N
3And A
3Physico-chemical property.
Example 4
Prepare gama-alumina by method provided by the invention.
Method by example 1 prepares pseudo-boehmite and gama-alumina, and different is with the aqueous ammonia to replace alkaline matter sodium aluminate solution of concentration 2 weight %, makes slurry pH value rise to 9.8 in 7 minutes, gets pseudo-boehmite N
4With gama-alumina A
4Table 1 has provided N
4And A
4Physico-chemical property.
Example 5
Prepare gama-alumina by method provided by the invention.
Method by example 1 prepares pseudo-boehmite and gama-alumina, and different is to replace the alkaline matter sodium aluminate solution with the alkaline matter volatile salt, makes the pH value of slurries rise to 9.5 within 9 minutes, gets pseudo-boehmite N
5With gama-alumina A
5Table 1 has provided N
5And A
5Physico-chemical property.
Table 1
| Example number | 1 | 2 | 3 | 4 | 5 | |
| Pseudo-boehmite | The pseudo-boehmite numbering | N 1 | N 2 | N 3 | N 4 | N 5 |
| Intend thin water aluminium content, weight % | 79 | 81 | 83 | 80 | 77 | |
| Alumina trihydrate content, weight % | 0 | 0 | 0 | 0 | 0 | |
| Relative crystallinity, % | 85 | 87 | 89 | 87 | 83 | |
| Alkali metal oxide content, weight % | 0.08 | 0.11 | 0.13 | 0.05 | 0.04 | |
| γ | aluminum oxide | Gama-alumina | A 1 | A 2 | A 3 | A 4 | A 5 |
| Pore volume, milliliter/gram | 0.55 | 0.56 | 0.58 | 0.67 | 0.73 | |
| Specific surface, rice 2/ gram | 281 | 274 | 269 | 256 | 258 | |
| Relative crystallinity, % | 86 | 86 | 87 | 86 | 81 | |
Example 6
Prepare gama-alumina by method provided by the invention.
With 1.5 liters of concentration is 60 gram Al
2O
3/ liter sodium aluminate solution place one 2 liters one-tenth glue jar, 60 ℃ of initial temperatures, feeding carbon dioxide content from pot bottom is carbonic acid gas and the Air mixing gas of 90 volume %, the flow of gas mixture is 1.5 meters
3/ hour, to react 15 minutes, the pH value drops to 8.8, and this moment, temperature of reaction was 73 ℃, stopped into the glue reaction, added yellow soda ash rapidly, made slurry pH value rise to 11.0 in 9 minutes.Temperature is risen to 90 ℃, aging 45 minutes, filter, with 20 times of 90 ℃ of deionized water wash four times, 110 ℃ of oven dry must pseudo-boehmite N
6, get part and obtain pseudo-boehmite in 850 ℃ of roastings 2 hours, get gama-alumina A
6Table 2 has provided N
6And A
6Physico-chemical property.
Example 7
Prepare gama-alumina by method provided by the invention.
Method by example 6 prepares pseudo-boehmite and gama-alumina, and the concentration of different is sodium aluminate solution is 80 gram Al
2O
3/ liter, react after 20 minutes the pH value and reduce to and promptly stopped into the glue reaction at 9.3 o'clock, must intend book diaspore N
7With gama-alumina A
7Table 2 has provided N
7And A
7Physico-chemical property.
Example 8
Prepare gama-alumina by method provided by the invention.
Method by example 6 prepares pseudo-boehmite and gama-alumina, and the concentration of different is sodium aluminate solution is 40 gram Al
2O
3/ liter, 30 ℃ of initial temperatures of reaction reacts after 20 minutes the pH value and are reduced to 7.8, and temperature of reaction at this moment is 45 ℃.The add-on of yellow soda ash made slurry pH value rise to 10.20 in 7 minutes.80 ℃ of aging temperatures, digestion time 2 hours gets pseudo-boehmite N
8With gama-alumina A
8Table 2 has provided N
8And A
8Physico-chemical property.
Example 9
Prepare gama-alumina by method provided by the invention.
Method by example 6 prepares pseudo-boehmite and gama-alumina, and different is that aging temperature is 33 ℃, and washing is 33 ℃ with the deionized water temperature, gets pseudo-boehmite N
9With gama-alumina A
9Table 2 has provided N
9And A
9Physico-chemical property.
Table 2
| Example number | 6 | 7 | 8 | 9 | |
| Pseudo-boehmite | The pseudo-boehmite numbering | N 6 | N 7 | N 8 | N 9 |
| Intend thin water aluminium content, weight % | 96 | 97 | 92 | 81 | |
| Alumina trihydrate content, weight % | 0 | 0 | 0 | 0 | |
| Relative crystallinity, % | 105 | 107 | 98 | 88 | |
| Sodium oxide content, weight % | 0.03 | 0.04 | 0.09 | 0.12 | |
| γ | aluminum oxide | Gama-alumina | A 6 | A 7 | A 8 | A 9 |
| Pore volume, milliliter/gram | 0.83 | 0.71 | 1.35 | 1.09 | |
| Specific surface, rice 2/ gram | 229 | 247 | 188 | 203 | |
| Relative crystallinity, % | 102 | 104 | 96 | 86 | |
Example 10
Prepare gama-alumina by method provided by the invention.
Become in the glue jar to add 150 ml deionized water in advance at one 400 milliliters, 30 ℃ of initial deionized water temperature, at carbonic acid gas and the Air mixing gas of the bottom of jar feeding carbon dioxide content 35 volume %, mixed gas flow is 0.7 meter
3/ hour, feeding concentration from the top of jar is 100 gram Al
2O
3/ liter sodium aluminate solution, make sodium aluminate solution and gas mixture counter current contact, the flow of sodium aluminate solution is 10 ml/min, becoming the glue process pH value is 8.2 ± 0.2, temperature of reaction maintains 40 ± 2 ℃, open into the valve of glue pot bottom after 15 minutes, making the slurries of generation flow into one, to fill 200 milliliters of temperature in advance be in 35 ℃ the digestion tank of deionized water, and effusive speed makes into liquid level in the glue jar and neither rises and also do not descend.And the speed adding concentration with 2 ml/min is 50 gram Al
2O
3/ liter the alkaline matter sodium aluminate solution, the pH value of adjusting slurries in the digestion tank remains on 10.0 ± 0.1, temperature maintenance is at 40 ± 2 ℃.Collect after 30 minutes, the slurries that become glue to generate are switched in another same digestion tank, simultaneously the alkaline matter sodium aluminate solution is switched in this digestion tank.With slurries in first digestion tank under 40 ± 2 ℃ temperature aging 4 hours, filter, with 20 times 90 ℃ deionized water wash 2 times, 120 ℃ dry pseudo-boehmite N
10Get the pseudo-boehmite N that part obtains
10650 ℃ of roastings 3 hours, get pseudo-boehmite N
10With gama-alumina A
10Table 3 has provided N
10And A
10Physico-chemical property.
Example 11
Prepare gama-alumina by method provided by the invention.
Method by example 10 prepares pseudo-boehmite and gama-alumina, and the temperature that different is is controlled to the glue reaction is 65 ± 2 ℃, and the temperature when being gathered into the slurries that the glue reaction generates in the digestion tank is 65 ± 2 ℃, 75 ± 2 ℃ of aging temperatures, pseudo-boehmite N
11With gama-alumina A
11Table 3 has provided N
11And A
11Physico-chemical property.
Example 12
Prepare gama-alumina by method provided by the invention.
Method by example 10 prepares pseudo-boehmite and gama-alumina, and different is to change the alkaline matter sodium aluminate solution into the alkaline matter sodium carbonate solution, and sodium carbonate solution concentration is 50 grams per liters, and adding speed is 8 ml/min, gets pseudo-boehmite N
12With gama-alumina A
12Table 3 has provided N
12And A
12Physico-chemical property.
Example 13
Prepare gama-alumina by method provided by the invention.
Method by example 10 prepares pseudo-boehmite and gama-alumina, and different is to change the alkaline matter sodium aluminate solution into alkaline matter ammoniacal liquor, and ammonia concn is 5 weight %, and adding speed is 1.2 ml/min, gets pseudo-boehmite N
13With gama-alumina A
13Table 3 has provided N
13And A
13Physico-chemical property.
Example 14
Prepare gama-alumina by method provided by the invention.
Method by example 10 prepares pseudo-boehmite and gama-alumina, and different to be into the glue reaction be 50 to restrain Al with the concentration of sodium aluminate solution
2O
3/ liter, flow is 24 ml/min, and gas concentration lwevel is 75 volume % in the gas mixture, and flow is 0.33 meter
3/ hour, get pseudo-boehmite N
14With gama-alumina A
14Table 3 has provided N
14And A
14Physico-chemical property.
Example 15
Prepare gama-alumina by method provided by the invention.
Method by example 10 prepares pseudo-boehmite and gama-alumina, and the flow of different is gas mixture is 0.85 meter
3/ hour, process pH value is 7.0 ± 0.2, is 2.4 ml/min as the flow of the sodium aluminate solution of alkaline matter, pseudo-boehmite N
15With gama-alumina A
15Table 3 has provided N
15And A
15Physico-chemical property.
Example 16
Prepare gama-alumina by method provided by the invention.
Method by example 1 prepares pseudo-boehmite and gama-alumina, different be into do not add alkaline matter after the glue reaction finishes, but filter rapidly, filter cake is with twice of 20 times 90 ℃ deionized water wash, the deionized water of cake after the washing with 10 times mixed, wore out 4 hours, filter at 90 ℃.Other conditions get pseudo-boehmite N with example 1
16With gama-alumina A
16Table 3 has provided N
16And A
16Physico-chemical property.
Table 3
| Example number | 10 | 11 | 12 | 13 | 14 | 15 | 16 | |
| Pseudo-boehmite | The pseudo-boehmite numbering | N 10 | N 11 | N 12 | N 13 | N 14 | N 15 | N 16 |
| Intend thin water aluminium content, weight % | 81 | 90 | 83 | 84 | 80 | 78 | 80 | |
| Alumina trihydrate content, weight % | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
| Relative crystallinity, % | 88 | 98 | 91 | 93 | 87 | 86 | 88 | |
| Sodium oxide content, weight % | 0.11 | 0.05 | 0.12 | 0.08 | 0.10 | 0 | 0 | |
| γ | aluminum oxide | Gama-alumina | A 10 | A 11 | A 12 | A 13 | A 14 | A 15 | A 16 |
| Pore volume, milliliter/gram | 0.69 | 0.73 | 1.04 | 0.95 | 0.71 | 0.88 | 1.55 | |
| Specific surface, rice 2/ gram | 258 | 248 | 195 | 205 | 238 | 237 | 323 | |
| Relative crystallinity, % | 87 | 95 | 89 | 90 | 85 | 84 | 85 | |
Comparative Examples 1
The preparation of reference gama-alumina.
With 1.5 liters of concentration is 60 gram Al
2O
3/ liter sodium aluminate solution place 2 liters to become the glue jars, feed carbonic acid gas and the Air mixing gas of carbon dioxide content 35 volume % from pot bottom, the flow of gas mixture is 0.9 meter
3/ hour, 30 ℃ of initial temperatures of reaction reacts that pH reduces to 10.50 after 20 minutes, and temperature of reaction is 41 ℃ at this moment, stop into the glue reaction, temperature is risen to 95 ℃, aging 4 hours, filter, with 20 times 90 ℃ deionization washings 4 times, 120 ℃ of oven dry get reference pseudo-boehmite NB
1, 600 ℃ of roastings got reference gama-alumina AB in 4 hours
1Table 4 has provided NB
1And AB
1Physico-chemical property.CN1250746A accompanying drawing 2 has provided pseudo-boehmite NB
1Amplify 50,000 times electromicroscopic photograph.
Comparative Examples 2
The preparation of reference gama-alumina.
The one-tenth glue reaction end pH value that contrasts 1 is reduced to 8.5, and the reaction times is 55 minutes, and other condition is constant, dried product NB
2Through X light analysis is dawsonite (NaAl (OH)
2CO
3), the aluminum oxide AB that obtains after the roasting
2Physico-chemical property list in the table 4.
Comparative Examples 3
The preparation of reference gama-alumina.
Do not add the alkaline matter sodium metaaluminate in the example 10 and adjust the pH value of slurries, other condition is constant, dried product NB
3Through X light diffracting analysis is dawsonite, the aluminum oxide AB that obtains after the roasting
3Physico-chemical property list in the table 4.
Comparative Examples 4
The preparation of reference gama-alumina.
Method by example 10 prepares pseudo-boehmite and gama-alumina, and the flow of different is gas mixture is 0.45 meter
3/ hour, process pH value is controlled at 10.5 ± 0.1, does not add the alkaline matter sodium aluminate solution, gets the NB of pseudo-boehmite
4With gama-alumina AB
4NB
4And AB
4Physico-chemical property list in the table 4.
Table 4
| Example number | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | |
| Dried product exhibited | The dried product exhibited numbering | NB 1 | NB 2 | NB 3 | NB 4 |
| Intend thin water aluminium content, weight % | 96 | - | - | 83 | |
| Alumina trihydrate content, weight % | 0 | - | - | 0 | |
| Relative crystallinity, % | 101 | - | - | 89 | |
| Sodium oxide content, weight % | 0.15 | - | - | 0.17 | |
| The roasting after product | Roasting after product numbering | AB 1 | AB 2 | AB 3 | AB 4 |
| Pore volume, milliliter/gram | 0.45 | 0.07 | 0.11 | 0.43 | |
| Specific surface, rice 2/ gram | 275 | 28 | 41 | 281 | |
Claims (10)
1. the preparation method of a gama-alumina, this method comprises a kind of pseudo-boehmite of roasting, it is characterized in that, described pseudo-boehmite adopts following method preparation: sodium metaaluminate or sodium aluminate solution are contacted with carbonated gas, intermittence or successive mode to become glue, the aging pseudo-boehmite that obtains, isolate solid product, washing is also dry, wherein, described gelatigenous endpoint pH or process pH value are controlled in 6～9.5 the scope, become the time or the residence time of glue reaction to be less than 40 minutes, become 10～100 ℃ of the temperature of glue reaction, become the glue reaction to finish the back and add alkaline matter rapidly, make the pH value of slurries rise to 9.5～11.5 or carry out solid-liquid separation rapidly and wash.
2. method according to claim 1 is characterized in that, the concentration of described sodium metaaluminate or sodium aluminate solution be 5～120 the gram aluminum oxide/liter.
3. method according to claim 1 is characterized in that, the content of carbonic acid gas is greater than 20 volume % in the described carbonated atmosphere.
4. method according to claim 1 is characterized in that, the temperature of described one-tenth glue reaction is 10～80 ℃.
5. method according to claim 1 is characterized in that, described terminal point pH or process pH value are controlled at 6.5～9.3.
6. method according to claim 1 is characterized in that, the time or the residence time of described one-tenth glue reaction are no more than 25 minutes.
7. method according to claim 1 is characterized in that, described alkaline matter is selected from one or more in mineral alkali, organic bases and their aqueous solution.
8. method according to claim 7, it is characterized in that described alkaline matter is selected from one or more in alkali-metal oxyhydroxide, meta-aluminate, carbonate, supercarbonate and volatile salt, ammoniacal liquor, water-soluble amine, urea, pyridine and their aqueous solution.
9. method according to claim 1 is characterized in that, the temperature of described roasting pseudo-boehmite is 500～900 ℃, and roasting time is 2～8 hours.
10. method according to claim 9 is characterized in that, the temperature of described roasting pseudo-boehmite is 550～850 ℃, and roasting time is 3～6 hours.
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