CN1188216C - Method for preparing alumina supporter - Google Patents
Method for preparing alumina supporter Download PDFInfo
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- CN1188216C CN1188216C CNB021331340A CN02133134A CN1188216C CN 1188216 C CN1188216 C CN 1188216C CN B021331340 A CNB021331340 A CN B021331340A CN 02133134 A CN02133134 A CN 02133134A CN 1188216 C CN1188216 C CN 1188216C
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- pseudo
- boehmite
- alumina supporter
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Abstract
The present invention discloses a method for preparing an alumina supporter. The method comprises: two different kinds of pseudo-boehmite solid elastomer powder is uniformly mixed, and then, the mixture is peptized, shape, dried and calcined to prepare the alumina supporter, wherein the first kind of pseudo-boehmite is characterized in that the pore volume is from 0.50 ml/g to 0.80 ml/g, and the added proportion accounts for 5w% to 50w% of the charged Al2O3; the second kind of pseudo-boehmite is characterized in that the pore volume is from 0.85 ml/g to 1.50 ml/g. With the method, no special environmental pollution occurs in the process of preparing the pseudo-boehmite solid elastomer, the pore diameters of the prepared alumina supporters are respectively concentrated in the range of 6 nm to 35 nm and the range of 100 nm to 2000 nm, and the prepared alumina supporter has high intensity and low abrasion rate. The alumina supporter prepared by the method can be used as a catalyst supporter in the process of producing heavy petroleum hydrogenating protective agents, demetallization catalysts and diffusion controlled reactions.
Description
Technical field
The present invention relates to a kind of preparation method of alumina supporter, particularly the reaction process structure of double peak holes catalyzer of heavy-oil hydrogenation protective material and catalyst for demetalation and the diffusion control preparation method of alumina supporter.
Background technology
At present; it is carrier that the reaction process of preparation hydrogenation protecting agent and catalyst for demetalation and diffusion control adopts large pore volume, wide-aperture structure of double peak holes aluminum oxide with catalyzer more; make it both have the macropore that is used for the metal oxide molecular migration, the aperture of the katalysis of providing is provided again.Introduce alumina preparation method as institutes such as CN1129606A, CN1103009A, all adopting different alumina dry glues is raw material, and big bore portion obtains by adding various pore-forming materials, and little bore portion is determined by the precursor character of aluminum oxide.So-called aperture bore dia is at 6nm～35nm, and its effect provides catalysis and the required surface of metal deposition; So-called macropore bore dia is many more than 100nm, is used for the reactant molecule passage and the sedimentary place of impurity of migration rapidly, and it does not provide more surface to catalysis, and diffusion and catalyzer that such pore structure helps reactant keep the long lifetime.
CN 1047957C has introduced a kind of preparation method of alumina supporter, this method adopts the dried glue of the pseudo-boehmite of two or more different material path of preparing, wherein contains the pseudo-boehmite dry glue powder of a kind of aluminum chloride-ammonia liquor neutralization process preparation at least.This dry glue powder uses hydrochloric acid, ammoniacal liquor etc. to be corrosive and toxic substance in preparation process, and hydrochloric acid is very serious to equipment corrosion, in the washings, and NH
+ 4Content is high, and is quite severe to water pollution; This method adopts repeatedly making beating washing, causes that product yield is lower, water consumption is big, and chloride ion content reaches about 1% in the filter cake.The dried adhesive process process of aluminium complexity, cost with the preparation of this method are higher, and the dried glue of aluminium that adopts this method preparation is that the price of alumina supporter of feedstock production is also higher.The heavy oil catalyst for demetalation is disposable products, and life cycle is shorter, and non-renewable utilization requires its preparation cost quite cheap, and the catalyzer cost that the alumina supporter that adopts this method to prepare is produced can be than higher.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the invention is to provide a kind of preparation to have the method for alumina supporter.The alumina supporter that adopts this method to prepare has large pore volume, wide aperture, high strength, low wear rate and characteristics cheaply.
It is raw material that alumina supporter of the present invention can be selected two kinds of pseudo-boehmites for use, the mixing solutions that adds an amount of mineral acid, organic acid or two kinds of acid, under whipped state, make flowability pasty state slurries preferably, the moulding process path of preparing by routine goes out alumina supporter of the present invention then.
The used pseudo-boehmite of the present invention can be mainly to be sodium metaaluminate by alkaline matter, acid mainly is aluminum nitrate, Tai-Ace S 150, carbonic acid gas or nitric acid, carry out neutralization reaction by suitable pairing, make pseudo-boehmite, neutralization reaction of the present invention is: aluminum nitrate+sodium metaaluminate, Tai-Ace S 150+sodium metaaluminate, nitric acid+sodium metaaluminate, carbonic acid gas+sodium metaaluminate etc.Preferably select the pseudo-boehmite of Tai-Ace S 150+sodium metaaluminate, carbonic acid gas+sodium metaaluminate method preparation for use.The used pseudo-boehmite of the present invention is determined by indexs such as relative crystallinity, pore volume, size-grade distribution.The relative crystallinity of pseudo-boehmite is to serve as with reference to being decided to be 100% with the SB dry glue powder that U.S. Condia company produces, and the test powder obtains the result in contrast.
The pseudo-boehmite of above two kinds of methods preparation is divided into two kinds, and its character is as shown in table 1.
The character of table 1 pseudo-boehmite
| First kind of pseudo-boehmite | Second kind of pseudo-boehmite | |
| Relative crystallinity, % | 65～100 | 45～60 |
| Size distribution, % | 0.04～15.65 μ m particles account for 75%～100% | 15.65～61.00 μ m particles account for 10%～40% |
| Pore volume, ml/g | 0.50～0.80 | 0.85～1.50 |
| Gibbsite content, m% | ≤3 | ≤3 |
The best physico-chemical property of described pseudo-boehmite is as shown in table 2.
The best physico-chemical property of table 2 pseudo-boehmite
| First kind of pseudo-boehmite | Second kind of pseudo-boehmite | |
| Relative crystallinity, % | 70～90 | 50～60 |
| Size distribution, % | 0.04～15.65 μ m particles account for 85%～98% | 15.65～61.00 μ m particles account for 15%～35% |
| Pore volume, ml/g | 0.60～0.75 | 0.90～1.30 |
| Gibbsite content, m% | ≤3 | ≤3 |
It is raw material that alumina supporter of the present invention is selected two kinds with low cost, that environmental pollution is little pseudo-boehmites for use.Two kinds of different pseudo-boehmites are mixed, add acidic solution,, become mobile pasty mixture through peptization as nitric acid and/or acetic acid water solution, and then through the balling-up of oil ammonia column forming method or through the extrusion moulding slivering, drying, roasting then can make alumina supporter of the present invention again.
First kind of pseudo-boehmite has formability preferably, can provide the aperture of a certain amount of bore dia between 6nm～35nm simultaneously; Second kind of pseudo-boehmite formability is relatively poor, but the aperture of bore dia between 6nm～35nm can be provided simultaneously, importantly also has the macropore of more bore dia between 100nm～2000nm.Have higher mechanical strength by adjusting the blending ratio of first kind of pseudo-boehmite and second kind of pseudo-boehmite, can making, wear rate is low, the bimodal porous aluminum oxide carrier that appropriate bore distributes.And physico-chemical properties such as the large and small boring ratio example of the bulk density of this kind alumina supporter can be in a big way modulation flexibly.Along with the increase of first kind of pseudo-boehmite add-on, the aperture ratio of carrier, bulk density, intensity increase, and rate of wear reduces.
The preparation method of alumina supporter of the present invention is: take by weighing a certain amount of first kind of pseudo-boehmite dry glue powder and second kind of pseudo-boehmite dry glue powder of surplus corresponding proportion.In the peptization jar, add nitric acid and/or aqueous acetic acid, stir the dry glue powder that will weigh up and add, in the peptization jar, mix slurries in the pasty state, then in oil column balling-up or in banded extruder extrusion, drying, roasting then can make alumina supporter again.
In preparation process of the present invention:
The add-on of (1) first kind of pseudo-boehmite dry glue powder is Al
2O
35w%～the 50w% of charging capacity is preferably in 10w%～40w%, and surplus is second kind of pseudo-boehmite dry glue powder.
(2) peptization is selected nitric acid and/or acetic acid for use with acid, and consumption is Al
2O
30.1w%～the 10w% of charging capacity.
(3) peptization time (being churning time) is 0.5～3 hour.
(4) time of drying and temperature: drying is 8～12 hours under 60～120 ℃ of conditions.
(5) roasting time and temperature: heat-up rate was 100～240 ℃/hour in retort furnace, 550～1200 ℃ of constant temperature 1～5 hour.
By the alumina supporter that the inventive method makes, its specific surface area is 50m
2/ g～300m
2/ g, pore volume are 0.55ml/g～1.50ml/g, and crushing strength 25N/ grain～110N/ grain, wear rate are 0.15w%～1.0w%.Bimodal bore dia concentrates on 6nm～35nm and two zones of 100nm～2000nm respectively, and the macropore of 100nm～2000nm accounts for total pore volume 15%～60%.
Alumina supporter by the inventive method preparation has following advantage:
(1) no special environmental pollution in the preparation process of the dried glue of pseudo-boehmite;
(2) bimodal bore dia concentrates on 6nm～35nm and two zones of 100nm～2000nm respectively;
(3) the carrier physico-chemical property can be adjusted flexibly, helps making suitable alumina supporter;
(4) preparation cost of the dried glue of pseudo-boehmite is cheap;
(5) alumina supporter intensity height, rate of wear is low, is fit to the reaction process structure of double peak holes catalyzer alumina supporter of heavy-oil hydrogenation protective material and catalyst for demetalation and diffusion control.
Embodiment
The physico-chemical property of testing used several pseudo-boehmites is as shown in table 3.
The physico-chemical property of several pseudo-boehmites of table 3
The preparation process of testing used several pseudo-boehmites is as follows:
| Dry glue powder | A | B-1 | B-2 | B-3 | |
| Relative crystallinity, % | 82 | 61 | 58 | 52 | |
| Size distribution % | 0.04～15.65μm | 91.3 | |||
| 15.65～61.0μm | 19 | 24 | 14.6 | ||
| Pore volume, ml/g | 0.76 | 0.98 | 1.40 | 0.97 | |
| Gibbsite content, m% | 2.6 | 0.6 | 0.9 | 2.8 | |
With alum liquor and sodium aluminate solution (is 26g/100ml in aluminum oxide concentration), and in the stream adding 100 liter stirring tanks, adjusting the interior pH value of still is 7.5, holding temperature, pH value are constant, after 45 minutes, stop the alum liquor charging, adjust pH value to 10.0 in the still with sodium aluminate solution; Slurries are pumped in the washable plate-and-frame filter press then, the elimination mother liquor makes filter cake be full of sheet frame, with industrial water purification washing pseudo-boehmite filter cake, removes foreign ion again; At last filter cake is placed 115 ℃ dry 20 hours of baking oven, can make B-1 pseudo-boehmite dry glue powder.
With alum liquor and sodium aluminate solution (is 19g/100ml in aluminum oxide concentration), and in the stream adding 100 liter stirring tanks, adjusting the interior pH value of still is 7.2, holding temperature, pH value are constant, after 45 minutes, stop the alum liquor charging, adjust pH value to 10.0 in the still with sodium aluminate solution; Slurries are pumped in the washable plate-and-frame filter press then, the elimination mother liquor makes filter cake be full of sheet frame, with industrial water purification washing pseudo-boehmite filter cake, removes foreign ion again; At last filter cake is placed 115 ℃ dry 20 hours of baking oven, can make B-2 pseudo-boehmite dry glue powder.
Pseudo-boehmite B-3 is by the preparation of the method for the embodiment among the Chinese patent CN 98110593.9 10.
Pseudo-boehmite A is by the preparation of the method for the embodiment among the Chinese patent CN 98110593.9 1.
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
Take by weighing pseudo-boehmite A dry glue powder 142.8g, pseudo-boehmite B-1 dry glue powder 571.2g, the aqueous nitric acid 820ml and the Glacial acetic acid 40g that add 1.5m%, stir into slurries, on the oil ammonia column shaped device, drip ball, the wet gel ball was descended dry 4 hours at 100 ℃, in stoving oven, reach 1000 ℃ with heat-up rate then with 200 ℃/hour, constant temperature 2 hours gets product.
Embodiment 2
Maturing temperature is 600 ℃, and other is described with embodiment 1.
Embodiment 3
Maturing temperature is 1150 ℃, and other is described with embodiment 1.
Embodiment 4
In embodiment 1, pseudo-boehmite B-1 dry glue powder changed into pseudo-boehmite B-3 dry glue powder 588.2g.Other is described with embodiment 1.
Embodiment 5
In embodiment 1, the quantitative change of pseudo-boehmite A powder is become 71.4g, pseudo-boehmite B-1 becomes 642.6g.Other is described with embodiment 1.
Embodiment 6
In embodiment 1, the quantitative change of pseudo-boehmite A powder is become 71.4g, pseudo-boehmite B-3 is 661.8g.Other is described with embodiment 1.
Embodiment 7
In embodiment 1, the quantitative change of pseudo-boehmite A powder is become 214.3g, pseudo-boehmite B-1 is 499.7g.Other is described with embodiment 1.
Embodiment 8
In embodiment 1, the quantitative change of pseudo-boehmite A powder is become 214.3g, pseudo-boehmite B-3 is 514.7g.Other is described with embodiment 1.
Embodiment 9
Changing the B-1 dry glue powder among the embodiment 1 into the B-2 add-on is 588g.Other is described with embodiment 1.
Embodiment 10
In embodiment 1, the quantitative change of pseudo-boehmite A powder is become 71.4g, it is 688g that pseudo-boehmite B-1 dry glue powder changes the B-2 add-on into.Other is described with embodiment 1.
Embodiment 11
In embodiment 1, the quantitative change of pseudo-boehmite A powder is become 214.3g, it is 534.8g that pseudo-boehmite B-1 dry glue powder changes the B-2 add-on into.Other is described with embodiment 1.
The physico-chemical property of table 4 alumina supporter
| Project | Embodiment | |||||
| Numbering | 1 | 2 | 3 | 4 | 5 | 6 |
| Bulk density, g/ml | 0.49 | 0.46 | 0.51 | 0.48 | 0.45 | 0.44 |
| Crushing strength, the N/ grain | 48 | 44 | 48 | 44 | 37 | 35 |
| Wear rate, m% | 0.4 | 0.4 | 0.4 | 0.5 | 0.8 | 0.8 |
| Specific surface, m 2/g(BET) | 167 | 278 | 108 | 186 | 161 | 181 |
| Total pore volume, ml/g (mercury penetration method) | 0.91 | 1.04 | 0.68 | 0.89 | 1.01 | 0.88 |
| Pore distribution, % | ||||||
| 6nm～35nm | 58 | 76 | 61 | 51 | 57 | 59 |
| 100nm～2000nm | 32 | 17 | 20 | 20 | 39 | 20 |
The physico-chemical property of continuous table 4 alumina supporter
| Project | Embodiment | ||||
| 7 | 8 | 9 | 10 | 11 | |
| Bulk density, g/ml | 0.54 | 0.51 | 0.46 | 0.42 | 0.51 |
| Crushing strength, the N/ grain | 61 | 56 | 41 | 31 | 44 |
| Wear rate, m% | 0.3 | 0.3 | 0.4 | 1.0 | 0.4 |
| Specific surface, m 2/g(BET) | 171 | 178 | 161 | 166 | 1.62 |
| Total pore volume, ml/g (mercury penetration method) | 0.88 | 0.91 | 1.02 | 1.31 | 0.94 |
| Pore distribution, % | |||||
| 6nm～35nm | 63 | 62 | 59 | 44 | 62 |
| 100nm～2000nm | 30 | 21 | 37 | 48 | 24 |
Claims (6)
1, a kind of preparation method of alumina supporter is characterized in that two kinds of different pseudo-boehmite dry glue powder uniform mixing, carries out peptization, moulding, drying, roasting then and makes described alumina supporter; Described two kinds of different pseudo-boehmites, wherein the pore volume of first kind of pseudo-boehmite is between 0.50ml/g～0.80ml/g, and relative crystallinity is that 65%～100%, 0.04 μ m～15.65 μ m particles account for 75%～100%, and additional proportion accounts for the Al that feeds intake
2O
35w%～50w%; The pore volume of second kind of pseudo-boehmite is between 0.85ml/g～1.50ml/g, and relative crystallinity is that 45%～60%, 15.65 μ m～61.00 μ m particles account for 10%～40%.
2, the preparation method of alumina supporter according to claim 1 is characterized in that described first kind of pseudo-boehmite additional proportion accounts for the Al that feeds intake
2O
310w%～40w%.
3, the preparation method of alumina supporter according to claim 1, the relative crystallinity that it is characterized in that described first kind of pseudo-boehmite is 70%～90%, 0.04 μ m～15.65 μ m particles account for 85%～98%, pore volume is between 0.60ml/g～0.75ml/g.
4, the preparation method of alumina supporter according to claim 1, the relative crystallinity that it is characterized in that described second kind of pseudo-boehmite is 50%～60%, 15.65 μ m～61.00 μ m particles account for 15%～35%, pore volume is between 0.90ml/g～1.30ml/g.
5, the preparation method of alumina supporter according to claim 1, it is characterized in that described two kinds of different pseudo-boehmite dry glue powders, all be selected from the pseudo-boehmite that obtains by sodium metaaluminate and carbonic acid gas, Tai-Ace S 150, nitric acid or aluminum nitrate neutralization reaction.
6, the preparation method of alumina supporter according to claim 1 is characterized in that the mixture nitric acid and/or the moulding of aqueous acetic acid peptization of two kinds of different pseudo-boehmite dry glue powders, and the consumption of acid is Al
2O
30.1w%～the 10.0w% of charging capacity.
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|---|---|---|---|
| CNB021331340A CN1188216C (en) | 2002-10-10 | 2002-10-10 | Method for preparing alumina supporter |
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| CN1188216C true CN1188216C (en) | 2005-02-09 |
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-
2002
- 2002-10-10 CN CNB021331340A patent/CN1188216C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962060A (en) * | 2012-11-22 | 2013-03-13 | 北京北大先锋科技有限公司 | Catalyst for synthetizing dimethyl oxalate and preparation method thereof |
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