CN1070385A - The preparation method of phosphorated aluminiferous collosol - Google Patents
The preparation method of phosphorated aluminiferous collosol Download PDFInfo
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- CN1070385A CN1070385A CN91108724.9A CN91108724A CN1070385A CN 1070385 A CN1070385 A CN 1070385A CN 91108724 A CN91108724 A CN 91108724A CN 1070385 A CN1070385 A CN 1070385A
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Abstract
A kind of binding agent that is applicable to the crystalline aluminosilicate zeolite---the preparation method of phosphorated aluminiferous collosol.We's genealogy of law is with metallic aluminium, hydrochloric acid (or aluminum chloride) and ortho-phosphoric acid (or aluminium dihydrogen phosphate) mixing solutions, and reaction under certain conditions can make desired product.Than higher, its binding agent performance is better than the industrial binding agent that is usually used in catalytic cracking catalyst---aluminium colloidal sol by the phosphorated aluminiferous collosol pH of the present invention preparation, aluminium chlorine.
Description
The invention belongs to a kind of preparation method of colloidal sol containing chloride and aluminium, more particularly belong to a kind of preparation method of aluminium colloidal sol of chloride and phosphorus.
Colloidal sol containing chloride and aluminium (being called for short aluminium colloidal sol) has good adhesive property, is commonly used for zeolite catalyst, particularly the binding agent of high-content zeolite catalyst.But be to use chloride aluminium colloidal sol also to bring some problems: when the time as the hydrocarbon cracking catalyzer binding agent, if no dechlorination step in the catalyzer manufacturing processed, chloride catalyzer has in catalytic cracking unit in the presence of the water vapor, because the effusion of hydrogen chloride gas plays destruction to the lattice of cracking catalyst mesolite, activity of such catalysts is significantly descended, and can make the equipment component corrosion; Simultaneously, hydrogen chloride gas enters the severe contamination that causes environment behind the atmosphere.
In order to reduce with aluminium colloidal sol is the content of chlorine in the catalyzer of binding agent, and the US4458023 patent has increased calcination steps after the spraying drying in the zeolitic cracking catalyst manufacturing processed, and remaining chlorine is overflowed with the hydrogenchloride form.The shortcoming of this method is that hydrogenchloride has corrosive nature to roasting apparatus, and surrounding environment is still had pollution.
The US4542118 patent adopts the catalyzer after ammonia and the spraying drying to contact to the dechlorination that contains aluminium colloidal sol cracking catalyst, makes wherein hydrogenchloride and ammonia effect generation ammonia chloride, washes with water and removes.Still there is problem of environment pollution caused in this method, and operates also more complicated.
The purpose of this invention is to provide a kind of method for preparing new phosphorated aluminiferous collosol, the phosphorated aluminiferous collosol made from this method can be used as zeolite type crystalline aluminosilicate molecular sieve catalyst, particularly SiO
2/ Al
2O
3The binding agent of lower crystalline aluminosilicate molecular sieve catalyst, its performance is better than aluminium colloidal sol, thereby can reduce binding agent consumption in the catalyzer, overcomes the problem of using aluminium sol adhesive to bring.
The objective of the invention is to realize, promptly use metallic aluminium, hydrochloric acid (or aluminum chloride) and ortho-phosphoric acid (or aluminium dihydrogen phosphate) mixed solution to react the generation desired product under certain condition by following proposal.Concrete preparation method is as follows:
Metallic aluminium and water or phosphide solution are put into container, be heated to greater than 60 ℃, the mixed solution or the muriatic solution that added muriate and phosphide then in 1～4 hour react.Reaction conditions: 80～105 ℃ of temperature, best 93～98 ℃, 12～72 hours time, best 16～24 hours, question response reached desired aluminum concentration, cooled off, and filtered and promptly got desired product.If the aluminum concentration of product can concentrate less than 10 heavy %, concentrate condition: 80～105 ℃ of temperature, 0.5～4 hour time.
The composition of the phosphorated aluminiferous collosol that makes according to the present invention: Al concentration 8～12 heavy %, Cl concentration 4.5～9 heavy %, Al/Cl(is heavy) 1.2～1.8: 1, P 0.3～2 heavy %, Al/P(is heavy) 5～30: 1; PH 2.5～4.2.
In prior art, also mention phosphorated aluminiferous collosol and preparation process thereof, but because their purpose is different with the present invention, thereby preparation process is also different.For example in the US3544476 patent, metallic aluminium powder is added in the hydrochloric acid soln, adds phosphoric acid after 2 o'clock, wore out 30 minutes down at 80 ℃ again in reaction under 90 ℃.Products obtained therefrom is formed: Al 7.0 heavy %, Cl 11.22 heavy %, the suitable Al/Cl of basicity 59.4%(0.62: 1), PO
46.1 the suitable P 1.99 heavy % of heavy %().This product is as water conditioner, because this product is to use under diluted state, so its aluminum concentration is not had strict demand, basicity is also only required and reached 60～70%.
In the US4521343 patent, mention the powder of crystalline silica is dispersed in the mixed solution of aluminium colloidal sol and P contained compound, the P/Al(mol of this mixed solution) is 1: 1 to 1: 100, aluminium colloidal sol is to be formed by metallic aluminium hydrolysis in acidic aqueous solution, its Al/Cl(is heavy) be 0.70～1.5: 1, used P contained compound is various inorganic and organic phosphides.The product that makes is the sorbent material as separation of fatty acids.Because the resistance to acid of crystalline silica is strong, therefore the PH to mixture does not propose special requirement.
In the US4629717 patent, emphasis is for producing the phosphorus modified aluminas on high surface.Its preparation method: be that metallic aluminium and hydrochloric acid are reacted generation aluminium colloidal sol down at 102 ℃, its aluminum concentration is 12.5%, and Al/Cl(is heavy) be 0.88: 1, phosphide is added in the aluminium colloidal sol then, add an amount of water again, making aluminum oxide and aluminum phosphate solid content therein is 25～30%.
Being shaped as of the metallic aluminium that the present invention is used approaches the globular aluminum shot, and its diameter is 6 ± 3mm, and purity is 95～99.7%, add-on should be aluminium consumption 110～220%, promptly add excessive aluminium.Aluminium excessive many more, speed of response is fast more, but excessive too many, product can go out muddy phenomenon.
The muriate that the present invention is used: (1) hydrochloric acid, chemical pure or technical pure all can, its concentration is 15～20 heavy %; (2) crystal aluminum chloride, chemical pure or technical pure, the liquor alumini chloridi of being prepared, the concentration of its chlorine is 15～20 heavy %.Their add-on should guarantee that the Al/Cl(of product is heavy) be 1.2～1.8: 1.If Al/Cl(is heavy)＜1.2: 1, this moment, aluminium colloidal sol contained a large amount of chlorine, as binding agent the time, increased the dechlorination burden of catalyzer; The PH of phosphorated aluminiferous collosol also can be lower than 2.5 on the other hand, when future and molecular sieve mix, the structure of molecular sieve is destroyed.But Al/Cl(is heavy) ratio also should not be too high, too highly makes speed of response slack-off, thereby in certain reaction times, compare with the aluminium colloidal sol of low aluminium chlorine ratio, its aluminum concentration is less, does not meet service requirements, and reaction product is prone to muddiness, and its adhesive property also can be affected.For the Al/Cl(that guarantees product weighs) be 1.2～1.8: 1, aluminium and muriate (in chlorine) feed ratio is that Al/Cl(is heavy) be 1.3～4.0: 1.
The used phosphide of the present invention comprises: (1) ortho-phosphoric acid, chemical pure or technical pure all can, its concentration is 42～82 heavy %; (2) aluminium dihydrogen phosphate, its material purity and preparation method see " inorganic chemicals industry ", [4] 8～12,1979, its Al concentration is 2.5～4.5 heavy %, P concentration is 10～13.5 heavy %.Their add-on depends on that the Al concentration, Al/Cl(of phosphorated aluminiferous collosol is heavy) ratio, PH etc., when product requires the Al/Cl(heavy) the ratio height, when Al concentration is big, its add-on can not be too high, otherwise the reaction times is very long, and the product that obtains is very muddy, thickness, this is because the superpolymer that generates sticks to the surface of aluminium, hinders Al and further dissolves.Test shows that the phosphorus concentration of phosphorated aluminiferous collosol of the present invention is controlled at 0.3～2 heavy %, and the feed ratio of aluminium and phosphide (in phosphorus) is that Al/P(is heavy) be 5～30: 1.
Can the water consumption when the present invention feeds intake bigger for making the binding agent relation that conforms with service requirements.Adopt bigger H
2O/Al(is heavy) ratio, help heat and mass, shorten the reaction times, but H
2The O/Al(weight) ratio is excessive, is prone to aluminum hydroxide precipitation, makes the reaction product muddiness.As the heavy % in product P＞1, can adopt bigger water aluminum ratio; Otherwise, then adopt less water aluminum ratio.The feed ratio of water of the present invention and aluminium is H
2O/Al(is heavy) be 5～8: 1.
Method of the present invention, can adopt interrupter method, also can adopt continuation method, promptly in reactor, place the amount of metallic aluminum grain, when going into operation, the phosphorated aluminiferous collosol for preparing with continuous processing or interrupter method is installing internal recycle, and progressively reactor is raised to the temperature of regulation, before phosphorated aluminiferous collosol enters reactor, constantly replenish the mixed solution of hydrochloric acid and phosphoric acid then, take out phosphorated aluminiferous collosol continuously from the top of reactor.Through after a while, need constantly to replenish aluminum shot, to keep bed certain altitude is arranged.
The invention has the advantages that:
1, ought partly replace the chlorine root with phosphate radical in aluminium colloidal sol, under the identical situation of total negatively charged ion equivalent, the pH value of phosphorated aluminiferous collosol will be higher than not phosphorated aluminium colloidal sol, the results are shown in following table:
The comparison of not phosphorous and phosphorated aluminiferous collosol performance
| Ⅰ | Ⅱ | |
| Reaction feeds intake: aluminum shot (gram) H 3PO 4+ HCl (gram equivalent) H 3PO 4: HCl (equivalence ratio) H 2O (milliliter) reaction times (hour) | 285.7 5.4 0:100 1140 10 10.22 7.10 / 0.037 1.26 3.10 | 285.7 5.4 25.7:74.3 1320 19 10.95 6.15 0.63 0.063 1.29 3.9 |
| Product property: Al, heavy % Cl, heavy % P, heavy % Fe, heavy % density, grams per milliliter PH |
This characteristic is very important for the binding agent as the zeolitic crystalline aluminosilicate molecular sieve catalyst.If the PH of aluminium colloidal sol is too low, when mixing, will make its lattice damage with the crystalline aluminosilicate molecular sieve, make the activity and the stability decreases of zeolite catalyst.The silica alumina ratio of molecular sieve is more little, and its resistance to acid is poor more, has improved the PH of aluminium colloidal sol now, and it is used as binding agent in wideer scope.
2, by the aluminium chlorine of the phosphorated aluminiferous collosol of the present invention preparation than higher, thereby reduced the content of the chlorine in the catalyzer.
3,, can make catalyzer through washing and its tear strength does not change with the phosphorated aluminiferous collosol of the present invention preparation binding agent as the crystalline aluminosilicate zeolite catalyst.
4, preparation technology of the present invention is simple, can utilize the equipment of original preparation aluminium colloidal sol, can also adopt continuous processing production.
Further demonstrate characteristics of the present invention below.
The analytical procedure that the present invention adopts:
1, the analysis GB3257.1-82 of aluminium, bauxite chemical analysis method, EDTA volumetric determination alumina amount.
2, the analysis GB3050-82 of chlorine, universal method-potentiometric titration that chloride content is measured in the inorganic chemical product.
3, the analysis GB3257.17-82 of phosphorus, bauxite chemical analysis method, molybdenum blue spectrophotometry are measured five phosphorus oxide.
4, the analysis GB6609.4-86 of iron, aluminum oxide chemical analysis method, phenanthrolene spectrphotometric method for measuring ferric oxide amount.
5, the analysis GB3257.9-82 of sodium, bauxite chemical analysis method, atomic absorption spectroscopy determination potassium oxide, sodium oxide amount.
Example 1
Aluminum shot 286 grams, 1245 milliliters of deionized waters are put into there-necked flask, are heated to 60 ℃.787 milliliters of 1: 1 chemical pure hydrochloric acid and 1: 1 chemical pure phosphoric acid are mixed for 37 milliliters mutually, progressively add in the there-necked flask, make and the aluminum shot reaction, in 3 hours, acid is added.Temperature of reaction is controlled at 90～95 ℃, reacts 16 hours.After question response finishes,, filter with the G-3 sinter funnel with the product cooling.
The remaining aluminum shot of reaction restrains through being weighed as 30, i.e. aluminium excessive 12 heavy %.
Product by analysis, the result is as follows: the heavy % of Al 9.02, Cl 6.7 heavy %, P 0.35 heavy %, Al/Cl(is heavy) 1.35: 1, Al/P(is heavy) 25.8: 1, Fe
2O
30.01 heavy %, Na
2O 0.0008 heavy %, PH 3.27.
Still keep water white transparency after the storage of this sample through the time more than 2 years.
Example 2
Aluminum shot 286 grams, 1320 milliliters of deionized waters are put into there-necked flask, are heated to 60 ℃.688 milliliters of 1: 1 chemical pure hydrochloric acid and 1: 1 chemical pure phosphoric acid are mixed for 63 milliliters mutually, progressively add in the there-necked flask, make and the aluminum shot reaction, in 3 hours, acid is added.Temperature of reaction is controlled at 90～95 ℃, coreaction 19 hours.Product is cooled to 60～70 ℃ afterwards, at G-3 sinter funnel inner filtration.
React remaining aluminum shot through being weighed as 48 grams, promptly aluminium excessive 20%.
Product contains by analysis: Al 12.10 heavy %, and Cl 6.43 heavy %, P 0.58%, Al/Cl(is heavy) 1.88: 1, Al/P(is heavy) 20.9: 1, Fe
2O
30.027 heavy %, Na
2O 0.001 heavy %, PH 3.75 is water white liquid.
After this sample was deposited through 3 years, still be water white transparency, do not have precipitation and occur.
Example 3
Aluminum shot 248 grams, 1480 milliliters of deionized waters are put into there-necked flask, are heated to 60 ℃.462 milliliters of 1: 1 chemical pure hydrochloric acid and 1: 1 chemical pure phosphatase 11 are mixed for 22 milliliters mutually, progressively add in the there-necked flask, make and the aluminum shot reaction, in 2 hours 45 minutes, acid is added.Temperature of reaction is controlled at 93～97 ℃, reacts 68 hours.Question response is cooled to 60～70 ℃ with product after finishing, and filters with the G-3 sinter funnel.React remaining aluminum shot through being weighed as 55 grams, i.e. aluminium excessive 28.5 heavy %.
Product contains by analysis: Al 8.55 heavy %, and Cl 4.51 heavy %, P 1.22 heavy %, Al/Cl(is heavy) 1.90: 1, Al/P(is heavy) 7.01: 1, Fe
2O
30.01 heavy %, PH 3.9.
This sample is a thick liquid, gelling voluntarily after placing for some time.
Example 4
Aluminium material 373 grams, 1480 milliliters of deionized waters are put into there-necked flask, are heated to 60 ℃.462 milliliters of 1: 1 chemical pure hydrochloric acid and 1: 1 chemical pure phosphatase 11 are mixed for 22 milliliters mutually, progressively add in the there-necked flask, make and the aluminum shot reaction, in 2 hours 45 minutes, acid is added.Temperature of reaction is controlled at 93～97 ℃, reacts 15 hours 50 minutes.Question response is cooled to 60～70 ℃ with product after finishing, and filters with the G-3 sinter funnel.Reacting remaining aluminum shot is 196 grams, and promptly aluminium is excessive is 110.7 heavy %.
Product contains Al 8.22 heavy % by analysis, Cl 4.62 heavy %, and P 1.20 heavy %, Al/Cl(is heavy) 1.78: 1, Al/P(is heavy) 6.85: 1, PH 3.97.
With example 3 comparisons, when aluminium excessive 28.5 heavy % were increased to 110.7 weight % when feeding intake, the reaction times foreshortened to 15.8 hours from 68 hours.
Example 5
Aluminum shot 372 grams, 1450 milliliters of deionized waters are put into there-necked flask, are heated to 60 ℃.509 milliliters of 1: 1 chemical pure hydrochloric acid and 1: 1 chemical pure phosphatase 11 are mixed for 10 milliliters mutually, progressively add in the there-necked flask, make and the aluminum shot reaction, in 2 hours 45 minutes, acid is added.Temperature of reaction is controlled at 93～97 ℃, reacts 22 hours.
Question response is cooled to 60～70 ℃ with product after finishing, and filters with the G-3 sinter funnel.
The remaining aluminum shot of reaction restrains through being weighed as 167, and promptly aluminium excessive 81.5%.
Product contains by analysis: Al 9.00 heavy %, and Cl 4.38 heavy %, P 1.04 heavy %, Al/Cl(is heavy) 2.05: 1, Al/P8.65: 1, Fe
2O
30.020 heavy %, Na
2O 0.001 heavy %, PH 4.35.
Example 6
Aluminum shot 250 grams, 800 milliliters of deionized waters, 71 milliliters of 85% chemical pure phosphoric acid are put into there-necked flask, are heated to 60 ℃.1: 1 industrial synthesis hydrochloric acid is progressively added in the there-necked flask for 950 milliliters, make it in 3 hours, to add acid and finish.Temperature of reaction is 95-100 ℃, coreaction 18 hours.Reaction is cooled to 60～70 ℃ with product after finishing, and filters with the G-3 sinter funnel.
Weigh to reacting remaining aluminum shot, get 37 grams, be i.e. aluminium excessive 17.4 heavy %.
Product contains by analysis: Al 10.9 heavy %, and Cl 8.49 heavy %, P 1.59 heavy %, Al/Cl(is heavy) 1.28: 1, Al/P(is heavy) 6.86: 1, Fe
2O
30.012 heavy %, Na
2O 0.0025 heavy %, PH2.68.
Example 7
Aluminum shot 373 grams, 1480 milliliters of deionized waters, aluminium dihydrogen phosphate (containing Al 4.5 heavy %, P 13.4 heavy %) 339 grams are put into there-necked flask, are heated to 60 ℃.1: 1 chemical pure hydrochloric acid is progressively added in the there-necked flask for 950 milliliters, make and the aluminum shot reaction, in 1 hour 50 minutes, acid is added.Temperature of reaction is controlled at 93～98 ℃, coreaction 16 hours.Question response is cooled to 60～70 ℃ with product after finishing, and filters with the G-3 sinter funnel.Reacting remaining aluminum shot is 110.7 grams, and promptly aluminium is excessive is 42.2 heavy %.
Contain Al 9.26 heavy % by analysis, Cl 5.5 heavy %, P 1.66 heavy %, Al/Cl(is heavy) 1.68, Al/P(is heavy) 5.58, Na
2The heavy % of O0.007, Fe
2O
30.020 heavy %, PH3.30.
This sample is taken by weighing 535 grams, be placed on the electric furnace and concentrate 20 minutes, weigh after the cooling, get sample 481 grams.
Contain Al 10.28 heavy % by analysis, Cl 6.05 heavy %, P 1.80 heavy %, Al/Cl(is heavy) 1.70: 1, Al/P(is heavy) 5.71: 1, Na
2O 0.007 heavy %, Fe
2O
30.022 heavy %, PH3.23.
Claims (6)
1, a kind of by metallic aluminium, the method of hydrochloric acid and ortho-phosphoric acid formulations prepared from solutions phosphorated aluminiferous collosol, it is characterized in that metallic aluminium and water or phosphide solution puts into container, be heated to greater than 60 ℃, mixed solution or the chloride soln that added muriate and phosphide in 1～4 hour reacts then, reaction conditions: 80～105 ℃ of temperature, 12～72 hours time, the add-on of raw material: the add-on of aluminium be aluminium consumption 110～220%, the feed ratio of aluminium and muriate (in chlorine) is Al/Cl (weight) 1.3～4.0: 1, the feed ratio of aluminium and phosphide (in phosphorus) is Al/P (weight) 5～30: 1, and water and aluminium feed ratio are H
2O/Al (weight) 5～8: 1, after cooling filter and promptly get desired product, if the aluminum concentration of product can concentrate 80～105 ℃ of thickening temperatures, 0.5～4 hour time when being lower than 10 weight %.
2, in accordance with the method for claim 1, it is characterized in that the shape of described metallic aluminium approaches spherical aluminum shot, its diameter 6 ± 3mm, the purity of aluminum shot is 95～99.7%.
3, in accordance with the method for claim 1, it is characterized in that described muriate is chemical pure or technical pure hydrochloric acid, its concentration is 15～20 heavy %.
4, in accordance with the method for claim 1, it is characterized in that described muriate is chemical pure or commercially pure crystal aluminum chloride, the liquor alumini chloridi of being prepared, the concentration of its chlorine is 15～20 heavy %.
5, in accordance with the method for claim 1, it is characterized in that described phosphide is chemical pure or technical pure ortho-phosphoric acid, its concentration is 42～82 heavy %.
6, in accordance with the method for claim 1, it is characterized in that described phosphide is an aluminium dihydrogen phosphate, its Al concentration is 2.5～4.5 heavy %, and P concentration is 10～13.5 heavy %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91108724.9A CN1029220C (en) | 1991-09-11 | 1991-09-11 | Method for preparation of phosphorated aluminiferous collosol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91108724.9A CN1029220C (en) | 1991-09-11 | 1991-09-11 | Method for preparation of phosphorated aluminiferous collosol |
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| CN1070385A true CN1070385A (en) | 1993-03-31 |
| CN1029220C CN1029220C (en) | 1995-07-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296279C (en) * | 2004-08-31 | 2007-01-24 | 中国石油化工股份有限公司 | Method for preparing colloidal sol containing chloride and aluminium |
| CN103523811A (en) * | 2013-09-22 | 2014-01-22 | 吉林市品前化工技术开发有限公司 | Method for preparing alumina sol by using byproduct acid liquor of methanol to olefin catalyst |
| CN105148985A (en) * | 2014-06-10 | 2015-12-16 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method thereof and application |
| CN105195217A (en) * | 2014-06-10 | 2015-12-30 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
| CN105195218A (en) * | 2014-06-10 | 2015-12-30 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
| CN105214739A (en) * | 2014-06-06 | 2016-01-06 | 中国石油化工股份有限公司 | Modified aluminium colloidal sol and preparation method thereof |
| CN105233856A (en) * | 2014-06-06 | 2016-01-13 | 中国石油化工股份有限公司 | Fluid catalytic cracking catalyst containing aluminum sol binder, and preparation method thereof |
| CN105268469A (en) * | 2014-06-10 | 2016-01-27 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, and preparation method and application thereof |
| CN105312068A (en) * | 2014-06-06 | 2016-02-10 | 中国石油化工股份有限公司 | Modified phosphorus-containing aluminum sol and preparation method thereof |
| CN107304332A (en) * | 2016-04-18 | 2017-10-31 | 中国石油天然气股份有限公司 | Phosphorus-containing aluminum sol and preparation method thereof |
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1991
- 1991-09-11 CN CN91108724.9A patent/CN1029220C/en not_active Expired - Fee Related
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| CN1296279C (en) * | 2004-08-31 | 2007-01-24 | 中国石油化工股份有限公司 | Method for preparing colloidal sol containing chloride and aluminium |
| CN103523811A (en) * | 2013-09-22 | 2014-01-22 | 吉林市品前化工技术开发有限公司 | Method for preparing alumina sol by using byproduct acid liquor of methanol to olefin catalyst |
| CN105312068B (en) * | 2014-06-06 | 2018-02-23 | 中国石油化工股份有限公司 | Modified phosphorated aluminiferous collosol and preparation method thereof |
| CN105312068A (en) * | 2014-06-06 | 2016-02-10 | 中国石油化工股份有限公司 | Modified phosphorus-containing aluminum sol and preparation method thereof |
| CN105214739B (en) * | 2014-06-06 | 2018-06-19 | 中国石油化工股份有限公司 | Modified Aluminum sol and preparation method thereof |
| CN105214739A (en) * | 2014-06-06 | 2016-01-06 | 中国石油化工股份有限公司 | Modified aluminium colloidal sol and preparation method thereof |
| CN105233856A (en) * | 2014-06-06 | 2016-01-13 | 中国石油化工股份有限公司 | Fluid catalytic cracking catalyst containing aluminum sol binder, and preparation method thereof |
| CN105233856B (en) * | 2014-06-06 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst containing aluminium sol adhesive and preparation method thereof |
| CN105148985A (en) * | 2014-06-10 | 2015-12-16 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method thereof and application |
| CN105268469B (en) * | 2014-06-10 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN105268469A (en) * | 2014-06-10 | 2016-01-27 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, and preparation method and application thereof |
| CN105195217A (en) * | 2014-06-10 | 2015-12-30 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
| CN105195218B (en) * | 2014-06-10 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN105195218A (en) * | 2014-06-10 | 2015-12-30 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
| CN105195217B (en) * | 2014-06-10 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN107304332A (en) * | 2016-04-18 | 2017-10-31 | 中国石油天然气股份有限公司 | Phosphorus-containing aluminum sol and preparation method thereof |
| CN112592074A (en) * | 2020-12-14 | 2021-04-02 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of aluminum phosphate super-hydrophilic film |
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| CN1029220C (en) | 1995-07-05 |
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