CN1229056A - Process for manufacture of dispersible alumino-silicates - Google Patents
Process for manufacture of dispersible alumino-silicates Download PDFInfo
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- CN1229056A CN1229056A CN 98108075 CN98108075A CN1229056A CN 1229056 A CN1229056 A CN 1229056A CN 98108075 CN98108075 CN 98108075 CN 98108075 A CN98108075 A CN 98108075A CN 1229056 A CN1229056 A CN 1229056A
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- aluminate
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Abstract
The present invention relates to a process for the manufacture of high-purity alumino-silicates which are dispersible in aqueous and/or aqueous-aidic media by hydrolysis of aluminium compounds and silicic acid compounds and hydrothermal treatment.
Description
The present invention relates to a kind of preparation method who is dispersed in the high purity silicon aluminate in water or the acid solution medium, it is realized by the hydrolysis and the hydrothermal treatment consists of aluminum compound and silicate compound.
There have been a large amount of various natural aluminosilicate hydrochlorates, comprised many compounds, as white mica, nepheline and chabazite with clear and definite crystalline structure.When with the part Siliciumatom in the netted structure of aluminium atom exchange silicate, keep reticulated structure simultaneously, then obtain zeolite.
Except that the natural aluminosilicate hydrochlorate, also have many this synthetic products.This product can be defined or be defined by aluminium hydroxide and the physical mixture that has the silicic acid of different quantities water by crystal chemistry.Except that physical mixture, the silico-aluminate that is defined by crystal chemistry also exists.
The ordinary method for preparing this silico-aluminate is carried out clay for using silicic acid and sodium hydroxide, as kaolinic conversion.Other route of synthesis is the cogelled precipitation (as GB 2166971-C) then of aluminum hydroxide sol and silicic acid sol.The precipitation of aluminium salt also is known (as CA 848966-A) in silicic acid sol.
Aforesaid method has many disadvantages, and promptly required colloidal sol or emulsion only are present in the moment of its preparation, and the powder that subsequent drying obtains can only disperse or need solvent mixture to reach dispersion by halves.Other disadvantage is to contain basic metal or the alkaline-earth metal that is used for stablizing silicic acid in a large number with colloidal sol or emulsion that this method prepares.Purifying subsequently as ion-exchange, is incomplete and causes the basic metal or the alkaline-earth metal concentration (as US3933621) of after purifying 0.1% (equaling 1000ppm).
Heterogeneous catalysis need contain the basic metal that is less than 100ppm and/or the high purity catalyst carrier of alkaline-earth metal, preferably is less than the sodium oxide of 50ppm.The preparation of the high purity silicon aluminate of this orthosilicic acid that has used ion-exchange has been described in German patent DE 3839580-C1.The gained silico-aluminate has the high purity of expectation, but they can not disperse.
Silico-aluminate is compared aspect physical/chemical not similar with aluminium hydroxide.For example because silicic acid has stronger Lewis acid characteristic, the surface of silico-aluminate has stronger acidity.This characteristic is used for many catalytic processs, as desulfurization, denitrogenation, oxidation, hydrocracking and appropriate hydrocracking.
Current catalyzer usually contains many different solid support materials (as GB 2166971-C).Is necessary with the catalyst support material uniform mixing to obtain uniform component.Therefore, the dispersive silico-aluminate has some advantages, as is used for coating substrate.This method can be used for catalysis and material coating field.Above-mentioned explanation shows needs dispersive high purity silicon aluminate.
The purpose of this invention is to provide the method that a kind of preparation has the dispersible silico-aluminate of following advantage:
-even in drying with after changing into powder, the silico-aluminate for preparing according to the present invention is not adding organic solvent or is just handling and can be dispersed in the aqueous solution with it.
-will have high purity according to the silico-aluminate of the present invention's preparation.
-the raw material that is used to prepare above-claimed cpd will be easy to obtain.
The price of-raw material makes that this method is more economical.
-this preparation technology can be continuously or discontinuous manner implement.
Find that surprisingly following method provides a kind of silico-aluminate that solves this problem, has realized the present invention based on this discovery.
The present invention relates to continuously a kind of or discontinuously preparation can be scattered in the method for the high purity silicon aluminate in water and/or the acid solution medium.Obtain desired characteristic by following process:
Preparation can be scattered in the method for the silico-aluminate in water and/or the acid solution medium, wherein
(A) with one or more hydrolyzable aluminum compounds common or intermittent hydrolysis or on the time in the space, preferred common hydrolysis and
(B) before the hydrolysis, during or afterwards, preferably before the hydrolysis or during, described compound contacted with one or more silicate compounds and
(C) under 40-220 ℃ of temperature, during the hydrolysis or afterwards with blended compound/reaction product in the aqueous solution, and in the presence of 1 to C6 acid of monovalence organic C or monovalence mineral acid, carry out the hydro-thermal ageing jointly more than 0.5 hour.
Can be at 20-98 ℃, preferred 50-98 ℃, more preferably be hydrolyzed under 85-98 ℃.Hydrolyzable aluminum compound in the scope of the invention be all aluminum compounds of formation Al-OH and/or Al-O-Al structure when reacting with water, for example aluminum alcoholate, hydroxyl aluminum alcoholate, keto-alcohol aluminium, acetylacetonate aluminium, alkyl aluminum chloride or ALUMINUM CARBOXYLIC.
The preferred Al of hydrolyzable aluminum compound (O-R-A-R ')
3-n(compound of O-R ") n type, wherein separate and randomly be differing from each other between each group
R " for having 1-30, the branch of preferred 2-12 carbon atom or unbranched, ring-type or acyclic, or fragrant alkyl,
R ' is for having the branch of 1-10 carbon atom or unbranched, and ring-type or acyclic, or fragrant alkyl especially have the alkyl of 4-8 carbon atom,
R be divalence with branch or unbranched, ring-type or acyclic, or the alkyl of C1-C10 of fragrance preferably have the alkyl of 1-5 carbon atom, more preferably the base of 1-3 carbon atom; The latter especially is a branch and acyclic not,
The heteroatoms of the 6th main group (chalcogen) or the 5th main group (nitrogen family) in the A representative element periodictable, preferred oxygen or nitrogen, wherein, if A represents the element of the 5th main group, then A have hydrogen or C1-C10 alkyl or C6-C10 aryl-/alkylaryl as additional substituting group so that valency is saturated
N refers to 0,1,2 or 3.
N preferred 0 or 3.If n be 0 and A be oxygen, then preferred Sanya butyl glycol aluminium.
If n is 3, the aluminium alkoxide compound is three aluminium alcoholates, progressively is preferably the alkyl of C2-C12, C4-C8 or C6-C8, and this group is saturated or unsaturated, ring-type or acyclic, branch or unbranched, or aromatics, preferred saturated.Especially the saturated straight-chain alkyl of preferred C6-C8.For example can prepare the aluminum alcoholate of hydrolysis according to disclosed method among the EP0111115-A1.
Before using, the metallic compound of hydrolysis can be passed through distillation, filtration or centrifugation make it purifying.Under the silicic acid situation, be a kind of effective purification process especially preferably for sodium ion containing on the exchange resin of ammonium ion the exchange metal ion.
For hydrothermal treatment consists, no matter during hydrolysis or must have afterwards acid existence.This acid is monovalence organic acid or the monovalence mineral acid (or the acid of monovalence ore deposit) of C1-C6, as HCl or HNO
3Also can add the people after hydrolysis should acid, as long as have acid in hydrothermal treatment consists.According to the present invention, add this acid or acidifier before the drying for the first time at silico-aluminate.
The monovalence organic acid of C1-C6 in the scope of the invention demonstrates acid-respons for having at least 1-6 carbon atom and Yu Shuizhong, promptly reacts as proton donor and can only discharge an organic compound that is referred to as the proton of acid molecule.This definition can comprise chloride of acid for example, sulfonic acid and other in water, form-COOH or-organic compound of COO-group.
The add-on of acid is the 0.1-2.0 gram in 1 gram solid material, preferred 0.2-0.8 gram.The preferred 1-22 of hydro-thermal digestion time hour.The temperature that has confirmed 2-18 hour and 80-130 ℃ is especially effective.
Another distinguishing feature in the inventive method is, just not saying educt and product, reaction can not contain any organic solvent and carry out the preferred aqueous solutions environment in alcohol/aqueous environment substantially.
Spendable educt Al
2O
3And SiO
2Ratio be from 99.5 weight %:0.5 weight % to 70 weight %:30 weight %, preferably from 98 weight %:2 weight % to 70 weight %:30 weight %, each ratio refers to Al
2O
3: SiO
2Ratio.In addition, can with reaction product of the present invention in 550 ℃ to 1500 ℃ temperature lower calcination 0.5-24 hour.
Dispersible silico-aluminate can be used as in the Catalytic processes, catalyzer and support of the catalyst in the Preparation of Catalyst, as the raw material of pottery, as coated material with as binder ingredients and rheology control agent in the aqueous solution system.
The silicate compound that the present invention uses is for example condensation product of orthosilicic acid, especially its low condensation product, and orthosilicic acid itself most preferably.The silicate compound that the present invention uses also can be at the scene hydrolysis by silicon tetrachloride prepare.Water is hydrolyzed.
The term " dispersible silico-aluminate " that the present invention uses mean exsiccant and only be Powdered silico-aluminate, it can be to be higher than 90 weight % at least, the content that preferably is higher than 95 weight % is dispersed in aqueous medium, promptly be higher than 90 weight %, the described product that preferably is higher than 95 weight % will be disperseed after dispersion.The method of definite dispersity has been described in the embodiment part as described below.Available currently known methods such as spraying drying or by means of a rotatory drier with gained aqueous product drying.The preparation method of silico-aluminate of the present invention can carry out continuously or intermittently.
The acid that dilute with water is crossed, as the monovalence mineral acid, for example hydrochloric acid or nitric acid, or C1-C6 organic acid, preferred monobasic acid disperses silico-aluminate of the present invention.Be used for the spendable concentration of dispersive acid and count 0.1-40 weight % with pure acid.The preferred lower concentration acid of using 0.1-5 weight %.To disperse also be possible to a water in some cases.
The compound of the present invention preparation can be in stove and preferably at 550 ℃-1500 ℃ temperature lower calcination, the preferred 3-24 of calcination time hour.Metal oxide with this method preparation has required high purity.
Following table 1 expression several silico-aluminate and dispersity D thereof according to the present invention's preparation.
Table 1
| Compound | ???Al 2O 3∶SiO 2(weight %: weight %) | ???HNO 3(weight %) | Ageing (hour/℃) | Dispersity D (%) |
| ????1 | ????95.0∶5.0 | ????0.5 | 16 hours/95 ℃ | ????98 |
| ????2 | ????90.5∶9.5 | ????0.8 | 16 hours/95 ℃ | ????95 |
| ????3 | ????94.9∶5.1 | ????0.6 | 5 hours/95 ℃ | ????97 |
| ????4 | ????90.7∶9.3 | ????1.0 | 5 hours/95 ℃ | ????96 |
| ????5 | ????70.5∶29.5 | ????- | 5 hours/95 ℃ | ????99 |
| ????A | ????95.1∶4.9 | ????30 | ??- | Dispersive not |
| ????B | ????50.4∶49.6 | ????30 | ??- | Dispersive not |
| ????C | ????68.8∶31.2 | ????30 | 5 hours/95 ℃ | Dispersive not |
" notes ": compd A and B are the silico-aluminate of conventional preparation.
C is the silico-aluminate according to the present invention's preparation, comprises hydrothermal treatment consists but interpolation acid
A to C is a reference substance; The solid silicon aluminate of each 10 weight % is disperseed
* be used for dispersive acid
The physical data of the silico-aluminate of the present invention that following table 2 expressions and two standard silicon aluminates (A and B) compare.Silico-aluminate A as a reference and B prepare by alumina sol and silicic acid are mixed.
Table 2
| Compound | ???Al 2O 3∶SiO 2(weight %) | Surface (m 2/G) | Void content (ml/g) |
| ????1 | ????95.0∶5.0 | ????368 | ????0.50 |
| ????2 | ????90.5∶9.5 | ????409 | ????0.50 |
| ????3 | ????94.9∶5.1 | ????350 | ????0.49 |
| ????4 | ????90.7∶9.3 | ????364 | ????0.48 |
| ????5 | ????70.5∶29.5 | ????246 | ????0.11 |
| ????A | ????95.1∶4.9 | ????314 | ????0.54 |
| ????B | ????50.4∶49.6 | ????452 | ????0.60 |
Dispersible silico-aluminate according to the present invention's preparation has high purity.In particular, it is very low to play the content of the basic metal of serious negative interaction and alkaline-earth metal when using above-mentioned product to be used for catalysis.The results are shown in Table 3 by the trace element of ICP spectroscopic analysis.By the further listed purity in the increase table 3 of the container that uses redistilled water and make by inert material.
Table 3
| Compound | ?Na 2O ?(ppm) | ???Li 2O ??(ppm) | ???MgO ??(ppm) | ????CaO ???(ppm) | ???TiO 2???(ppm) | ??Fe 2O 3??(ppm) |
| ????1 | ???＜10 | ???＜5 | ???＜10 | ???＜10 | ???＜50 | ????50 |
| ????2 | ???＜10 | ???＜5 | ???＜10 | ???＜10 | ???＜50 | ????34 |
| ????3 | ????15 | ???＜5 | ???＜10 | ???＜10 | ???＜50 | ????28 |
" notes ": other element, Pb for example, Zn, Ni, Cr, Cu, Mn, the total concn of Mo and Ga is less than 50ppm.
Embodiment (generally)
To pass through its trace impurity of inductively coupled plasma (ICP) spectroscopic analysis by the compound of the present invention's preparation.Measure its surface by the BET method, (Autopore II 9220 porosimeters, Mikromeritics) (FlowPrep 060, and Gemini 2360,2375, Mikromeritics) measures its pore volume in addition with the nitrogen porosimeter by the mercury porosimeter simultaneously.Compound of the present invention is calcined in retort furnace and under 550 ℃-1500 ℃ temperature.The use deionized water is hydrolyzed.
Measure dispersity D by the following method.Quantitative drying solid material is put into flask also to be mixed with diluted acid such as nitric acid while stirring.Continue to stir 10 minutes (stirring velocity 800-850rpm).The suspension that so obtains is quantitatively changed in the Glass tubing of a whizzer.Then in 2400rpm
-1Following centrifuging 20 minutes, decantation goes out the upper strata stillness of night, and makes the residue in the Glass tubing descend drying at least 0.5 hour in 573K (300 ℃).Weighing then comprises the Glass tubing of residue, and weighing does not afterwards contain the Glass tubing of residue.The gained difference is the weight of dispersible solid not.
Dispersion amount not, %=(gram number * 100 of residue)/(in the initial weight of the aluminum oxide of gram number)
Dispersion amount D, %=100-be the per-cent of dispersion amount not
Embodiment 1 (compound 1)
In the 2000ml three-necked flask, put into 487 gram water and 87.7 gram moisture silicic acid (3.6 weight %).Inclusion is heated to 75 ℃.With total amount is that 500g three hexanol aluminium (the Al content of 6.35 weight %) divide three parts and join in this mixture with each 15 minutes timed interval.Stirred this mixture 30 minutes.The nitric acid that adds 6.3 grams 65% then.Decantation goes out alcohol and residue is diluted to the solids content of about 5% expectation.Colloidal sol is heated to 95 ℃ and remained on this temperature following 16 hours.By distillation, then spraying drying is disengaged remaining water from pure residue.
Embodiment 2 (compound 2)
In the 2000ml three-necked flask, put into 390 gram water and 185 gram moisture silicic acid (3.6 weight %).Inclusion is heated to 75 ℃.With total amount is that 500g three hexanol aluminium (the Al content of 6.35 weight %) divide three parts and join in this mixture with each 15 minutes timed interval.Stirred this mixture 30 minutes.The nitric acid that adds 6.7 grams 65% then.Decantation goes out alcohol and residue is diluted to the solids content of about 5% expectation.Colloidal sol is heated to 95 ℃ and remained on this temperature following 16 hours.By distillation, then spraying drying is disengaged remaining water from pure residue.
Embodiment 3 (compound 3)
In the 2000ml three-necked flask, put into 490 gram water and 78.3 gram moisture silicic acid (4.0 weight %).Inclusion is heated to 75 ℃.With total amount is that 500g three hexanol aluminium (the Al content of 6.3 weight %) divide three parts and join in this mixture with each 15 minutes timed interval.Stirred this mixture 30 minutes.The nitric acid that adds 6.3 grams 65% then.Decantation goes out alcohol and residue is diluted to about 5% solids content.Colloidal sol is heated to 95 ℃ and remained on this temperature following 5 hours.By distillation, then spraying drying is disengaged remaining water from pure residue.
Embodiment 4 (compound 4)
In the 2000ml three-necked flask, put into 383 gram water and 185 gram moisture silicic acid (3.6 weight %).Inclusion is heated to 75 ℃.With total amount is that 500g three hexanol aluminium (the Al content of 6.35 weight %) divide three parts and join in this mixture with each 15 minutes timed interval.Stirred this mixture 30 minutes.The nitric acid that adds 6.7 grams 65%.Decantation goes out alcohol and residue is diluted to the solids content of about 5% expectation.Colloidal sol is heated to 95 ℃ and remained on this temperature following 5 hours.By distillation, then spraying drying is disengaged remaining water from pure residue.
Embodiment 5 (compound 5)
In the 2000ml three-necked flask, put into 654 gram moisture silicic acid (3.9 weight %) and 67 gram nitric acid (65 weight %).Inclusion is heated to 75 ℃.With total amount is that 500g three hexanol aluminium (the Al content of 6.3 weight %) divide three parts and join in this mixture with each 15 minutes timed interval.Stirred this mixture 30 minutes.Colloidal sol is heated to 95 ℃ and remained on this temperature following 5 hours, then is diluted to about 5% solids content.Decantation goes out upper strata alcohol liquid, and by distillation then spraying drying from pure residue, disengage remaining water.
Embodiment 6 (compound 6)
In the 2000ml three-necked flask, put into the moisture silicic acid of 638 grams that is heated to 75 ℃.With total amount is that 500g three hexanol aluminium (the Al content of 6.35 weight %) divide three parts and join in this mixture with each 15 minutes timed interval.Stirred this mixture 30 minutes.Decantation goes out alcohol and residue is diluted to about 5% solids content.Colloidal sol is heated to 95 ℃ and remained on this temperature following 5 hours.By distillation, then spraying drying is disengaged remaining water from pure residue.
Claims (18)
1. the preparation method that can be dispersed in the silico-aluminate in water and/or the aqueous acid medium is characterized in that
(A) with one or more hydrolyzable aluminum compounds common or intermittent hydrolysis or on the time in the space, preferred common hydrolysis and
(B) before the hydrolysis, during or afterwards, described compound contacted with one or more silicate compounds and
(C) under 40-220 ℃ of temperature, after hydrolysis or also during the hydrolysis with reaction product in aqueous medium, and in the presence of monovalence C1 to C6 organic acid or monovalence mineral acid, carry out the hydro-thermal ageing jointly more than 0.5 hour,
(D) randomly, calcine above-mentioned product.
2. according to the method for claim 1, the aluminum compound that it is characterized in that hydrolysis is Al (O-R-A-R ＇)
3-n(compound of O-R ") n type, wherein
R " be alkyl with 1-30 carbon atom,
R ' is the alkyl with 1-10 carbon atom,
R be have 1-10 carbon atom bivalent hydrocarbon radical and
The heteroatoms of the 6th main group (chalcogen) or the 5th main group (nitrogen family) in the A representative element periodictable, preferred oxygen or nitrogen, wherein, if A represents the element of the 5th main group, then A have hydrogen or C1-C10 alkyl or C6-C10 aryl-/alkylaryl as additional substituting group so that valency is saturated and
N is 0,1,2 or 3.
3. according to the method for claim 2, it is characterized in that n is 0.
4. according to the method for claim 2, it is characterized in that n is 3.
5. according to claim 1,2 or 4 method, it is characterized in that hydrolyzable aluminum compound is for having C2-C12, preferred C4-C8, the aluminum alcoholate of more preferably saturated C6-C8 alkyl.
6. according to the method for above-mentioned arbitrary claim, it is characterized in that orthosilicic acid and/or its condenses can be used as silicate compound.
7. according to the method for above-mentioned arbitrary claim, it is characterized in that hydrolyzable metallic compound at first by distillation, purifying is carried out in filtration or centrifugation, and/or by ion-exchange, preferably carries out ion-exchange and disengage silicic acid on containing the exchange resin of ammonium ion from metal ion.
8. according to the method for above-mentioned arbitrary claim, it is characterized in that hydrolysis at 20-98 ℃, preferably carries out under 85-98 ℃.
9. according to the method for above-mentioned arbitrary claim, it is characterized in that before hydrolysis, during or add acid afterwards and before hydrothermal treatment consists.
10. according to each method of claim 1-8, it is characterized in that after hydrolysis and before the hydrothermal treatment consists or during add acid.
11. according to the method for above-mentioned arbitrary claim, it is characterized in that the hydro-thermal ageing carried out 0.5-24 hour, preferred 2-18 hour.
12., it is characterized in that the hydro-thermal ageing carries out under 80-130 ℃ according to the method for above-mentioned arbitrary claim.
13. according to the method for above-mentioned arbitrary claim, the ratio that it is characterized in that aluminum compound/silicon compound is that each ratio refers to Al from 99.5 weight %:0.5 weight % to 70 weight %:30 weight %
2O
3: SiO
2Ratio.
14., it is characterized in that reaction product was calcined 0.5-24 hour down in 550 ℃ to 1500 ℃ according to the method for above-mentioned arbitrary claim.
15. the silico-aluminate that the method that defines according to aforementioned claim prepares is as catalyzer and support of the catalyst in the Preparation of Catalyst, raw material as pottery, as coated material with as the binder ingredients in the aqueous solution system and/or the purposes of rheology control agent.
16. silico-aluminate according to the either party's method preparation that defines among the claim 1-14.
17. dispersive silico-aluminate in water or water/pure medium is characterized in that this silico-aluminate is by preparing according to the either party's method that defines among the claim 1-14.
18. according to the silico-aluminate in water or the water/pure medium of being dispersed in of claim 17, it is characterized in that this silico-aluminate is in being scattered in water or water/pure medium before, exist with dry and basic dewatering state.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB981080758A CN1142891C (en) | 1998-03-12 | 1998-03-12 | Process for manufacture of dispersible alumino-silicates |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB981080758A CN1142891C (en) | 1998-03-12 | 1998-03-12 | Process for manufacture of dispersible alumino-silicates |
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| Publication Number | Publication Date |
|---|---|
| CN1229056A true CN1229056A (en) | 1999-09-22 |
| CN1142891C CN1142891C (en) | 2004-03-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796022A (en) * | 2019-04-01 | 2019-05-24 | 四川广阳环保科技有限公司 | A method of poly aluminium iron silicate is produced using chlorosilane raffinate, aluminum dross and acid sludge |
-
1998
- 1998-03-12 CN CNB981080758A patent/CN1142891C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796022A (en) * | 2019-04-01 | 2019-05-24 | 四川广阳环保科技有限公司 | A method of poly aluminium iron silicate is produced using chlorosilane raffinate, aluminum dross and acid sludge |
| CN109796022B (en) * | 2019-04-01 | 2020-09-29 | 四川广阳环保科技有限公司 | Method for producing poly-aluminum ferric silicate by using chlorosilane residual liquid, waste aluminum slag and acid sludge |
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| Publication number | Publication date |
|---|---|
| CN1142891C (en) | 2004-03-24 |
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