CN105271332A - Method for preparing silicon-aluminum mixed oxide by taking waste silicon-aluminum molecular sieve - Google Patents
Method for preparing silicon-aluminum mixed oxide by taking waste silicon-aluminum molecular sieve Download PDFInfo
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- CN105271332A CN105271332A CN201510689842.7A CN201510689842A CN105271332A CN 105271332 A CN105271332 A CN 105271332A CN 201510689842 A CN201510689842 A CN 201510689842A CN 105271332 A CN105271332 A CN 105271332A
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Abstract
The invention relates to a method for preparing a silicon-aluminum mixed oxide by taking a waste silicon-aluminum molecular sieve as a raw material. The method mainly comprises the following steps of uniformly mixing the waste silicon-aluminum molecular sieve and an acid compound solution for reaction for 0.5-10h at 60-110 DEG C, filtering to form an acid reaction solution and undissolved substance, mixing the undissolved substance and a basic compound solution after washing and drying, performing hydrothermal treatment for 2-10h at 120-200 DEG C to form a basic reaction solution, neutralizing the acid reaction solution and the basic reaction solution into gel, treating slurry for 2-6h at 60-90 DEG C after the reaction finishes, and carrying out solid-liquid separation, washing and drying to form silicon-aluminum mixed oxide powder. Compared with the prior art, the method substitutes the waste silicon-aluminum molecular sieve for expensive industrial raw materials to prepare the silicon-aluminum mixed oxide, enlarges a raw material source, lowers preparation cost of the silicon-aluminum mixed oxide and treatment cost of the waste molecular sieve, prevents environmental pollution caused by the waste molecular sieve, allows the waste to be recycled and has better economic and social benefits.
Description
Technical field
The invention belongs to field of inorganic material preparing technology, relate to a kind of with discarded Si-Al molecular sieve for the method for sial composite oxides prepared by raw material.
Background technology
At petrochemical industry, Si-Al molecular sieve widespread use, but after using for some time, the catalytic capability of molecular sieve reduces, and usually by its discarded landfill disposal, but its composition does not change substantially, is rich in SiO to these
2and Al
2o
3molecular sieve give it up, not only cause environmental pollution, and be the waste of resource.
Sial composite oxides are as the important carrier of catalyzer and active ingredient, there is larger specific surface and pore volume, high crush strength and high surface acidity and thermostability etc., be widely used in the technical fields such as oil refining and petrochemical complex, particularly in hydrocracking, hydrofining and catalytic cracking, demonstrate vital role.
At present, the method of industrial production sial composite oxides has multiple, as aluminate or aluminium salt precipitation method, aluminium salt neutralisation and aluminium alcoholates hydrolysis method etc., normally adopts the inorganic or industrial raw material such as organosilicon source and aluminium source in preparation process, raw material sources are limited, and cost intensive.
Summary of the invention
For the deficiencies in the prior art, the present invention adopts discarded Si-Al molecular sieve to replace expensive industrial raw material to prepare sial composite oxides, expand raw material sources, reduce the preparation cost of amorphous aluminum silicide and the processing cost of discarded molecular sieve, and decrease the environmental pollution caused thus.
Sial composite oxides preparation method of the present invention comprises the steps:
(1) discarded Si-Al molecular sieve is mixed with acidic cpd solution, the mass ratio of discarded Si-Al molecular sieve and acidic cpd solution is 1:(5 ~ 50), wherein the concentration of acidic cpd solution is 0.1 ~ 10mol/L, and acidic cpd solution is: the solution of at least one acid in hydrochloric acid, sulfuric acid, nitric acid;
(2) mixture that the first step is obtained is reacted 0.5 ~ 10h at 60 ~ 110 DEG C, filter to obtain acid-reaction liquid and insolubles, insolubles washing is dry;
(3) insolubles that second step is obtained is mixed with alkaline compound solution, the mass ratio of insolubles and basic cpd is 1:(5 ~ 50), wherein the concentration of alkaline compound solution is 0.1 ~ 10mol/L, and alkaline compound solution is: the solution of at least one alkali in sodium hydroxide, sodium carbonate, potassium hydroxide;
(4) by mixture hydrothermal treatment consists 2 ~ 10h at 120 ~ 200 DEG C that the 3rd step is obtained, alkali reaction liquid is obtained;
(5) in acid-reaction liquid and alkali reaction liquid being carried out and plastic, the temperature controlling plastic is 30-80 DEG C, and pH value is 6.0 ~ 10.0, after reaction terminates, by above-mentioned slurries at 60 ~ 90 DEG C of process 2 ~ 6h, solid-liquid separation, washing, drying, obtain sial composite oxide powder.
In sial composite oxides preparation process of the present invention, in the acid-reaction liquid described in step (5) and alkali reaction liquid and plastic can be alkali reaction liquid be end liquid, add in acid-reaction liquid and plastic; Or acid-reaction liquid is end liquid, add in alkali reaction liquid and plastic; Or alkali reaction liquid and acid-reaction liquid flow plastic.
Sial composite oxide powder of the present invention has following character, and alumina weight content is 10% ~ 50%, and specific surface is 200 ~ 350m
2/ g, pore volume is 0.3 ~ 1.0ml/g, and mean pore size is at 3 ~ 15nm.
Sial composite oxides prepared by the present invention reach the index preparing sial composite oxides with industrial raw material.
The present invention replaces expensive industrial raw material to prepare sial composite oxides with discarded Si-Al molecular sieve, and the chemical composition of discarded molecular sieve catalyst more than 90% is SiO
2and Al
2o
3through suitable process, may be used for the preparation of sial composite oxides, not only expand raw material sources, again reduce the preparation cost of amorphous aluminum silicide and the processing cost of discarded molecular sieve, avoid discarded molecular sieve and cause environmental pollution, make waste be able to recycling, there is valuable economic benefit and social benefit.And preparation process of the present invention is simple, with low cost, be applicable to suitability for industrialized production.
Specific embodiment
Example 1
200g is discarded Si-Al molecular sieve and add the sulphuric acid soln that 1000g concentration is 10mol/L, be warming up to 110 DEG C, process 1h, has reacted rear filtration, has obtained acid-reaction liquid and insolubles; Adding 1000g concentration after insolubles washing is dry is in the sodium hydroxide solution of 5mol/L, is placed in hydrothermal reaction kettle and is warming up to 120 DEG C of process 4h, obtain alkali reaction liquid; With alkali reaction liquid for end liquid, add in acid-reaction liquid and plastic, the temperature controlling reaction is 30 DEG C, and pH value is 8.0, after cemented into bundles, and raised temperature adjust ph is carried out aging, and aging temperature is 90 DEG C, and aging pH value is 8.0, and digestion time is 2h; The solidliquid mixture of aging rear gained filters, and adds water washing during cake filtration, and 80 DEG C of dryings 12 hours, are designated as SA-1.
Example 2
200g is discarded Si-Al molecular sieve and add the salpeter solution that 5000g concentration is 1mol/L, be warming up to 60 DEG C, process 5h, has reacted rear filtration, has obtained acid-reaction liquid and insolubles; Adding 5000g concentration after insolubles washing is dry is in the sodium carbonate solution of 1mol/L, is placed in hydrothermal reaction kettle and is warming up to 200 DEG C of process 4h, obtain alkali reaction liquid; Acid-reaction liquid and alkali reaction liquid are flowed plastic, and the temperature controlling reaction is 80 DEG C, and pH value is 8.0, after cemented into bundles, and raised temperature adjust ph is carried out aging, and aging temperature is 90 DEG C, and aging pH value is 8.0, digestion time is 6h; The solidliquid mixture of aging rear gained filters, and adds water washing during cake filtration, and 120 DEG C of dryings 2 hours, are designated as SA-2.
Example 3
200g is discarded Si-Al molecular sieve and add the salpeter solution that 4000g concentration is 2mol/L, be warming up to 100 DEG C, process 6h, has reacted rear filtration, has obtained acid-reaction liquid and insolubles; Adding 1000g concentration after insolubles washing is dry is in the potassium hydroxide solution of 8mol/L, is placed in hydrothermal reaction kettle and is warming up to 180 DEG C of process 4h, obtain alkali reaction liquid; With alkali reaction liquid for end liquid, add in acid-reaction liquid and plastic, the temperature controlling reaction is 40 DEG C, and pH value is 9.0, after cemented into bundles, and raised temperature adjust ph is carried out aging, and aging temperature is 90 DEG C, and aging pH value is 9.0, and digestion time is 2h; The solidliquid mixture of aging rear gained filters, and adds water washing during cake filtration, and 100 DEG C of dryings 10 hours, are designated as SA-3.
Example 4
200g is discarded Si-Al molecular sieve and add the sulphuric acid soln that 1000g concentration is 10mol/L, be warming up to 70 DEG C, process 5h, has reacted rear filtration, has obtained acid-reaction liquid and insolubles; Adding 1000g concentration after insolubles washing is dry is in the sodium hydroxide solution of 2mol/L, is placed in hydrothermal reaction kettle and is warming up to 150 DEG C of process 4h, obtain alkali reaction liquid; With acid-reaction liquid for end liquid, add in alkali reaction liquid and plastic, the temperature controlling reaction is 60 DEG C, and pH value is 6.0, after cemented into bundles, and raised temperature adjust ph is carried out aging, and aging temperature is 90 DEG C, and aging pH value is 6.0, and digestion time is 4h; The solidliquid mixture of aging rear gained filters, and adds water washing during cake filtration, and 90 DEG C of dryings 8 hours, are designated as SA-4.
Comparative example
Get Al
2o
3content is 60g/L alum liquor is end liquid, is warming up to 40 DEG C, adds SiO with certain flow velocity
2content is the silicon sol solution of 80g/L, and the temperature controlling reaction is 60 DEG C, and pH value is 7.0, after cemented into bundles, and raised temperature adjust ph is carried out aging, and aging temperature is 90 DEG C, and aging pH is 7.0, and digestion time is 4h.The solidliquid mixture of gained filters, and adds water washing, 100 DEG C of dryings 10 hours, be designated as comparative example during cake filtration.
Table 1 sial composite oxides product property
Claims (3)
1. with discarded Si-Al molecular sieve for the methods of sial composite oxides prepared by raw material, it is characterized in that comprising the steps:
1) discarded Si-Al molecular sieve is mixed with acidic cpd solution, the mass ratio of discarded Si-Al molecular sieve and acidic cpd solution is 1:5 ~ 1:50, wherein the concentration of acidic cpd solution is 0.1 ~ 10mol/L, and acidic cpd solution is the solution of at least one acid in hydrochloric acid, sulfuric acid, nitric acid;
2) mixture that the first step is obtained is reacted 0.5 ~ 10h at 60 ~ 110 DEG C, filter to obtain acid-reaction liquid and insolubles, insolubles washing is dry;
3) insolubles that second step is obtained is mixed with alkaline compound solution, the mass ratio of insolubles and basic cpd is 1:5 ~ 1:50, wherein the concentration of alkaline compound solution is 0.1 ~ 10mol/L, and alkaline compound solution is: the solution of at least one alkali in sodium hydroxide, sodium carbonate, potassium hydroxide;
4) by mixture hydrothermal treatment consists 2 ~ 10h at 120 ~ 200 DEG C that the 3rd step is obtained, alkali reaction liquid is obtained;
5) in acid-reaction liquid and alkali reaction liquid being carried out and plastic, the temperature controlling plastic is 30-80 DEG C, and pH value is 6.0 ~ 10.0, after reaction terminates, by above-mentioned slurries at 60 ~ 90 DEG C of process 2 ~ 6h, solid-liquid separation, washing, drying, obtain sial composite oxide powder.
2. method according to claim 1, is characterized in that step 5) described in acid-reaction liquid and alkali reaction liquid in and plastic be alkali reaction liquid be end liquid, add in acid-reaction liquid and plastic; Or acid-reaction liquid is end liquid, add in alkali reaction liquid and plastic; Or alkali reaction liquid and acid-reaction liquid flow plastic.
3. method according to claim 1, is characterized in that, gained sial composite oxide powder alumina weight content is at 10wt% ~ 50wt%, and specific surface is 200 ~ 350m
2/ g, pore volume is 0.3 ~ 1.0ml/g, and mean pore size is at 3 ~ 15nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569545A (en) * | 2018-11-19 | 2019-04-05 | 山西大学 | A kind of coal ash for manufacturing for aluminium silicon porous material method |
| CN110128163A (en) * | 2019-06-26 | 2019-08-16 | 中南大学 | A method of porous cordierite ceramics material is prepared using waste catalyst |
| CN113697826A (en) * | 2021-08-06 | 2021-11-26 | 中海油天津化工研究设计院有限公司 | Method for synthesizing SAPO-34 molecular sieve by using waste silicoaluminophosphate molecular sieve as raw material |
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| RO64842A2 (en) * | 1970-12-16 | 1978-10-15 | Univ Alexandru Ioan Cuza | PROCESS FOR THE PREPARATION OF MOLECULAR SIEVES |
| CN1686813A (en) * | 2005-03-29 | 2005-10-26 | 煤炭科学研究总院抚顺分院 | Method for preparing polyaluminium chloride through catalyst of deposed molecular sieve |
| CN101590357A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of method of utilizing catalyst of deposed molecular sieve to prepare desulfurizing agent |
| CN101591032A (en) * | 2009-06-29 | 2009-12-02 | 同济大学 | The method for preparing modified polyaluminium chloride flocculating agent with the depleted molecular sieve |
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2015
- 2015-10-22 CN CN201510689842.7A patent/CN105271332B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO64842A2 (en) * | 1970-12-16 | 1978-10-15 | Univ Alexandru Ioan Cuza | PROCESS FOR THE PREPARATION OF MOLECULAR SIEVES |
| CN1686813A (en) * | 2005-03-29 | 2005-10-26 | 煤炭科学研究总院抚顺分院 | Method for preparing polyaluminium chloride through catalyst of deposed molecular sieve |
| CN101590357A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of method of utilizing catalyst of deposed molecular sieve to prepare desulfurizing agent |
| CN101591032A (en) * | 2009-06-29 | 2009-12-02 | 同济大学 | The method for preparing modified polyaluminium chloride flocculating agent with the depleted molecular sieve |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569545A (en) * | 2018-11-19 | 2019-04-05 | 山西大学 | A kind of coal ash for manufacturing for aluminium silicon porous material method |
| CN110128163A (en) * | 2019-06-26 | 2019-08-16 | 中南大学 | A method of porous cordierite ceramics material is prepared using waste catalyst |
| CN113697826A (en) * | 2021-08-06 | 2021-11-26 | 中海油天津化工研究设计院有限公司 | Method for synthesizing SAPO-34 molecular sieve by using waste silicoaluminophosphate molecular sieve as raw material |
| CN113697826B (en) * | 2021-08-06 | 2024-05-07 | 中海油天津化工研究设计院有限公司 | Method for synthesizing SAPO-34 molecular sieve by taking waste silicon-phosphorus-aluminum molecular sieve as raw material |
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