CN1350053A - Synthesis of detergent 4A zeolite with waste alkali and kaoline - Google Patents
Synthesis of detergent 4A zeolite with waste alkali and kaoline Download PDFInfo
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- CN1350053A CN1350053A CN 00131817 CN00131817A CN1350053A CN 1350053 A CN1350053 A CN 1350053A CN 00131817 CN00131817 CN 00131817 CN 00131817 A CN00131817 A CN 00131817A CN 1350053 A CN1350053 A CN 1350053A
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- kaolin
- zeolite
- salkali waste
- detergent
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Abstract
The present invention uses the waste sodium hydroxide solution produced by electrochemical treatment of aluminium section material surface and natural kaoline as raw material, and adopts alkaline combustion method to activate kaoline, through the processes of gel-forming and crystallization, and can synthesize 4A zeolite. Its calcium exchange rate is up to above 310 mg/g dried zeolite. Said invention can eliminate the pollution due to waste alkali discharge, and can remove the pollution due to sodium tripolyphosphate.
Description
The present invention relates to utilize the kaolin resource of wide salkali waste of aluminium and China's abundant to be raw material, after adopting alkali burning method activation kaolin, through becoming the synthetic 4A zeolite of technologies such as glue, crystallization, to eliminating the pollution that the salkali waste discharging causes, it is all significant to make full use of natural resource.
The 4A zeolite is a kind of purposes staple product extremely widely, and is very noticeable as the auxiliary agent of washing composition in recent years.The 4A zeolite is safe and reliable, and ecological aspect is not had influence yet, though under high density to human body also nontoxicity, non-stimulated to eyes, skin, can not cause allergy, safe and reliable.Cause " nutrition accumulation " to pollute the washing 4A zeolite that arises at the historic moment for solving tripoly phosphate sodium STPP to waters such as rivers, lakes, output increases rapidly since the seventies, all in newly-built or enlarging zeolite factory, the output of U.S.'s washing zeolite increases by three times approximately in the period of 1988-2000 for the Ethyl company of the U.S. and Cyosfield company etc.; Domestic the phosphorus-containing detergent discharging of waste liquid certainly will cause water pollution along with the synthetic detergent consumption increases, and produces therefore that low-phosphorous or without phosphorus to contain zeolite detergent imperative, is important measures that reduce water pollution.But, because industrial aluminium hydroxide appreciates significantly, make and improve greatly from the cost of traditional industrial chemicals synthesis of detergent with the 4A zeolite, influenced zeolite applying in washing composition, therefore, be that the synthetic 4A zeolite of raw material is subjected to generally paying attention to natural crystal (as kaolin).Kaolin reserves at home is very abundant, and the quantity of the salkali waste that aluminium manufacturer's aluminium section bar electrochemical surface course of processing is produced is also considerable, as the synthetic 4A zeolite of raw material, to eliminating the pollution that the salkali waste discharging causes, the development and use kaolin resource, reduce production costs, increasing economic efficiency has realistic meaning.
The 4A zeolite is as washing auxiliary detergent, and it must meet the following standard of " washing 4A zeolite " product: (1) calcium ion exchange capacity, according to the literature, the 4A zeolite calcium exchange capacity that states such as Japan, West Germany and the U.S. produce is generally at 286mg CaCO
3About the dried zeolite of/g, the about 288mg CaCO of 4A zeolite calcium exchange capacity that China grand industrial and trading company of Foochow credit produces
3The dried zeolite of/g.(2) size-grade distribution directly affects calcium exchange capacity and the adhesion amount on fabric thereof, and according to the data introduction, size distribution should be at 2-8 μ m, average out to 2-4 μ m.Because particle diameter＜during 10 μ m, the calcium exchange velocity is near STPP; During particle diameter＞15 μ m, will hang on the fabric; And during particle diameter＜1 μ m, because the effect of Van der Waals force also can be bonded on the fabric.(3) pH value answers≤11.0, when basicity is too high, can impact the washing powder quality.(4) whiteness answers 〉=95%, and whiteness is low excessively, can directly influence the application of 4A zeolite in the washing industry.Therefore, can synthetic 4A zeolite be applied in the washing industry, and key is the quality of sintetics.
Why the 4A zeolite can be its synthesis material with kaolin, mainly is because the similarity that their structures are formed.Kaolin is the layer aluminium silicate of a kind of 1: 1 type, and chemical essentially consist is Al
2O
3SiO
2, its structural unit is S-O tetrahedron and Al-(O, OH) octahedra be combined into; And the 4A zeolite has silica (SiO
4) tetrahedron and alumina (AlO
4) the tetrahedron skeleton structure, because kaolin has acidproof not alkali proof chemical property, so itself and alkali effect can be able to be synthesized the 4A zeolite.
At present, all having delivered both at home and abroad many is the research article of the synthetic 4A zeolite of raw material with kaolin, and be that raw material synthesizes the 4A zeolite simultaneously with aluminium manufacturer's salkali waste and natural kaolin, does not but see relevant bibliographical information.
The objective of the invention is to disclose a kind of salkali waste and kaolin that produces with aluminium manufacturer's aluminium section bar electrochemical surface processing is raw material, behind the employing alkali burning method activation kaolin, synthesizes the 4A zeolite technology through becoming technologies such as glue, crystallization, filtration, washing and drying.
Synthesis technique of the present invention is: (1) concentrates back kaolin (salkali waste/kaolinic weight ratio is 2-5) with calculated amount with waste lye and stirs, and descends scorching hot 1-6 hour at 500-1000 ℃; (2) alkali is burnt thing cooling, soluble in water, under 50-70, stirred into glue 1-3 hour; (3) will become the glue thing 80-100 ℃ of following backflow crystallization 1-3 hour then, through cooling, decompress filter, be washed to PH＜11, then 110 ℃ dry 2 hours down, can obtain the finished product.Silica alumina ratio during kaolin is formed (mol ratio) is advisable with 1.8-2.3, and the best is 2.1-2.3; Al during salkali waste is formed
2O
3Be about 3.3% (weight), the about 3.5N of NaOH equivalent concentration; Alkali burns purpose except that reducing the roasting temperature of reaction, and alkali also generates the silico-aluminate of solubility, Al wherein with the disintegrate sieve and silica-sesquioxide of separating out of kaolin structure
3+Ion becomes four-coordination by original hexa-coordinate, and it is 500-1000 ℃ that alkali burns temperature, and the best is 650-700 ℃; The alkali burning time is 1-6 hour, best 2-3 hour; Raw material ratio, promptly salkali waste/kaolin (weight) is advisable with 2-5, and the best is 2-3; Become 50-70 ℃ of glue temperature, the best is 62-63 ℃; Gelation time is 1-3 hour, and the best is 1.5 hours; Crystallization temperature is 80-100 ℃, and the best is 89-91 ℃; Crystallization time is 2-6 hour, and the best is 2 hours.
The present invention has following outstanding advantage: (1) is raw material with salkali waste, has eliminated the pollution that aluminium manufacturer's salkali waste discharging causes.(2) contain 3.3%Al in the salkali waste
2O
3, when synthesizing the 4A zeolite, need not to replenish Al (OH) with high silicon kaolin
3(3) opened up a new application approach for natural kaolin.(4) adopt alkali to burn method technology, impel dirt compositions such as quartz in the kaolin, hydromica all to be converted into active ingredient, extract content is brought up to more than 98%, the calcium exchange capacity is brought up to 315mg Ca (OH)
2More than the dried zeolite of/g, degree of crystallinity brings up to 95%, and causes the finished product crystal grain many, and particle diameter is little.(4) abundant raw material, technology is simple, cost is low, help the 4A zeolite applies in the industry in washing.
Embodiment one: the waste lye of 2000 gram concentration about 15% is concentrated into thick shape, adds 150 gram kaolin, stir, 700 ℃ of following calcinations 2 hours, cooling, soluble in water, under 59-61 ℃, stirred into glue 1.5 hours, 89-91 ℃ of following backflow crystallization 2 hours, the cooling, decompress filter, with filter cake washing to PH＜11.0, descended dry 2 hours at 110 ℃ then, be the 4A zeolite product.The calcium exchange rate is 336mg CaCO after testing
3The dried zeolite of/g.
Embodiment two: removing alkali burning temperature is 650 ℃, and outside 3 hours, other is operated with example one.The calcium exchange rate is the dried zeolite of 310mg/g as a result.
Comparative example one: with direct scorching hot method with kaolin 900 ℃ of following calcinations 2 hours, other operation is identical with example one, the calcium exchange rate is the dried zeolite of 211mg/g as a result.
Comparative example two: with direct calcination method with kaolin 700 ℃ of following calcinations 3 hours, other operation is identical with example one, the calcium exchange rate is the dried zeolite of 112mg/g as a result.
Claims (6)
1. salkali waste and kaolin synthesis of detergent are with 4A zeolite method, and it is characterized in that: this method is made up of the following step: (1) stirred salkali waste and the kaolin weight ratio by 2-5, at 500-1000 ℃ time scorching hot 1-6 hour; (2) alkali burns the water-soluble back of thing, stirred under 50-70 ℃ glue 1-3 hour; (3) will become the glue thing 80-100 ℃ of following backflow crystallization 1-3 hour, through cooling, decompress filter, be washed to PH＜11, then 110 ℃ dry 2 hours down, can obtain the finished product; Wherein kaolinic sial mol is than about 1.8-2.3.
2. salkali waste as claimed in claim 1 and kaolin synthesis of detergent 4A zeolite method is characterized in that: aluminium manufacturer's salkali waste is as one of synthesis material, and described salkali waste is that aluminium manufacturer's aluminium section bar electrochemical surface is handled the useless sodium hydroxide solution that produces, wherein Al
2O
3Weight content is about 3.3%, the about 3.5N of NaOH equivalent concentration.
3. salkali waste as claimed in claim 1 and kaolin synthesis of detergent 4A zeolite method is characterized in that: described kaolinic sial mol is than being 2.1-2.3.
4. salkali waste as claimed in claim 1 and kaolin synthesis of detergent 4A zeolite method, it is characterized in that: when described alkali burning method activated kaolin, salkali waste/kaolinic weight ratio was 2-3.
5. salkali waste as claimed in claim 1 and kaolin synthesis of detergent 4A zeolite method is characterized in that: when described alkali burning method activated kaolin, it was 650-700 ℃ that alkali burns temperature.
6. salkali waste as claimed in claim 1 and kaolin synthesis of detergent 4A zeolite method, it is characterized in that: when described alkali burning method activated kaolin, the alkali burning time was 2-3 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00131817 CN1350053A (en) | 2000-10-19 | 2000-10-19 | Synthesis of detergent 4A zeolite with waste alkali and kaoline |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00131817 CN1350053A (en) | 2000-10-19 | 2000-10-19 | Synthesis of detergent 4A zeolite with waste alkali and kaoline |
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| CN1350053A true CN1350053A (en) | 2002-05-22 |
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| CN 00131817 Pending CN1350053A (en) | 2000-10-19 | 2000-10-19 | Synthesis of detergent 4A zeolite with waste alkali and kaoline |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434364C (en) * | 2006-03-10 | 2008-11-19 | 浙江师范大学 | 4A zeolite synthesized from kaolin by low-temperature alkali fusion method |
| CN102107880B (en) * | 2009-12-23 | 2012-11-14 | 深圳市海川实业股份有限公司 | Method for preparing zeolite 4A |
-
2000
- 2000-10-19 CN CN 00131817 patent/CN1350053A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434364C (en) * | 2006-03-10 | 2008-11-19 | 浙江师范大学 | 4A zeolite synthesized from kaolin by low-temperature alkali fusion method |
| CN102107880B (en) * | 2009-12-23 | 2012-11-14 | 深圳市海川实业股份有限公司 | Method for preparing zeolite 4A |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
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