CN103693655B - Efficient continuous production method of 4A zeolite - Google Patents
Efficient continuous production method of 4A zeolite Download PDFInfo
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- CN103693655B CN103693655B CN201310688440.6A CN201310688440A CN103693655B CN 103693655 B CN103693655 B CN 103693655B CN 201310688440 A CN201310688440 A CN 201310688440A CN 103693655 B CN103693655 B CN 103693655B
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Abstract
The invention discloses an efficient continuous production method of 4A zeolite. The efficient continuous production method is characterized by comprising the following steps: (1) preparing a sodium metaaluminate solution; (2) preparing a sodium silicate solution; (3) chemical combination and crystallization: respectively crystallizing the sodium metaaluminate solution and the sodium silicate solution according to a molar ratio of Al2O3:SiO2 being 1:(1.85-1.95) inside a reaction tank, and then filtering, washing and centrifugally dewatering; drying at 105-110 DEG C to obtain a 4A zeolite product. The content of solids in the materials can be up to 25-35%, and the production method is a continuous production technology and is high in production efficiency, and an energy source is saved. The main raw materials disclosed by the invention are wide in source. The product disclosed by the invention is high in calcium ion exchange capacity, good in compatibility with a surfactant, good in whiteness, uniform in particle size distribution, and good in degree of crystallinity, and the quality index can completely reach the national industry standard.
Description
Technical field
The present invention relates to a kind of 4A zeolite production method, especially a kind of 4A zeolite high-efficiency and continuous production method.
Background technology
As everyone knows, multifunctional assistant tripoly phosphate sodium STPP (STPP) introducing in detergent formulation, brings a qualitative leap to detergent industry, make the soil removability of washing composition, dispersion of calcium soap, anti-dirt again deposition capability etc. greatly improve.But microcosmic salt is a kind of rich nutritive material, and it enters the earth surface waters such as rivers and lakes with wash water, make the phytoplankton bloom in water, cause the dissolved oxygen content in water to decline, water colour is dimmed, and transparency reduces, and waters sensory trait worsens.Time serious, cause the biotic population in water to change, the hydrocoles mortalities such as fish, affect the production of the mankind, living environment and drinking water safety simultaneously.Many developed countries progressively realize washing composition without phosphatization, and China also has many places to take measures limit or forbid that phosphorus-containing detergent uses.In addition, along with the shortage of energy shortage and phosphate rock resource, the price continuous rise of tripoly phosphate sodium STPP is made.Therefore, select the washing auxiliary detergent of economic environmental protection to substitute common issue that tripoly phosphate sodium STPP becomes detergent industry, replaces the mainly 4A zeolite of tripoly phosphate sodium STPP at present.But due to manufacture craft, the select materials difference of 4A zeolite, its price and aspect of performance differ greatly, and as the company represented with Japan Cao Dawei of German Henkel, Degussa and Japan, adopt with Al (OH)
3, Na
2onSiO
2be raw-material Synthesis of 4 A-type Zeolite by Hydrothermal production method cost intensive with NaOH, complex manufacturing.The kaolin Synthesis technique being representative with U.S. combinating carbide company, with kaolin [AL
2si
2o
5(OH)
4] be raw material, carry out chloridizing roasting at 600-800 DEG C after, carry out the 4A zeolite that the stripping of benefit alkali, plastic and crystallization obtain, although production cost has got off, this complex process, and require high to kaolin starting material, raw material sources is few, unstable product quality, often causes product density high, granularity and whiteness defective, and chlorination technique difficulty is large, easily cause environmental pollution, simultaneously because density is high, uncomfortable cooperation washing auxiliary detergent uses.Therefore it is very necessary for developing a kind of process drum list, raw material is easy to get, production efficiency is high, being suitable for the highly effective continuous production method of 4A zeolite making washing auxiliary detergent.
Summary of the invention
The object of the invention is to overcome prior art deficiency, provide the 4A zeolite high-efficiency and continuous production method that a kind of quality is good, cost performance is high, object of the present invention is realized by following technical proposals; The present invention follows these steps to carry out:
1, sodium aluminate solution is prepared: become Na with the sodium hydroxide solution water use regulation of 50% concentration
2o content is the dissolution fluid of 170-200 grams per liter, by dissolution fluid and Al
2o
3na pressed by 200 order gibbsite breezes of content>=50%
2o:Al
2o
3the mixed in molar ratio of=3.25-3.65, this mixed solution is squeezed into autoclave and be warming up to 135 DEG C ~ 145 DEG C reaction 25 – 35 minutes, after press filtration, the solution with water of gained is adjusted to Al
2o
3content 95-110 grams per liter, is cooled to 40 DEG C ~ 50 DEG C as stand-by sodium aluminate solution using this solution;
2, sodium silicate solution is prepared: get SiO
2quartz sand 8 parts by weight of crushed of>=99% is to 200-250 order, add caustic soda (NaOH) 4 weight part, be placed in autoclave the 10-14 weight part that adds water again, 50 – is dissolved 70 minutes under 170 DEG C ~ 190 DEG C high temperature, after press filtration, the solution with water of gained regulates proportion to 1.32-1.36, is cooled to 30 DEG C ~ 40 DEG C and namely obtains stand-by sodium silicate solution;
3, chemical combination, crystallization; Respectively above-mentioned sodium aluminate solution and sodium silicate solution are pressed Al
2o
3: SiO
2the mol ratio of=1:1.85-1.95 is by adding up to flow 3-4m
3/ hour to squeeze into continuously in the retort being provided with high speed agitator and mix, the volume of retort is 15-20m
3; Question response tank canful rate is that 70-75%(keeps 70-75% canful rate) time continuously by 3-4m
3/ hour flow squeeze into 10-12m
3a crystallization tank be heated to 50-55 DEG C of crystallization, be that 70-75%(keeps 70-75% canful rate until a crystallization tank canful rate) time again by the material of a crystallization tank continuously by 3-4m
3/ hour flow squeeze into 12-15m
3no. two crystallization tanks, being heated to 60-70 DEG C of crystallization, is that 70-75%(keeps 70-75% canful rate until No. two crystallization tank canful rates) time again by the material of No. two crystallization tanks continuously by 3-4m
3/ hour flow squeeze into 12-15m
3no. three crystallization tanks, be heated to 95-100 DEG C of crystallization, be that 70-75%(keeps 70-75% canful rate until No. three crystallization tank canful rates) time continuous overflow go out that material carries out filtering, washes, centrifuge dehydration, under 105-110 DEG C of condition after drying 4A zeolite finished product.
Compared with prior art, the furnish solids thing content that usual way produces 4A zeolite is generally less than 15%, and furnish solids thing content of the present invention can reach 25-35%, and this production method is continuous production processes, production efficiency is high, save energy, and production quality product is easy to control.Main raw material wide material sources of the present invention.Product calcium ion exchange capacity of the present invention is high, with the compatibleness of tensio-active agent is good, whiteness is good, even particle size distribution, better crystallinity degree, its quality index can reach national sector standard completely.This product detects through Administration of Quality and Technology Supervision of Sichuan Province inspection center, and quality product is excellent, and its detection data are:
1, test basis: QB/T 1768-2003
2, Calc-alkaline volcanic rocks (mgCaCO
3/ g-butt): 314.56
3, loss on ignition (800 DEG C, 1h), %: 20.56
4, loose density (mg/ml): 350
5, pH value (1% solution 25 DEG C): 10.89
6, relative whiteness (W=Y), %:103.22
7, median size, μm: 2.41
8 ,≤4 μm of particle diameters, %:95.2
9, >=10 μm of particle diameters, %:0.51
10, Al
3+ (butt), %:18.56.
Embodiment
Embodiment 1, follows these steps to carry out:
1, sodium aluminate solution is prepared: become Na with the sodium hydroxide solution water use regulation of 50% concentration
2o content is the dissolution fluid of 170 grams per liters, by dissolution fluid and Al
2o
3na pressed by 200 order gibbsite breezes of content>=50%
2o:Al
2o
3the mixed in molar ratio of=3.25, this mixed solution is squeezed into autoclave and be warming up to 135 DEG C of reactions 35 minutes, after press filtration, the solution with water of gained is adjusted to Al
2o
3content 95 grams per liter, is cooled to 50 DEG C as stand-by sodium aluminate solution using this solution;
2, sodium silicate solution is prepared: get SiO
2quartz sand 8 parts by weight of crushed of>=99% is to 200-250 order, add caustic soda (NaOH) 4 weight part, be placed in autoclave 10 weight parts that add water again, dissolve 70 minutes under 170 DEG C of high temperature, after press filtration, the solution with water of gained regulates proportion to 1.32-1.36, is cooled to 30 DEG C ~ 40 DEG C and namely obtains stand-by sodium silicate solution;
3, chemical combination, crystallization; Respectively above-mentioned sodium aluminate solution and sodium silicate solution are pressed Al
2o
3: SiO
2the mol ratio of=1:1.85 is by adding up to flow 3-4m
3/ hour to squeeze into continuously in the retort being provided with high speed agitator and mix, the volume of retort is 15-20m
3; Question response tank canful rate is that 70-75%(keeps 70-75% canful rate) time continuously by 3-4m
3/ hour flow squeeze into 10-12m
3a crystallization tank, being heated to 50-55 DEG C of crystallization, is that 70-75%(keeps 70-75% canful rate until a crystallization tank canful rate) time again by the material of a crystallization tank continuously by 3-4m
3/ hour flow squeeze into 12-15m
3no. two crystallization tanks, being heated to 60 DEG C of crystallization, is that 70-75%(keeps 70-75% canful rate until No. two crystallization tank canful rates) time again by the material of No. two crystallization tanks continuously by 3-4m
3/ hour flow squeeze into 12-15m
3no. three crystallization tanks, being heated to 95 DEG C of crystallization, is that 70-75%(keeps 70-75% canful rate until No. three crystallization tank canful rates) time continuous overflow go out that material carries out filtering, washes, centrifuge dehydration, under 105 DEG C of conditions after drying 4A zeolite finished product.
Embodiment 2, follows these steps to carry out:
1, sodium aluminate solution is prepared: become Na with the sodium hydroxide solution water use regulation of 50% concentration
2o content is the dissolution fluid of 190 grams per liters, by dissolution fluid and Al
2o
3na pressed by 200 order gibbsite breezes of content>=50%
2o:Al
2o
3the mixed in molar ratio of=3.45, this mixed solution is squeezed into autoclave and be warming up to 140 DEG C of reactions 30 minutes, after press filtration, the solution with water of gained is adjusted to Al
2o
3content 100 grams per liter, is cooled to 45 DEG C as stand-by sodium aluminate solution using this solution;
2, sodium silicate solution is prepared: get SiO
2quartz sand 8 parts by weight of crushed of>=99% is to 200-250 order, add caustic soda (NaOH) 4 weight part, be placed in autoclave 12 weight parts that add water again, dissolve 60 minutes under 180 DEG C of high temperature, after press filtration, the solution with water of gained regulates proportion to 1.32-1.36, is cooled to 30 DEG C ~ 40 DEG C and namely obtains stand-by sodium silicate solution;
3, chemical combination, crystallization; Respectively above-mentioned sodium aluminate solution and sodium silicate solution are pressed Al
2o
3: SiO
2the mol ratio of=1:1.90 is by adding up to flow 3-4m
3/ hour to squeeze into continuously in the retort being provided with high speed agitator and mix, the volume of retort is 15-20m
3; Question response tank canful rate is that 70-75%(keeps 70-75% canful rate) time continuously by 3-4m
3/ hour flow squeeze into 10-12m
3a crystallization tank, being heated to 50-55 DEG C of crystallization, is that 70-75%(keeps 70-75% canful rate until a crystallization tank canful rate) time again by the material of a crystallization tank continuously by 3-4m
3/ hour flow squeeze into 12-15m
3no. two crystallization tanks, being heated to 65 DEG C of crystallization, is that 70-75%(keeps 70-75% canful rate until No. two crystallization tank canful rates) time again by the material of No. two crystallization tanks continuously by 3-4m
3/ hour flow squeeze into 12-15m
3no. three crystallization tanks, being heated to 98 DEG C of crystallization, is that 70-75%(keeps 70-75% canful rate until No. three crystallization tank canful rates) time continuous overflow go out that material carries out filtering, washes, centrifuge dehydration, under 108 DEG C of conditions after drying 4A zeolite finished product.
Embodiment 3, follows these steps to carry out:
1, sodium aluminate solution is prepared: become Na with the sodium hydroxide solution water use regulation of 50% concentration
2o content is the dissolution fluid of 200 grams per liters, by dissolution fluid and Al
2o
3na pressed by 200 order gibbsite breezes of content>=50%
2o:Al
2o
3the mixed in molar ratio of=3.65, this mixed solution is squeezed into autoclave and be warming up to 145 DEG C of reactions 25 minutes, after press filtration, the solution with water of gained is adjusted to Al
2o
3content 110 grams per liter, is cooled to 40 DEG C as stand-by sodium aluminate solution using this solution;
2, sodium silicate solution is prepared: get SiO
2quartz sand 8 parts by weight of crushed of>=99% is to 200-250 order, add caustic soda (NaOH) 4 weight part, be placed in autoclave 14 weight parts that add water again, dissolve 50 minutes under 190 DEG C of high temperature, after press filtration, the solution with water of gained regulates proportion to 1.32-1.36, is cooled to 30 DEG C ~ 40 DEG C and namely obtains stand-by sodium silicate solution;
3, chemical combination, crystallization; Respectively above-mentioned sodium aluminate solution and sodium silicate solution are pressed Al
2o
3: SiO
2the mol ratio of=1:1.95 is by adding up to flow 3-4m
3/ hour to squeeze into continuously in the retort being provided with high speed agitator and mix, the volume of retort is 15-20m
3; Question response tank canful rate is that 70-75%(keeps 70-75% canful rate) time continuously by 3-4m
3/ hour flow squeeze into 10-12m
3a crystallization tank, being heated to 50-55 DEG C of crystallization, is that 70-75%(keeps 70-75% canful rate until a crystallization tank canful rate) time again by the material of a crystallization tank continuously by 3-4m
3/ hour flow squeeze into 12-15m
3no. two crystallization tanks, being heated to 70 DEG C of crystallization, is that 70-75%(keeps 70-75% canful rate until No. two crystallization tank canful rates) time again by the material of No. two crystallization tanks continuously by 3-4m
3/ hour flow squeeze into 12-15m
3no. three crystallization tanks, being heated to 100 DEG C of crystallization, is that 70-75%(keeps 70-75% canful rate until No. three crystallization tank canful rates) time continuous overflow go out that material carries out filtering, washes, centrifuge dehydration, under 110 DEG C of conditions after drying 4A zeolite finished product.
Claims (1)
1. a 4A zeolite high-efficiency and continuous production method, is characterized in that, follows these steps to carry out:
(1) sodium aluminate solution is prepared: become Na with the sodium hydroxide solution water use regulation of 50% concentration
2o content is the dissolution fluid of 170-200 grams per liter, by dissolution fluid and Al
2o
3na pressed by 200 order gibbsite breezes of content>=50%
2o:Al
2o
3the mixed in molar ratio of=3.25-3.65, this mixed solution is squeezed into autoclave and be warming up to 135 DEG C ~ 145 DEG C reaction 25 – 35 minutes, after press filtration, the solution with water of gained is adjusted to Al
2o
3content 95-110 grams per liter, is cooled to 40 DEG C ~ 50 DEG C as stand-by sodium aluminate solution using this solution;
(2) sodium silicate solution is prepared: get SiO
2quartz sand 8 parts by weight of crushed of>=99% is to 200-250 order, add caustic soda 4 weight part, be placed in autoclave the 10-14 weight part that adds water again, 50 – is dissolved 70 minutes under 170 DEG C ~ 190 DEG C high temperature, after press filtration, the solution with water of gained regulates proportion to 1.32-1.36, is cooled to 30 DEG C ~ 40 DEG C and namely obtains stand-by sodium silicate solution;
(3) chemical combination, crystallization; Respectively above-mentioned sodium aluminate solution and sodium silicate solution are pressed Al
2o
3: SiO
2the mol ratio of=1:1.85-1.95 is by adding up to flow 3-4m
3/ hour to squeeze into continuously in the retort being provided with high speed agitator and mix, the volume of retort is 15-20m
3; Continuously by 3-4m when question response tank canful rate is 70-75%
3/ hour flow squeeze into 10-12m
3a crystallization tank be heated to 50-55 DEG C of crystallization, when a crystallization tank canful rate is 70-75% again by the material of a crystallization tank continuously by 3-4m
3/ hour flow squeeze into 12-15m
3no. two crystallization tanks, be heated to 60-70 DEG C of crystallization, when No. two crystallization tank canful rates are 70-75% again by the material of No. two crystallization tanks continuously by 3-4m
3/ hour flow squeeze into 12-15m
3no. three crystallization tanks, be heated to 95-100 DEG C of crystallization, when No. three crystallization tank canful rates are 70-75%, continuous overflow goes out that material carries out filtering, washes, centrifuge dehydration, under 105-110 DEG C of condition after drying 4A zeolite finished product.
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| CN103693655B true CN103693655B (en) | 2015-04-15 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5474753A (en) * | 1990-11-09 | 1995-12-12 | Laviosa Rhone-Poulenc | Preparation of crystalline 4A zeolites |
| CN1775675A (en) * | 2005-12-01 | 2006-05-24 | 中国日用化学工业研究院 | Process for preparing zeolite |
| CN101428816A (en) * | 2008-11-27 | 2009-05-13 | 中国日用化学工业研究院 | Process and equipment for synthesis of sub-micron 4A zeolite with continuous crystallization |
| CN101445254A (en) * | 2008-12-31 | 2009-06-03 | 平朔煤炭工业公司 | Method for producing 4A molecular sieve |
| CN101654257A (en) * | 2009-10-21 | 2010-02-24 | 中国铝业股份有限公司 | Method for preparing 4A zeolite by continuous crystallization |
| CN101891212A (en) * | 2010-05-19 | 2010-11-24 | 南充春飞纳米晶硅技术有限公司 | Poly sodium aluminosilicate ultramicro powder compound and production method thereof |
-
2013
- 2013-12-17 CN CN201310688440.6A patent/CN103693655B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5474753A (en) * | 1990-11-09 | 1995-12-12 | Laviosa Rhone-Poulenc | Preparation of crystalline 4A zeolites |
| CN1775675A (en) * | 2005-12-01 | 2006-05-24 | 中国日用化学工业研究院 | Process for preparing zeolite |
| CN101428816A (en) * | 2008-11-27 | 2009-05-13 | 中国日用化学工业研究院 | Process and equipment for synthesis of sub-micron 4A zeolite with continuous crystallization |
| CN101445254A (en) * | 2008-12-31 | 2009-06-03 | 平朔煤炭工业公司 | Method for producing 4A molecular sieve |
| CN101654257A (en) * | 2009-10-21 | 2010-02-24 | 中国铝业股份有限公司 | Method for preparing 4A zeolite by continuous crystallization |
| CN101891212A (en) * | 2010-05-19 | 2010-11-24 | 南充春飞纳米晶硅技术有限公司 | Poly sodium aluminosilicate ultramicro powder compound and production method thereof |
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