CN101654257B - Method for preparing 4A zeolite by continuous crystallization - Google Patents
Method for preparing 4A zeolite by continuous crystallization Download PDFInfo
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- CN101654257B CN101654257B CN2009103085388A CN200910308538A CN101654257B CN 101654257 B CN101654257 B CN 101654257B CN 2009103085388 A CN2009103085388 A CN 2009103085388A CN 200910308538 A CN200910308538 A CN 200910308538A CN 101654257 B CN101654257 B CN 101654257B
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- 238000002425 crystallisation Methods 0.000 title claims abstract description 177
- 230000008025 crystallization Effects 0.000 title claims abstract description 173
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 50
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000010457 zeolite Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims description 48
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 235000019353 potassium silicate Nutrition 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 239000004115 Sodium Silicate Substances 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 229910052911 sodium silicate Inorganic materials 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 4
- 238000010923 batch production Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000037390 scarring Effects 0.000 description 1
- 239000005432 seston Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing 4A zeolite by continuous crystallization. A sodium metaaluminate solution and sodium silicate are used as raw materials to prepare the 4A zeolite, groove type devices connected in series are divided into two groups to carry out continuous crystallization at two temperatures, and the continuous crystallization is divided into two processes of precrystallization and growing crystallization; a guiding agent is added in the phase of the precrystallization at lower temperature to induce a crystal nucleus so that a crystal initially grows; the temperature rises in the phase of the growing crystallization, the 4A crystal fully grows till the crystallization is perfect, and the process of continuous crystallization is finally finished. The method can effectively lower a manual control point to carry out centralized control, reduce the labor intensity and improve the production efficiency; and because the temperature gradually rises, thereby effectively inhibiting a mixed crystal and ensuring stable quality of products.
Description
Technical field
The invention belongs to chemical industry, washing technology field, be specifically related to the method that a kind of continuous crystallization prepares the 4A zeolite.
Background technology
At present, domestic general employing sodium aluminate solution is that building-up reactions production 4A zeolite is carried out in the silicon source as the raw material of producing the 4A zeolite as the aluminium source with water glass with it.The production of 4A zeolite belongs to single groove batch production more, has only reached the quantity-produced requirement on pulp and separating, washing and baking operation, and main synthesis phase is grabbed the crystallization stage and is still single groove batch production mode.Every groove all needs strict control condition, satisfies the requirement of technology, could guarantee the qualified up to standard of product index.The reference mark is many, causes the quality product fluctuation easily, has influenced user's use.CN 1453213A discloses the technology of having mentioned a kind of continuous crystallization in a kind of technology of the 4A of preparation zeolite and the specific equipment thereof, the crystallization device that adopts is a kind of canalization equipment, crystallization temperature is single temperature, and itself has many insurmountable problems as canalization production: problems such as, residence time of material difficult as the pipeline scarring cleaning is long.
Summary of the invention
The present invention is directed to the method that problems of the prior art provide a kind of continuous crystallization to prepare the 4A zeolite, it can realize that continuous crystallization synthesizes the 4A zeolite, can effectively reduce the Artificial Control point, reduce labour intensity, enhance productivity, and can carry out centralized Control, guarantee constant product quality.
Technical thought of the present invention is:
The present invention with placed in-line slot type equipment be divided into two groups, adopt two temperature carry out crystallization realize crystallization process continuously.Continuous crystallization technology is divided into pre-crystallization section and two processes of growth crystallization section, keeps lesser temps in pre-crystallization section, adds the 4A guiding agent for zeolite and causes initial nucleus and make crystal one-step growth just in slurries; Improve temperature in growth crystallization section, promote that crystal growth is perfect to crystallization.Adopt temperature to improve piecemeal, can effectively suppress the generation of stray crystal.
The present invention is achieved by the following technical programs:
A kind of continuous crystallization prepares the method for 4A zeolite, and it may further comprise the steps:
A. pulp process: will purify deployed with Al
2O
3Meter concentration is the sodium aluminate solution of 40 ~ 120g/l and with SiO
2Meter concentration is that 8 ~ 25% water glass solution joins in the reactive tank that is stirring simultaneously according to silica alumina ratio 1 ~ 2.5, makes sodium aluminate solution and water glass thorough mixing homogenizing slurry, and temperature of reaction is controlled at 30 ~ 70 ℃, slip.Wherein cleaning section is solution to be filtered remove seston, and the allotment operation is that water is adjusted to the concentration that needs with each original solution flushing, is prior art.
B. pre-crystallization process: the slip that step a is obtained is continuously pumped into the placed in-line first pre-crystallization groove with the conveying pump housing, add the 4A guiding agent for zeolite, wherein the 4A guiding agent for zeolite is 3 ~ 7 ‰ with the slurry volume ratio, then with carry pump housing successive above slip send into the second pre-crystallization groove, to the pre-crystallization groove of n, wherein n is 2 ~ 8, carry out pre-crystallization and cause nucleus making 4A crystal one-step growth just, controlling all pre-crystallization groove temperature is 30 ~ 70 ℃, and calculating the pump housing flow control residence time of slurries in each pre-crystallization groove is 10 ~ 300min.Wherein the 4A guiding agent for zeolite is " to prepare 4A zeolite directed agents " according to Chinese patent (patent No. is: method 200410155445.3) makes.
C. the crystallization process of growing: with the slurries after the pre-crystallization of step b be continuously pumped into placed in-line first growth crystallization groove, the second growth crystallization groove, to n growth crystallization groove, wherein n is 2 ~ 8, then slurries are improved temperature, crystallization is the 4A zeolite of pure phase to make crystal fully grow also, it is the gel complete crystallization in the slurries, controlling all growth crystallization groove temperature is 50 ~ 100 ℃, and the residence time of control slurries in each growth crystallization groove is 10 ~ 300min.
D. filter, washing, drying process: the material that step c crystallization is good carries out solid-liquid separation, and solid obtains the 4A zeolite product after washing and drying.
Preferably, above-mentioned continuous crystallization prepares the method for 4A zeolite, and pre-crystallization process temperature is controlled at 40 ~ 60 ℃ among the described step b, and the residence time is controlled at 20 ~ 150min, and the quantity of pre-crystallization groove is controlled at 5 ~ 6.
Preferably, above-mentioned continuous crystallization prepares the method for 4A zeolite, and growth crystallization process temperature is controlled at 60 ~ 80 ℃ among the described step c, and the residence time is controlled at 20 ~ 150min, and the quantity of growth crystallization groove is controlled at 5 ~ 6.
Preferably, in the described pre-crystallization process in the n value of pre-crystallization groove and the growth crystallization process n value of growth crystallization groove equal.
In each crystallization groove, the pattern of slurry is the plug flow pattern.Plug flow model: also claim plug flow model or desirable replacement model.Be that a kind of back-mixing amount is zero ideal flow model, its assumed response thing is gone into reactor with regime flow, moves forward as cylinder piston abreast in reactor; Its feature is, flow direction along material, material temperature, the continuous conversion of concentration, and perpendicular to all parameters of the material on arbitrary sagittal plane of Flow of Goods and Materials direction, all identical as concentration, temperature, pressure, flow velocity, therefore, all material particles have the identical residence time in reactor.Produce in the 4A zeolite technological process at continuous crystallization, obvious this model helps avoiding the back-mixing of fresh pulp liquid, 4A zeolite crystal, crystallization mother liquor three components, thereby suppress the generation of stray crystal phase, in the altitude range of a certain sagittal plane, can regard intermittent type list groove crystallization as.
The present invention compared with prior art has following beneficial effect:
The present invention utilizes sodium aluminate solution as the synthetic 4A zeolite of raw material, adopt the continuous pulp mode of material in the building-up process, soon the good material of pulp enters the pre-crystallization groove of series connection continuously and adds directed agents and carry out pre-crystallization in early stage, enter placed in-line growth crystallization groove then continuously and carry out complete crystallization, reached product index, the successive discharging of end crystallization groove, its whole technology can realize that continuous crystallization synthesizes the 4A zeolite, can carry out centralized Control, effectively reduce the Artificial Control point, reduce labour intensity, improve plant factor and production efficiency, also can guarantee constant product quality simultaneously.Improve the production production capacity on the whole, reduced production cost.
Description of drawings
Fig. 1 is the continuous crystallization schematic flow sheet of embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiment of the present invention is elaborated:
Fig. 1 is the continuous crystallization schematic flow sheet of embodiment of the present invention.C is a reactive tank, and a1, a2 ~ an are respectively the first pre-crystallization groove, second pre-crystallization groove ~ pre-crystallization groove of n, and n can be 2 ~ 8; B1, b2, b3 ~ bn are the first growth crystallization groove, the second growth crystallization groove, the 3rd growth crystallization groove ~ n growth crystallization groove, and n can be 2 ~ 8; Be connected in series successively with the pump housing and pipeline between each pre-crystallization groove a1, a2 ~ an and each growth crystallization groove b1, b2, the b3 ~ bn, can realize the continuous crystallization of 4A zeolite thus.
Embodiment 1
Pulp process: will purify deployed with Al
2O
3Meter concentration is the sodium aluminate solution of 40g/l and with SiO
2Meter concentration is that 8% water glass solution joins among the reactive tank c that is stirring simultaneously according to silica alumina ratio 1, makes sodium aluminate solution and water glass thorough mixing homogenizing slurry, and temperature of reaction is controlled at 30 ℃, slip;
Pre-crystallization process: the slip of above-mentioned steps is continuously pumped into placed in-line first pre-crystallization groove a1 with the conveying pump housing, add the 4A guiding agent for zeolite, wherein the 4A guiding agent for zeolite is 3 ‰ with the slurry volume ratio, with carrying pump housing successive that above slip is sent into the second pre-crystallization groove a2, the 3rd pre-crystallization groove a3 Pang the 8th pre-crystallization groove a8 (n is 8); Slurries carry out pre-crystallization and cause nucleus making 4A crystal one-step growth just in pre-crystallization groove, controlling all pre-crystallization groove temperature is 30 ℃, and calculating the pump housing flow control residence time of slurries in each pre-crystallization groove is 300min.
Growth crystallization process: the slurries after the above-mentioned pre-crystallization are continuously pumped into placed in-line first growth crystallization groove b1, the second growth crystallization groove b2, the 3rd growth crystallization groove b3 Pang the 8th growth crystallization groove b8 (n is 8); Slurries are improved temperature, crystal in the slurries is fully grown and crystallization is the 4A zeolite (Na of pure phase
2O2SiO
2Al
2O
34.5H
2O); Controlling all growth crystallization groove temperature is 50 ℃, and the residence time of control slurries in each growth crystallization groove is 300min.
Filtration, washing, drying process: the material that above-mentioned crystallization is good carries out solid-liquid separation, and solid obtains the 4A zeolite product after washing and drying.
Embodiment 2
Pulp process: will purify deployed with Al
2O
3Meter concentration is the sodium aluminate solution of 80g/l and with SiO
2Meter concentration is that 13% water glass solution joins among the reactive tank c that is stirring simultaneously according to silica alumina ratio 1.5, makes sodium aluminate solution and water glass thorough mixing homogenizing slurry, and temperature of reaction is controlled at 50 ℃, slip;
Pre-crystallization process: the slip of above-mentioned steps is continuously pumped into placed in-line first pre-crystallization groove a1 with the conveying pump housing, add the 4A guiding agent for zeolite, wherein the 4A guiding agent for zeolite is 4 ‰ with the slurry volume ratio, with carrying pump housing successive that above slip is sent into the second pre-crystallization groove a2, the 3rd pre-crystallization groove a3, the 4th pre-crystallization groove a4 (n is 4); Slurries carry out pre-crystallization and cause nucleus making 4A crystal one-step growth just in pre-crystallization groove, each crystallization groove temperature of control is 50 ℃, and calculating the pump housing flow control residence time of slurries in all pre-crystallization grooves is 100min.
Growth crystallization process: the slurries after the above-mentioned pre-crystallization are continuously pumped into placed in-line first growth crystallization groove b1, the second growth crystallization groove b2, the 3rd growth crystallization groove b3, the 4th growth crystallization groove b4 (n is 4); Slurries are improved temperature, crystal in the slurries is fully grown and crystallization is the 4A zeolite (Na of pure phase
2O2SiO
2Al
2O
34.5H
2O); Controlling all growth crystallization groove temperature is 70 ℃, and the residence time of control slurries in each growth crystallization groove is 100min.
Filtration, washing, drying process: the material that above-mentioned crystallization is good carries out solid-liquid separation through band filter, and solid obtains the 4A zeolite product after washing and drying.
Embodiment 3
Pulp process: will purify deployed with Al
2O
3Meter concentration is the sodium aluminate solution of 100g/l and with SiO
2Meter concentration is that 19% water glass solution joins among the reactive tank c that is stirring simultaneously according to silica alumina ratio 2, makes sodium aluminate solution and water glass thorough mixing homogenizing slurry, and temperature of reaction is controlled at 70 ℃, slip;
Pre-crystallization process: the slip of above-mentioned steps is continuously pumped into placed in-line first pre-crystallization groove a1 with the conveying pump housing, add the 4A guiding agent for zeolite, wherein the 4A guiding agent for zeolite is 6 ‰ with the slurry volume ratio, with carrying pump housing successive that above slip is sent into the second pre-crystallization groove a2 (n is 2); Slurries carry out pre-crystallization and cause nucleus making 4A crystal one-step growth just in pre-crystallization groove, controlling all pre-crystallization groove temperature is 70 ℃, and calculating the pump housing flow control residence time of slurries in each pre-crystallization groove is 200min.
Growth crystallization process: the slurries after the above-mentioned pre-crystallization are continuously pumped into placed in-line first growth crystallization groove b1, the second growth crystallization groove b2 (n is 2); Slurries are improved temperature, crystal in the slurries is fully grown and crystallization is the 4A zeolite (Na of pure phase
2O2SiO
2Al
2O
34.5H
2O); Controlling all growth crystallization groove temperature is 100 ℃, and the residence time of control slurries in each growth crystallization groove is 200min.
Filtration, washing, drying process: the material that above-mentioned crystallization is good carries out solid-liquid separation through band filter, and solid obtains the 4A zeolite product after washing and drying.
Embodiment 4
Pulp process: will purify deployed with Al
2O
3Meter concentration is the sodium aluminate solution of 120g/l and with SiO
2Meter concentration is that 25% water glass solution joins among the reactive tank c that is stirring simultaneously according to silica alumina ratio 2.5, makes sodium aluminate solution and water glass thorough mixing homogenizing slurry, and temperature of reaction is controlled at 60 ℃, slip;
Pre-crystallization process: the slip of above-mentioned steps is continuously pumped into placed in-line first pre-crystallization groove a1 with the conveying pump housing, add the 4A guiding agent for zeolite, wherein the 4A guiding agent for zeolite is 7 ‰ with the slurry volume ratio, with carrying pump housing successive that above slip is sent into the second pre-crystallization groove a2, the 3rd pre-crystallization groove a3, the 4th pre-crystallization groove a4, the 5th pre-crystallization groove a5 (n is 5); Slurries carry out pre-crystallization and cause nucleus making 4A crystal one-step growth just in pre-crystallization groove, controlling all pre-crystallization groove temperature is 65 ℃, and calculating the pump housing flow control residence time of slurries in each pre-crystallization groove is 10min.
Growth crystallization process: the slurries after the above-mentioned pre-crystallization are continuously pumped into placed in-line first growth crystallization groove b1, the second growth crystallization groove b2, the 3rd growth crystallization groove b3, the 4th growth crystallization groove b4, the 5th growth crystallization groove b5 (n is 5); Slurries are improved temperature, crystal in the slurries is fully grown and crystallization is the 4A zeolite (Na of pure phase
2O2SiO
2Al
2O
34.5H
2O); Controlling all growth crystallization groove temperature is 100 ℃, and the residence time of control slurries in each growth crystallization groove is 10min.
Filtration, washing, drying process: the material solid-liquid separation that above-mentioned crystallization is good, solid obtains the 4A zeolite product after washing and drying.
Claims (4)
1. a continuous crystallization prepares the method for 4A zeolite, it is characterized in that it may further comprise the steps:
A. pulp process: will purify deployed with Al
2O
3Meter concentration is the sodium aluminate solution of 40～120g/L and with SiO
2Meter concentration is that 8～25% water glass solution joins in the reactive tank that is stirring simultaneously according to silica alumina ratio 1～2.5, makes sodium aluminate solution and water glass thorough mixing homogenizing slurry, and temperature of reaction is controlled at 30～70 ℃, slip;
B. pre-crystallization process: the slip of step a is continuously pumped into the placed in-line first pre-crystallization groove with the conveying pump housing, add the 4A guiding agent for zeolite, wherein the 4A guiding agent for zeolite is 3～7 ‰ with the slurry volume ratio, then with carry pump housing successive above slip send into the second pre-crystallization groove, to the pre-crystallization groove of n, wherein n is 2～8, carry out pre-crystallization and cause nucleus making 4A crystal one-step growth just, controlling all pre-crystallization groove temperature is 30～70 ℃, and calculating the pump housing flow control residence time of slurries in each pre-crystallization groove is 10～300min;
C. the crystallization process of growing: with the slurries after the pre-crystallization of step b be continuously pumped into the placed in-line first growth crystallization groove, the second growth crystallization groove, to n growth crystallization groove, wherein n is 2～8, then slurries are improved temperature, crystallization is the 4A zeolite of pure phase to make crystal fully grow also, it is the gel complete crystallization in the slurries, controlling all growth crystallization groove temperature is 50～100 ℃, and the residence time of control slurries in each growth crystallization groove is 10～300min;
D. filter, washing, drying process: the material that step c crystallization is good carries out solid-liquid separation through band filter, and solid obtains the 4A zeolite product after washing and drying.
2. continuous crystallization as claimed in claim 1 prepares the method for 4A zeolite, it is characterized in that, pre-crystallization process temperature is controlled at 40～60 ℃ among the described step b, and the residence time is controlled at 20～150min, and the quantity of pre-crystallization groove is controlled at 5～6.
3. continuous crystallization as claimed in claim 1 prepares the method for 4A zeolite, it is characterized in that, growth crystallization process temperature is controlled at 60～80 ℃ among the described step c, and the residence time is controlled at 20～150min, and the quantity of growth crystallization groove is controlled at 5～6.
4. continuous crystallization as claimed in claim 1 prepares the method for 4A zeolite, it is characterized in that, the n value of the crystallization groove of growing in the n value of pre-crystallization groove and the growth crystallization process in the described pre-crystallization process equates.
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| CN103253680A (en) * | 2013-05-24 | 2013-08-21 | 杭州电子科技大学 | Method for synthesizing zeolite by using waste cathode-ray tube as raw material |
| CN103693655B (en) * | 2013-12-17 | 2015-04-15 | 南充春飞纳米晶硅技术有限公司 | Efficient continuous production method of 4A zeolite |
| CN103723742A (en) * | 2013-12-31 | 2014-04-16 | 中国天辰工程有限公司 | Post-treatment method for washing, drying and calcining SAPO (silicoaluminophosphate) molecular sieve |
| CN110652950B (en) * | 2019-09-04 | 2021-04-23 | 北京化工大学 | Microwave coupling hypergravity reaction system for continuous production of porous materials |
| CN111453743B (en) * | 2020-03-19 | 2023-05-23 | 中铝山东新材料有限公司 | Preparation method of modified 4A zeolite for washing auxiliary agent and product thereof |
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|---|---|---|---|---|
| US6440885B1 (en) * | 1998-12-30 | 2002-08-27 | Corning Incorporated | Zeolite membrane and a process for the production thereof |
| CN1594523A (en) * | 2004-06-18 | 2005-03-16 | 中国铝业股份有限公司 | Method for continuous synthesis of 4A zeolite for detergent auxiliary |
| CN1775675A (en) * | 2005-12-01 | 2006-05-24 | 中国日用化学工业研究院 | Process for preparing zeolite |
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2009
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6440885B1 (en) * | 1998-12-30 | 2002-08-27 | Corning Incorporated | Zeolite membrane and a process for the production thereof |
| CN1594523A (en) * | 2004-06-18 | 2005-03-16 | 中国铝业股份有限公司 | Method for continuous synthesis of 4A zeolite for detergent auxiliary |
| CN1775675A (en) * | 2005-12-01 | 2006-05-24 | 中国日用化学工业研究院 | Process for preparing zeolite |
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