CN101591025A - A kind of method of utilizing kaolin to prepare binderless A type zeolite molecular sieve - Google Patents
A kind of method of utilizing kaolin to prepare binderless A type zeolite molecular sieve Download PDFInfo
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- CN101591025A CN101591025A CNA2009103038052A CN200910303805A CN101591025A CN 101591025 A CN101591025 A CN 101591025A CN A2009103038052 A CNA2009103038052 A CN A2009103038052A CN 200910303805 A CN200910303805 A CN 200910303805A CN 101591025 A CN101591025 A CN 101591025A
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- molecular sieve
- zeolite molecular
- kaolin
- type zeolite
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Abstract
The invention discloses a kind of method of utilizing kaolin to prepare binderless A type zeolite molecular sieve.It is raw material that the present invention adopts cheap common natural kaolin, first moulding granulation, again through after the calcination process with NaOH solution mixings ageing, crystallization, pass through separation, washing, drying at last and obtain product.The present invention mainly solved the zeolite powder exist in actual applications difficult reclaim, easily inactivation and accumulative shortcoming, and in moulding process, add binding agent and can cause that effective surface area reduces the problem with diffusional limitation.It is simple that the present invention has technological process, and cost is lower, and loose operation condition, and the recycle of employed NaOH solution energy are technique of zero discharge, and be little to environmental influence.The prepared binderless A type zeolite molecular sieve of the present invention has purity height, few, the loading capacity advantages of higher of stray crystal, is a kind of non-corrosiveness, no water-swelling, "dead", nontoxic, non-deliquescent inorganic multifunctional material.
Description
Technical field
The present invention relates to a kind of synthetic technology of zeolite molecular sieve, be specifically related to a kind of method of utilizing kaolin to prepare binderless A type zeolite molecular sieve.
Background technology
A type zeolite molecular sieve is a kind of have uniform sequential micropore, bigger specific surface area and inorganic multifunctional material of pore volume.Because it has characteristics such as good adsorption properties, ion-exchange performance, selectivity, thermostability and chemical modifiability, is widely used in Industrial Catalysis, aspects such as fractionation by adsorption and ion-exchange.Usually synthetic A type zeolite molecular sieve is Powdered, can form dust in actual applications, and there are shortcomings such as difficult recovery, easy inactivation and gathering in inconvenient operation.Present method is the binding agent that adds 20%-30% in A type zeolite molecular sieve powder, makes the particle with certain physical strength and shape.Binding agent commonly used comprises clay minerals such as oxide compound such as aluminum oxide, silicon-dioxide and kaolin, polynite.Introduce the aperture that binding agent can reduce effective zeolite molecular sieve components contents and may partly stop up zeolite molecular sieve, cause adsorptive power to weaken and increased diffusional limitation, cause the decline of adsorption selectivity and absorption and desorption rate, in application, then show as adsorptive power, activity and selectivity and descend, and the binding agent composition also may cause some side reactions.
The binder free zeolite molecular sieve is meant and does not contain inert binder in the zeolite molecular sieve particle or only contain small amount of binder, the zeolite block of material with definite shape and size that mainly relies on the interaction self-supporting between zeolite grain to exist.The content of binder free zeolite molecular sieve mesolite molecular sieve is higher, and therefore available effective surface area is bigger, have good performance at aspects such as fractionation by adsorption, ion-exchange and catalysis, so the research of binder free zeolite molecular sieve receives much concern.Li Shanan etc. are raw material with inorganic ammonium salt, mineral acid, water glass, prepare the silica hydrogel bead with the oil column spherical container shaping method, through washing, soak tensio-active agent, drying, roasting, make the silicon-dioxide bead, again the silicon-dioxide bead is mixed with sodium aluminate solution, after aging, crystallization, obtain binder-free spherical model-A molecular sieves [the kind peace of Lee production method of binder-free spherical model-A molecular sieves patent No.: CN87105499].Aforesaid method adopts chemical feedstocks preparation silicon-dioxide bead earlier, and raw materials cost is higher, and processing condition require tighter, the industrial flow complexity.Guan Weihong etc. have proposed will be through the kaolin after 800 ℃ of calcinings, sodium hydroxide and water mixing moulding, reacting in 30% sodium hydroxide solution at 110 ℃ behind 700 ℃ of following roasting certain hours, obtain binder free 4A molecular sieve [the grand Shaanxi of Guan Wei chemical industry 2000, (1) 29:46-48] at last.This method needs the double roasting process, and energy consumption is higher, and has mixed sodium hydroxide in the kaolin before the moulding, and will use high alkali liquid in the subsequent technique, and equipment is had bigger corrosion, has reduced the work-ing life of equipment.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of binderless A type zeolite molecular sieve, this method raw material is easy to get, inexpensive; Technical process is simple, the disposable A type zeolite that changes into of raw material; Only need the bakes to burn the article process, energy consumption is lower; A little less than the corrosion to equipment, and the recycle of reaction solution energy, zero release, little to environmental influence.A type zeolite in the binding agent A type zeolite molecular sieve that makes has that particle diameter is little, degree of crystallinity is high and advantage such as impurity is few; The content of product mesolite molecular sieve is higher, and available effective surface area is bigger, has good adsorption performance, ion-exchange performance, selectivity etc.
The objective of the invention is to realize in the following manner.
A kind of method of utilizing kaolin to prepare binderless A type zeolite molecular sieve may further comprise the steps:
(1) with SiO
2/ Al
2O
3Mol ratio is that the kaolin fragmentation of 2.0-2.4 is sieved, and dries after the granulation that tempers, then at 500-900 ℃ of following roasting 0.5-6h;
(2) will the particle after roasting join ageing in the NaOH solution of 1.0-4.0mol/L;
(3) crystallization then promptly obtains binderless A type zeolite molecular sieve with prepared zeolite molecular sieve particle again after separation, washing, drying.
The kaolin that described (1) was chosen in the step is crossed the 100-200 mesh sieve after fragmentation.
The consumption of regulating NaOH solution in described (2) step makes Na in the reaction system
2O/SiO
2Mol ratio remains on 2.0-6.0.
Aged temperature is 50-60 ℃ in described (2) step, and the time is 4-24h.
The temperature of crystallization is 80-130 ℃ in described (3) step, and the time is 6-24h.
In described (3) step, the zeolite molecular sieve particle utilizes as the NaOH solution circulated in the step (2) through the liquid that after separating obtains.
Compared with prior art, the present invention has the following advantages:
(1) the selected raw material of the present invention is common natural kaolin, and raw material is easy to get and is cheap.Because the Si/Al (mol ratio) in the selected kaolin in Si/Al (mol ratio) and the A type zeolite molecular sieve is close, so need not to add silicon source and aluminium source in preparation process, has reduced production cost;
(2) to adopt clay mineral be main raw material in the present invention, utilizes the high characteristic of the viscosity of raw material own, need not to add binding agent in the raw material before the moulding, also need not to add sodium hydroxide, and moulding process can not cause corrosion to equipment;
(3) this technological process is simple, and cost is lower, and loose operation condition only needs the bakes to burn the article process, is low power technology, and a little less than the low corrosion to equipment of employed NaOH strength of solution, and the recycle of NaOH solution energy, be technique of zero discharge, little to environmental influence;
(4) because the present invention has increased aging step in preparation process, can make the molecular sieve that makes have purity height, few, the loading capacity advantages of higher of stray crystal;
(5) binderless A type zeolite molecular sieve that makes of the present invention not only has characteristics such as stronger adsorptive power, stable performance, and non-corrosiveness, no water-swelling, "dead", nontoxic, deliquescence not.
Description of drawings
Fig. 1 is a binderless A type zeolite molecular sieve preparation technology schema;
Fig. 2 is the XRD figure of embodiment 1 product A 1;
Fig. 3 is the sem photograph (magnification is 4000 times) of embodiment 1 product A 1;
Fig. 4 is the XRD figure of embodiment 5 product A 5;
Fig. 5 is the sem photograph (magnification is 3000 times) of embodiment 5 product A 5.
Embodiment
Embodiment 1
Choose SiO
2/ Al
2O
3(mol ratio) is 2.0 kaolin, and raw material is crossed 100 mesh sieves after fragmentation, adds the suitable quantity of water mediation and carries out granulation.Kaolin particle is put into 500 ℃ of following roasting 6h of retort furnace behind dryness in the sun.Particle after the roasting joins in the 1.0mol/L NaOH solution, makes Na by the consumption of regulating NaOH solution
2O/SiO
2=2.0 (mol ratios) are at 50 ℃ of following ageing 4h, then at 80 ℃ of following crystallization 6h, after promptly obtain product A 1 after the separation, washing, drying.Technical process as shown in Figure 1, synthetic binderless A type zeolite molecular sieve XRD figure is composed as shown in Figure 2, Fig. 3 has provided the sem photograph of product.The Static Water adsorptive value (wt%) of product and ultimate compression strength (N/) are as shown in table 1.
Embodiment 2
Choose SiO
2/ Al
2O
3(mol ratio) is 2.2 kaolin, and raw material is crossed 120 mesh sieves after fragmentation, adds the suitable quantity of water mediation and carries out granulation.Kaolin particle is put into 600 ℃ of following roasting 4h of retort furnace behind dryness in the sun.Particle after the roasting joins in the 3.0mol/L NaOH solution, makes Na by the consumption of regulating NaOH solution
2O/SiO
2=3.8 (mol ratios) are at 55 ℃ of following ageing 8h, then at 100 ℃ of following crystallization 10h, after promptly obtain product A 2 after the separation, washing, drying.The Static Water adsorptive value (wt%) of product and ultimate compression strength (N/) are as shown in table 1.
Embodiment 3
Choose SiO
2/ Al
2O
3(mol ratio) is 2.4 kaolin, and raw material is crossed 200 mesh sieves after fragmentation, adds the suitable quantity of water mediation and carries out granulation.Kaolin particle is put into 700 ℃ of following roasting 3h of retort furnace behind dryness in the sun.Particle after the roasting joins in the 4.0mol/L NaOH solution, makes Na by the consumption of regulating NaOH solution
2O/SiO
2=4.0 (mol ratios) are at 60 ℃ of following ageing 12h, then at 90 ℃ of following crystallization 12h, after promptly obtain product A 3 after the separation, washing, drying.The Static Water adsorptive value (wt%) of product and ultimate compression strength (N/) are as shown in table 1.
Embodiment 4
Choose SiO
2/ Al
2O
3(mol ratio) is 2.4 kaolin, and raw material is crossed 150 mesh sieves after fragmentation, adds the suitable quantity of water mediation and carries out granulation.Kaolin particle is put into 900 ℃ of following roasting 2h of retort furnace behind dryness in the sun.Particle after the roasting joins in the NaOH solution that embodiment 2 separates at last, makes Na by the consumption of regulating NaOH solution
2O/SiO
2=5.0 (mol ratios) are at 60 ℃ of following ageing 18h, then at 120 ℃ of following crystallization 16h, after promptly obtain product A 4 after the separation, washing, drying.The Static Water adsorptive value (wt%) of product and ultimate compression strength (N/) are as shown in table 1.
Embodiment 5
Choose SiO
2/ Al
2O
3(mol ratio) is 2.41 kaolin, and raw material is crossed 200 mesh sieves after fragmentation, adds the suitable quantity of water mediation and carries out granulation.Kaolin particle is put into 900 ℃ of following roasting 0.5h of retort furnace behind dryness in the sun.Particle after the roasting joins in the NaOH solution that embodiment 3 separates at last, makes Na by the consumption of regulating NaOH solution
2O/SiO
2=6.0 (mol ratios) are at 50 ℃ of following ageing 24h, then at 130 ℃ of following crystallization 24h, after promptly obtain product A 5 after the separation, washing, drying.Synthetic binderless A type zeolite molecular sieve XRD figure is composed as shown in Figure 4, and Fig. 5 has provided the sem photograph of product.The Static Water adsorptive value (wt%) of product and ultimate compression strength (N/) are as shown in table 1.
Table 1 does not have the physical property measurement data that bonding is squeezed A type zeolite molecular sieve
Claims (6)
1. a method of utilizing kaolin to prepare binderless A type zeolite molecular sieve is characterized in that, described method may further comprise the steps:
(1) is that the kaolin fragmentation of 2.0-2.4 is sieved with the SiO2/Al2O3 mol ratio, dries after the granulation that tempers, then at 500-900 ℃ of following roasting 0.5-6h;
(2) will the particle after roasting join ageing in the NaOH solution of 1.0-4.0mol/L;
(3) crystallization then promptly obtains binderless A type zeolite molecular sieve with prepared zeolite molecular sieve particle again after separation, washing, drying.
2. the method for preparing molecular sieve according to claim 1 is characterized in that, the kaolin that described (1) was chosen in the step is crossed the 100-200 mesh sieve after fragmentation.
3. the method for preparing molecular sieve according to claim 1 is characterized in that, described (2) regulate NaOH solution in the step consumption makes that the Na2O/SiO2 mol ratio remains on 2.0-6.0 in the reaction system.
4. the method for preparing molecular sieve according to claim 1 is characterized in that, aged temperature is 50-60 ℃ in described (2) step, and the time is 4-24h.
5. the method for preparing molecular sieve according to claim 1 is characterized in that, the temperature of crystallization is 80-130 ℃ in described (3) step, and the time is 6-24h.
6. the method for preparing molecular sieve according to claim 1 is characterized in that, in described (3) step, the zeolite molecular sieve particle utilizes as the NaOH solution circulated in the step (2) through the liquid that after separating obtains.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905145A (en) * | 2010-09-15 | 2010-12-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Molecular sieve cellular material and preparation method thereof |
| CN102774852A (en) * | 2012-08-21 | 2012-11-14 | 王万森 | Synthesis method of4A molecular sieve for rotary dehumidifier |
| CN102815718A (en) * | 2012-09-03 | 2012-12-12 | 中国地质大学（武汉） | One-step method for preparing 3A type zeolite molecular sieve by kaoline |
| WO2019068135A1 (en) * | 2017-10-04 | 2019-04-11 | Neomaterials Pty Ltd | Synthesis of zeolites |
-
2009
- 2009-06-29 CN CNA2009103038052A patent/CN101591025A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905145A (en) * | 2010-09-15 | 2010-12-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Molecular sieve cellular material and preparation method thereof |
| CN101905145B (en) * | 2010-09-15 | 2012-11-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Molecular sieve cellular material and preparation method thereof |
| CN102774852A (en) * | 2012-08-21 | 2012-11-14 | 王万森 | Synthesis method of4A molecular sieve for rotary dehumidifier |
| CN102815718A (en) * | 2012-09-03 | 2012-12-12 | 中国地质大学（武汉） | One-step method for preparing 3A type zeolite molecular sieve by kaoline |
| CN102815718B (en) * | 2012-09-03 | 2014-07-23 | 中国地质大学（武汉） | One-step method for preparing 3A type zeolite molecular sieve by kaoline |
| WO2019068135A1 (en) * | 2017-10-04 | 2019-04-11 | Neomaterials Pty Ltd | Synthesis of zeolites |
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Open date: 20091202 |