CN101289196B - Method for preparing LiLSX molecular screen - Google Patents
Method for preparing LiLSX molecular screen Download PDFInfo
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- CN101289196B CN101289196B CN2008100500702A CN200810050070A CN101289196B CN 101289196 B CN101289196 B CN 101289196B CN 2008100500702 A CN2008100500702 A CN 2008100500702A CN 200810050070 A CN200810050070 A CN 200810050070A CN 101289196 B CN101289196 B CN 101289196B
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Abstract
The invention relates to a preparation method for a LiLSX molecular sieve, which comprises the steps that LSX zeolite is prepared, LSX is exchanged into KLSX, K2SO4 solution is adopted and KOH solution is used for regulating the PH value to 8.5, a method of displacing for a plurality of times is used with 2 minutes of replacing time for each replacement and the temperature of the solution is about 80 DEG C, exchange liquid after being exchanged a plurality times is used in the next group of the exchange process of K<+>; then a method that is similar to the replacement of K<+> solution is adopted to exchange into NH4LSX, the PH value of the solution is 8.5; then LiOH solution is used for exchanging Li<+> into LiLSX at the temperature of 50 DEG C and air is added to discharging NH3 at the same time; finally, washing, drying, and the like, are carried out and finished products are obtained. The method is characterized by adopting ion exchange in a short time, using substances exchanged circularly and having suitable temperature and PH values of exchange solutions and high utilization ratio of Li, and finally the LiLSX molecular sieve with high degree of crystallinity is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve, particularly relate to a kind of preparation method of LiLSX molecular sieve.
Background technology
The LiLSX molecular sieve is as the separating oxygen from air by means of pressure swing adsorption sorbent material, oxygen nitrogen separation factor is traditional 5A and 13X 2-3 a times, with the large-scale separating oxygen from air by means of pressure swing adsorption device that this sorbent material produces, sorbent material is 1/5 of a 5A molecular sieve, and system oxygen power consumption is also low more than 20%.The key problem in technology of preparation LiLSX adsorbent of molecular sieve is Li
+Switching technology.Because the LSX molecular sieve that is synthesized contains Na
+And K
+, through Li
+Exchange change the LiLSX molecular sieve into, and Li
+The exchange degree general requirement more than 88%, with Li
+Exchange degree increase its performance can be better.Because Li
+Radius little, hydratability is extremely strong, adopts prior art, carries out ion-exchange and be suitable difficulty in the aqueous solution, be through the exchange of 5 secondary ions, each exchange, Li
+Want excessive consumption more than 6 times, swap time is quite long, wants several hours at every turn, even tens hours, cause the utilization ratio of Li extremely low, the production cycle is long, because costing an arm and a leg of Li causes LiLSX molecular sieve cost quite high.
People such as Toufar has announced new Li in United States Patent (USP) 5916836 (1999)
+Switching method is passed through K with LSX earlier
+Be exchanged into KLSX, again through NH
4 +Be exchanged into NH
4LSX is at last with NH
4LSX carries out Li
+Be exchanged into LiLSX, the utilization ratio of Li in this preparation method, is used K greater than 90%
2SO
4Carry out K
+Exchange, 80 ℃ of temperature each 1 hour, repeat 3 times, with (NH
4)
2SO
4Carry out NH
4 +Exchange, 80 ℃ of temperature, each 2 hours, repeat 4 times, the cycle of preparation LiLSX molecular sieve is quite long, is difficult to suitability for industrialized production, and, K
2SO
4The PH=3-4 of solution, at 80 ℃, the long-time immersion, the LSX framework of molecular sieve suffers destruction to a certain degree, KLSX is exchanged into NH
4LSX 80 ℃ of destructions that also have to a certain degree, is exchanged into LiLSX at last, and its degree of crystallinity obviously descends, and influences absorption property and the life-span of LiLSX.
Summary of the invention
Invent technical problem to be solved and provide a kind of cycle weak point, easy suitability for industrialized production, the LSX framework of molecular sieve does not destroy, and degree of crystallinity does not reduce, to absorption property and the little LiLSX molecular sieve preparation method of life-span influence of LiLSX.
The further technical solution problem of invention institute provides the high LiLSX molecular sieve preparation method of a kind of Li utilization ratio
An invention institute more step technical solution problem provides a kind of preparation method of LiLSX molecular sieve, and this method adopts short period of time ion-exchange, and the exchange material recycles, and the exchange liquid temp and the pH value that suit obtain the high LiLSX molecular sieve of degree of crystallinity at last.
In order to realize the purpose of foregoing invention, adopt following technical scheme: the preparation of LiLSX molecular sieve comprises the LSX prepare zeolite, LSX is passed through K
+Be exchanged into KLSX, through NH
4 +Be exchanged into NH
4LSX, NH
4LSX carries out Li
+Be exchanged into LiLSX, LSX is being passed through K
+Be exchanged into the process of KLSX, employing will contain K
+Solution be adjusted to the pH value more than 8 with KOH solution, preferred pH value is 8.5; This contains K
+Solution be the common K that contains
+Salts solution, preferably adopt K
2SO
4Solution; Adopt repeatedly with containing K
+The solution method of replacement, be preferably five displacements; Time swap was at 1～10 minute each time, and the preferred time is 2 minutes; About 80 ℃ of solution temperatures of exchange, after the preceding exchange several times exchange liquid be applied to the K of next batch
+Be exchanged in the KLSX process.
NH
4 +Be exchanged into NH
4In the LSX process, employing will contain NH
4 +Solution be adjusted to the pH value more than 8 with ammoniacal liquor, preferred pH value is 8.5; Adopt repeatedly NH
4 +Solution displacement K
+Method, time swap is at 1～10 minute each time, the preferred time is 2 minutes; About 70-75 ℃ of solution temperature of exchange, after the preceding exchange several times exchange liquid be applied to the NH of next batch
4 +Be exchanged into NH
4In the LSX process.
NH
4LSX carries out Li
+Be exchanged in the LiLSX process, NH
4LSX makes the suspension of 5-50%, and preferred suspension concentration is 20%; Suspension is poured in the ion-exchange still or jar of band stirring, is heated to 30-80 ℃, and 50 ℃ of preferred temperature are carried out Li with LiOH solution
+The simultaneously an amount of bubbling air of exchange makes the NH that exchanges
4 +The NH that forms
3Discharge with air, when the PH of exchange liquid no longer changes, represent Li
+Exchange is finished, and filters, and collects filtrate and utilizes, uses a certain amount of deionized water wash then, with filtration cakes torrefaction, promptly obtains purpose product LiLSX molecular sieve.The concentration of described LiOH solution is 1-10%, is preferably 5%, and the adding speed of preferred LiOH solution should make the pH of exchange liquid remain between the 11-12.Can be with the NH that discharges
3Introduce H
2SO
4In the solution, form (NH
4)
2SO
4, be NH again
4 +Usefulness during exchange prevents from again to pollute.
Owing to adopt scheme as mentioned above, the present invention has following superiority:
One, the present invention adopts K in described preparation process
2SO
4Solution, PH is adjusted to 8.5, NH
4 +During exchange, the exchange temperature is 70-75 ℃, Li
+Exchange is carried out under 50 ℃, and gained LiLSX molecular sieve crystallinity is without prejudice, and obtains Li
+The LiLSX molecular sieve of exchange degree more than 95.0%, and keep high loading capacity.25 ℃, 50% relative humidity, saturated water adsorptive value is 32.0-33.0%.
Two, the present invention adopts " curve " Li
+The method of exchange makes Li
+Utilization ratio greater than 90%, and the NH that discharges
3Recycle, prevent to pollute.At K
+And NH
4 +In the exchange, swap time is very short, and exchange liquid recycles, and exchange process can be realized on the belt filter, is easy to suitability for industrialized production, and product recovery rate improves, and product cost reduces.
Embodiment
Embodiment:
1, K
+Exchange
Adopt B, the exchange of finding time, each 2 minutes swap times, exchange 80 ℃ of solution temperatures (PH is adjusted to 8.5 with KOH), concrete operations are:
The former powder of 25gLSX adds the 100ml deionized water, mixes, and forms the thick filter cake of 4-5mm on B, carries out K then
+Exchange is poured B 500ml into, the K of 0.5M at every turn
2SO
4Solution (transferring PH=8.5 with KOH solution), repeated exchanged 5 times is used the 500ml deionized water wash at last.
When carrying out the exchange of next filter cake, with top first time filtrate be mixed with filter cake with the former powder of LSX, when the 5th exchanges, use fresh K
2SO
4Solution, and the like, exchanging 7 samples altogether, analytical results is listed in table 1, and 5,6,7 three samples have only added three parts of fresh K
2SO
4Solution, each sample equal only to consume a fresh solution, K
+Exchange degree all more than 93.0%.
Table 1K
+The K of exchange sample
+Exchange degree
Sample K
2O (%) Na
2O (%) K
+Exchange degree (%)
1 22.8 0.70 95.54
2 22.2 0.80 94.81
3 23.0 1.75 89.90
4 25.0 1.30 92.68
5 25.0 1.00 94.27
6 20.2 0.95 93.00
7 20.9 0.75 93.54
2, NH
4 +Exchange
With K
+KLSX (the K that exchange obtains
+Exchange degree is 93.04%), get 6 parts, every part of 25g adds the 100ml deionized water, mixes, and makes the filter cake of 4-5mm on B, uses 250ml then, (the NH of 1M
4)
2SO
4Solution (is used NH
4OH transfers PH=8.5) carry out ion-exchange, 75 ℃ of exchange temperature repeat 5 times 2 minutes swap times of suction filtration, use 500ml deionized water wash filter cake then, sample NH
4 +Exchange degree is listed in the table 2.
Table 2NH
4 +The NH of exchange sample
4 +Exchange degree *
Sample K
2O (%) Na
2O (%) NH
4 +Exchange degree (%)
1 0.20 1.00 96.45
2 0.30 1.00 96.24
3 0.40 1.30 95.09
4 0.25 1.40 94.25
5 0.40 1.40 94.78
6 0.40 1.30 95.09
* contain 5.2%K among the LSX
2O, 12.5%Na
2O uses NH
4 +Exchange back K
2O and Na
2The reduction of O is calculated NH
4 +Exchange degree.
NH
4 +Exchange liquid recycles same K
+Exchange is the same, when carrying out next sample exchange, is exchanged liquid the top first time with the KLSX powder is mixed with filter cake, and the 5th exchanges with fresh (NH
4)
2SO
4Solution, the rest may be inferred, and from the 5th sample, each sample only consumes a fresh (NH later on
4)
2SO
4Solution.
K
+And NH
4 +The principle that ion exchange liquid recycles is, make desire the lower filtrate of exchange ion concentration earlier the contact molecular sieve contain by the higher sample of exchange ion concentration, the filtrate cycle service condition is shown in Table 3.
The signal of table 3 exchange liquid service condition
Sample 1234567
1
2 2
3 3 3
Hand over 4444
5 5 5 5 5
Change 66666
7 7 7 7 7
Liquid 8888
9 9 9
10 10
11
3, Li
+Exchange
Li
+Ion-exchange is carried out in the swap tank that band stirs, and 50 ℃ of exchange liquid constant temperature are with 25gNH
4LSX makes 20% suspension with deionized water, and the LiOH solution with 5% carries out ion-exchange, and LiOH solution slowly adds, and its adding speed makes between the PH=11-12 of exchange liquid, feeds an amount of air simultaneously, makes the NH that exchanges
4 +The NH that forms
3Discharge with air, use rare H
2SO
4Solution absorption forms (NH
4)
2SO
4Solution is recycled.When exchange proceeds to PH and no longer changes, show Li
+Exchange finishes.Filter, collect filtrate, next time is usefulness again, and the LiOH consumption is no more than 110% of stoichiometric quantity, and promptly the utilization ratio of Li is greater than 90%, the filter cake deionized water wash, and 100 ℃ of dryings down are purpose product LiLSX.Product flame spectrophotometer measuring Na
2O, K
2O and Li
2The content of O is respectively 0.50%, 0.45% and 7.52%, Li
+Exchange degree is 95.24%.
Claims (7)
1. the preparation method of a LiLSX molecular sieve comprises the LSX prepare zeolite, LSX is passed through K
+Be exchanged into KLSX, through NH
4 +Be exchanged into NH
4LSX, NH
4LSX carries out Li
+Be exchanged into LiLSX, it is characterized in that: LSX is passed through K
+Be exchanged into the process of KLSX, employing will contain K
+Solution be adjusted to the pH value more than 8 with KOH solution, repeatedly with containing K
+The solution method of replacement, time swap is at 1～10 minute each time, 80 ℃ of exchange solution temperatures, the exchange liquid after the preceding exchange several times is applied to the K of next batch
+Be exchanged in the KLSX process; NH
4 +Be exchanged into NH
4In the LSX process, employing will contain NH
4 +Solution be adjusted to the pH value more than 8 with ammoniacal liquor, repeatedly with containing NH
4 +The solution method of replacement, time swap is at 1～10 minute each time, 70-75 ℃ of exchange solution temperature, the exchange liquid after the preceding exchange several times is applied to the NH of next batch
4 +Be exchanged into NH
4In the LSX process; NH
4LSX carries out Li
+Be exchanged in the LiLSX process, NH
4The suspension that LSX makes is poured in the ion-exchange jar that band stirs, and is heated to 30-80 ℃, is that the LiOH solution of 1-10% carries out Li with concentration
+The simultaneously an amount of bubbling air of exchange, exchange is finished when the pH of exchange liquid no longer changes, and through washing, drying, obtains the LiLSX molecular sieve.
2. according to the preparation method of the described LiLSX molecular sieve of claim 1, it is characterized in that the described K of containing
+The pH value of solution value be 8.5.
3. according to the preparation method of the described LiLSX molecular sieve of claim 1, it is characterized in that described usefulness contains K
+Solution when displacement, each time swap is 2 minutes.
4. according to the preparation method of claim 1,2 or 3 each described LiLSX molecular sieves, it is characterized in that the described K of containing
+Solution be K
2SO
4Solution.
5. according to the preparation method of the described LiLSX molecular sieve of claim 1, it is characterized in that described NH
4 +Solution displacement K
+Shi Hanyou NH
4 +The pH value of solution value be 8.5, each time swap is 2 minutes.
6. according to the preparation method of the described LiLSX molecular sieve of claim 1, it is characterized in that described NH
4It is 50 ℃ that the suspension that LSX makes is heated to temperature.
7. according to the preparation method of the described LiLSX molecular sieve of claim 1, it is characterized in that the adding speed of described LiOH solution should make the pH of exchange liquid remain between the 11-12.
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|---|---|---|---|
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|---|---|---|---|
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101524637B (en) * | 2009-04-23 | 2011-02-02 | 中国海洋石油总公司 | Preparation method of LSX-molecular-sieve-rich cementing-agent-free absorbent |
| CN102500315A (en) * | 2011-10-10 | 2012-06-20 | 于向真 | LiX molecular sieve adsorbent and preparation method thereof |
| CN102502694A (en) * | 2011-10-11 | 2012-06-20 | 于向真 | Li-modified X molecular sieve and preparation method thereof |
| CN103359760A (en) * | 2012-04-06 | 2013-10-23 | 华东理工大学 | Method for removing sodium from sodium zeolite molecular sieve through ion exchange |
| CN103055805B (en) * | 2013-01-21 | 2015-05-13 | 青岛大学 | Synthesis method of interface micro-pore sequence structure LSX (low-silica X-zeolite) molecular sieve for spatially dividing oxygen-enriched adsorbent |
| CN112588258B (en) * | 2021-03-03 | 2021-05-25 | 苏州立昂新材料有限公司 | Composite A-type molecular sieve raw powder containing wave absorbing material and full-zeolite molecular sieve, and preparation method and application thereof |
| CN113264538B (en) * | 2021-05-29 | 2022-11-08 | 山西腾茂科技股份有限公司 | Preparation method and application of molecular sieve adsorbent based on LiNaKLSX |
| CN113772689B (en) * | 2021-09-23 | 2023-04-07 | 润和催化剂股份有限公司 | Preparation method of nitrogen-oxygen separation Li-LSX molecular sieve |
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|---|---|---|---|---|
| CN1148568A (en) * | 1992-10-05 | 1997-04-30 | 气体产品与化学公司 | Crystalline X-zeolite |
| US5916836A (en) * | 1996-12-27 | 1999-06-29 | Tricat Management Gmbh | Method of manufacture of molecular sieves |
| CN1250025A (en) * | 1998-08-21 | 2000-04-12 | 液体空气乔治洛德方法利用和研究有限公司 | Method for producing X zeolite particle exchanged with metal cation |
| CN101125664A (en) * | 2007-09-14 | 2008-02-20 | 北京工业大学 | Ion exchange method for preparing lithium type low silicon aluminum X-shape zeolite molecular sieve |
-
2008
- 2008-06-13 CN CN2008100500702A patent/CN101289196B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148568A (en) * | 1992-10-05 | 1997-04-30 | 气体产品与化学公司 | Crystalline X-zeolite |
| US5916836A (en) * | 1996-12-27 | 1999-06-29 | Tricat Management Gmbh | Method of manufacture of molecular sieves |
| CN1250025A (en) * | 1998-08-21 | 2000-04-12 | 液体空气乔治洛德方法利用和研究有限公司 | Method for producing X zeolite particle exchanged with metal cation |
| CN101125664A (en) * | 2007-09-14 | 2008-02-20 | 北京工业大学 | Ion exchange method for preparing lithium type low silicon aluminum X-shape zeolite molecular sieve |
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