CN102557061A - Sodium type zeolite molecular sieve hydrogen ion exchange method - Google Patents
Sodium type zeolite molecular sieve hydrogen ion exchange method Download PDFInfo
- Publication number
- CN102557061A CN102557061A CN2010105946914A CN201010594691A CN102557061A CN 102557061 A CN102557061 A CN 102557061A CN 2010105946914 A CN2010105946914 A CN 2010105946914A CN 201010594691 A CN201010594691 A CN 201010594691A CN 102557061 A CN102557061 A CN 102557061A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- zeolite
- acid
- roasting
- zeolite molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a zeolite molecular sieve hydrogen ion exchange method. Zeolite molecular sieves are mixed with water and/or a hydrogen-ion-containing exchange solution, wherein the exchange solution is added in a discontinuous or continuous method; and the pH value of the mixed slurry is stably controlled within the interval between any two pH values between 2.5 and 5.5 for 5 minutes to 48 hours. The method can replace the traditional ammonium exchange process of the zeolite molecular sieves or reduce the consumption of the ammonium salt in the ammonium exchange process, thereby lowering the ammonia nitrogen waste water pollution.
Description
Technical field
The present invention relates to a kind of zeolite molecular sieve ion-exchange techniques, more specifically to a kind of method of zeolite molecular sieve acid modification.
Background technology
Na type molecular sieve comprises faujusite, the β zeolite; Mordenite, Y zeolite during ZSM series zeolite, especially catalytic cracking catalyst are produced; Traditional technology all adopts the method for ammonium salt and rare earth exchanged to reduce sodium content, to improve the catalyst activity and the stability of zeolite molecular sieve.The sodium content that makes zeolite molecular sieve and contain the molecular sieve active constituent catalyst satisfies request for utilization, often need adopt excessive ammonium salt exchange modification, therefore produces the spent process water that contains a large amount of ammonia nitrogen materials.And NH in the zeolite
4 +NH is sloughed in thermolysis more subsequently
3, stay H
+If directly use H
+IX, both the conservation cost can fundamentally solve the ammonia and nitrogen pollution problem again.At present, all documents all think, than zeolite, can not use acid exchange or s.t. dealuminzation for y-type zeolite or generally low Si/Al, otherwise the destruction that will cause crystalline structure.(work such as Xu Ruren, " molecular sieve and porous material chemistry ", the 443rd page, Beijing Science Press, 2004; The Chen Junwu chief editor, " catalytic cracking process is in engineering " second edition, the 193rd page of the first volume, Beijing: Sinopec press; The Huang Zhongtao chief editor, " Industrial Catalysis ", institution of higher education's teaching material, the 45th page, Beijing: Chemical Industry Press, 1994).
Summary of the invention
The object of the invention is to provide a kind of Na type zeolite molecular sieve directly to exchange the method for taking off sodium with hydrogeneous solion.
Technical scheme of the present invention is that zeolite molecular sieve is mixed with water and/or hydrogeneous ion exchanged soln; Be interrupted or add hydrogeneous ion exchanged soln continuously; Slurry pH value is stabilized between any two the pH values between the 2.5-5.5 5 minutes to 48 hours, preferably slurry pH value is stabilized between any two the pH values between the 2.8-4.0 5 minutes to 12 hours.
Zeolite molecular sieve of the present invention comprises Y zeolite, X type molecular sieve, ZSM series molecular sieve, mordenite molecular sieve, one or more in the beta-zeolite molecular sieve.Described Y zeolite hands over a roasting Y zeolite and two to hand over two roasting Y zeolites for comprising gel method synthetic and kaolin in-situ crystallization synthetic NaY molecular sieve and one of which.Described kaolin in-situ crystallization synthetic NaY molecular sieve is blended in the crystallization material of the percent crystallinity of acquisition in 70-120 ℃ of following crystallization 8-72 hour at 15-85% for the kaolin microsphere (particle diameter 20-150 micron accounts for more than 60%) through 600-1000 ℃ of roasting with water glass, sodium hydroxide and NaY directed agents and water.Described one hands over a roasting and two to hand over two roasting Y zeolites to comprise ultra-steady Y molecular sieve, rare earth containing zeolite, rare earth hydrogen Y molecular sieve and hydrogen Y molecular sieve.
The H that contains of the present invention
+Ion exchanged soln comprises and does not contain other cationic H
+Ionic compound or H
+Ionic compound and Re
3+Salt and/or NH
4 +The mixture of salt.The described H that contains
+Ionic compound comprises hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, formic acid, acetate, propionic acid, tartrate, silicofluoric acid, one or more among the H4EDTA.Described Re
3+Salt comprises rare earth chloride, a kind of in the rare earth nitrate or two kinds.Described NH
4 +Salt comprises one or more in ammonium chloride, ammonium sulfate, an ammonium nitrate, the ammonium phosphate.
The interpolation speed that pH value of slurry according to the invention adopts the automatic pH meter of numerical control to control hydrogeneous ion exchanged soln is controlled.The automatic pH meter of said numerical control comprises potential electrode, numerical control instrument and topworks.
Slurry according to the invention continuously stirring between commutation period.
Slurry temperature according to the invention is 0-100 ℃, is preferably room temperature.
Na type zeolite molecular sieve provided by the invention is with containing H
+The method that solion directly exchanges is saved ammonium exchange, has both saved the exchange cost, has fundamentally solved ammonia and nitrogen pollution again, and makes the zeolite molecular sieve exchange take off sodium and/or dealuminzation is accurately controlled.
Further specify the present invention with embodiment below, but therefore do not limit the present invention.
Embodiment
Embodiment 1
(percent crystallinity=48.4%, silica alumina ratio are 4.83, Na to get 300g kaolin in-situ crystallization NaY material
2O=6.5%, Shanghai is received auxiliary agent ltd of section and is produced), add the deionized water of 10 times of PH=3.5, Dropwise 5 %HCl solution stops when regulating PH=3.3 dripping.When PH＞3.5, continue to drip, rise to after time of 3.5 surpasses 20 minutes by 3.3, filter, wash, blot,, record Na 150 ℃ of oven dry 2 hours down until PH
2O content is 2.82%, and percent crystallinity is 44.0%, and silica alumina ratio is 5.8.
Comparative Examples 1
Get the in-situ crystallization NaY material of 300g with embodiment 1, add 10 times of deionized waters, add the 150g solid ammonium sulfate, behind the adjusting PH=3.3-3.5, be warming up to 90 ℃, constant temperature 1 hour filters, washs, blots, and dries 2 hours down at 150 ℃, records Na
2O content is 2.85%, and percent crystallinity is 44.5%, and silica alumina ratio is 5.7.
Embodiment 2
(percent crystallinity=90.5%, silica alumina ratio are 5.25, Na to get the 200gNaY material
2O=13.5%, Shanghai is received auxiliary agent ltd of section and is produced), add the deionized water of 10 times of PH=3.3, Dropwise 5 %HCl solution stops when regulating PH=3.0 dripping.When PH＞3.3, continue to drip, rise to after time of 3.3 surpasses 30 minutes by 3.0, filter, wash, blot,, record Na 150 ℃ of oven dry 2 hours down until PH
2O content 4.9%, percent crystallinity are 83.5%, and silica alumina ratio is 6.0.
Comparative Examples 2
Get the NaY material of 200g with embodiment 2, add 10 times of deionized waters, add the 100g solid ammonium chloride, regulate PH=3.0-3.3, be warming up to 90 ℃, constant temperature 1 hour filters, washs, blots, and dries 2 hours down at 150 ℃, records Na
2O content is 4.8%, and percent crystallinity is 84.4%, and silica alumina ratio is 5.8.
Embodiment 3
(percent crystallinity=68%, silica alumina ratio are 5.9, Na to get 200g RENaY one roasting material
2O=4.9%, Shanghai is received auxiliary agent ltd of section and is produced), add the deionized water of 10 times of PH=3.8, Dropwise 5 %HCl solution stops when regulating PH=3.5 dripping.When PH＞3.8, continue to drip, rise to after time of 3.8 surpasses 40 hours by 3.5, filter, wash, blot,, record Na 150 ℃ of oven dry 2 hours down until PH
2O content is 1.5%, and percent crystallinity is 61%, and silica alumina ratio is 6.9.
Embodiment 4
The REHY that gets the production of 500g in-situ crystallization method expects that (percent crystallinity=38.5%, silica alumina ratio are 5.6, Na
2O=1.68%, Shanghai is received auxiliary agent ltd of section and is produced), add the deionized water of 10 times of PH=4.0, Dropwise 5 %HCl solution stops when regulating PH=3.8 dripping.When PH＞4.0, continue to drip, rise to after time of 4.0 surpasses 10 hours by 3.8, filter, wash, blot,, record Na 150 ℃ of oven dry 2 hours down until PH
2O content is 0.48%, and percent crystallinity is 32.5%, and silica alumina ratio is 7.1.
Comparative Examples 3
Get the REHY material that 500g produces with the in-situ crystallization method of embodiment 4, add 10 times of deionized waters, add the 100g solid ammonium sulfate, behind the adjusting PH=3.3-3.5, be warming up to 90 ℃, constant temperature 1 hour filters, washs, blots, and oven dry is 2 hours under 150 ℃, records Na
2O content is 0.5%, and percent crystallinity is 33.5%, and silica alumina ratio is 7.0.
Embodiment 5
With the embodiment 4 products obtained therefroms stainless steel tube of packing into; Put into tube furnace; Be warming up to 650 ℃, fed ammonia and water vapour aging 10 hours, on the small fixed flowing bed experimental installation, estimate then; Raw material picks up from the catalytic cracking combined device of Chang Ling petrochemical industry, and mixing 20% vacuum residuum with 80% decompression wide fraction wax oil is reaction raw materials.Reaction conditions is: 490 ℃ of temperature of reaction, and agent-oil ratio is 5, the result lists in the table 1.
Comparative Examples 4
With the Comparative Examples 3 products obtained therefroms stainless steel tube of packing into; Put into tube furnace; Be warming up to 650 ℃, fed water vapour aging 10 hours, on the small fixed flowing bed experimental installation, estimate then; Raw material picks up from the catalytic cracking combined device of Chang Ling petrochemical industry, and mixing 20% vacuum residuum with 80% decompression wide fraction wax oil is reaction raw materials.Reaction conditions is: 490 ℃ of temperature of reaction, and agent-oil ratio is 5, the result lists in the table 1.
Table 1
| Instance 5 | Comparative Examples 4 | |
| Dry gas, W% | 1.7 | 1.8 |
| Liquefied gas, W% | 18.6 | 18.5 |
| Gasoline, W% | 48.2 | 48.5 |
| Diesel oil, W% | 16.9 | 16.4 |
| Heavy oil, W% | 8.1 | 8.3 |
| Coke, W% | 6.5 | 6.5 |
Claims (11)
1. the method for zeolite molecular sieve hydrogen ion exchange; It is characterized in that; Zeolite molecular sieve is mixed with water and/or hydrogeneous ion exchanged soln, be interrupted or add hydrogeneous ion exchanged soln continuously, slurry pH value is stabilized between any two the pH values between the 2.5-5.5 5 minutes to 48 hours.
2. method according to claim 1 is characterized in that described zeolite molecular sieve comprises Y zeolite, X type molecular sieve, ZSM series molecular sieve, mordenite molecular sieve, one or more in the beta-zeolite molecular sieve.
3. method according to claim 2 is characterized in that, described Y zeolite hands over a roasting Y zeolite and two to hand over two roasting Y zeolites for comprising gel method synthetic and kaolin in-situ crystallization synthetic NaY molecular sieve and one of which.
4. method according to claim 3; It is characterized in that described kaolin in-situ crystallization synthetic NaY molecular sieve is blended in the crystallization material of the percent crystallinity of acquisition in 70-120 ℃ of following crystallization 8-72 hour at 15-85% for the kaolin microsphere (particle diameter 20-150 micron accounts for more than 60%) through 600-1000 ℃ of roasting with water glass, sodium hydroxide and NaY directed agents and water.
5. method according to claim 3 is characterized in that, described one hands over a roasting and two to hand over two roasting Y zeolites to comprise ultra-steady Y molecular sieve, rare earth containing zeolite, rare earth hydrogen Y molecular sieve and hydrogen Y molecular sieve.
6. method according to claim 1 is characterized in that, the described H that contains
+Ion exchanged soln comprises and does not contain other cationic H
+Ionic compound or contain H
+Ionic compound and Re
3+Salt and/or NH
4 +The mixture of salt.
7. method according to claim 1 is characterized in that, the described H that contains
+Ionic compound comprises hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, formic acid, acetate, propionic acid, tartrate, silicofluoric acid, H
4Among the EDTA one or more.
8. method according to claim 6 is characterized in that, described Re
3+Salt comprises rare earth chloride, a kind of in the rare earth nitrate or two kinds; Described NH
4 +Salt comprises one or more in ammonium chloride, ammonium sulfate, an ammonium nitrate, the ammonium phosphate.
9. method according to claim 1 is characterized in that, said pH value of slurry is stabilized between the 2.8-4.0 between any two pH values 5 minutes to 12 hours.
10. according to claim 1,9 described methods, it is characterized in that said pH value of slurry adopts the automatic pH meter of numerical control to measure and control through the interpolation speed of regulating hydrogeneous ion exchanged soln.
11. method according to claim 11 is characterized in that, said automatic pH meter comprises potential electrode, numerical control instrument and topworks.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105946914A CN102557061A (en) | 2010-12-16 | 2010-12-16 | Sodium type zeolite molecular sieve hydrogen ion exchange method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105946914A CN102557061A (en) | 2010-12-16 | 2010-12-16 | Sodium type zeolite molecular sieve hydrogen ion exchange method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102557061A true CN102557061A (en) | 2012-07-11 |
Family
ID=46403886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105946914A Pending CN102557061A (en) | 2010-12-16 | 2010-12-16 | Sodium type zeolite molecular sieve hydrogen ion exchange method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102557061A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069889A (en) * | 2013-03-28 | 2014-10-01 | 中国科学院大连化学物理研究所 | Preparation method of rare earth MCM-49 molecular sieve catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4346067A (en) * | 1981-06-29 | 1982-08-24 | Exxon Research & Engineering Co. | Method of ion exchange zeolites |
| CN1806908A (en) * | 2005-10-27 | 2006-07-26 | 复旦大学 | Macroporous zeolite absorbent and preparation method thereof |
| CN101823727A (en) * | 2009-03-04 | 2010-09-08 | 中国石油天然气股份有限公司 | Method for modifying molecular sieve |
-
2010
- 2010-12-16 CN CN2010105946914A patent/CN102557061A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4346067A (en) * | 1981-06-29 | 1982-08-24 | Exxon Research & Engineering Co. | Method of ion exchange zeolites |
| CN1806908A (en) * | 2005-10-27 | 2006-07-26 | 复旦大学 | Macroporous zeolite absorbent and preparation method thereof |
| CN101823727A (en) * | 2009-03-04 | 2010-09-08 | 中国石油天然气股份有限公司 | Method for modifying molecular sieve |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069889A (en) * | 2013-03-28 | 2014-10-01 | 中国科学院大连化学物理研究所 | Preparation method of rare earth MCM-49 molecular sieve catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2868629B1 (en) | Rare-earth contained y type molecular sieve and preparation method thereof | |
| CN101296748B (en) | Denitrification catalyst, honeycomb structure type denitrification catalyst, and method of denitrification with the same | |
| EP2812281A1 (en) | Iron- and copper-containing zeolite beta from organotemplate-free synthesis and use thereof in the selective catalytic reduction of nox | |
| US20070037697A1 (en) | High surface area ceramic catalysts and the manufacture thereof | |
| US4692236A (en) | Catalytic cracking process for heavy oil with mixture of alumina and zeolite | |
| CN103011192A (en) | Silicon-aluminium carrier comprising molecular sieve and preparation method thereof | |
| CN101555417A (en) | Denitrifier and preparation method thereof | |
| CN102773117A (en) | Medium-oil-type hydrocracking catalyst and preparation method thereof | |
| CN102502695B (en) | NaY molecular sieve modifying method | |
| CN103055917B (en) | Preparation method of catalytic cracking catalyst | |
| US4415439A (en) | Catalytic cracking catalyst | |
| CN102553630B (en) | High- silica alumina ratio small- crystal grain Y zeolite catalytic cracking catalyst and preparation method thereof | |
| CN102133539A (en) | Modified Y type molecular sieve/matrix composite material and preparation method thereof | |
| CN102557061A (en) | Sodium type zeolite molecular sieve hydrogen ion exchange method | |
| CN101428232A (en) | Process for producing ZSM-5 molecular sieve | |
| CN102442686B (en) | Preparation method of ZSM-5 molecular sieve | |
| CN102974384A (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN103100434B (en) | Preparation method of catalyst carrier material containing molecular sieve and alumina | |
| CN103657702A (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN102974385B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN100404432C (en) | Method of reducing ammonia and nitrogen pollution in process of zeolite modification | |
| CN1436600A (en) | Method of raising the catalytic activity of zeolite molecular sieve | |
| CN101745416B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN1370814A (en) | Saturated loaded noble metal catalyst for distilling oil arenes and its prep. | |
| CN103359760A (en) | Method for removing sodium from sodium zeolite molecular sieve through ion exchange |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120711 |