CN1058513C - Method for extraction method of high-efficiency molecular sieve template agent - Google Patents
Method for extraction method of high-efficiency molecular sieve template agent Download PDFInfo
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- CN1058513C CN1058513C CN97121727A CN97121727A CN1058513C CN 1058513 C CN1058513 C CN 1058513C CN 97121727 A CN97121727 A CN 97121727A CN 97121727 A CN97121727 A CN 97121727A CN 1058513 C CN1058513 C CN 1058513C
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Abstract
The present invention provides a method for removing and recovering an organic template agent in an MCM-41 super macroporous molecular sieve series. An organic template agent extraction agent adopted by a method is composed of cheap straight-run gasoline, alcohol, and partial inorganic acid. A compound solvent has good functions of extraction and dissolution for the organic template agent CnH<2n-1>(CH<3>) <3>NX/OH<->(X is a halogen ion or OH<->, n is from 8 to 30) in an MCM-41 molecular sieve. The present invention has the advantages of simple technology, low cost, high speed, high efficiency for a dewatering template agent and no damage action for an MCM-41 molecular sieve structure.
Description
The present invention relates to the method for extracting of organic formwork agent in the MCM-41 super macroporous molecular sieve synthesis technique, belong to catalysis and separation field in the oil-refining chemical.International Patent classificating number is C10G47/00.
Since 1992, the U.S. has reported the MOBIL oil company the synthetic patent and the document of a series of synthetic MCM-41 super macroporous molecular sieves.This molecular sieve has aperture big (15-100A), and the duct is regular, and the characteristics that the pore volume specific surface is big are ideal composition, carrier and the sorbing material of the catalyzed reaction of many organic macromolecules participations.Expect that this material has broad application prospects, many scientific research institutions are devoted to the research of synthesis technique, the U.S. develops the MOBIL oil company normal heptane-methyl alcohol-ammonium nitrate and normal heptane-ethanol-hydrochloric acid system comes organic formwork agent in the extracting MCM-41 molecular sieve (USP 5143879), obtained certain effect, but there is the too high unfavorable factor of cost simultaneously, do not come into one's own always.And the present invention to adopt with perfectly straight gasoline first be the remove solvent of the gasoline-ethanol-nitric acid system of main component as MCM-41 molecular sieve template, have cost low, separate easily, removal efficiency is high and fireballing characteristics.
The method for extracting that the purpose of this invention is to provide a kind of high-efficiency molecular sieve template agent, it can overcome effectively adopts roasting method to remove the environmental pollution that molecular sieve causes and the loss of template.Reduce the extracting cost, improve removal efficiency and speed.
Embodiment of the present invention are that the molecular sieve of Different Silicon aluminum ratio reacts extracting in gasoline-ethanol-nitric acid azeotropic system.Concrete grammar: 3-10 gram silica alumina ratio is that the molecular sieve of N (N=0,30,40,80) is in 90 ℃ baking oven after dry 1-5 hour, join in the system of gasoline/ethanol (54/46,52/48,50/50,48/52,46/54WT/WT), mix the there-necked flask that places band cold reflux and thermometer, be warming up to and stir after 60 minutes about 60 ℃, be cooled to 15-30 ℃ of suction filtration and isolate molecular sieve, liquid portion reclaims template by distillation.Distillation is in still kettle organic double compound to be separated under normal pressure 60-200 ℃ condition, and the extraction solvent that distills out can use repeatedly.
The present invention is that the perfectly straight gasoline with cheapness replaces expensive normal heptane (50 yuan of its market value/500ML), and technology is simple, extracting speed is fast, efficient is high.Have wide society and economic benefit.
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
The preparation of MCM-41 molecular sieve
Take by weighing 225 gram distilled water, to wherein adding 24 gram cetyl trimethylammonium bromides, be warming up to 35 ℃, be stirred to template and be dissolved in the water white solution of formation in the water fully, stop heating, to wherein adding 108 gram water glass (moduluses 3, dioxide-containing silica 20wt%), continue to stir an amount of Tai-Ace S 150 of adding after 30 minutes, if preparation pure silicon molecular sieve does not add the aluminium source in system.Colloid is encased in the band teflon-lined stainless steel pressure still, and crystallization is 24 hours under 150 ℃ of conditions, product after filtration, obtain containing the MCM-41 molecular sieve of the Different Silicon aluminum ratio of template after washing and the drying.
Embodiment 2
With 3 gram silica alumina ratios of method for preparing is 30 MCM-41 molecular sieve, join in the system by 52 gram straight-run spirit, 48 gram ethanol and 9 gram 68wt% nitric acid, be warming up to about 50 ℃ and stirred 30 minutes, after the cooling molecular sieving is come out, liquid portion is by the air distillation still, between 60-200 ℃ gasoline-ethanol is separated from complex system (promptly containing gasoline, ethanol, mineral acid, template), the template available bases is handled, and ethyl acetate is refining to be reclaimed.Roasting can be removed organism wherein fully and remain template after 2 hours in 550 ℃ of air atmospheres after extractive molecular sieve is by drying.The MCM-41 molecular sieve that contains template is measured structure by the X-ray powder diffraction of direct roasting and two kinds of methods of solvent removal and is shown, adopts the XRD peak intensity of the MCM-41 molecular sieve that the solvent extraction template agent method obtains higher by 20% than direct roasting method.
Embodiment 3
3 gram silica alumina ratios are in 80 the baking oven of MCM-41 molecular sieve about 90 ℃ after the drying, join in the system by 54 gram straight-run spirit, 46 gram ethanol and 9 gram 68wt% nitric acid, are warming up to about 60 ℃ and stir 60 minutes, and cooling back suction filtration is isolated molecular sieve.Liquid portion is by distilling recovery template and extraction solvent to use repeatedly.Weigh after extractive molecular sieve is by drying, weight reduces 36%.Simultaneously, be the roasting 6 hours in 550 ℃ of air atmospheres of 80 MCM-41 molecular sieve with 3 gram silica alumina ratios, remove organic formwork agent in the MCM-41 molecular sieve fully, weight reduces 40%.So by straight-run spirit, ethanol and nitric acid system carry out solvent removal, the template extract content can reach about 90wt%.
Embodiment 4
5 gram silica alumina ratios are after 40 the MCM-41 molecular sieve drying, join in the system by 52 gram straight-run spirit, 48 gram ethanol and 9 gram 68wt% nitric acid, are warming up to about 60 ℃ and stir 60 minutes, and cooling back suction filtration is isolated the MCM-41 molecular sieve.Through weighing after the drying in the baking oven of extractive molecular sieve about 90 ℃, weight reduces 20%.The roasting 6 hours in 550 ℃ of muffle furnaces of molecular sieve after the extracting, remove organic formwork agent in the molecular sieve fully, weight reduces 23%, and data show: silica alumina ratio is 40 MCM-41 molecular sieve, react in straight-run spirit, ethanol and nitric acid system, the template extract content can reach about 85wt%.Liquid portion reclaims and can use repeatedly by the distillation of template.
Embodiment 5
The MCM-41 molecular sieve of 4 gram pure silicons after the drying, joins in the system by 54 gram straight-run spirit, 56 gram ethanol and 9 gram 68wt% nitric acid in 90 ℃ baking oven, is warming up to 60 ℃ of reactions 60 minutes in there-necked flask, and cooling back suction filtration is isolated molecular sieve.Liquid portion reclaims template by distillation and extraction solvent uses repeatedly, after extractive molecular sieve drying, be sample 1: the molecular sieve after the extracting continues roasting and removed remaining organic formwork agent in 6 hours under 550 ℃ high temperature, be sample 2: same, the directly roasting 6 hours under 550 ℃ high temperature of the MCM-41 molecular sieve of pure silicon, be sample 3: the NICOLET51OP fourier infrared spectrographic result of these three samples shows: organic formwork agent removes substantially fully in sample 2 and the sample 3, sample 3 is more thorough, and sample 1 extract content can reach about 92%.
Reference examples
In the normal heptane-methyl alcohol-nitric acid system of MOBIL company exploitation, add 4 gram MCM-41 molecular sieves, place reactor, be warming up to 65 ℃, reacted 90 minutes, extraction efficiency reaches 80%, and the MCM-41 molecular sieve of same amount is added in gasoline-ethanol of the present invention-nitric acid, puts into there-necked flask and is warming up to 30 minutes extraction efficiencies of 60 ℃ of reactions and can reaches 85%.At present, the template that synthetic MCM-41 molecular sieve adopts, market value (industrial goods) is above 20000 yuan/ton, the MCM-41 molecular sieve contains the template of 30-50% approximately, if the template rate of recovery according to 80% is calculated, the cost of MCM-41 molecular sieve per ton reduces 6000-10000 unit approximately, deduct some solvent losses and process cost, estimate that the production per ton cost that adopts method for extracting can make the MCM-41 molecular sieve reduces about 4000-5000 unit, can find out that from embodiment technology of the present invention is simple, extracting speed is fast, the efficient height, and with low cost.
Claims (2)
1, a kind of method for extracting that is suitable for organic formwork agent among the super macroporous molecular sieve MCM-41 is characterized in that:
(1) azeotropic system is made up of straight-run spirit, ethanol and mineral acid, and straight-run spirit and alcoholic acid weight ratio are 1: 5 to 5: 1;
(2) described mineral acid is that the weight ratio of sulfuric acid, nitric acid, hydrochloric acid and organic double compound (referring to gasoline and alcoholic acid mixture) is 0.01-0.5; Wherein sulfuric acid and mixture weight ratio scope are 0.01-0.3; Nitric acid and mixture weight ratio scope are 0.05-0.1; Hydrochloric acid and mixture weight ratio scope are 0.01-0.5; In organic double compound, the shared weight ratio scope of gasoline is 20-80%, and the shared weight ratio scope of ethanol is 20-80%, preferably 40-70%;
(3) the quaternary amine organic formwork agent of 10-50% weight ratio is arranged in the described MCM-41 molecular sieve;
(4) contain the MCM-41 molecular sieve of template and the mixture of extraction solvent, the weight ratio of the two is 0.1-10 to 1: 5;
(5) extracting of organic formwork agent in the described MCM-41 molecular sieve, i.e. temperature control to 50 ℃ under stirring condition.Churning time is 30-60 minute.
2, according to the template method for extracting described in the claim 1, it is characterized in that:
(1) molecular sieve that will contain template is with after extraction solvent mixes, and with molecular sieve and separated from solvent, organic formwork agent material in the solvent can adopt the distillatory process to reclaim wherein template under stirring condition;
(2) extraction solvent of forming according to a certain percentage under suitable condition the rate of recovery of its template reach more than 80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121727A CN1058513C (en) | 1997-12-16 | 1997-12-16 | Method for extraction method of high-efficiency molecular sieve template agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121727A CN1058513C (en) | 1997-12-16 | 1997-12-16 | Method for extraction method of high-efficiency molecular sieve template agent |
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| Publication Number | Publication Date |
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| CN1220301A CN1220301A (en) | 1999-06-23 |
| CN1058513C true CN1058513C (en) | 2000-11-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97121727A Expired - Lifetime CN1058513C (en) | 1997-12-16 | 1997-12-16 | Method for extraction method of high-efficiency molecular sieve template agent |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1314001B1 (en) * | 1999-11-19 | 2002-12-03 | Enichem Spa | METHOD FOR REMOVING THE TEMPLANT FROM SYNTHETIC ZEOLITES |
| CN100444940C (en) * | 2006-03-13 | 2008-12-24 | 南京工业大学 | A kind of preparation method of MCM-48 separation membrane |
| CN106145142B (en) * | 2015-04-13 | 2019-04-12 | 中国石油化工股份有限公司 | Remove molecular sieve organic formwork agent method |
| CN109081362B (en) * | 2017-06-13 | 2021-01-22 | 神华集团有限责任公司 | Method for recovering residual template agent in molecular sieve preparation process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032809A (en) * | 1987-09-04 | 1989-05-10 | 联合碳化公司 | The processing method of hydrocracking catalyst and use non-zeolite molecular sieve |
| CN1016626B (en) * | 1989-04-18 | 1992-05-13 | 弗朗茨普拉瑟尔铁路机械工业有限公司 | Travelling track tamping machine comprising transversely and vertically adjustable tamping units |
| US5143879A (en) * | 1991-07-18 | 1992-09-01 | Mobil Oil Corporation | Method to recover organic templates from freshly synthesized molecular sieves |
-
1997
- 1997-12-16 CN CN97121727A patent/CN1058513C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032809A (en) * | 1987-09-04 | 1989-05-10 | 联合碳化公司 | The processing method of hydrocracking catalyst and use non-zeolite molecular sieve |
| CN1016626B (en) * | 1989-04-18 | 1992-05-13 | 弗朗茨普拉瑟尔铁路机械工业有限公司 | Travelling track tamping machine comprising transversely and vertically adjustable tamping units |
| US5143879A (en) * | 1991-07-18 | 1992-09-01 | Mobil Oil Corporation | Method to recover organic templates from freshly synthesized molecular sieves |
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| CN1220301A (en) | 1999-06-23 |
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