CN102744103A - Regeneration method of zeolite molecular sieve catalyst - Google Patents
Regeneration method of zeolite molecular sieve catalyst Download PDFInfo
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- CN102744103A CN102744103A CN2011100999394A CN201110099939A CN102744103A CN 102744103 A CN102744103 A CN 102744103A CN 2011100999394 A CN2011100999394 A CN 2011100999394A CN 201110099939 A CN201110099939 A CN 201110099939A CN 102744103 A CN102744103 A CN 102744103A
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Abstract
The invention relates to a regeneration method of a zeolite molecular sieve catalyst to mainly solve technical problems of catalyst structure destroy and catalytic performance decrease caused by present zeolite catalyst regeneration technologies. The method, which allows the problems to be well solved through a technical scheme that the structure and catalytic performances of a regenerated catalyst are near to that of a fresh catalyst by contacting an ammonia-containing raw material with a deactivated catalyst at 100-300DEG C, can be applied to the regeneration of the zeolite catalyst.
Description
Technical field
The present invention relates to a kind of renovation process of zeolite molecular sieve catalyst.
Background technology
The regeneration of zeolite molecular sieve catalyst at present is to adopt traditional air atmosphere roasting regeneration method; Because catalyst in use; Heavy component in the reaction system and deep reaction product occupy the activity of such catalysts position and perhaps stop up the duct and cause the catalytic performance of catalyst to descend, and perhaps boiling point is high-leveled and difficult to remove by force because these materials are with the catalyst surface ability to function.And catalyst is placed the air atmosphere roasting, and adopt the method for high temperature oxidation process, these materials are changed into micromolecular low-boiling point material; Spread out mutually from the body of catalyst, the activity of such catalysts position is exposed again or the duct unimpeded, yet this traditional method of roasting; Temperature is higher, and occurs focus easily in the process of regeneration, thereby brings changing of catalyst structure; Through the catalyst after this kind Regeneration Treatment; The initial activity of its regeneration activity and catalyst all is lower than initial activity, and generating azirane with the monoethanolamine cyclodehydration is example, through traditional air roasting; The regeneration activity of its catalyst is starkly lower than initial activity (Hideaki Tsuneki, Kimio Ariyoshi; Deactivation and regeneration of ethylenimine production catalyst, applied catalysis A:General 313 (2007) 95-99).The system of renovation process explain in words to(for) solid acid catalyst causes the structure of catalyst that marked change has taken place, descends like the micropore pore volume, and the generation of hard carbon distribution, the irreversible recovery in catalyst activity position, this all is because traditional renovation process causes.
Summary of the invention
Technical problem to be solved by this invention is the technical problem that existing regeneration techniques causes catalyst structure and performance decline, and a kind of renovation process of new zeolite molecular sieve catalyst is provided.This method has the advantage that through regeneration catalyst performance is recovered through the present invention.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of renovation process of zeolite molecular sieve catalyst; The raw material that employing contains ammonia contacts with decaying catalyst in 100～300 ℃, and its structure of the catalyst after the regeneration and catalytic performance are approaching with fresh catalyst.
In the technique scheme, the zeolite molecular sieve catalyst preferred version is selected from MFI zeolite, MOR zeolite, faujasite or Beta zeolite.Contain in the raw material of ammonia preferred version for except that containing ammonia, also contain and be selected from nitrogen, hydrogen, argon gas or the helium one or more.The raw material preferred version that contains ammonia is a kind of in mutually of liquid, gaseous state or gas-liquid mixed.System pressure maintains 0.1～10.0MPa during decaying catalyst regeneration, and preferred pressure is 0.1～6MPa.The concentration preferable range of ammonia preferably counts 10～90% with molar content.
The present invention proposes a kind of zeolite molecular sieve catalyst renovation process that is different from prior art; Technical scheme through above-mentioned is handled decaying catalyst; The silica alumina ratio of regeneration rear catalyst changes within 5%, and particle diameter does not almost have marked change, and specific area remains on 220m
2More than/the g, pore volume 0.15cm
3More than/the g, the acid strength of catalyst does not descend, and sour density fall is within 01～20%.
The renovation process of zeolite molecular sieve catalyst of the present invention: 1) improved regeneration efficiency; 2) considerably beyond traditional renovation process, this mainly is based on the strong solubility property of regenerating medium to this renovation process to the protection of catalyst, and based on the similar principle that mixes, regenerating medium can carry out wash-out with the part of compounds of catalyst surface; Second is because regenerating medium is micromolecular ammonia; Anti-disproportionated reaction can take place with senior compound in it; Generate the compound of molecular dimension between between higher-order compound and ammonia; Thereby desorption in the surface of catalyst and the duct discharges the activity of such catalysts position or from being diffused out in the duct that occupies; 3) this renovation process brings catalyst pores structure and sour variable density little, and the mass-transfer performance of catalyst changes little; When 4) having avoided the conventional regeneration method, the generation of making charcoal.
With oxirane catalytic ammoniation synthesizing ethanolamine on zeolite is example, at 80 ℃, and 12.0MPa, 9.0h
-1, the initial activity 960% of catalyst; React after 900 hours, activity drops to 60%, and after adopting this method, activity of such catalysts returns to 95.9%, and is approaching with fresh catalyst initial activity, obtained better technical effect.
Through embodiment the present invention is done further elaboration below, but these embodiment in no case constitute restriction to scope of the present invention.
The specific embodiment
[embodiment 1]
Reaction with oxirane catalytic ammoniation synthesizing ethanolamine on the ZSM-5 zeolite is an example, examination process conditions: reaction temperature: 90 ℃, and system pressure: 12.0MPa, total liquid phase air speed: 9.0h
-1, the conversion ratio 99.5% of oxirane; React after 900 hours; Activity drops to 60%; After adopting this programme; Activity of such catalysts returns to 85.9%, and the regenerative process of catalyst is following: the zeolite molecular sieve catalyst of inactivation is placed the 10mL fixed bed reactors, and decaying catalyst can be the sample behind normal reaction inactivation or the acceleration inactivation.Earlier in reactor, feed nitrogen, and the temperature of reactor is risen to 220 ℃, and the pressure of entire reaction system is risen to 6.0MPa.Liquefied ammonia is fed in the reactor, and flow rate of liquid is controlled at 30～100mL/hr, and constant temperature 5 hours, slowly is cooled to room temperature then and gets final product, and whole catalyst regeneration process is accomplished.
[embodiment 2～15]
According to each Step By Condition of embodiment 1 renovation process of catalyst has been carried out modulation, only kind, regeneration temperature and the pressure of regenerating medium, kind of decaying catalyst or the like, and the result listed in form 1.
Form 1
Annotate: MEA is a MEA.
Claims (5)
1. the renovation process of a zeolite molecular sieve catalyst adopts the raw material that contains ammonia to contact with decaying catalyst in 100～300 ℃, and its structure of the catalyst after the regeneration and catalytic performance are approaching with fresh catalyst.
2. the renovation process of zeolite molecular sieve catalyst according to claim 1 is characterized in that zeolite molecular sieve catalyst is selected from MFI zeolite, MOR zeolite, faujasite or Beta zeolite.
3. the renovation process of zeolite molecular sieve catalyst according to claim 1 is characterized in that containing in the raw material of ammonia except that containing ammonia, also contains to be selected from nitrogen, hydrogen, argon gas or the helium one or more.
4. the renovation process of zeolite molecular sieve catalyst according to claim 1, the raw material that it is characterized in that containing ammonia is a kind of in mutually of liquid, gaseous state or gas-liquid mixed.
5. the renovation process of zeolite molecular sieve catalyst according to claim 1, system pressure maintains 0.1～10.0MPa, preferred pressure 0.1～6MPa when it is characterized in that decaying catalyst regeneration.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100999394A CN102744103A (en) | 2011-04-20 | 2011-04-20 | Regeneration method of zeolite molecular sieve catalyst |
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| CN2011100999394A CN102744103A (en) | 2011-04-20 | 2011-04-20 | Regeneration method of zeolite molecular sieve catalyst |
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| CN102744103A true CN102744103A (en) | 2012-10-24 |
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| CN2011100999394A Pending CN102744103A (en) | 2011-04-20 | 2011-04-20 | Regeneration method of zeolite molecular sieve catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437617A (en) * | 2014-11-11 | 2015-03-25 | 中国海洋石油总公司 | Regeneration method of molecular sieve type carbon deposited catalyst |
| CN107199054A (en) * | 2016-03-18 | 2017-09-26 | 中国石油化工股份有限公司 | A kind of metal catalyst recovery method |
| CN110582481A (en) * | 2017-05-03 | 2019-12-17 | 巴斯夫欧洲公司 | Process for converting ethylene oxide to monoethanolamine and ethylenediamine using zeolite |
| CN110860306A (en) * | 2018-08-27 | 2020-03-06 | 中国石油化工股份有限公司 | Regeneration method of inactivated ZSM-5 molecular sieve |
| CN111359657A (en) * | 2018-12-25 | 2020-07-03 | 中国科学院大连化学物理研究所 | Regeneration method of molecular sieve catalyst |
Citations (4)
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|---|---|---|---|---|
| US5270272A (en) * | 1992-05-26 | 1993-12-14 | Uop | Sulfur removal from molecular-sieve catalyst |
| JPH08309200A (en) * | 1995-05-18 | 1996-11-26 | Arco Chem Technol Lp | Regeneration method for molecular sieve containing used titanium |
| CN1297884A (en) * | 1999-11-26 | 2001-06-06 | 株式会社日本触媒 | Process and apparatus for producing alkane hydramine |
| CN1565738A (en) * | 2003-06-30 | 2005-01-19 | 中国石油化工股份有限公司 | Method for reactivating carbon contained molecular sieve catalyzer in liquid-phase alkylating reaction of benzene and ethene |
-
2011
- 2011-04-20 CN CN2011100999394A patent/CN102744103A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5270272A (en) * | 1992-05-26 | 1993-12-14 | Uop | Sulfur removal from molecular-sieve catalyst |
| JPH08309200A (en) * | 1995-05-18 | 1996-11-26 | Arco Chem Technol Lp | Regeneration method for molecular sieve containing used titanium |
| CN1297884A (en) * | 1999-11-26 | 2001-06-06 | 株式会社日本触媒 | Process and apparatus for producing alkane hydramine |
| CN1565738A (en) * | 2003-06-30 | 2005-01-19 | 中国石油化工股份有限公司 | Method for reactivating carbon contained molecular sieve catalyzer in liquid-phase alkylating reaction of benzene and ethene |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437617A (en) * | 2014-11-11 | 2015-03-25 | 中国海洋石油总公司 | Regeneration method of molecular sieve type carbon deposited catalyst |
| CN107199054A (en) * | 2016-03-18 | 2017-09-26 | 中国石油化工股份有限公司 | A kind of metal catalyst recovery method |
| CN107199054B (en) * | 2016-03-18 | 2019-09-17 | 中国石油化工股份有限公司 | A kind of metal catalyst recovery method |
| CN110582481A (en) * | 2017-05-03 | 2019-12-17 | 巴斯夫欧洲公司 | Process for converting ethylene oxide to monoethanolamine and ethylenediamine using zeolite |
| CN110860306A (en) * | 2018-08-27 | 2020-03-06 | 中国石油化工股份有限公司 | Regeneration method of inactivated ZSM-5 molecular sieve |
| CN110860306B (en) * | 2018-08-27 | 2022-08-09 | 中国石油化工股份有限公司 | Regeneration method of inactivated ZSM-5 molecular sieve |
| CN111359657A (en) * | 2018-12-25 | 2020-07-03 | 中国科学院大连化学物理研究所 | Regeneration method of molecular sieve catalyst |
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