CN101045209A - Catalyst for synthesizing iso-propylbenzene - Google Patents
Catalyst for synthesizing iso-propylbenzene Download PDFInfo
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- CN101045209A CN101045209A CNA2006100251039A CN200610025103A CN101045209A CN 101045209 A CN101045209 A CN 101045209A CN A2006100251039 A CNA2006100251039 A CN A2006100251039A CN 200610025103 A CN200610025103 A CN 200610025103A CN 101045209 A CN101045209 A CN 101045209A
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- catalyst
- propylbenzene
- molecular sieve
- synthesizing iso
- synthesizing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A catalyst for synthesizing isopropylbenzene with low reaction temp (120-170 deg.C) and benzene/hydrocarbon ratio (2-5) and high stability is a modified molecular sieve.
Description
Technical field
The present invention relates to a kind of catalyst of synthesizing iso-propylbenzene.
Background technology
Isopropylbenzene is an important intermediate raw material of producing phenol, acetone and AMS.Phenol more than 90% is to adopt cumene method production in the world at present.The conventional method of industrial production isopropylbenzene has the solid phosphoric acid method (SPA method) of UOP (UOP) and the improvement AlCl of Monsanto/Lummus Crest company
3Method.SPA operating condition harshness, impurity is many, can not improve the productive rate of isopropylbenzene by reverse alkylation.And AlCl
3Though method has the reaction condition that relaxes, and can improve the productive rate of isopropylbenzene by reverse alkylation, this catalytic erosion is strong, pollution is heavy and post processing is numerous and diverse.
Molecular sieve liquid phase alkylation methods because reaction condition mitigations, conversion ratio height, selectivity is good, impurity is few, pollution-free, do not have to corrode; main accessory substance polyisopropylbenzene can change isopropylbenzene into via reverse alkylation; make the isopropylbenzene productive rate up to more than 99%; be each institute of big industrial group company common concern in recent years, and an advanced technology of competitively developmental research, to significant " cleaning procedure " technology of environmental protection.
The isopropylbenzene molecular sieve catalyst of heavy industrialization has the Y zeolite of Uop Inc., the beta-molecular sieve of EniChem company, the MCM-22 molecular sieve of Mobil company at present.
CN1113649 provides a kind of steam treatment process of zeolite catalyst being carried out the part dealuminzation; CN1125641 provides a kind of method for preparing the isopropylbenzene zeolite catalyst of high activity, high selectivity, is mainly used in the reaction of bubbling bed, and CN1227770 then adopts mineral acid treatment β zeolite to prepare alkylation catalyst.The common drawback of all above-mentioned catalyst is reaction temperature height, high, low, the poor stability of propylene air speed of benzene hydrocarbon ratio, is difficult to commercial Application.
Summary of the invention
Technical problem to be solved by this invention is to exist the reaction temperature height of catalyst and benzene hydrocarbon than problem high, poor stability in the prior art, and a kind of catalyst of new synthesizing iso-propylbenzene is provided.The reaction that this catalyst is used for synthesizing iso-propylbenzene has the advantage that reaction temperature is low, benzene hydrocarbon compares low and good stability.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the catalyst of～kind of synthesizing iso-propylbenzene comprises following component by weight percentage:
A) 50～80% be selected from Y, β or the MCM-22 molecular sieve at least a;
B) 20～50% inorganic oxide;
Wherein molecular sieve is handled with ammoniacal liquor, sodium aluminate and the modification of tetraethylammonium bromide mixed liquor earlier before the preparation catalyst.
The molecular sieve preferred version is a beta-molecular sieve in the technique scheme.The inorganic oxide preferred version is at least a in aluminium oxide, titanium oxide, zinc oxide or the zirconia.In the used mixed liquor of modified molecular screen in weight percent concentration: the ammonia concn preferable range is 8%～17%, and the concentration of sodium aluminate preferable range is 3%～7%, and tetraethylammonium bromide concentration preferable range is 2%～10%.The treatment temperature preferable range of mixed liquor modified molecular screen is 120～160 ℃.The processing time preferable range of mixed liquor modified molecular screen is 1～6 hour.
Catalyst of the present invention can prepare as follows:
A) according to conventional method synthesis of molecular sieve β;
B) synthetic molecular sieve β is exchanged with ammonium salt, the content that makes alkali metal ion wherein is below 0.01% (weight);
C) will exchange good molecular sieve is to handle under 120～160 ℃ of conditions with the mixture of sodium aluminate, ammoniacal liquor and tetraethylammonium bromide in temperature, dries then;
D) beta-molecular sieve of handling well is mixed with aluminium oxide, add an amount of dilute nitric acid solution kneading, extruded moulding, oven dry back pelletizing got finished catalyst in 4 hours 580 ℃ of roastings then.
The present invention handles by molecular sieve being carried out modification, dealuminzation phenomenon in the exchange process is effectively improved, thereby improved the reaction stability of catalyst, make that catalyst can be that 145 ℃, benzene hydrocarbon ratio are to react under 2.02 (mole) condition in reaction temperature, do not show catalysqt deactivation after 300 hours, and outlet isopropylbenzene concentration can reach 45%, has obtained better technical effect.
The invention will be further elaborated below by embodiment, and all specific embodiments just illustrate and are not restriction.
The specific embodiment
[embodiment 1]
According to the synthetic beta-molecular sieve of method described in the CN1249270A, synthetic good molecular sieve is exchanged to wherein alkali metal ion content measured less than 100ppm with ammonium nitrate, get the above-mentioned molecular sieve of 200 grams and add 500 milliliters of analytically pure concentrated ammonia liquors, add 40 gram tetraethylammonium bromides and 5 gram sodium aluminate dissolvings under the strong agitation, add 500 ml deionized water continuation stirring and change 2000 milliliters of autoclaves over to after 10 minutes, be warming up to 150 ℃ and handled 2 hours, sample spends deionised water to ph=8～9.
[embodiment 2]
Get molecular sieve 100 grams of handling well in the above-mentioned example 1, mix evenly with 25 gram aluminium oxide, 10 gram zinc oxide, 5 gram zirconias, 5 gram titanium oxide, add 160 milliliter of 5% (weight) salpeter solution, 5 gram pseudo-ginseng powder are mediated extruded moulding after 2 hours, with the catalyst of forming 150 ℃ of oven dry, under air atmosphere, be warming up to 580 ℃ of roastings 4 hours then, obtain finished catalyst.
[embodiment 3]
The catalyst powder of preparation among the embodiment 2 is broken into 20～60 purpose particles, gets 1.0 gram catalyst and carry out propylene liquid-phase alkylation reaction in fixed bed reactors, reaction condition is, propylene air speed=2.5 hour
-1, reaction temperature=150 ℃, reaction pressure=2.7MPa, product is an isopropylbenzene, propylene conversion=100%, product propyl group selectivity is greater than 99.2%, total benzene hydrocarbon ratio is 2.1 (moles), reacts and does not observe the catalyst activity loss in 3000 hours, and outlet isopropylbenzene concentration reaches 44%.
[embodiment 4]
According to the synthetic beta-molecular sieve of method described in the CN1249270A, synthetic good molecular sieve is exchanged to wherein alkali metal ion content measured less than 100ppm with ammonium nitrate, get the above-mentioned molecular sieve of 200 grams and add 300 milliliters of analytically pure concentrated ammonia liquors, add 60 gram tetraethylammonium bromides and 7 gram sodium aluminate dissolvings under the strong agitation, add 500 ml deionized water continuation stirring and change 2000 milliliters of autoclaves over to after 10 minutes, be warming up to 130 ℃ and handled 5 hours, sample spends deionised water to ph=8～9.
[embodiment 5]
Get molecular sieve 100 grams of handling well in the above-mentioned example 4, mix evenly with 25 gram aluminium oxide, 10 gram zinc oxide, 5 gram zirconias, 5 gram titanium oxide, add 155 milliliter of 5% (weight) salpeter solution, 5 gram pseudo-ginseng powder are mediated extruded moulding after 2 hours, with the catalyst of forming 150 ℃ of oven dry, under air atmosphere, be warming up to 580 ℃ of roastings 4 hours then, obtain finished catalyst.
[embodiment 6]
The catalyst powder of preparation among the embodiment 5 is broken into 20～60 purpose particles, gets 1.0 gram catalyst and carry out propylene liquid-phase alkylation reaction in fixed bed reactors, reaction condition is, propylene air speed=2.0 hour
-1, reaction temperature=145 ℃, reaction pressure=2.5MPa, product is an isopropylbenzene, propylene conversion=100%, product propyl group selectivity is greater than 99.2%, total benzene hydrocarbon ratio is 2.02 (moles), reacts and does not observe the catalyst activity loss in 3000 hours, and outlet isopropylbenzene concentration reaches 45%.
[comparative example 1]
To exchange repeatedly with ammonium nitrate solution with β zeolite 200 grams of method preparation among the CN1249270A, make in the molecular sieve alkali metal ion content measured less than 100ppm, get the qualified molecular sieve of exchange 100 grams, mix evenly with 25 gram aluminium oxide, 10 gram zinc oxide, 5 gram zirconias, 5 gram titanium oxide, add 160 milliliter of 5% (weight) salpeter solution, 5 gram pseudo-ginseng powder are mediated extruded moulding after 2 hours, with the catalyst of forming 150 ℃ of oven dry, under air atmosphere, be warming up to 580 ℃ of roastings 4 hours then, obtain finished catalyst.Above-mentioned catalyst powder is broken into 20～60 purpose particles, gets 1.0 gram catalyst and carry out propylene liquid-phase alkylation reaction in fixed bed reactors, reaction condition is, propylene air speed=0.6 hour
-1, reaction temperature=165 ℃, reaction pressure=3.0MPa, product is an isopropylbenzene, initial propylene conversion=100%, product propyl group selectivity is greater than 99.2%, total benzene hydrocarbon ratio is 3.5 (moles), reacts after 2000 hours propylene conversion and reduces to 92%, and exporting isopropylbenzene concentration is 32%.
Claims (6)
1, a kind of catalyst of synthesizing iso-propylbenzene comprises following component by weight percentage:
A) 50～80% be selected from Y, β or the MCM-22 molecular sieve at least a;
B) 20～50% inorganic oxide;
Wherein molecular sieve is handled with ammoniacal liquor, sodium aluminate and the modification of tetraethylammonium bromide mixed liquor earlier before the preparation catalyst.
2, according to the described catalyst that is used for synthesizing iso-propylbenzene of claim 1, it is characterized in that molecular screening is from beta-molecular sieve.
3,, it is characterized in that inorganic oxide is selected from least a in aluminium oxide, titanium oxide, zinc oxide or the zirconia according to the described catalyst that is used for synthesizing iso-propylbenzene of claim 1.
4, according to the described catalyst that is used for synthesizing iso-propylbenzene of claim 1, it is characterized in that in the used mixed liquor of modified molecular screen in weight percent concentration: ammonia concn is 8%～17%, concentration of sodium aluminate is 3%～7%, and tetraethylammonium bromide concentration is 2%～10%.
5, according to the described catalyst that is used for synthesizing iso-propylbenzene of claim 1, the treatment temperature that it is characterized in that the mixed liquor modified molecular screen is 120～160 ℃.
6, according to the described catalyst that is used for synthesizing iso-propylbenzene of claim 1, the processing time that it is characterized in that the mixed liquor modified molecular screen is 1～6 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100251039A CN100453178C (en) | 2006-03-27 | 2006-03-27 | Catalyst for synthesizing iso-propylbenzene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100251039A CN100453178C (en) | 2006-03-27 | 2006-03-27 | Catalyst for synthesizing iso-propylbenzene |
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| CN101045209A true CN101045209A (en) | 2007-10-03 |
| CN100453178C CN100453178C (en) | 2009-01-21 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295516A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for producing isopropyl benzene |
| CN102294257A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst applied to preparation of isopropyl benzene by performing liquid-phase alkylation on propylene |
| CN109046445A (en) * | 2018-06-25 | 2018-12-21 | 万华化学集团股份有限公司 | A kind of preparation method of H β/MCM-22 composite molecular sieves and the method for preparing tert-butyl phenol |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5227558A (en) * | 1992-02-10 | 1993-07-13 | Fina Technology, Inc. | Aromatic alkylation process employing steam modified zeolite beta catalyst |
| CN1234457C (en) * | 2003-09-12 | 2006-01-04 | 北京服装学院 | Zeolite catalyst for synthesis of isopropyl benzene from benzene and propylene |
-
2006
- 2006-03-27 CN CNB2006100251039A patent/CN100453178C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295516A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for producing isopropyl benzene |
| CN102294257A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst applied to preparation of isopropyl benzene by performing liquid-phase alkylation on propylene |
| CN102294257B (en) * | 2010-06-24 | 2013-01-09 | 中国石油化工股份有限公司 | Catalyst applied to preparation of isopropyl benzene by performing liquid-phase alkylation on propylene |
| CN102295516B (en) * | 2010-06-24 | 2013-06-05 | 中国石油化工股份有限公司 | Method for producing isopropyl benzene |
| CN109046445A (en) * | 2018-06-25 | 2018-12-21 | 万华化学集团股份有限公司 | A kind of preparation method of H β/MCM-22 composite molecular sieves and the method for preparing tert-butyl phenol |
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| CN100453178C (en) | 2009-01-21 |
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