CN100531907C - Catalyst for alkyl transfer of polyalkylbenzene - Google Patents
Catalyst for alkyl transfer of polyalkylbenzene Download PDFInfo
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- CN100531907C CN100531907C CNB2006100279142A CN200610027914A CN100531907C CN 100531907 C CN100531907 C CN 100531907C CN B2006100279142 A CNB2006100279142 A CN B2006100279142A CN 200610027914 A CN200610027914 A CN 200610027914A CN 100531907 C CN100531907 C CN 100531907C
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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
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Abstract
The invention relates to a catalyst for alkyl transfer of multi-alkyl benzene, mainly solving the problems in the prior techniques that the catalyst activity is low, benzene dosage is large, and the impurity content is high. And the invention solves these problems by a technical solution of modifying molecular sieve with aluminum trichloride and can be used in industrial production of alkyl transfer of multi-alkyl benzene.
Description
Technical field
The present invention relates to a kind of catalyst of polyalkylbenzene transalkylation.
Background technology
Alkylbenzene is important basic Organic Chemicals, comprises isopropylbenzene, ethylbenzene, butylbenzene and long-chain alkyl benzene etc.Wherein isopropylbenzene is an important intermediate raw material of producing phenol, acetone and AMS, and the phenol more than 90% is to adopt cumene method production in the world at present; Ethylbenzene is to produce cinnamic primary raw material; Long-chain alkyl benzene then is the important source material of producing washing agent.The conventional method of industrial production alkylbenzene 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 alkylbenzene by reverse alkylation.And AlCl
3Though method has the reaction condition that relaxes, and can improve the productive rate of alkylbenzene 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 polyalkylbenzene can change alkylbenzene into via reverse alkylation; make the alkylbenzene 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.
Important process process in the molecular sieve liquid phase alkylation methods is the transalkylation reaction of polyalkylbenzene, can improve the productive rate of alkylbenzene by the transalkylation reaction of polyalkylbenzene.CN1139658A provides a kind of preparation method of transalkylation catalyst of many alkylaromatic hydrocarbons, but the transalkylation activity of many alkylaromatic hydrocarbons of this little crystal grain alumina silicate catalyst is extremely low, reaction temperature is up to more than 250 ℃; CN1142986A has investigated the transalkylation performance of multiple large pore molecular sieve, and the catalyst that is provided can carry out the transalkylation reaction of many alkylaromatic hydrocarbons at lower temperature, but needs often regeneration; CN1171096A and CN1310051A provide the method and the catalyst of many ethylbenzene gas phase transalkylation, the catalyst that is adopted be with ZSM-5 as active component, CN1323739A and CN1323769A have introduced with ammonia and have handled the method for Y molecular sieve as many ethylbenzene transalkylation catalyst.All there is impurity content problem of higher in the large usage quantity, product of benzene in active lower, the transalkylation reaction in the catalyst that conventional art adopted.
Summary of the invention
Technical problem to be solved by this invention is to have the problem that activity of such catalysts is low, impurity content is high, the benzene consumption is big in the prior art, and a kind of catalyst of new polyalkylbenzene transalkylation is provided.The transalkylation reaction that this catalyst is used for polyalkylbenzene has that catalyst activity height, product impurity content are low, the few advantage of benzene consumption in the course of reaction.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst of polyalkylbenzene transalkylation comprises following component by weight percentage:
A) 30～80% zeolite molecular sieve;
B) 20～70% binding agent;
Wherein zeolite molecular sieve adopts alchlor aqueous solution exchange modification.
In the technique scheme, the molecular sieve preferred version is selected from Y, β or MCM-22 molecular sieve; The binding agent preferred version is selected from least a in aluminium oxide, titanium oxide, zinc oxide or the zirconia; Molecular sieve modified concentration preferable range with alchlor is 0.2～1.0 mol, and the temperature preferable range of modification is 80～97 ℃, and the time preferable range of modification is 0.5～1.5 hour.
Catalyst of the present invention can prepare as follows:
A) synthesis zeolite Y, β or MCM-22;
B) synthetic zeolite molecular sieve is exchanged modification with the alchlor aqueous solution, the content that makes alkali metal ion is wherein dried below 0.05% (weight) then.
C) will exchange qualified zeolite molecular sieve and inorganic oxide and mix, add shaping assistant, kneading, extrusion, oven dry roasting, pelletizing gets finished catalyst again.
The present invention has improved exchange efficiency effectively owing to adopt the aluminum trichloride solution modified molecular screen, has prevented in modifying process removing of aluminium in the molecular sieve.When this catalyst was used for the transalkylation reaction of polyalkylbenzene, impurity content can reach less than 50ppm in the product, and the polyalkylbenzene conversion ratio can reach 85%, has obtained better technical effect.
The invention will be further elaborated below by embodiment, and all specific embodiment just illustrate and are not restriction.
The specific embodiment
[embodiment 1]
Getting the commercially available NaY zeolite of 200 grams handled 3 hours at 550 ℃ with the air that contains 1% (weight) water vapour, aluminum trichloride solution with 0.5 mol exchanges 80 minutes at 90 ℃ then, repeat above-mentioned steps 6 times, the Na ion concentration in the assurance molecular sieve is less than 0.05% (weight), and is stand-by.
[embodiment 2]
Get the good Y zeolite of above-mentioned exchange 100 grams, mix evenly with 25 gram aluminium oxide, 10 gram zinc oxide, add 150 milliliter of 2.5% (weight) salpeter solution, 5 gram pseudo-ginseng powder are mediated extruded moulding after 1 hour, the catalyst of forming 150 ℃ of oven dry, is warming up to 500 ℃ of roastings then and obtained finished catalyst in 4 hours under air atmosphere.
[embodiment 3]
The catalyst powder of preparation among the embodiment 2 is broken into 20～60 purpose particles, gets 2.0 gram catalyst and carry out the liquid phase transalkylation reaction of diisopropylbenzene (DIPB) in fixed bed reactors, reaction condition is benzene/diisopropylbenzene (DIPB)=2 (weight), liquid air speed=2.0 hour
-1, reaction temperature=160 ℃, reaction pressure=2.5MPa, product is an isopropylbenzene, diisopropylbenzene (DIPB) conversion per pass=66%, n-proplbenzene content is less than 250ppm.
[embodiment 4]
Get commercially available β zeolite 200 grams, add 1 mol aluminum trichloride solution, be warming up to 95 ℃ of exchanges 1 hour, exchange repeatedly 6 times, make alkali metal ion content measured in the zeolite less than 0.05% (weight), beta-molecular sieve 100 grams that above-mentioned exchange is good are evenly mixed with 60 gram aluminium oxide, add 130 milliliter of 5% (weight) salpeter solution, 5 gram pseudo-ginseng powder are mediated extruded moulding after 1 hour, with the catalyst of forming after 150 ℃ of oven dry under air atmosphere temperature programming to 580 ℃ roasting obtained finished catalyst in 4 hours.
[embodiment 5]
The catalyst powder of preparation among the embodiment 4 is broken into 20～60 purpose particles, gets 2.0 gram catalyst and carry out many ethylbenzene liquid phase transalkylation reaction in fixed bed reactors, reaction condition is benzene/many ethylbenzene=5 (mole), liquid air speed=3.0 hour
-1, reaction temperature=250 ℃, reaction pressure=3.8MPa, product is an ethylbenzene, many ethylbenzene conversion per pass=85%, xylene content is less than 50ppm.
[embodiment 6]
Get commercially available MCM-22 zeolite 200 grams, add 0.3 mol aluminum trichloride solution, be warming up to 82 ℃ of exchanges 0.5 hour, exchange repeatedly 6 times, make alkali metal ion content measured in the zeolite less than 0.05% (weight), MCM-22 molecular sieve 100 grams that above-mentioned exchange is good are evenly mixed with 50 gram aluminium oxide, add 150 milliliter of 5% (weight) salpeter solution, 5 gram pseudo-ginseng powder are mediated extruded moulding after 1 hour, with the catalyst of forming after 150 ℃ of oven dry under air atmosphere temperature programming to 550 ℃ roasting obtained finished catalyst in 4 hours.
[embodiment 7]
The catalyst powder of preparation among the embodiment 6 is broken into 20～60 purpose particles, gets 2.0 gram catalyst and carry out diisopropylbenzene (DIPB) liquid phase transalkylation reaction in fixed bed reactors, reaction condition is benzene/diisopropylbenzene (DIPB)=4 (moles), liquid air speed=2.0 hour
-1, reaction temperature=200 ℃, reaction pressure=2.8MPa, product is an isopropylbenzene, diisopropylbenzene (DIPB) conversion per pass=58%, n-proplbenzene content is less than 320ppm.
[comparative example 1]
Commercially available Y zeolite is exchanged 80 minutes with 0.5 mol ammonium nitrate solution at 90 ℃, repeat above-mentioned steps 6 times, Na ion concentration in the assurance molecular sieve is less than 0.05% (weight), be prepared into catalyst with aluminium oxide and zinc oxide mixing extruded moulding then, be ground into 20～60 purpose particles, get 2.0 gram catalyst and carry out diisopropylbenzene (DIPB) liquid phase transalkylation reaction in fixed bed reactors, reaction condition is benzene/diisopropylbenzene (DIPB)=2 (weight), liquid air speed=1.6 hour
-1, reaction temperature=160 ℃, reaction pressure=2.5MPa, product is an isopropylbenzene, diisopropylbenzene (DIPB) conversion per pass=45%, n-proplbenzene content are 350ppm.
[comparative example 2]
With commercially available β zeolite with 1 mol ammonium chloride solution, be warming up to 95 ℃ of exchanges 1 hour, exchange repeatedly 6 times, make alkali metal ion content measured in the zeolite less than 0.05% (weight), mix the back extruded moulding again with aluminium oxide and be prepared into catalyst, be ground into 20～60 purpose particles, get 2.0 gram catalyst and in fixed bed reactors, carry out many ethylbenzene liquid phase transalkylation reaction, reaction condition is benzene/many ethylbenzene=6 (mole), liquid air speed=3.0 hour
-1, reaction temperature=260 ℃, reaction pressure=3.8MPa, product is an ethylbenzene, many ethylbenzene conversion per pass=53%, xylene content are 95ppm.
[comparative example 3]
With commercially available MCM-22 zeolite with 0.3 mol ammonium chloride solution, be warming up to 82 ℃ of exchanges 0.5 hour, exchange repeatedly 6 times, make alkali metal ion content measured in the zeolite less than 0.05% (weight), mix the back extruded moulding again with aluminium oxide and be prepared into catalyst, be ground into 20～60 purpose particles, get 2.0 gram catalyst and in fixed bed reactors, carry out diisopropylbenzene (DIPB) liquid phase transalkylation reaction, reaction condition is benzene/diisopropylbenzene (DIPB)=4 (moles), liquid air speed=2.0 hour
-1, reaction temperature=200 ℃, reaction pressure=2.8MPa, product is an isopropylbenzene, diisopropylbenzene (DIPB) conversion per pass=31%, n-proplbenzene content are 400ppm.
[embodiment 8]
Press each Step By Condition of embodiment 1, the concentration that just changes alchlor is 0.2 mol, treatment temperature be 96 ℃, processing time be made in 90 minutes after the exchange the Y zeolite molecular sieve, each Step By Condition by embodiment 2 makes catalyst again, press the condition examination of embodiment 3, reaction result is: product is an isopropylbenzene, and the diisopropylbenzene (DIPB) conversion per pass is 65%, and n-proplbenzene content is less than 256ppm.
[embodiment 9]
Press each Step By Condition of embodiment 1, the concentration that just changes alchlor is 1.0 mol, treatment temperature is that 83 ℃, processing time are 40 minutes, get the Y zeolite molecular sieve after making exchange, each Step By Condition by embodiment 4 makes catalyst again, presses the examination condition examination of embodiment 5, and reaction result is: product is an ethylbenzene, many ethylbenzene conversion per pass is 84.5%, and xylene content is less than 55ppm.
Claims (4)
1, a kind of catalyst of polyalkylbenzene transalkylation comprises following component by weight percentage:
A) 30～80% zeolite molecular sieve;
B) 20～70% binding agent;
Wherein zeolite molecular sieve adopts alchlor aqueous solution exchange modification.
2,, it is characterized in that molecular screening is from Y, β or MCM-22 molecular sieve according to the catalyst of the described polyalkylbenzene transalkylation of claim 1.
3,, it is characterized in that binding agent is selected from least a in aluminium oxide, titanium oxide, zinc oxide or the zirconia according to the catalyst of the described polyalkylbenzene transalkylation of claim 1.
4, according to the catalyst of the described polyalkylbenzene transalkylation of claim 1, it is characterized in that modification is 0.2～1.0 mol with the concentration of alchlor, the temperature of modification is 80～97 ℃, the time of modification is 0.5～1.5 hour.
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| CNB2006100279142A CN100531907C (en) | 2006-06-21 | 2006-06-21 | Catalyst for alkyl transfer of polyalkylbenzene |
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| CNB2006100279142A CN100531907C (en) | 2006-06-21 | 2006-06-21 | Catalyst for alkyl transfer of polyalkylbenzene |
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| CN100531907C true CN100531907C (en) | 2009-08-26 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101734989B (en) * | 2008-11-21 | 2013-10-30 | 中国石油化工股份有限公司 | Method for selective toluene disproportionation and transalkylation of benzene and C9 aromatics |
| CN102407156B (en) * | 2010-09-21 | 2013-09-04 | 中国石油天然气股份有限公司 | Preparation method of alkyl transferring catalyst |
| CN103657710B (en) * | 2013-12-09 | 2015-09-02 | 中国科学院山西煤炭化学研究所 | For the catalyst of fixed bed reactors synthesizing poly alpha-olefin and method for making and application |
| CN108530250A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | The method of benzene and diisopropylbenzene (DIPB) production n-proplbenzene |
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- 2006-06-21 CN CNB2006100279142A patent/CN100531907C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 三氯化铝负载HY沸石催化β-甲基萘转移烷基化反应. 吴伟等.现代化工，第24卷第12期. 2004 |
| 三氯化铝负载HY沸石催化β-甲基萘转移烷基化反应. 吴伟等.现代化工，第24卷第12期. 2004 * |
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