CN1883800A - Process for producing alkylbenzene catalyst - Google Patents
Process for producing alkylbenzene catalyst Download PDFInfo
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- CN1883800A CN1883800A CNA2005100270266A CN200510027026A CN1883800A CN 1883800 A CN1883800 A CN 1883800A CN A2005100270266 A CNA2005100270266 A CN A2005100270266A CN 200510027026 A CN200510027026 A CN 200510027026A CN 1883800 A CN1883800 A CN 1883800A
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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
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- 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 preparation method for alkyl benzene catalyst. The method resolves problems in anciently technique that reactive temperature and ratio of benzene and hydrocarbon is high in producing alkyl benzene by adding at least one organic acid solution of 0.1-10 wt. % from acetic acid, oxalic acid, citric acid or tartaric acid in catalyst forming process. The invention can be used in industrial production for alkyl benzene catalyst.
Description
Technical field
The present invention relates to a kind of alkylbenzene Preparation of catalysts method that is used to produce.
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 at present.
CN1096470 provides the alkylation catalyst of a kind of halogen-containing β zeolite and gama-alumina, is mainly used in benzene and ethylene alkylation under the high temperature; 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, the poor stability of benzene hydrocarbon ratio, is difficult to commercial Application.
Summary of the invention
Technical problem to be solved by this invention is the alkylbenzene catalyst for preparing in the above-mentioned document, exists reaction temperature height, benzene hydrocarbon than high problem, and a kind of new alkylbenzene Preparation of catalysts method that is used to produce is provided.Have when being used to produce alkylbenzene that reaction temperature is low with the catalyst of this method preparation, benzene hydrocarbon is than characteristics low, that the catalyst regeneration cycle is long, selectivity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind ofly be used to produce alkylbenzene Preparation of catalysts method, to be selected from least a zeolite powder in MCM-22, MCM-56, Y zeolite, β zeolite, modenite or the ZSM-5 zeolite with after binding agent mixes, add concentration and be at least a organic acid soln in acetate, oxalic acid, citric acid or the tartaric acid of being selected from of 0.1～10 weight %, make the catalyst of producing alkylbenzene through kneading, extruded moulding, roasting.
In the technique scheme, the organic acid preferred version is for being selected from acetate; Organic acid concentration preferable range is 1～5% weight; The binding agent preferred version is for being selected from aluminium oxide or silica; The sintering temperature preferable range is 480～600 ℃, and the roasting time preferable range is 1～15 hour.
The present invention is owing to adopt organic monoacid in the process of shaping of catalyst, avoided the zeolitic frameworks dealuminzation, improved the voidage in the preformed catalyst simultaneously, therefore improved catalytic activity, suppress the carbon distribution that reaction mass generates at the catalyst surface dehydrocyclization effectively, thereby improved the reaction stability of catalyst.With the catalyst that the inventive method makes, be used for the reaction of benzene and propylene reaction preparing isopropylbenzene, in fixed bed reactors, 120～190 ℃ of reaction temperatures, reaction pressure 2.0～3.5MPa, liquid phase air speed 0.1～5 hour
-1Under the condition, make catalyst under low benzene hydrocarbon ratio, to react, obtained better technical effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Get the Ludox of 600 grams 40% (weight), add 700 gram water, 38.9 gram sodium metaaluminate [Al
2O
3, 42% (weight)] and 2 gram NaOH, after stirring, add 125 gram hexamethylene imines (HMI) again.Said mixture ageing at room temperature is after 3 days, rising temperature to 138 ℃ crystallization, crystallization 48 hours.Distilled water cleans to neutral, oven dry.The X-ray powder diffraction shows that the product that (XRD) synthesized is MCM-56.
With the former powder of above-mentioned synthetic MCM-56, add 1 mol ammonium nitrate solution, be warming up to 95 ℃ of exchanges 2 hours, exchange repeatedly 3 times, distilled water cleans to neutral, oven dry.
[embodiment 2]
Get MCM-56 zeolite 15 grams of [embodiment 1] handling, after 5 gram aluminium oxide fully mix, add 28 grams, 5 weight % acetic acid solutions, mediating extruded moulding is the shape of 1.6 * 2 millimeters of φ, 120 ℃ of oven dry, and 530 ℃ of roastings 5 hours obtain finished catalyst.
Get above-mentioned synthetic catalyst 4 grams and place fixed bed reactors, under 140 ℃, 2.3MPa condition, benzene and propylene are reacted by beds, wherein the benzene inlet amount is 300 Grams Per Hours, the propylene feed amount is 20 Grams Per Hours, is 5.0 hours with propylene calculated weight liquid air speed
-1This reaction was investigated through 90 hours, and propylene conversion is 97.4% in the product, and selectivity is 99.5% (calculating with propyl group).
[embodiment 3]
Get MCM-56 zeolite 15 grams of [embodiment 1] handling, after 5 gram aluminium oxide fully mix, add 28 grams, 10 weight % acetic acid solutions, mediating extruded moulding is the shape of 1.6 * 2 millimeters of φ, 120 ℃ of oven dry, and 550 ℃ of roastings 4 hours obtain finished catalyst.
Get above-mentioned synthetic catalyst 4 grams and check and rate under the examination condition identical with [embodiment 1], investigated through 90 hours, propylene conversion is 96.7% in the product, and selectivity is 99.6% (calculating with propyl group).
[embodiment 4]
Get MCM-56 zeolite 15 grams of [embodiment 1] handling, after 5 gram aluminium oxide fully mix, add 28 grams, 3 weight % citric acid solutions, mediating extruded moulding is the shape of 1.6 * 2 millimeters of φ, 120 ℃ of oven dry, and 510 ℃ of roastings 10 hours obtain finished catalyst.
Get above-mentioned synthetic catalyst 4 grams and check and rate under the examination condition identical with [embodiment 1], investigated through 90 hours, propylene conversion is 97.0% in the product, and selectivity is 98.5% (calculating with propyl group).
[embodiment 5]
Get MCM-56 zeolite 15 grams of [embodiment 1] handling, after 5 gram aluminium oxide fully mix, add 28 grams, 4 weight % oxalic acid solutions, mediating extruded moulding is the shape of 1.6 * 2 millimeters of φ, 120 ℃ of oven dry, and 580 ℃ of roastings 6 hours obtain finished catalyst.
Get above-mentioned synthetic catalyst 4 grams and check and rate under the examination condition identical with [embodiment 1], investigated through 90 hours, propylene conversion is 96.5% in the product, and selectivity is 98.9% (calculating with propyl group).
[comparative example 1]
Get MCM-56 zeolite 15 grams of [embodiment 1] handling, after 5 gram aluminium oxide fully mix, add 28 grams, 5% salpeter solution, mediating extruded moulding is the shape of 1.6 * 2 millimeters of φ, 120 ℃ of oven dry, and 550 ℃ of roastings 5 hours obtain finished catalyst.
Above-mentioned synthetic catalyst 4 grams are placed fixed bed reactors, under 165 ℃, 2.6MPa condition, benzene and propylene are reacted by beds, wherein the benzene inlet amount is 500 Grams Per Hours, the propylene feed amount is 20 Grams Per Hours, is 5.0 hours with propylene calculated weight liquid air speed
-1This reaction was investigated through 90 hours, and propylene conversion reduces to 90%, and the propyl group selectivity is 98.0% (calculating with propyl group).
[comparative example 2]
Get MCM-56 zeolite 15 grams of [embodiment 1] handling, after 5 gram aluminium oxide fully mix, add 28 grams, 10% salpeter solution, mediating extruded moulding is the shape of 1.6 * 2 millimeters of φ, 120 ℃ of oven dry, and 535 ℃ of roastings 8 hours obtain finished catalyst.
Above-mentioned synthetic catalyst 4 grams are placed fixed bed reactors, under 160 ℃, 2.5MPa condition, benzene and propylene are reacted by beds, wherein the benzene inlet amount is 500 Grams Per Hours, the propylene feed amount is 20 Grams Per Hours, is 5.0 hours with propylene calculated weight liquid air speed
-1This reaction was investigated through 96 hours, and propylene conversion reduces to 71%, and selectivity is 98.5% (calculating with propyl group).
Claims (5)
1, a kind ofly is used to produce alkylbenzene Preparation of catalysts method, to be selected from least a zeolite powder in MCM-22, MCM-56, Y zeolite, β zeolite, modenite or the ZSM-5 zeolite with after binding agent mixes, add concentration and be at least a organic acid soln in acetate, oxalic acid, citric acid or the tartaric acid of being selected from of 0.1～10 weight %, make the catalyst of producing alkylbenzene through kneading, extruded moulding, roasting.
2, be used to produce alkylbenzene Preparation of catalysts method according to claim 1 is described, it is characterized in that organic acid is an acetate.
3, be used to produce alkylbenzene Preparation of catalysts method according to claim 1 is described, it is characterized in that organic acid concentration is 1～5 weight %.
4, be used to produce alkylbenzene Preparation of catalysts method according to claim 1 is described, it is characterized in that binding agent is selected from aluminium oxide or silica.
5, be used to produce alkylbenzene Preparation of catalysts method according to claim 1 is described, it is characterized in that sintering temperature is 480～600 ℃, roasting time is 1～15 hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100270266A CN100553772C (en) | 2005-06-22 | 2005-06-22 | Be used to produce alkylbenzene Preparation of catalysts method |
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| CNB2005100270266A CN100553772C (en) | 2005-06-22 | 2005-06-22 | Be used to produce alkylbenzene Preparation of catalysts method |
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| CN1883800A true CN1883800A (en) | 2006-12-27 |
| CN100553772C CN100553772C (en) | 2009-10-28 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039157B (en) * | 2009-10-13 | 2012-07-18 | 中国石油化工股份有限公司 | Non-binder MCM-22 molecular sieve catalyst and preparation method thereof |
| CN105498827A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for efficient preparation of biomass based aromatic hydrocarbon |
| CN110562995A (en) * | 2018-06-06 | 2019-12-13 | 中国石油化工股份有限公司 | Synthesis method of nano Y zeolite, synthesized nano Y zeolite and application |
-
2005
- 2005-06-22 CN CNB2005100270266A patent/CN100553772C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039157B (en) * | 2009-10-13 | 2012-07-18 | 中国石油化工股份有限公司 | Non-binder MCM-22 molecular sieve catalyst and preparation method thereof |
| CN105498827A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for efficient preparation of biomass based aromatic hydrocarbon |
| CN105498827B (en) * | 2014-09-25 | 2018-08-17 | 中国石油化工股份有限公司 | The method for efficiently preparing biomass-based aromatic hydrocarbons |
| CN110562995A (en) * | 2018-06-06 | 2019-12-13 | 中国石油化工股份有限公司 | Synthesis method of nano Y zeolite, synthesized nano Y zeolite and application |
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|---|---|
| CN100553772C (en) | 2009-10-28 |
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