CN1120976A - Catalyst for preparing styrene and ethylbenzene - Google Patents
Catalyst for preparing styrene and ethylbenzene Download PDFInfo
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- CN1120976A CN1120976A CN95108757A CN95108757A CN1120976A CN 1120976 A CN1120976 A CN 1120976A CN 95108757 A CN95108757 A CN 95108757A CN 95108757 A CN95108757 A CN 95108757A CN 1120976 A CN1120976 A CN 1120976A
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- molecular sieve
- catalyzer
- toluene
- ethylbenzene
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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
On type X, type Y, type M, ZSM-5 and Beta molecular sieves for alkali metal ion exchange, oxide and bromide of alkali metal are carried through impregnation so as to prepare the said catalyst. The catalyst is used for the oxidation and methylation of toluene and methane to synthesize styrene and ethylbenzene. The said catalyst has high activity and selectivity, and at the conditions of normal pressure and 700-770 deg.C, total yield can reach 58.3%, total selectivity 76.4%.
Description
The present invention is the catalyzer that carrying alkali metal bromide on X type, Y type, M type, ZSM-5 type and the beta molecular sieve of alkalimetal ion exchange, alkalimetal oxide constitute.Be used for toluene and methane and oxygen reaction and directly prepare vinylbenzene and ethylbenzene.
Vinylbenzene is one of important chemical material, it is mainly used in synthetic rubber and polystyrene, up to now, 90% vinylbenzene is to be made by ethylbenzene dehydrogenation, and ethylbenzene mainly is to be obtained by benzene and ethylene reaction, and this method not only expends crude oil in a large number, and the technical process complexity, side reaction is many, the energy consumption height.People had also once developed by toluene and methyl alcohol and carried out side chain alkylation system ethylbenzene or directly obtain ethylbenzene and vinylbenzene, but this method need synthesizing methanol when exploring by toluene system ethylbenzene and cinnamic operational path, thereby also economical inadequately.
The oxidative methylation synthesizing styrene of toluene and methane and the method for ethylbenzene are people such as Khcheyan [Neftekhimiya, 1980; 20 (6): 876] find.In recent years, some investigators are used for the oxidative methylation of toluene with some catalyzer that are used for methane oxidation coupling, find that these catalyzer also are effective to the oxidative methylation of toluene.They have have mainly researched and developed the basic oxide catalyzer, are alkaline earth metal oxide, transition metal oxide and the rare-earth oxide etc. of auxiliary agent as basic metal.
The purpose of this invention is to provide a kind of new catalyst with high reactivity, highly selective, molecular sieve with the alkalimetal ion exchange is a carrier, the catalyzer that carrying alkali metal bromide or alkalimetal oxide constitute, being used for toluene, methane and oxygen is direct synthesizing styrene of raw material and ethylbenzene, and the total recovery of the transformation efficiency of its toluene, vinylbenzene and ethylbenzene and overall selectivity all are better than various catalyzer in the past.
The present invention is carrying alkali metal bromide or an alkalimetal oxide on the molecular sieve that exchanges with alkalimetal ion, and charge capacity is 1-8% (weight).What the molecular sieve of alkalimetal ion exchange was often selected for use is Y type, X type or ZSM-5 type of K exchange, and alkali metal bromide is the most normal, and that select for use is NaBr or KBr.Alkalimetal oxide is the most normal, and that select for use is Li
2O or Cs
2O.
Preparation of catalysts method of the present invention comprises the exchange of molecular sieve, bakes to burn the article, and dipping alkali metal bromide or base metal nitrate and re-baking four procedures:
(1) exchange of molecular sieve: with KOH or the KNO of 0.5M
3Or CsNO
3, RuCl is exchange liquid, 90 ℃ of down exchanges 4 times, uses the 30g molecular sieve at every turn, 300ml exchanges liquid, be 2 hours swap time.Afterwards, wash, suction filtration, filter cake was dried 5-8 hours down at 125 ℃;
(2) bakes to burn the article: the goods that will handle through (1) are at 500 ℃ of following roastings 5 hours, naturally cooling then;
(3) dipping alkali metal bromide or alkali-metal nitrate: the NaBr or the LiNO that take by weighing 0.5-5.0g
3Or other alkali metal bromide or alkali-metal nitrate, adding water 100ml and at room temperature flood the goods that bakes to burn the article is crossed, dipping time is 24-48 hours.Afterwards after filtration, again in 125 ℃ of oven dry 5-6 hours;
(4) re-baking: the goods that (3) were handled are 550 ℃ of roastings 5 hours, then naturally cooling.Afterwards, carry out compressing tablet and be broken into 40-60 purpose particles, make catalyzer of the present invention.
The invention has the advantages that: catalyzer of the present invention working conditions in the oxidative methylation reaction of toluene is a normal pressure, methane/toluene/oxygen/nitrogen is 24/2.33/6/20 (mol), W/F is 0.34s.g/ml, temperature of reaction is 750 ℃, reactor is the continuous flow fixed-bed quartz reactor, the transformation efficiency of toluene is up to 76.3%, C
8The highest yield (the Y of compound (vinylbenzene+ethylbenzene)
ST+EB) be 58.3%, its selectivity (S
ST+EB) be 76.4%, wherein, the ratio (Y of vinylbenzene and ethylbenzene
ST/ Y
EB) be 9.8: 1.
The basic oxide catalyzer of the present invention and bibliographical information (refer to here external, domestic do not see that as yet bibliographical information is arranged) is compared the advantage that has and is:
(1) C
8The selectivity height of compound (vinylbenzene+ethylbenzene), and at C
8Cinnamic content height in the compound.
(2) with the external SrO that adopts, BaO or rare-earth oxide etc. compares, and it is lower that the alkaline molecular sieve that the present invention adopts has price, easily preparation.
Following embodiment can embody the substantive distinguishing features that the present invention gives prominence to, but is not that the present invention is imposed any restrictions.
Embodiment 1.
Get the 30gNaY molecular screen primary powder and be put in the 500ml four-necked bottle, add 0.5M KOH solution 300ml again, exchange four times each 2 hours in 90 ℃ down.Washing, suction filtration, filter cake descends roastings for the first time 5 hours, naturally cooling then at 500 ℃ again 125 ℃ of oven dry 6 hours in muffle furnace.Claim that 3.0gNaBr adds the 100ml water dissolution, in order to the goods that flood naturally cooling behind the above-mentioned bakes to burn the article 24 hours, afterwards, after its filtration, again in 125 ℃ of oven dry 6 hours, again with said products in muffle furnace in 550 ℃ of following re-bakings 5 hours, be broken into 40-60 purpose particulate state goods then, be catalyzer of the present invention.During use, get above-mentioned pellet type catalyst goods 0.3g and pack in the reactor, at logical O
2And N
2Under make it be warming up to 750 ℃, open CH then
4Gas, and three kinds of air-flows are transferred to required flow, behind the mixing through the toluene saturex, enter reactor reaction again, product is bathed the cooling reaction by cryosel and is taken out liquid after 2 hours, analyzes with the 501N gas chromatograph, lead Tianjin CRI-B computer processing data, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 2.
Change dipping NaBr among the embodiment 1 into dipping KBr, other are all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 3.
Change dipping NaBr among the embodiment 1 into dipping LiNO
3Solution, other are all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 4.
Change dipping NaBr among the embodiment 1 into dipping CsNO
3Solution, other are all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 5.
Change the exchange liquid among the embodiment 1 into CsNO
3Solution, other are all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 6.
Change the exchange liquid among the embodiment 1 into RuCl solution, other are all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 7.
Change the NaY molecular screen primary powder among the embodiment 1 into the NaX molecular screen primary powder, other are all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 8.
Change the NaY molecular screen primary powder among the embodiment 1 into the NaM molecular screen primary powder, other are all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 9.
Change the NaY molecular screen primary powder among the embodiment 1 into NaZSM-5 molecular screen primary powder, other are all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 10.
Change the NaY molecular screen primary powder among the embodiment 1 into Na beta-molecular sieve former powder, other are all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 11.
Change the NaY molecular screen primary powder among the embodiment 1 into the NaX molecular screen primary powder, will flood NaBr change into the dipping KBr other all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 12.
Change the NaY molecular screen primary powder among the embodiment 1 into NaZSM-5 molecular screen primary powder, will flood NaBr change into the dipping KBr other all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 13.
Change the NaY molecular screen primary powder among the embodiment 1 into Na beta-molecular sieve former powder, will flood NaBr change into the dipping KBr other all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 14.
Change the exchange liquid among the embodiment 1 into CsNO
3, will flood NaBr change into the dipping KBr other all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.
Embodiment 15.
Change the exchange liquid among the embodiment 1 into RuCl, will flood NaBr change into the dipping KBr other all with embodiment 1, the transformation efficiency of toluene, C
8The yield and the selectivity of compound see Table 1.The reaction conversion ratio of different compositions of table 1. and different preparation condition catalyzer, C
8Yield and selectivity
| Effect toluene conversion (%) | C 8Selectivity (%) | C 8Yield (%) | Vinylbenzene/ethylbenzene (mol) |
| Embodiment 1 63.5 | ????77.6 | ?49.3 | ????13.5 |
| Embodiment 2 58.9 | ????68.9 | ?40.6 | ????2.9 |
| Embodiment 3 36.1 | ????65.3 | ?23.5 | ????1.4 |
| Embodiment 4 52.8 | ????60.9 | ?32.2 | ????2.0 |
| Embodiment 5 69.0 | ????73.1 | ?50.4 | ????7.5 |
| Embodiment 6 69.1 | ????76.9 | ?53.4 | ????10.2 |
| Embodiment 7 65.0 | ????75.7 | ?49.2 | ????5.7 |
| Embodiment 8 52.0 | ????78.8 | ?49.9 | ????6.3 |
| Embodiment 9 76.3 | ????76.4 | ?58.3 | ????9.8 |
| Embodiment 10 61.7 | ????75.8 | ?46.8 | ????9.7 |
| Embodiment 11 52.2 | ????64.9 | ?33.9 | ????2.6 |
| Embodiment 12 58.2 | ????72.2 | ?42.0 | ????4.3 |
| Embodiment 13 60.3 | ????71.3 | ?42.8 | ????4.4 |
| Embodiment 14 47.2 | ????69.8 | ?33.0 | ????2.7 |
| Embodiment 15 54.3 | ????73.8 | ?40.1 | ????3.2 |
Claims (3)
1. one kind is used for the methylate catalyzer of direct synthesizing styrene and ethylbenzene of toluene and methane oxidation, it is characterized in that it is is carrier with the alkaline molecular sieve, carrying alkali metal bromide or alkalimetal oxide, charge capacity is 1-8% (weight), and alkaline molecular sieve is Y, X, M, β or ZSM-5 type molecular sieves that K, Ru or Cs exchanged.
2. according to the said catalyzer of claim 1, it is characterized in that alkaline molecular sieve load NaBrKBr, Li
2O or Cs
2O.
3. method that is used to prepare the said catalyzer of claim 1 is characterized in that it comprises following step:
(1) chooses alkaline molecular sieve (Y, X, M, β or ZSM-5 types), with KOH, the KNO of 0.5M
3, CsNO
3Perhaps RuCl exchanges 4 times down at 90 ℃ for exchange liquid, uses the 30g molecular sieve at every turn, and 300ml exchanges liquid, and be 2 hours swap time.Afterwards, washing, suction filtration, filter cake was dried 5-8 hours down at 125 ℃.
(2) goods that will handle through (1) are at 500 ℃ of following roastings 5 hours, naturally cooling then.
(3) alkali metal bromide or alkali-metal nitrate is soluble in water, at room temperature flood the goods that bakes to burn the article is crossed, dipping time is 24-48 hours.Afterwards after filtration, oven dry is 5-6 hours.
(4) goods that (3) were handled are 550 ℃ of roastings 5 hours, then naturally cooling.Compressing tablet and be broken into 40-60 purpose particles makes catalyzer of the present invention afterwards.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95108757A CN1050071C (en) | 1995-08-16 | 1995-08-16 | Catalyst for preparing styrene and ethylbenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95108757A CN1050071C (en) | 1995-08-16 | 1995-08-16 | Catalyst for preparing styrene and ethylbenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1120976A true CN1120976A (en) | 1996-04-24 |
| CN1050071C CN1050071C (en) | 2000-03-08 |
Family
ID=5076875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95108757A Expired - Fee Related CN1050071C (en) | 1995-08-16 | 1995-08-16 | Catalyst for preparing styrene and ethylbenzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1050071C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101970384A (en) * | 2008-03-13 | 2011-02-09 | 弗纳技术股份有限公司 | Process for production of ethylbenzene from toluene and methane |
| CN102029174A (en) * | 2010-11-25 | 2011-04-27 | 邵素英 | Catalyst for producing fuel oil |
| CN101623649B (en) * | 2008-07-08 | 2011-08-17 | 中国石油化工股份有限公司 | Alkaline molecular sieve catalyst for preparing styrene |
| WO2013044854A1 (en) * | 2011-09-28 | 2013-04-04 | 株式会社日本触媒 | Catalyst for preparing acrylic acid from lactic acid and process for preparing acrylic acid with the catalyst |
| CN104353443A (en) * | 2014-11-18 | 2015-02-18 | 沈阳化工大学 | Method for preparing styrene catalyst by ethylbenzene dehydrogenation |
| CN106179459A (en) * | 2016-07-15 | 2016-12-07 | 中国科学院大连化学物理研究所 | The preparation of a kind of high-performance Benzyl Side-Chain alkylation catalyst and application thereof |
| CN112844448A (en) * | 2019-11-28 | 2021-05-28 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylbenzene by directly converting catalytic synthesis gas and methylbenzene and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115424A (en) * | 1976-12-22 | 1978-09-19 | Monsanto Company | Zeolite catalyst |
| ZA805231B (en) * | 1980-05-19 | 1981-08-26 | Mobil Oil Corp | Low acidity alkali metal containing zeolites |
| FR2623423B1 (en) * | 1987-11-23 | 1990-03-30 | Centre Nat Rech Scient | NOVEL ZEOLITH-BASED CATALYSTS MODIFIED BY ALKALINE ELEMENTS IN METALLIC FORM, THEIR PREPARATION AND THEIR APPLICATION TO THE ALKYLATION OF ALKYL-AROMATIC DERIVATIVES |
| US5015796A (en) * | 1989-12-14 | 1991-05-14 | Shell Oil Company | Methyl alkylation of toluene using basic zeolite catalysts |
-
1995
- 1995-08-16 CN CN95108757A patent/CN1050071C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101970384A (en) * | 2008-03-13 | 2011-02-09 | 弗纳技术股份有限公司 | Process for production of ethylbenzene from toluene and methane |
| CN101623649B (en) * | 2008-07-08 | 2011-08-17 | 中国石油化工股份有限公司 | Alkaline molecular sieve catalyst for preparing styrene |
| CN102029174A (en) * | 2010-11-25 | 2011-04-27 | 邵素英 | Catalyst for producing fuel oil |
| WO2013044854A1 (en) * | 2011-09-28 | 2013-04-04 | 株式会社日本触媒 | Catalyst for preparing acrylic acid from lactic acid and process for preparing acrylic acid with the catalyst |
| CN104353443A (en) * | 2014-11-18 | 2015-02-18 | 沈阳化工大学 | Method for preparing styrene catalyst by ethylbenzene dehydrogenation |
| CN106179459A (en) * | 2016-07-15 | 2016-12-07 | 中国科学院大连化学物理研究所 | The preparation of a kind of high-performance Benzyl Side-Chain alkylation catalyst and application thereof |
| CN106179459B (en) * | 2016-07-15 | 2019-04-02 | 中国科学院大连化学物理研究所 | A kind of preparation and its application of high-performance Benzyl Side-Chain alkylation catalyst |
| CN112844448A (en) * | 2019-11-28 | 2021-05-28 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylbenzene by directly converting catalytic synthesis gas and methylbenzene and application thereof |
| CN112844448B (en) * | 2019-11-28 | 2023-07-04 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylbenzene by directly converting catalytic synthesis gas and toluene and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1050071C (en) | 2000-03-08 |
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