CN102274746A - Catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene - Google Patents
Catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene Download PDFInfo
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- CN102274746A CN102274746A CN2010102000205A CN201010200020A CN102274746A CN 102274746 A CN102274746 A CN 102274746A CN 2010102000205 A CN2010102000205 A CN 2010102000205A CN 201010200020 A CN201010200020 A CN 201010200020A CN 102274746 A CN102274746 A CN 102274746A
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- benzene
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Abstract
The invention relates to a catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene and mainly solves problems of catalysts for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene. The problems are all undisclosed in previous literatures. The catalyst provided by the invention comprises the following components of: by weight, a) 40-90% of a ZSM-5 molecular sieve with the silica alumina mol ratio SiO2/Al2O3 being 30-400 and the crystal diameter being 5-350 nm; b) 9-59% of a binder alumina or silicon dioxide; and c) 0.1-10% of rare-earth oxide. The catalyst successively undergoes high-temperature vapor and phosphoric acid processing before use. The technical scheme greatly solves the problem. In addition, the catalyst provided by the invention can be used in the industrial production for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene.
Description
Technical field
The present invention relates to a kind of catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase.
Background technology
Ethylbenzene is important petrochemical materials, is mainly used in cinnamic production, and styrene is the primary raw material of producing polystyrene and other copolymer resins.Ethylbenzene can be produced with various process, mainly contains traditional AlCl
3Liquid-phase alkylation method and molecular sieve alkylation process two big classes, wherein molecular sieve alkylation production technology has obtained very ten-strike.The eighties in 20th century, Mobil and Badger company have successfully released molecular sieve producing ethyl benzene through alkylation in gas phase technology, this process using ZSM-5 zeolite is a catalyst, have that no burn into is pollution-free, flow process is simple and the heat energy recovery rate advantages of higher, U.S. Pat 3751504, US3751506, US4016218 and US4547605 all are described in detail this.Early 1990s, Lummus and Uop Inc. have released molecular sieve liquid-phase alkylation process for preparing ethylbenzene, and this process using β and y-type zeolite are catalyst, advantage such as have that reaction temperature is low, processing ease and accessory substance are few.US4891458, US5227558 and ZL02151177.2 all are described in detail this.
No matter this shows, be traditional AlCl
3The liquid-phase alkylation method still is that all to adopt with ethene and benzene be raw material to the molecular sieve alkylation process.Grow continuously and fast along with socioeconomic, people enlarge day by day to the demand of base stock-oil of producing ethene, the gesture that causes oil to be petering out.Along with the growing tension of the world petroleum resource and the energy, people on the one hand advocate energetically and the encourage frugality resource and the energy actively seek and explore the utilization of renewable resource on the other hand.Living beings ethanol is green renewable raw materials, and along with biology system ethanol continuous advancement in technology and maturation, the price of ethanol is expected to descend significantly.Therefore, adopt ethanol to substitute ethene process route direct and benzene alkylation reaction production ethylbenzene and have stronger competitiveness.But the key technology of this process route is a catalyst, and the catalyst of preparation will satisfy the needs of industrial production long-term operation, and long regeneration period and service life promptly will be arranged; Simultaneously, guaranteeing that catalyst will have good selectivity, reduces the generation of impurity such as dimethylbenzene as far as possible, at present, does not see relevant report both domestic and external as yet on the basic basis that all transforms of ethanol.
Summary of the invention
Technical problem to be solved by this invention is all unexposed catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase of document in the past, and a kind of new catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase is provided.When this catalyst is used for ethanol and the reaction of benzene vapor-phase alkylation production ethylbenzene, has the ethanol conversion height, ethyl selectivity height, and the good characteristics of catalyst stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase, contain following component by weight percentage:
A) 40～90% silica alumina ratio SiO
2/ Al
2O
3Be 30～400, crystal grain diameter is the ZSM-5 molecular sieve of 5～350 nanometers;
B) 9～59% binding agent aluminium oxide or silica;
C) 0.1～10% rare-earth oxide;
Described catalyst is handled with steam and phosphoric acid successively, and drying, roasting obtain required finished product then; Wherein the steam treatment condition is normal pressure, 400～800 ℃ of temperature, steam treatment 1～20 hour; The phosphoric acid treatment conditions were handled 1～20 hour down for 5～95 ℃ in temperature for the phosphoric acid solution with concentration 0.05～15.0 mol, and the weight ratio of phosphoric acid solution and catalyst is 1～20.
In the technique scheme, the crystal grain diameter preferable range of ZSM-5 molecular sieve is 10～250 nanometers, and more preferably scope is 20～200 nanometers.ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2O
3Preferable range is 50～300.The consumption preferable range of ZSM-5 molecular sieve is 55～85% by weight percentage, and the consumption preferable range of binding agent is 14～44%, and the consumption preferable range of rare-earth oxide is 0.1～2.0%.Described rare-earth oxide preferred version is for being selected from lanthana, cerium oxide or praseodymium oxide, and more preferably scheme is for being selected from lanthana.Steam treatment condition preferred version is normal pressure, 480～650 ℃ of temperature, steam treatment 3～10 hours.Phosphoric acid treatment conditions preferred version was handled 3～16 hours down for 30～95 ℃ in temperature for the phosphoric acid solution with concentration 0.1～2.5 mol, and the weight ratio of phosphoric acid solution and catalyst is 2～10.
Ethanol described in the present invention can be the ethanol of 95 weight %, also can be absolute ethyl alcohol.
Catalyst of the present invention prepares in accordance with the following methods:
1) with silica alumina ratio SiO
2/ Al
2O
3The ZSM-5 molecular sieve that be 30～400, crystal grain diameter is 5～350 nanometers well known to a person skilled in the art that hydrochloric acid exchange, washing, oven dry and roasting obtain the HZSM-5 molecular sieve under the condition.
2) molecular sieve carried rare-earth oxide.The rare earth salt aqueous solution that is 0.002～2.0 mol with above-mentioned HZSM-5 molecular sieve concentration flooded 1～15 hour at 10～60 ℃, the weight ratio of rare earth salt aqueous solution and HZSM-5 molecular sieve is 0.5～10, oven dry, roasting then obtains containing the HZSM-5 molecular sieve of rare earth.The immersion condition preferred version is 0.05～1.0 mol for rare earth salt aqueous solution concentration, and the weight ratio of rare earth salt aqueous solution and HZSM-5 molecular sieve is 1～5, and dipping temperature is 20～40 ℃, and dip time is 2～10 hours.
3) shaping of catalyst.With step 2) preparation the HZSM-5 molecular sieve that contains rare earth and aluminium oxide or Ludox moulding, extrusion becomes the bar shaped catalyst of 1.8 millimeters of Φ.Above-mentioned catalyst is again through 110 ℃ of oven dry in 10 hours and 550 ℃ of roastings in 4 hours.
4) steam treatment.Preformed catalyst is through 400～800 ℃ of steam treatment 1～20 hour, to improve the hydrothermal stability of catalyst.
5) phosphoric acid is handled.Catalyst is that the phosphoric acid solution of 0.05～15.0 mol was handled 1～20 hour down for 5～95 ℃ in temperature with concentration after steam treatment, and the weight ratio of phosphoric acid solution and catalyst is 1～20.
6) last drying, roasting obtain required finished product.
In the catalytic reaction process of benzene and ethanol vapor phase alkylation system ethylbenzene, dehydration at first takes place and generates ethene and water in ethanol under the effect of catalyst; Alkylated reaction generation ethylbenzene takes place in ethene and benzene under with a kind of effect of catalyst then.Therefore, can produce a large amount of water in the course of reaction, water can produce adverse influence to activity of such catalysts stability under reaction condition.Adopting high-temperature vapor to handle among the present invention is exactly in order to improve the hydrothermal stability of catalyst, to improve the water repelling property of catalyst under reaction condition.Adopting rare-earth element modified among the present invention also is hydrothermal stability and selectivity in order to improve catalyst, because rare earth element is to the stabilization of framework of molecular sieve aluminium, delayed the aluminium atom and under the high-temperature vapor reaction condition, come off, can keep the acidity-chain carrier of catalyst for a long time from skeleton.Use phosphoric acid solution that catalyst is handled among the present invention, can play certain regulating action to acid matter, B acid, L acid and the strong and weak sour distribution of molecular sieve catalyst on the one hand, increase the total amount of B acid, reduce the intensity of acid.Can remove amorphous substance in the molecular sieve pore passage on the other hand or remove the materials such as non-framework aluminum that get off, play modification molecular sieve pore passage from framework of molecular sieve; Simultaneously, can further increase the adhesion of alumina key in the molecular sieve, thereby suppress the generation of framework of molecular sieve dealuminzation, improve activity of such catalysts stability, reach the purpose that prolongs catalyst regeneration cycle and service life.
Use catalyst of the present invention, 390 ℃ of reaction temperatures, reaction pressure 1.2MPa, ethanol weight space velocity (WHVS) 0.8 hour
-1, under the condition of benzene/ethanol mol ratio 6.5, ethanol conversion can reach 99.9%, and the ethyl selectivity can reach 99.0%, and xylene content is below 800ppm in the product ethylbenzene, and the catalyst regeneration cycle has reached half a year, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
200 gram silica alumina ratio SiO
2/ Al
2O
3=100, crystal grain diameter be the ZSM-5 molecular sieve of 200 nanometers with 2 liters 85 ℃ exchanges of the hydrochloric acid of 0.1 mol three times, spend deionised water to there not being the chlorine root, 110 ℃ of oven dry, standby after 4 hours 580 ℃ of roastings again.
The lanthanum nitrate aqueous solution of above-mentioned molecular sieve 20 grams and 35 milliliter of 0.5 mol was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 2 hours.Itself and alumina binder were mixed by 70: 30, and the dilute nitric acid solution that adds 2% sesbania powder and 10 weight % mixes, and to pinch the back extruded moulding be 1.8 millimeters of Φ.After 10 hours, 550 ℃ of roastings 4 hours, the catalyst that obtains contained La again 110 ℃ of bakings
2O
32.0 weight %.
Above-mentioned catalyzer with water steam was handled 2 hours for 580 ℃ at normal pressure, handled 5 hours down at 50 ℃ with the phosphoric acid solution of 1.5 mol, phosphoric acid solution is 3 with the ratio of the weight of catalyst, and dry back obtains finished catalyst 500 ℃ of following roastings 3 hours.
[embodiment 2～11]
[embodiment 1] is identical together, just changes the SiO of ZSM-5 molecular sieve
2/ Al
2O
3Proportioning, the catalyst of mol ratio, crystal grain diameter, molecular sieve and aluminium oxide contain La
2O
32.0 amount, steam treatment and phosphoric acid treatment conditions.Specifically see Table 1.
[comparative example 1]
Identical with [embodiment 1], just catalyst is handled without lanthanum nitrate aqueous solution dipping, steam treatment and phosphoric acid.
[comparative example 2]
Identical with [embodiment 1], catalyst contains La
2O
32.0 weight %, but handle without steam treatment and phosphoric acid.
[comparative example 3]
Identical with [embodiment 1], just catalyst is handled through steam treatment and phosphoric acid, but floods without lanthanum nitrate aqueous solution.
[comparative example 4]
Identical with [embodiment 1], catalyst contains La
2O
32.0 weight %.Just ZSM-5 zeolite crystal diameter is 2 nanometers.
[comparative example 5]
Identical with [embodiment 1], catalyst contains La
2O
32.0 weight %.Just ZSM-5 zeolite crystal diameter is 500 nanometers.
[embodiment 12]
Identical with [embodiment 1], just catalyst contains Ce
2O
32.0 weight %.
[embodiment 13]
On the fixing pressurization static bed reaction unit of continuous-flow, carry out benzene and ethanol vapor phase alkylation system ethylbenzene process.Estimate the reactivity and the selectivity of [embodiment 1～12], [comparative example 1～5] catalyst.Reaction condition: 390 ℃ of reaction temperatures, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1, reaction result sees Table 1.
Table 1
[embodiment 14]
On the pressurization static bed reaction unit of continuous-flow, estimate [embodiment 1～12], [comparative example 1～5] activity of such catalysts stability, the i.e. regeneration period of catalyst.Reaction condition: 400 ℃ of reaction temperatures, reaction pressure 1.0MPa, benzene/ethanol=1.0 (moles/mole), ethanol weight space velocity (WHSV)=3.0 hour
-1, the reaction time is 100 hours.Reaction result sees Table 2.
Table 2
As seen catalyst of the present invention has minimum deactivation rate, shows optimum activity stability.
Claims (8)
1. catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase, contain following component by weight percentage:
A) 40～90% silica alumina ratio SiO
2/ Al
2O
3Be 30～400, crystal grain diameter is the ZSM-5 molecular sieve of 5～350 nanometers;
B) 9～59% binding agent aluminium oxide or silica;
C) 0.1～10% rare-earth oxide;
Described catalyst is handled with steam and phosphoric acid successively, and drying, roasting obtain required finished product then; Wherein the steam treatment condition is normal pressure, 400～800 ℃ of temperature, steam treatment 1～20 hour; The phosphoric acid treatment conditions were handled 1～20 hour down for 5～95 ℃ in temperature for the phosphoric acid solution with concentration 0.05～15.0 mol, and the weight ratio of phosphoric acid solution and catalyst is 1～20.
2. according to the described catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase of claim 1, the crystal grain diameter that it is characterized in that the ZSM-5 molecular sieve is 10～250 nanometers.
3. according to the method for described ethanol of claim 2 and benzene producing ethyl benzene through alkylation in gas phase, the crystal grain diameter that it is characterized in that the ZSM-5 molecular sieve is 20～200 nanometers.
4. according to the described catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase of claim 1, it is characterized in that ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2O
3Be 50～300.
5. according to the described catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase of claim 1, it is characterized in that the consumption of ZSM-5 molecular sieve is 55～85% by weight percentage, the consumption of binding agent is 14～44%, and the consumption of rare-earth oxide is 0.1～2.0%.
6. according to the described catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase of claim 1, it is characterized in that described rare-earth oxide is selected from lanthana, cerium oxide or praseodymium oxide.
7. according to the described catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase of claim 6, it is characterized in that described rare-earth oxide is selected from lanthana.
8. according to the described catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase of claim 1, it is characterized in that the steam treatment condition is normal pressure, 480～650 ℃ of temperature, steam treatment 3～10 hours; The phosphoric acid treatment conditions were handled 3～16 hours down for 30～95 ℃ in temperature for the phosphoric acid solution with concentration 0.1～2.5 mol, and the weight ratio of phosphoric acid solution and catalyst is 2～10.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102000205A CN102274746B (en) | 2010-06-11 | 2010-06-11 | Catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene |
| BRPI1103071-2A BRPI1103071B1 (en) | 2010-06-11 | 2011-06-13 | ETHYL BENZEN SYNTHESIS PROCESS FROM ETHANOL AND BENZENE |
| US13/158,709 US8519208B2 (en) | 2010-06-11 | 2011-06-13 | Processes for synthesizing ethylbenzene from ethanol and benzene |
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|---|---|---|---|
| CN2010102000205A CN102274746B (en) | 2010-06-11 | 2010-06-11 | Catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene |
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| CN102274746B CN102274746B (en) | 2013-04-10 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418419A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for alkylation production of ethyl benzene, and preparation method thereof |
| WO2020019276A1 (en) | 2018-07-23 | 2020-01-30 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof |
| WO2020047902A1 (en) * | 2018-09-07 | 2020-03-12 | 中国科学院大连化学物理研究所 | Preparation method and use of molecular sieve catalyst |
| CN114073976A (en) * | 2020-08-10 | 2022-02-22 | 中国科学院大连化学物理研究所 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
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| CN101279283A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Modified ZSM-5 molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof |
| CN101584993A (en) * | 2009-06-19 | 2009-11-25 | 中国科学院大连化学物理研究所 | Catalyst for preparing phenylethane from dilute ethylene and benzene alkylation and method for preparing same |
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2010
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| US5753716A (en) * | 1997-02-21 | 1998-05-19 | Air Products And Chemicals, Inc. | Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process |
| CN1772381A (en) * | 2005-11-01 | 2006-05-17 | 大连理工大学 | Industrial sulfur tolerant catalyst for vapor ethylation of coking benzene to prepare ethyl benzene |
| CN101279283A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Modified ZSM-5 molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418419A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for alkylation production of ethyl benzene, and preparation method thereof |
| CN103418419B (en) * | 2012-05-16 | 2016-01-13 | 中国石油化工股份有限公司 | The Catalysts and its preparation method of alkylation to prepare ethylbenzene |
| WO2020019276A1 (en) | 2018-07-23 | 2020-01-30 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof |
| US11434183B2 (en) | 2018-07-23 | 2022-09-06 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof |
| WO2020047902A1 (en) * | 2018-09-07 | 2020-03-12 | 中国科学院大连化学物理研究所 | Preparation method and use of molecular sieve catalyst |
| CN110882715A (en) * | 2018-09-07 | 2020-03-17 | 中国科学院大连化学物理研究所 | Preparation method and application of molecular sieve catalyst |
| CN110882715B (en) * | 2018-09-07 | 2021-03-26 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylbenzene by ethanol and benzene vapor phase alkylation and preparation and application thereof |
| CN114073976A (en) * | 2020-08-10 | 2022-02-22 | 中国科学院大连化学物理研究所 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
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