CN102274746B - 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 PDF

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CN102274746B
CN102274746B CN2010102000205A CN201010200020A CN102274746B CN 102274746 B CN102274746 B CN 102274746B CN 2010102000205 A CN2010102000205 A CN 2010102000205A CN 201010200020 A CN201010200020 A CN 201010200020A CN 102274746 B CN102274746 B CN 102274746B
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benzene
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molecular sieve
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CN102274746A (en
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孙洪敏
杨为民
张斌
沈震浩
宦明耀
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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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

The catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase
Technical field
The present invention relates to a kind of catalyst 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 large 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 technique, this process using ZSM-5 zeolite is catalyst, have the simple and heat energy recovery rate advantages of higher of, flow process pollution-free without burn into, US Patent No. 3751504, US3751506, US4016218 and US4547605 all are described in detail this.Early 1990s, Lummus and Uop Inc. have released molecular sieve preparing ethylbenzene by liquid phase alkylation technique, and this process using β and y-type zeolite are catalyst, the 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 3Liquid-phase alkylation method or molecular sieve alkylation process all adopt take ethene and benzene as raw material.Grow continuously and fast along with socioeconomic, people are to the demand expanding day of base stock-oil of producing ethene, the gesture that causes oil to be petering out.Along with the growing tension of world petroleum resource and the energy, people on the one hand advocate energetically and 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 continuous progress and the maturation of biology ethanol technology processed, the price of ethanol is expected to significant decline.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 catalyst, and the catalyst of preparation will satisfy the needs of industrial production long-term operation, and long regeneration period and service life namely will be arranged; Simultaneously, guaranteeing on the basic bases that all transform of ethanol that catalyst will have good selective, reduces the generation of the impurity such as dimethylbenzene as far as possible, at present, not yet sees relevant report both domestic and external.
Summary of the invention
Technical problem to be solved by this invention is all unexposed catalyst for ethanol and benzene producing ethyl benzene through alkylation in gas phase of previous literature, 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, have the ethanol conversion height, ethyl is selectively high, 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 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 processed with steam and phosphoric acid successively, and then drying, roasting obtain required finished product; Wherein the steam treatment condition is normal pressure, 400～800 ℃ of temperature, steam treatment 1～20 hour; The phosphoric acid treatment conditions are to use the phosphoric acid solution of concentration 0.05～15.0 mol/L 5～95 ℃ of lower processing 1～20 hour of temperature, 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 is to use the phosphoric acid solution of concentration 0.1～2.5 mol/L 30～95 ℃ of lower processing 3～16 hours of temperature, 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 % by 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/L 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, then oven dry, roasting obtains containing the HZSM-5 molecular sieve of rare earth.The immersion condition preferred version is that rare earth salt aqueous solution concentration is 0.05～1.0 mol/L, 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 processed.Catalyst after steam treatment, with concentration be the phosphoric acid solution of 0.05～15.0 mol/L 5～95 ℃ of lower processing 1～20 hour of temperature, the weight ratio of phosphoric acid solution and catalyst is 1～20.
6) obtain required finished product finally by dry, roasting.
In the catalytic reaction process of benzene and ethanol vapor phase alkylation ethylbenzene processed, dehydration at first occurs and generates ethene and water in ethanol under the effect of catalyst; Then alkylated reaction generation ethylbenzene occurs in ethene and benzene under the effect of same catalyst.Therefore, can produce a large amount of water in the course of reaction, water can produce adverse influence to the activity stability of catalyst under reaction condition.Adopting high-temperature vapor to process 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 for the hydrothermal stability that improves catalyst and selective, because rare earth element is to the stabilization of framework of molecular sieve aluminium, delay the aluminium atom and under the high-temperature vapor reaction condition, come off from skeleton, can keep for a long time the acidity-chain carrier of catalyst.Use phosphoric acid solution that catalyst is processed among the present invention, on the one hand can be to Acidity, the B acid of molecular sieve catalyst, L is sour and certain regulating action is played in the distribution of strong and weak acid, increases the total amount of B acid, reduces the intensity of acid.Can remove on the other hand amorphous substance in the molecular sieve pore passage or remove the materials such as non-framework aluminum that get off from framework of molecular sieve, play the modification to molecular sieve pore passage; Simultaneously, can further increase the adhesion of alumina key in the molecular sieve, thereby suppress the generation of framework of molecular sieve dealuminzation, improve the activity stability of catalyst, reach the purpose in extending catalyst regeneration period 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 ethyl selectively 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 preferably technique 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/L three times, with the deionized water washing to without the chlorine root, 110 ℃ of oven dry, for subsequent use 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/L 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 add that extruded moulding is 1.8 millimeters of Φ after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight.After 10 hours, 550 ℃ of roastings 4 hours, the catalyst that obtains contained La again 110 ℃ of bakings 2O 32.0 % by weight.
Above-mentioned catalyzer with water steam was processed 2 hours 580 ℃ of normal pressures, processed 5 hours under 50 ℃ with the phosphoric acid solution of 1.5 mol/L, phosphoric acid solution is 3 with the ratio of the weight of catalyst, and is dry rear 500 ℃ of lower roastings 3 hours, obtains finished catalyst.
[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 processed without lanthanum nitrate aqueous solution dipping, steam treatment and phosphoric acid.
[comparative example 2]
Identical with [embodiment 1], catalyst contains La 2O 32.0 % by weight, but process without steam treatment and phosphoric acid.
[comparative example 3]
Identical with [embodiment 1], just catalyst is processed 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 % by weight.Just the ZSM-5 molecular sieve crystal grain diameter is 2 nanometers.
[comparative example 5]
Identical with [embodiment 1], catalyst contains La 2O 32.0 % by weight.Just the ZSM-5 molecular sieve crystal grain diameter is 500 nanometers.
[embodiment 12]
Identical with [embodiment 1], just catalyst contains Ce 2O 32.0 % by weight.
[embodiment 13]
On the fixing pressurization static bed reaction unit of continuous-flow, carry out benzene and ethanol vapor phase alkylation ethylbenzene process processed.Estimate the reactivity of [embodiment 1～12], [comparative example 1～5] catalyst with selective.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
Figure BSA00000158333400051
[embodiment 14]
On the pressurization static bed reaction unit of continuous-flow, estimate the activity stability of [embodiment 1～12], [comparative example 1～5] catalyst, i.e. the 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
Figure BSA00000158333400061
As seen catalyst of the present invention has minimum deactivation rate, shows optimum activity stability.

Claims (2)

1. catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase, described method for preparing catalyst is as follows: 200 restrain 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/L three times, with the deionized water washing to without the chlorine root, 110 ℃ of oven dry, for subsequent use 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/L 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 add that extruded moulding is 1.8 millimeters of Ф after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight; After 10 hours, 550 ℃ of roastings 4 hours, the catalyst that obtains contained La again 110 ℃ of bakings 2O 32.0 % by weight; Above-mentioned catalyzer with water steam was processed 2 hours 580 ℃ of normal pressures, processed 5 hours under 50 ℃ with the phosphoric acid solution of 1.5 mol/L, phosphoric acid solution is 3 with the ratio of the weight of catalyst, and is dry rear 500 ℃ of lower roastings 3 hours, obtains finished catalyst.
2. one kind is adopted the as claimed in claim 1 method of catalyst synthesizing ethyl benzene, on the fixing pressurization static bed reaction unit of continuous-flow, carry out benzene and ethanol vapor phase alkylation ethylbenzene processed, reaction temperature is 390 ℃, reaction pressure is 1.2MPa, and the ethanol weight space velocity is 0.8 hour -1, benzene/ethanol mol ratio is 6.5, and ethanol conversion is 99.5%, and ethyl selectively is 99.6%.
CN2010102000205A 2010-06-11 2010-06-11 Catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene Active CN102274746B (en)

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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
US13/158,709 US8519208B2 (en) 2010-06-11 2011-06-13 Processes for synthesizing ethylbenzene from ethanol and benzene
BRPI1103071-2A BRPI1103071B1 (en) 2010-06-11 2011-06-13 ETHYL BENZEN SYNTHESIS PROCESS FROM ETHANOL AND BENZENE

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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
CN110743605B (en) 2018-07-23 2021-07-27 中国科学院大连化学物理研究所 Catalyst for preparing ethylbenzene from ethanol and benzene and preparation and application thereof
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
CN114073976B (en) * 2020-08-10 2023-04-07 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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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
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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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