CN102872899A - Catalyst for preparation of ethylbenzene by ethanol and benzene vapor-phase alkylation - Google Patents

Catalyst for preparation of ethylbenzene by ethanol and benzene vapor-phase alkylation Download PDF

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CN102872899A
CN102872899A CN2011101926297A CN201110192629A CN102872899A CN 102872899 A CN102872899 A CN 102872899A CN 2011101926297 A CN2011101926297 A CN 2011101926297A CN 201110192629 A CN201110192629 A CN 201110192629A CN 102872899 A CN102872899 A CN 102872899A
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catalyst
benzene
alkylation
ethanol
gas phase
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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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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a catalyst for the preparation of ethylbenzene by ethanol and benzene vapor-phase alkylation and mainly solves the problem that the content of xylene impurity in the product ethylbenzene is high and a catalyst has poor stability and short regeneration period in the prior art. The catalyst provided by the invention comprises the following ingredients: by weight, a) 40-90% of a ZSM-5 molecular sieve with the silicon-aluminium mol ratio SiO2/Al2O3 being 30-400 and grain size being 5-350 nm; b) 9-59% of a binder alumina or silicon dioxide; and c) 0.1-10% of alkaline earth oxide. By the adoption of the technical scheme, the above problem is well solved. The catalyst can be used in the industrial production of ethylbenzene prepared by ethanol and benzene vapor-phase alkylation.

Description

The catalyst of ethanol and benzene producing ethyl benzene through alkylation in gas phase
Technical field
The present invention relates to the catalyst of a kind of 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, catalyst will have good selective, reduces the generation of the impurity such as dimethylbenzene as far as possible.Document CN200710094399.4 discloses a kind of method for ethanol and benzene synthesizing ethyl benzene, wherein said catalyst contains binding agent 20～45 % by weight, ZSM-540～70 % by weight and modified component 5～15 % by weight, modified component are selected from least a in IIA, IIIA, VA family and the rare-earth oxide.But the method exists in the product ethylbenzene dimethylbenzene impurity content high, poor catalyst stability, the problem that the regeneration period is short.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists in the product ethylbenzene dimethylbenzene impurity content high, poor catalyst stability, and the problem that the regeneration period is short provides a kind of new ethanol and the catalyst of benzene producing ethyl benzene through alkylation in gas phase.When this catalyst is used for ethanol with the benzene producing ethyl benzene through alkylation in gas phase, have an ethanol conversion high, ethyl is selectively high, and the dimethylbenzene impurity content is low in the product ethylbenzene, and the characteristics that catalyst stability is good, the regeneration period is grown.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the catalyst of a kind of 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% alkaline earth oxide.
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 alkaline-earth oxide is 0.1～2.0%.Described alkaline earth oxide preferred version is for being selected from magnesia, calcium oxide or beryllium oxide, and more preferably scheme is for being selected from magnesia.Described catalyst preferred version is for processing with steam and phosphoric acid successively, and then drying, roasting obtain required finished product.Wherein steam treatment condition preferable range is normal pressure, 400～800 ℃ of temperature, steam treatment 1～20 hour; More preferably scope is: normal pressure, 480～650 ℃ of temperature, steam treatment 3～10 hours.Phosphoric acid treatment conditions preferable range is 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; More preferably scope is for being that the phosphoric acid solution of 0.1～2.5 mol/L is 30～95 ℃ of lower processing 3～16 hours in temperature with concentration, and the weight ratio of phosphoric acid solution and catalyst is 2～10.
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 alkaline earth oxide.The alkaline 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 the alkaline 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 alkaline earth.The immersion condition preferred version is that the alkaline earth salt concentration of aqueous solution is 0.05～1.0 mol/L, and the weight ratio of the alkaline 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 alkaline 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 was through 400～800 ℃ of steam treatment 1～20 hour.
5) phosphoric acid is processed.Catalyst is that the phosphoric acid solution of 0.05～15.0 mol/L is 5～95 ℃ of lower acid treatments 1～20 hour in temperature with concentration after steam treatment, and the weight ratio of phosphoric acid solution and catalyst is 1～20.
6) obtain required finished product finally by dry, roasting.
When catalyst of the present invention was used for ethanol and benzene producing ethyl benzene through alkylation in gas phase, reaction condition was: 300～460 ℃ of reaction temperatures, reaction pressure 0.5～2.8MPa, ethanol weight space velocity 0.1～5.0 hour -1, benzene/ethanol mol ratio 2～10.
Ethanol described in the present invention can be the ethanol of 95 % by weight, also can be absolute ethyl alcohol.
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.Adopt the alkaline earth element modification can the regulating catalyst acid strength among the present invention, suppress easily to occur the strong acidic site of coking reaction, improve the activity stability of catalyst and selective.Preferred version of the present invention is processed with steam and phosphoric acid successively.Adopting high-temperature vapor to process is in order to improve the hydrothermal stability of catalyst, to improve the water repelling property of catalyst under reaction condition.Use phosphoric acid solution that catalyst is processed, 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 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.
Adopt 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 600ppm in the product ethylbenzene, and the catalyst regeneration cycle has reached 8 months, 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 magnesium nitrate aqueous solution of above-mentioned molecular sieve 20 grams and 50 milliliter of 0.25 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 4 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 the MgO1.0 % by weight again 110 ℃ of bakings.
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, the ratio of the weight of phosphoric acid solution and catalyst is 3, and is dry rear 500 ℃ of lower roastings 3 hours, obtains finished catalyst.
[embodiment 2～11]
Same [embodiment 1] is identical, just changes the SiO of ZSM-5 molecular sieve 2/ Al 2O 3The proportioning of mol ratio, crystal grain diameter, molecular sieve and aluminium oxide and alkaline earth oxide, steam treatment and phosphoric acid treatment conditions.Specifically see Table 1.
[comparative example 1]
Identical with [embodiment 1], just catalyst is processed without magnesium nitrate aqueous solution dipping, steam treatment and phosphoric acid.
[comparative example 2]
Identical with [embodiment 1], just catalyst is processed through steam treatment and phosphoric acid, but floods without magnesium nitrate aqueous solution.
[comparative example 3]
Identical with [embodiment 1], catalyst contains the MgO1.0 % by weight.Just the ZSM-5 molecular sieve crystal grain diameter is 2 nanometers.
[comparative example 4]
Identical with [embodiment 1], catalyst contains the MgO1.0 % by weight.Just the ZSM-5 molecular sieve crystal grain diameter is 500 nanometers.
[embodiment 12]
Identical with [embodiment 1], just catalyst contains the CaO1.0 % 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 1～4] 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.
[embodiment 14]
On the pressurization static bed reaction unit of continuous-flow, estimate the activity stability of [embodiment 1～12], [comparative example 1～4] 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 1
Figure BDA0000074931420000061
Annotate: xylene content refers to the xylene content in the product ethylbenzene
Table 2
Figure BDA0000074931420000071
By as seen from Table 2, adopt the inventive method, per hour average deactivation rate is minimum only is 0.04% for catalyst.Be applied on the commercial plant, 0.01 percentage point of the average every minimizing of deactivation rate means and can on commercial plant move 2～3 months more.

Claims (9)

1. the catalyst of an 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% alkaline earth oxide.
2. the catalyst of described ethanol and benzene producing ethyl benzene through alkylation in gas phase according to claim 1, the crystal grain diameter that it is characterized in that ZSM-5 molecular sieve is 10～250 nanometers.
3. the catalyst of described ethanol and benzene producing ethyl benzene through alkylation in gas phase according to claim 2, the crystal grain diameter that it is characterized in that ZSM-5 molecular sieve is 20～200 nanometers.
4. the catalyst of described ethanol and benzene producing ethyl benzene through alkylation in gas phase according to claim 1 is characterized in that ZSM-5 molecular sieve silica alumina ratio SiO 2/ Al 2O 3Be 50～300.
5. the catalyst of described ethanol and benzene producing ethyl benzene through alkylation in gas phase according to 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 alkaline earth oxide is 0.1～2.0%.
6. the catalyst of described ethanol and benzene producing ethyl benzene through alkylation in gas phase according to claim 1 is characterized in that described alkaline earth oxide is selected from magnesia, calcium oxide or beryllium oxide.
7. the catalyst of described ethanol and benzene producing ethyl benzene through alkylation in gas phase according to claim 6 is characterized in that described alkaline earth oxide is selected from magnesia.
8. the catalyst of described ethanol and benzene producing ethyl benzene through alkylation in gas phase according to claim 1 is characterized in that described catalyst processes 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.
9. the catalyst of described ethanol and benzene producing ethyl benzene through alkylation in gas phase according to claim 1 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 are 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.
CN2011101926297A 2011-07-11 2011-07-11 Catalyst for preparation of ethylbenzene by ethanol and benzene vapor-phase alkylation Pending CN102872899A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109277113A (en) * 2017-07-19 2019-01-29 中国科学院大连化学物理研究所 The preparation method of catalyst for etherification and the method for producing methylanisole
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1508105A (en) * 2002-12-17 2004-06-30 中国石油化工股份有限公司上海石油化 Method for preparing ethylbenzene by liquid phase alkylation of ethylene
CN101485993A (en) * 2008-01-18 2009-07-22 上海师范大学 Novel nano molecular sieve catalyst for benzene alkylation as well as preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1508105A (en) * 2002-12-17 2004-06-30 中国石油化工股份有限公司上海石油化 Method for preparing ethylbenzene by liquid phase alkylation of ethylene
CN101485993A (en) * 2008-01-18 2009-07-22 上海师范大学 Novel nano molecular sieve catalyst for benzene alkylation as well as preparation method and application

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109277113A (en) * 2017-07-19 2019-01-29 中国科学院大连化学物理研究所 The preparation method of catalyst for etherification and the method for producing methylanisole
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

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