CN102875316B - Method for preparing ethylbenzene by alkylation of dry gas and benzene - Google Patents

Method for preparing ethylbenzene by alkylation of dry gas and benzene Download PDF

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CN102875316B
CN102875316B CN201110193348.3A CN201110193348A CN102875316B CN 102875316 B CN102875316 B CN 102875316B CN 201110193348 A CN201110193348 A CN 201110193348A CN 102875316 B CN102875316 B CN 102875316B
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benzene
alkylation
dry gas
oxide
molecular sieve
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CN102875316A (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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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to a method for preparing ethylbenzene by alkylation of dry gas and benzene, mainly solving the problems of bad catalyst stability and short regeneration period in ethylbenzene production process by reacting dilute ethylene(dry gas) with benzene in the prior art. The method disclosed herein is characterized by using dry gas and benzene as reaction raw materials, contacting the reaction raw materials with a catalyst to conduct gas-phase alkylation to generate ethylbenzene, wherein the catalyst comprises the following ingredients: a) 40-90wt% of ZSM-5 molecular sieve with a particle size of 5-500nm and a SiO2/Al2O3 molar ratio of 30-400; b) 9-59wt% of alumina or silica as binder; and c) 0.1-10wt% of alkaline earth metal oxide and 0.1-10wt% of rare-earth metal oxide, and the catalyst is processed by high temperature steam. The method well solves the problem and can be used in the industrial production of ethylbenzene by alkylation of dry gas and benzene.

Description

The method of dry gas and producing phenylethane from alkylation of benzene
Technical field
The present invention relates to a kind of method of dry gas and producing phenylethane from alkylation of benzene, particularly a kind of dry gas and benzene are produced the method for ethylbenzene under vapor-phase alkylation condition.
Background technology
Ethylbenzene is important petrochemical materials, is mainly used in cinnamic production, and vinylbenzene is the main raw material of producing polystyrene and other copolymer resins.
Ethylbenzene can be produced by various processing method, and traditional catalyzer has crystallization and noncrystalline silicon-dioxide, boron fluoride, aluminum oxide, phosphoric acid, aluminum chloride and solid phosphoric acid catalyst.All there is the shortcomings such as seriously corroded, facility investment is large, the three wastes are many in these conventional catalyst techniques.In recent years, people have carried out extensive and deep research to molecular sieve, and some companies are constantly devoted to utilize molecular sieve to produce the new technology of ethylbenzene as catalyzer.Wherein obtain great a kind of commercial method and be under a kind of solid acid ZSM-5 zeolite catalyzer exists, carried out vapor phase alkylation with pure ethylene and benzene.US Patent No. 3751504, US3751506, US4016218 and US4547605 are all described in detail this, but all exist short shortcoming of catalyst regeneration cycle.
ZL96100371.5 and ZL98113847.0 have reported respectively the technique of two kinds of dry gas and benzene preparing ethylbenzene by reaction.A kind of technique is the dry gas from plant catalytic refinery or catalytic pyrolysis or thermo-cracking, do not need to react through the refining vapor phase alkylation device that molecular sieve catalyst is housed that directly enters, the many ethylbenzene that produce enter a gas phase transalkylation reactor, be converted into again ethylbenzene, and another technique alkylation part is substantially similar, difference is that the many ethylbenzene that produce enter a liquid-phase transalkylation reactor, are translated into ethylbenzene.But the shortcomings such as these two kinds of techniques all exist poor catalyst stability, and regeneration period and work-ing life are short.
ZL94113403.2, ZL96106561.3 and ZL200510011505.9 have reported respectively ZSM-5/ZSM-11 eutectic molecular sieve and the application of Y zeolite in preparing ethylbenzene from dry gas reaction, wherein only have ZL96106561.3 to relate to the activity stability (regeneration period) of catalyzer, with containing 19.5% (body) ethene, the catalytic cracked dry gas of 0.8% (body) propylene is that raw material is while carrying out benzene and ethylene alkylation, at reaction pressure 0.9MPa, weight ethylene air speed 0.8h-1, benzene/ethylene molecule is than under 10 condition, can only continuous operation 95 days, can not meet the requirement of industrial production long-period stable operation.
CN200810032814.8 discloses a kind of benzene alkylation nano molecular sieve catalyst and its preparation method and application.Can be used for benzene alkylation reaction although the document discloses nano molecular sieve, in disclosed embodiment, the particle diameter of synthetic molecular sieve is not how many nanometers actually, and the work-ing life of catalyzer.The inventor has synthesized molecular sieve catalyst according to the disclosed preparation method of the document, uses it in the reaction of preparing ethylbenzene from dry gas, finds still to exist poor catalyst stability, the shortcoming that work-ing life is short.
In sum, in prior art, exist rare ethene (dry gas) to react with benzene in the process of producing ethylbenzene, poor catalyst stability, the problem that the regeneration period is short.
Summary of the invention
Technical problem to be solved by this invention is in prior art, to exist rare ethene (dry gas) to react with benzene to produce in the process of ethylbenzene, poor catalyst stability, and the problem that the regeneration period is short, provides a kind of method of new dry gas and producing phenylethane from alkylation of benzene.It is good that the method has catalyst stability, the feature that the regeneration period is long.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of dry gas and producing phenylethane from alkylation of benzene, taking dry gas and benzene as reaction raw materials, 280～430 DEG C of temperature of reaction, reaction pressure 0.5～2.8MPa, weight ethylene air speed 0.2～5.0 hour -1, under the condition of total benzene/ethylene molar ratio 2～10, reaction raw materials contacts with catalyzer vapor phase alkylation generation ethylbenzene occurs; Catalyzer used contains following component by weight percentage:
A) 40～90% crystal grain diameter is 5～500 nanometers, silica alumina ratio SiO 2/ Al 2o 3it is 30～400 ZSM-5 molecular sieve;
B) 9～59% binding agent aluminum oxide or silicon-dioxide;
C) 0.1～10% alkaline earth metal oxide and 0.1～10% rare-earth oxide;
Described catalyzer is through high-temperature vapor processing, and then drying, roasting obtain required finished product; Wherein steam treatment condition is to be under 400～800 DEG C of conditions in normal pressure, temperature, steam treatment 1～20 hour.
In technique scheme, the crystal grain diameter preferable range of ZSM-5 molecular sieve is 10～450 nanometers, and more preferably scope is > 100～400 nanometers.ZSM-5 molecular sieve silica alumina ratio SiO 2/ Al 2o 3preferable range is 50～300.In catalyzer used, the consumption preferable range of ZSM-5 molecular sieve is 55～85% by weight percentage, the consumption preferable range of binding agent is 14～44%, and the consumption preferable range of alkaline earth metal oxide is 0.1～3.0%, and the consumption preferable range of rare-earth oxide is 0.1～3.0%.Described alkaline earth metal oxide preferred version is for being selected from magnesium oxide, calcium oxide or beryllium oxide, and more preferably scheme is for being selected from magnesium oxide.Described rare-earth oxide preferred version is for being selected from lanthanum trioxide, cerium oxide or Praseodymium trioxide, and more preferably scheme is for being selected from lanthanum trioxide.Steam treatment condition optimization scheme is that normal pressure, temperature are 480～650 DEG C, steam treatment 3～10 hours.The operational condition preferable range of alkylation reactor is: 320～400 DEG C of temperature of reaction, reaction pressure is 0.7～1.6MPa, weight ethylene air speed 0.4～3.0 hour -1, total benzene/ethylene molar ratio 5～8.Raw material dry gas is not containing free-water, H 28500 milligrams/meter of S content < 3, CO 2content < 4.0 volume %, C 3 =and C 4 =content < 0.8 volume %, does not need to refine in advance directly and can react with benzene.
Catalyzer in the present invention is prepared in accordance with the following methods:
1) by crystal grain diameter be 5～500 nanometers, silica alumina ratio SiO 2/ Al 2o 3be that 30～400 ZSM-5 molecular sieve well known to a person skilled in the art that under condition, hydrochloric acid exchange, washing, oven dry and roasting obtain HZSM-5 molecular sieve.
2) molecular sieve carried alkaline earth metal oxide and rare-earth oxide.The alkaline earth salt aqueous solution that by above-mentioned HZSM-5 molecular sieve by concentration is 0.002～2.0 mol/L floods 1～15 hour at 10～60 DEG C, and the weight ratio of the alkaline earth salt aqueous solution and HZSM-5 molecular sieve is 0.5～10, then oven dry, roasting; The rare earth salt aqueous solution that containing the HZSM-5 molecular sieve of alkaline earth by concentration is 0.002～2.0 mol/L is flooded 1～15 hour at 10～60 DEG C, the weight ratio of rare earth salt aqueous solution and HZSM-5 molecular sieve is 0.5～10, then oven dry, roasting again.Immersion condition preferred version is that alkaline earth salt and rare earth salt aqueous solution concentration are 0.05～1.0 mol/L, and the weight ratio of alkaline earth salt and rare earth salt aqueous solution and HZSM-5 molecular sieve is 1～5, and dipping temperature is 20～40 DEG C, and dipping time is 2～10 hours.
3) shaping of catalyst.By step 2) HZSM-5 molecular sieve and aluminum oxide or the silicon sol moulding containing alkaline earth and rare earth prepared, extrusion is in strip catalyzer.Above-mentioned catalyzer is dried and 550 DEG C of roastings in 4 hours through 110 DEG C for 10 hours again.
4) steam treatment.Preformed catalyst, normal pressure, 400～800 DEG C of steam treatment 1～20 hour, obtains described catalyzer.
In the catalytic reaction process of benzene and ethene vapor phase alkylation ethylbenzene processed, because reaction is carried out under hot conditions, therefore catalyzer is easy to because of coking inactivation, and activity stability is poor, and the regeneration period is short.First, the present invention adopts nano level ZSM-5 molecular sieve, because Kong Cheng is relatively short, reactant and product are at the time shorten of pore diffusion, in hole, there is the probability reduction that the side reaction such as oligomerisation, cyclisation generates polycyclic aromatic hydrocarbons, thereby effectively suppressed the generation of catalyzer coking, improve the activity stability of catalyzer.Secondly, the present invention adopts alkaline earth and rare-earth element modified catalyst, and alkaline earth element can regulating catalyst strength of acid on the one hand, suppresses easily to occur the strong acidic site of coking reaction, improves activity stability and the selectivity of catalyzer; Rare earth element is to improve hydrothermal stability and the selectivity of catalyzer on the other hand, due to the stabilization of rare earth element to framework of molecular sieve aluminium, thereby suppress the generation of framework of molecular sieve dealuminzation, improved the activity stability of catalyzer, reached the object of extending catalyst regeneration period.Finally, crucial, the present invention adopts high-temperature vapor processing, has further improved the hydrothermal stability of catalyzer, has improved the water repelling property of catalyzer under reaction conditions.In a word, the present invention adopts nano molecular sieve, adopts alkaline earth and rare-earth element modified catalyst, high-temperature vapor to process the method that three combines, taking the catalytic cracked dry gas containing 18.9% (body) ethene, 1.5% (body) propylene when raw material carries out benzene and ethylene alkylation, at reaction pressure 0.9MPa, weight ethylene air speed 0.8 hour -1, under the condition of benzene/ethylene molar ratio 8, conversion of ethylene can reach 99.5%, and ethyl selectivity can reach 99.0%, and the catalyst regeneration cycle has reached more than 1 year, has obtained good technique effect.
Give further instruction below by embodiment to the present invention.
Embodiment
[embodiment 1]
By 20 grams of silica alumina ratio SiO 2/ Al 2o 3=100, crystal grain diameter is that the ZSM-5 molecular sieve of 200 nanometers and the magnesium nitrate aqueous solution of 30 milliliter of 0.02 mol/L at room temperature flood 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution containing magnesian molecular sieve and 35 milliliter of 0.5 mol/L is at room temperature flooded 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and to add extruded moulding after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight be 1.8 millimeters of Φ.Dry after 10 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtain the catalyzer containing 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides; Above-mentioned catalyzer with water steam is processed after 6 hours normal pressure, 560 DEG C, and drying, roasting obtain finished catalyst.
[embodiment 2]
By 20 grams of silica alumina ratio SiO 2/ Al 2o 3=100, crystal grain diameter is that the ZSM-5 molecular sieve of 200 nanometers and the magnesium nitrate aqueous solution of 30 milliliter of 0.3 mol/L at room temperature flood 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution containing magnesian molecular sieve and 30 milliliter of 0.01 mol/L is at room temperature flooded 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and to add extruded moulding after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight be 1.8 millimeters of Φ.Dry after 10 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtain the catalyzer containing 1.5 % by weight magnesium oxide and 0.2 % by weight lanthanum trioxide; Above-mentioned catalyzer with water steam is processed after 5 hours normal pressure, 580 DEG C, and drying, roasting obtain finished catalyst.
[embodiment 3]
By 20 grams of silica alumina ratio SiO 2/ Al 2o 3=100, crystal grain diameter is that the ZSM-5 molecular sieve of 110 nanometers and the magnesium nitrate aqueous solution of 50 milliliter of 0.5 mol/L at room temperature flood 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution containing magnesian molecular sieve and 30 milliliter of 0.05 mol/L is at room temperature flooded 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 65: 35, and to add extruded moulding after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight be 1.8 millimeters of Φ.Dry after 10 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtain the catalyzer containing 3.0 % by weight magnesium oxide and 0.5 % by weight lanthanum trioxide; Above-mentioned catalyzer with water steam is processed after 4 hours normal pressure, 600 DEG C, and drying, roasting obtain finished catalyst.
[embodiment 4]
By 20 grams of silica alumina ratio SiO 2/ Al 2o 3=100, crystal grain diameter is that the ZSM-5 molecular sieve of 110 nanometers and the lanthanum nitrate aqueous solution of 50 milliliter of 0.5 mol/L at room temperature flood 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Again the above-mentioned magnesium nitrate aqueous solution containing magnesian molecular sieve and 35 milliliter of 0.02 mol/L is at room temperature flooded 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 60: 40, and to add extruded moulding after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight be 1.8 millimeters of Φ.Dry after 10 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtain the catalyzer containing 0.3 % by weight magnesium oxide and 3.0 % by weight lanthanum trioxides; Above-mentioned catalyzer with water steam is processed after 3 hours normal pressure, 650 DEG C, and drying, roasting obtain finished catalyst.
[embodiment 5]
By 20 grams of silica alumina ratio SiO 2/ Al 2o 3=50, crystal grain diameter is that the ZSM-5 molecular sieve of 250 nanometers and the magnesium nitrate aqueous solution of 30 milliliter of 0.02 mol/L at room temperature flood 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution containing magnesian molecular sieve and 35 milliliter of 0.5 mol/L is at room temperature flooded 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and to add extruded moulding after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight be 1.8 millimeters of Φ.Dry after 10 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtain the catalyzer containing 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides; Above-mentioned catalyzer with water steam is processed after 7 hours normal pressure, 525 DEG C, and drying, roasting obtain finished catalyst.
[embodiment 6]
By 20 grams of silica alumina ratio SiO 2/ Al 2o 3=200, crystal grain diameter is that the ZSM-5 molecular sieve of 250 nanometers and the magnesium nitrate aqueous solution of 30 milliliter of 0.02 mol/L at room temperature flood 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution containing magnesian molecular sieve and 35 milliliter of 0.5 mol/L is at room temperature flooded 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and to add extruded moulding after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight be 1.8 millimeters of Φ.Dry after 10 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtain the catalyzer containing 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides; Above-mentioned catalyzer with water steam is processed after 8 hours normal pressure, 500 DEG C, and drying, roasting obtain finished catalyst.
[embodiment 7]
By 20 grams of silica alumina ratio SiO 2/ Al 2o 3=300, crystal grain diameter is that the ZSM-5 molecular sieve of 250 nanometers and the magnesium nitrate aqueous solution of 30 milliliter of 0.02 mol/L at room temperature flood 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution containing magnesian molecular sieve and 35 milliliter of 0.5 mol/L is at room temperature flooded 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and to add extruded moulding after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight be 1.8 millimeters of Φ.Dry after 10 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtain the catalyzer containing 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides; Above-mentioned catalyzer with water steam is processed after 9 hours normal pressure, 480 DEG C, and drying, roasting obtain finished catalyst.
[embodiment 8]
By 20 grams of silica alumina ratio SiO 2/ Al 2o 3=100, crystal grain diameter is that the ZSM-5 molecular sieve of 200 nanometers and the calcium nitrate aqueous solution of 30 milliliter of 0.02 mol/L at room temperature flood 4 hours, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; At room temperature flood 4 hours containing the molecular sieve of calcium oxide and the cerous nitrate aqueous solution of 35 milliliter of 0.5 mol/L above-mentioned again, then 110 DEG C of oven dry, then 550 DEG C of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and to add extruded moulding after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight be 1.8 millimeters of Φ.Dry after 10 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtain the catalyzer containing 0.1 % by weight calcium oxide and 1.5 % by weight cerium oxide; Above-mentioned catalyzer with water steam is processed after 5 hours normal pressure, 580 DEG C, and drying, roasting obtain finished catalyst.
[comparative example 1]
Identical with [embodiment 1], just adopt ZSM-5/ZSM-11 eutectic molecular sieve.
[comparative example 2]
Identical with [embodiment 1], just molecular sieve without magnesium nitrate and lanthanum nitrate aqueous solution dipping, catalyzer without steam treatment.
[comparative example 3]
Identical with [embodiment 1], catalyzer contains 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides, but without steam treatment.
[comparative example 4]
Identical with [embodiment 1], just catalyzer is through steam treatment, but molecular sieve floods without lanthanum nitrate aqueous solution.
[comparative example 5]
Identical with [embodiment 1], catalyzer is containing 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides, and just ZSM-5 molecular sieve crystal grain diameter is 2 nanometers.
[comparative example 6]
Identical with [embodiment 1], catalyzer is containing 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides, and just ZSM-5 molecular sieve crystal grain diameter is 550 nanometers.
[comparative example 7]
According to [embodiment 1] disclosed method synthesis of molecular sieve in document CN200810032814.8, then prepare catalyzer according to [embodiment 7] disclosed method, the lanthanum trioxide of the magnesium oxide that contains 3.8 % by weight in gained catalyzer and 5.7 % by weight.
[embodiment 9]
On the pressurization static bed reaction unit of continuous flow, evaluate the activity stability of [embodiment 1～8], [comparative example 1～7] catalyzer, i.e. the regeneration period of catalyzer.Reaction conditions: 400 DEG C of temperature of reaction, reaction pressure 1.0MPa, benzene/ethene=1.0 (moles/mole), weight ethylene air speed (WHSV)=2.5 hour -1, the reaction times is 100 hours.Reaction result is in table 1.
Table 1
Catalyzer in visible the present invention has minimum deactivation rate, shows optimum activity stability.On full scale plant, move, the catalyst regeneration cycle has reached more than 1 year.

Claims (6)

1. a method for dry gas and producing phenylethane from alkylation of benzene, taking dry gas and benzene as reaction raw materials, 280～430 DEG C of temperature of reaction, reaction pressure 0.5～2.8MPa, weight ethylene air speed 0.2～5.0 hour -1, under the condition of total benzene/ethylene molar ratio 2～10, reaction raw materials contacts with catalyzer vapor phase alkylation generation ethylbenzene occurs; Catalyzer used contains following component by weight percentage:
A) 40～90% crystal grain diameter is for being greater than 100 nanometers and being less than or equal to 400 nanometers, silica alumina ratio SiO 2/ Al 2o 3it is 50～300 ZSM-5 molecular sieve;
B) 9～59% binding agent aluminum oxide or silicon-dioxide;
C) 0.1～10% alkaline earth metal oxide and 0.1～10% rare-earth oxide;
Described catalyzer is through high-temperature vapor processing, and then drying, roasting obtain required finished product;
Wherein steam treatment condition is that normal pressure, temperature are 480～650 DEG C, steam treatment 3～10 hours.
2. the method for dry gas according to claim 1 and producing phenylethane from alkylation of benzene, it is characterized in that catalyzer used by weight percentage the consumption of ZSM-5 molecular sieve be 55～85%, the consumption of binding agent is 14～44%, the consumption of alkaline earth metal oxide is 0.1～3.0%, and the consumption of rare-earth oxide is 0.1～3.0%.
3. the method for dry gas according to claim 1 and producing phenylethane from alkylation of benzene, is characterized in that described alkaline earth metal oxide is selected from magnesium oxide, calcium oxide or beryllium oxide, and described rare-earth oxide is selected from lanthanum trioxide, cerium oxide or Praseodymium trioxide.
4. the method for dry gas according to claim 3 and producing phenylethane from alkylation of benzene, is characterized in that described alkaline earth metal oxide is selected from magnesium oxide, and described rare-earth oxide is selected from lanthanum trioxide.
5. the method for dry gas according to claim 1 and producing phenylethane from alkylation of benzene, is characterized in that the operational condition of alkylation reactor is: 320～400 DEG C of temperature of reaction, reaction pressure is 0.7～1.6MPa, weight ethylene air speed 0.4～3.0 hour -1, total benzene/ethylene molar ratio 5～8.
6. the method for dry gas according to claim 1 and producing phenylethane from alkylation of benzene, is characterized in that raw material dry gas is not containing free-water, H 2s content <8500 milligram/rice 3, CO 2content <4.0 volume %, C 3 =and C 4 =content <0.8 volume %, does not need to refine in advance directly and can react with benzene.
CN201110193348.3A 2011-07-11 2011-07-11 Method for preparing ethylbenzene by alkylation of dry gas and benzene Active CN102875316B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547605A (en) * 1983-09-28 1985-10-15 Mobil Oil Corporation Catalyst for alkylation of aromatic hydrocarbons
CN1055075C (en) * 1996-01-16 2000-08-02 中国石油化工总公司 Technology for prepn. of ethyl benzene by reaction of thin ethylene and benzene
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547605A (en) * 1983-09-28 1985-10-15 Mobil Oil Corporation Catalyst for alkylation of aromatic hydrocarbons
CN1055075C (en) * 1996-01-16 2000-08-02 中国石油化工总公司 Technology for prepn. of ethyl benzene by reaction of thin ethylene and benzene
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

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