CN102875316A - 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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CN102875316A
CN102875316A CN2011101933483A CN201110193348A CN102875316A CN 102875316 A CN102875316 A CN 102875316A CN 2011101933483 A CN2011101933483 A CN 2011101933483A CN 201110193348 A CN201110193348 A CN 201110193348A CN 102875316 A CN102875316 A CN 102875316A
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benzene
alkylation
dry gas
molecular sieve
oxide
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CN102875316B (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
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    • 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 the method for a kind 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 the 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 with 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 are 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 constantly are devoted to utilize molecular sieve to produce the new technology of ethylbenzene as catalyzer.Wherein having obtained great commercial a kind of method is in the presence of a kind of solid acid ZSM-5 zeolite catalyzer, carries out vapor phase alkylation with pure ethylene and benzene.US Patent No. 3751504, US3751506, US4016218 and US4547605 all are 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 directly to enter the vapor phase alkylation device that molecular sieve catalyst is housed and react through refining, 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 the preparing ethylbenzene from dry gas reaction, wherein only have ZL96106561.3 to relate to the activity stability (regeneration period) of catalyzer, namely to contain 19.5% (body) ethene, the catalytic cracked dry gas of 0.8% (body) propylene is that raw material is when 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 the condition, can only continuous operation 95 days, can not satisfy 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, how many nanometers the particle diameter of synthetic molecular sieve is not actually in the disclosed embodiment, 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, exist rare ethene (dry gas) and benzene reaction to produce in the process of ethylbenzene poor catalyst stability, the problem that the regeneration period is short in the prior art.
Summary of the invention
Technical problem to be solved by this invention is to exist rare ethene (dry gas) and benzene reaction to produce in the process of ethylbenzene in the prior art, poor catalyst stability, and the problem that the regeneration period is short provides a kind of new dry gas and the method for producing phenylethane from alkylation of benzene.It is good that the method has a catalyst stability, the characteristics 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: the method for a kind of dry gas and producing phenylethane from alkylation of benzene, take dry gas and benzene as reaction raw materials, 280～430 ℃ 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; Used catalyzer 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 processed through high-temperature vapor, and then drying, roasting obtain required finished product; Wherein the steam treatment condition is for being under 400～800 ℃ of conditions in normal pressure, temperature, steam treatment 1～20 hour.
In the 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 the used catalyzer, 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 ℃, steam treatment 3～10 hours.The operational condition preferable range of alkylation reactor is: 320～400 ℃ of temperature of reaction, reaction pressure are 0.7～1.6MPa, weight ethylene air speed 0.4～3.0 hour -1, total benzene/ethylene molar ratio 5～8.The raw material dry gas does not contain free-water, H 2S content＜8500 milligram/meter 3, CO 2Content＜4.0 volume %, C 3 =And C 4 =Content＜0.8 volume % does not need to make with extra care in advance directly and can react with benzene.
Catalyzer among the present invention prepares in accordance with the following methods:
1) with crystal grain diameter is 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 hydrochloric acid exchange, washing, oven dry and roasting obtain the HZSM-5 molecular sieve under the condition.
2) molecular sieve carried alkaline earth metal oxide and rare-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 ℃, 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 HZSM-5 molecular sieve concentration that will contain again alkaline earth is that the rare earth salt aqueous solution of 0.002～2.0 mol/L flooded 1～15 hour at 10～60 ℃, and the weight ratio of rare earth salt aqueous solution and HZSM-5 molecular sieve is 0.5～10, then oven dry, roasting.The 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 ℃, and dipping time is 2～10 hours.
3) shaping of catalyst.With step 2) preparation the HZSM-5 molecular sieve that contains alkaline earth and rare earth and aluminum oxide or silicon sol moulding, extrusion is in strip catalyzer.Above-mentioned catalyzer is again through 110 ℃ of oven dry in 10 hours and 550 ℃ of roastings in 4 hours.
4) steam treatment.Preformed catalyst obtains described catalyzer normal pressure, 400～800 ℃ of steam treatment 1～20 hour.
In the catalytic reaction process of benzene and ethene vapor phase alkylation ethylbenzene processed, because reaction carries out under hot conditions, so catalyzer is easy to because of the coking inactivation, and activity stability is relatively poor, and the regeneration period is short.At 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, the probability reduction that the side reactions such as oligomerisation, cyclisation generate polycyclic aromatic hydrocarbons occurs in the hole, thereby establishment the generation of catalyzer coking, improved the activity stability of catalyzer.Secondly, the present invention adopts alkaline earth and rare-earth element modified catalyst, but one side alkaline earth element regulating catalyst strength of acid suppresses the easily strong acidic site of generation coking reaction, activity stability and the selectivity of raising catalyzer; Rare earth element is to improve hydrothermal stability and the selectivity of catalyzer on the other hand, because rare earth element is to the stabilization of framework of molecular sieve aluminium, thereby suppressed the generation of framework of molecular sieve dealuminzation, improved the activity stability of catalyzer, reached the purpose of extending catalyst regeneration period.At last, crucial is that the present invention adopts high-temperature vapor to process, and 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 the three combines, when carrying out benzene and ethylene alkylation take the catalytic cracked dry gas that contains 18.9% (body) ethene, 1.5% (body) propylene as raw material, 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 the ethyl selectivity can reach 99.0%, and the catalyst regeneration cycle reached more than 1 year, had obtained preferably technique effect.
Give further instruction below by embodiment to the present invention.
Embodiment
[embodiment 1]
With 20 gram 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 flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 35 milliliter of 0.5 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve 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, again 550 ℃ of roastings 4 hours, obtain containing the catalyzer of 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides 110 ℃ of bakings; After normal pressure, 560 ℃ were processed 6 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 2]
With 20 gram 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 flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 30 milliliter of 0.01 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve 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, again 550 ℃ of roastings 4 hours, obtain containing the catalyzer of 1.5 % by weight magnesium oxide and 0.2 % by weight lanthanum trioxide 110 ℃ of bakings; After normal pressure, 580 ℃ were processed 5 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 3]
With 20 gram 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 flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 30 milliliter of 0.05 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 65: 35, 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, again 550 ℃ of roastings 4 hours, obtain containing the catalyzer of 3.0 % by weight magnesium oxide and 0.5 % by weight lanthanum trioxide 110 ℃ of bakings; After normal pressure, 600 ℃ were processed 4 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 4]
With 20 gram 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 flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned magnesium nitrate aqueous solution that contains magnesian molecular sieve and 35 milliliter of 0.02 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 60: 40, 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, again 550 ℃ of roastings 4 hours, obtain containing the catalyzer of 0.3 % by weight magnesium oxide and 3.0 % by weight lanthanum trioxides 110 ℃ of bakings; After normal pressure, 650 ℃ were processed 3 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 5]
With 20 gram 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 flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 35 milliliter of 0.5 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve 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, again 550 ℃ of roastings 4 hours, obtain containing the catalyzer of 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides 110 ℃ of bakings; After normal pressure, 525 ℃ were processed 7 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 6]
With 20 gram 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 flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 35 milliliter of 0.5 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve 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, again 550 ℃ of roastings 4 hours, obtain containing the catalyzer of 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides 110 ℃ of bakings; After normal pressure, 500 ℃ were processed 8 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 7]
With 20 gram 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 flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 35 milliliter of 0.5 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve 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, again 550 ℃ of roastings 4 hours, obtain containing the catalyzer of 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides 110 ℃ of bakings; After normal pressure, 480 ℃ were processed 9 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 8]
With 20 gram 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 flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Contain the molecular sieve of calcium oxide and the cerous nitrate aqueous solution of 35 milliliter of 0.5 mol/L at room temperature flooded 4 hours with above-mentioned again, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve 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, again 550 ℃ of roastings 4 hours, obtain containing the catalyzer of 0.1 % by weight calcium oxide and 1.5 % by weight cerium oxide 110 ℃ of bakings; After normal pressure, 580 ℃ were processed 5 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[comparative example 1]
Identical with [embodiment 1], just adopt the 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 contains 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides, and just the ZSM-5 molecular sieve crystal grain diameter is 2 nanometers.
[comparative example 6]
Identical with [embodiment 1], catalyzer contains 0.1 % by weight magnesium oxide and 1.5 % by weight lanthanum trioxides, and just the ZSM-5 molecular sieve crystal grain diameter is 550 nanometers.
[comparative example 7]
According to [embodiment 1] disclosed method synthesis of molecular sieve among the document CN200810032814.8, then prepared catalyzer according to [embodiment 7] disclosed method, contain the magnesium oxide of 3.8 % by weight and the lanthanum trioxide of 5.7 % by weight in the gained catalyzer.
[embodiment 9]
On the pressurization static bed reaction unit of continuous flow, estimate the activity stability of [embodiment 1～8], [comparative example 1～7] catalyzer, i.e. the regeneration period of catalyzer.Reaction conditions: 400 ℃ 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 sees Table 1.
Table 1
Figure BDA0000074951480000081
As seen the catalyzer among the present invention has minimum deactivation rate, shows optimum activity stability.Move at full scale plant, the catalyst regeneration cycle reached more than 1 year.

Claims (10)

1. the method for a dry gas and producing phenylethane from alkylation of benzene, take dry gas and benzene as reaction raw materials, 280～430 ℃ 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; Used catalyzer 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 processed through high-temperature vapor, and then drying, roasting obtain required finished product; Wherein the steam treatment condition is for being under 400～800 ℃ of conditions in normal pressure, temperature, steam treatment 1～20 hour.
2. the method for dry gas according to claim 1 and producing phenylethane from alkylation of benzene, the crystal grain diameter that it is characterized in that ZSM-5 molecular sieve is 10～450 nanometers.
3. the method for dry gas according to claim 2 and producing phenylethane from alkylation of benzene is characterized in that the crystal grain diameter of ZSM-5 molecular sieve is＞100～400 nanometers.
4. the method for dry gas according to claim 1 and producing phenylethane from alkylation of benzene is characterized in that ZSM-5 molecular sieve silica alumina ratio SiO 2/ Al 2O 3Be 50～300.
5. the method for dry gas according to claim 1 and producing phenylethane from alkylation of benzene, it is characterized in that used catalyzer 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%.
6. 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.
7. the method for dry gas according to claim 6 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.
8. the method for dry gas according to claim 1 and producing phenylethane from alkylation of benzene is characterized in that the steam treatment condition is that normal pressure, temperature are 480～650 ℃, steam treatment 3～10 hours.
9. the method for dry gas according to claim 1 and producing phenylethane from alkylation of benzene, it is characterized in that the operational condition of alkylation reactor is: 320～400 ℃ of temperature of reaction, reaction pressure are 0.7～1.6MPa, weight ethylene air speed 0.4～3.0 hour -1, total benzene/ethylene molar ratio 5～8.
10. the method for dry gas according to claim 1 and producing phenylethane from alkylation of benzene is characterized in that the raw material dry gas does not contain free-water, H 2S content＜8500 milligram/meter 3, CO 2Content＜4.0 volume %, C 3 =And C 4 =Content＜0.8 volume % does not need to make with extra care in advance directly and can react with benzene.
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CN106244224A (en) * 2015-06-12 2016-12-21 中国石油化工股份有限公司 Dry gas produces the method for gasoline mediation component
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CN106244224A (en) * 2015-06-12 2016-12-21 中国石油化工股份有限公司 Dry gas produces the method for gasoline mediation component
CN106281433A (en) * 2015-06-12 2017-01-04 中国石油化工股份有限公司 Oil refinery dry gas produces the method for gasoline mediation component
CN106281433B (en) * 2015-06-12 2018-02-13 中国石油化工股份有限公司 The method of oil refinery dry gas production gasoline mediation component

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