CN102040458A - Method for producing ethylbenzene by reacting pure ethylene or dry gas with benzene - Google Patents
Method for producing ethylbenzene by reacting pure ethylene or dry gas with benzene Download PDFInfo
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- CN102040458A CN102040458A CN2009102016662A CN200910201666A CN102040458A CN 102040458 A CN102040458 A CN 102040458A CN 2009102016662 A CN2009102016662 A CN 2009102016662A CN 200910201666 A CN200910201666 A CN 200910201666A CN 102040458 A CN102040458 A CN 102040458A
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Abstract
The invention relates to a method for producing ethylbenzene by reacting pure ethylene or dry gas with benzene, mainly solving the problems of high dimethylbenzene impurity content in the product ethylbenzene, low ethylbenzene purity, poor catalyst stability and short regeneration period and service life in the process of producing ethylbenzene by reacting pure ethylene or dry gas with benzene in the prior art. In the invention, at least a section of ZSM-5 molecular sieve catalyst I the SiO2/Al2O3 mol ratio of which is 50-150, and at least a section of ZSM-5 molecular sieve catalyst II the SiO2/Al2O3 mol ratio of which is 160-300 are loaded in an alkylation fixed bed type reactor; 30-70wt% of pure ethylene or dry gas enters the bed loaded with the catalyst I, and the residual pure ethylene or dry gas enters the bed loaded with the catalyst II; 80-100wt% of benzene enters the first section of the bed loaded with the catalyst I from the top of the reactor, and the residual benzene enters each catalyst bed below section by section; and the difference between the inlet temperature of each section of catalyst bed and the material inlet temperature at the top of the reactor is controlled not to exceed +/-5 DEG C. The technical scheme better solves the problems and can be used in the industrial production of ethylbenzene by reacting the pure ethylene or the dry gas with the benzene.
Description
Technical field
The present invention relates to the method that ethylbenzene is produced in the reaction of a kind of pure ethylene or dry gas and benzene.
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 shortcomings such as seriously corroded, facility investment is big, the three wastes are many in these conventional catalyst technologies.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 catalyst, carries out vapor phase alkylation with pure ethylene and benzene.U.S. Pat 3751504, US3751506, US4016218 and US4547605 all are described in detail this, but it is short all to exist the catalyst regeneration cycle, the high shortcoming of xylene content in the not high and product of selectivity.
ZL00111720.3 and ZL00111721.1 disclose a kind of method that improves pure ethylene and benzene vapor-phase alkylation catalyst stability, after ZSM-5 molecular sieve catalyst process water vapour and organic acid are handled, can effectively improve the stability of catalyzer, and be successfully applied to the industrial production of ethylbenzene, but the content of dimethylbenzene is still higher in the product ethylbenzene, has reached 780ppm.
ZL1154957A and ZL9811347.0 have reported the technology of two kinds of dry gas and benzene preparing ethylbenzene by reaction respectively.A kind of technology 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 ethylbenzene again, and another technology alkylation part is similar substantially, difference is that the many ethylbenzene that produce enter a liquid-phase transalkylation reactor, are translated into ethylbenzene.Shortcomings such as the impurity dimethylbenzene in these two kinds of handicraft product ethylbenzene is respectively up to 2000ppm and 1000ppm, and exists poor catalyst stability, and regeneration period and work-ing life are short.
Summary of the invention
Technical problem to be solved by this invention is to exist pure ethylene or dry gas and benzene reaction to produce in the process of ethylbenzene in the prior art, dimethylbenzene foreign matter content height in the product ethylbenzene, ethylbenzene purity are low, poor catalyst stability, the problem that regeneration period and work-ing life are short provides a kind of new pure ethylene or the method for dry gas and benzene reaction production ethylbenzene.This method has the reduction xylene content, improves product ethylbenzene purity, the characteristics that prolong catalyst regeneration cycle and work-ing life.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method that ethylbenzene is produced in a kind of pure ethylene or dry gas and benzene reaction, comprise that with pure ethylene or dry gas and benzene be raw material, in alkylation reactor, carry out alkylated reaction, after reacted effluent was isolated benzene, ethylbenzene, propyl benzene and many ethylbenzene successively, many ethylbenzene entered transalkylation reactor and are converted into ethylbenzene again; It is characterized in that:
Described alkylation reactor is fixed-bed reactor, wherein is mounted with at least one section SiO
2/ Al
2O
3Mol ratio is ZSM-5 molecular sieve catalyst I and at least one section SiO of 50～150
2/ Al
2O
3Mol ratio is 160～300 ZSM-5 molecular sieve catalyst II; Reactant flow flow through the earlier catalyst I and then the catalyst I I that flows through;
Wherein, the operational condition of alkylation reactor is: 300～430 ℃ of temperature of reaction, reaction pressure 0.5～2.8MPa, weight ethylene air speed 0.2～5.0 hour
-1, total benzene/ethylene molar ratio 2～10; The pure ethylene of 30～70 weight % or dry gas enter the bed that is mounted with catalyst I, and remaining pure ethylene or dry gas enter the bed that is mounted with catalyst I I; The benzene of 80～100 weight % enters first section bed that catalyst I is housed by reactor head, remaining benzene segmentation enters following each section beds, with control every section beds temperature in and reactor head logistics temperature in differ be no more than ± 5 ℃.
In the technique scheme, in the alkylation reactor, the SiO of catalyst I
2/ Al
2O
3The mol ratio preferable range is 60～140, and more preferably scope is 80～120; The SiO of catalyst I I
2/ Al
2O
3The mol ratio preferable range is 170～280, and more preferably scope is 180～250.The temperature of reaction preferable range is 320～400 ℃, and the reaction pressure preferable range is 0.7～1.6MPa, and weight ethylene air speed preferable range is 0.4～3.0 hour
-1It is, total that benzene/the ethylene molar ratio preferable range is 5～8.Described alkylation reactor preferred version is for being divided into 4 or 6 layers, and catalyst I is loaded superincumbent 2 or 3 layers, and catalyst I I is seated in following 2 or 3 layers.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 can react with benzene.The transalkylation catalyst preferred version is for being selected from beta-molecular sieve or Y zeolite.Transalkylation reaction is to carry out under liquid-phase condition, and its operational condition preferable range is: 120～320 ℃ of temperature of reaction, reaction pressure 2.0～5.0MPa, the mol ratio 2～25 of benzene/many ethylbenzene, total air speed 0.5～6.0 hour
-1More preferably scope be that the mol ratio of 160～280 ℃ of temperature of reaction, reaction pressure 2.8～4.0Mpa, benzene/many ethylbenzene is 5～10, total air speed 0.8～3.0 hour
-1
Because the benzene alkylation with ethylene reaction is a strong exothermal reaction, therefore, produce ethylbenzene for vapor phase alkylation, no matter be to adopt pure ethylene or dry gas, industrial many beds fixed-bed reactor that all adopt generally have 4～6 beds.Each beds all is equipped with active identical alkylation catalyst, adopts between each beds and introduces the lower chilling benzene of pure ethylene or dry gas and temperature to control the temperature rise of every section beds, reduces the growing amount of dimethylbenzene impurity as far as possible.Generally speaking, on the industrial installation, about 50% benzene directly enters first bed at alkylation reactor top, remaining benzene is introduced respectively between every section remaining beds as chilling benzene, to control the temperature rise of every section beds, the inlet operating temperature that makes every section beds is identical basically.This operation format has caused reactor first beds and the most beneath beds to have minimum and the highest benzene/alkene ratio respectively, and bigger temperature rise appears in device first beds that induces reaction; Produce and not wish the by product wanted in a large number, as dimethylbenzene, isopropyl benzene and butylbenzene etc.; Simultaneously, also cause the easy coking of catalyzer, the regeneration period of catalyzer and work-ing life are shortened.The inventive method adopts combination catalyst, a kind of silica alumina ratio is low, active high molecular sieve catalyst be seated in many bed reactors top which floor, and another silica alumina ratio height, active low molecular sieve catalyst be seated in many bed reactors following which floor.The inventive method can make every section beds carry out under lower temperature of reaction, can reduce or do not need intersegmental chilling benzene, 80%～100% benzene enters first section beds by reactor head, so just help increasing the benzene alkene ratio of several sections beds above the reactor, reduce temperature rise, reduce dimethylbenzene, the growing amount of impurity such as isopropyl benzene and butylbenzene, the purity of raising product ethylbenzene; Also help suppressing the generation of catalyzer coking, prolong the regeneration period and the work-ing life of catalyzer.Use the inventive method, conversion of ethylene can reach 99.8～100%, the ethyl selectivity can reach 99.7～99.8%, xylene content in the ethylbenzene drops to 500ppm by original 850ppm, product ethylbenzene purity brings up to 99.8% by original 99.6%, the regeneration period of alkylation catalyst extended to 18 months by original 12 months, and extended to 3 year by original 2 years work-ing life, obtained better technical effect.
Description of drawings
Fig. 1 is six bed alkylation fixed-bed reactor synoptic diagram among the present invention.
Fig. 2 is a process flow diagram of the present invention.
Among Fig. 1, A～F is a beds, and 1～12 is pipeline.
Among Fig. 1, bed A, B, C are mounted with catalyst I, and bed D, E, F are mounted with catalyst I I. Main flow benzene and pure ethylene or dry gas enter beds A from the overhead line 1 of reactor and carry out alkylated reaction. Because alkylated reaction heat release, reacting rear material in the temperature in A section exit than inlet temperature height, this material mixes with the benzene that enters by pipeline 2 with by pure ethylene or dry gas that pipeline 3 enters when arriving B section entrance, in cold benzene and cold pure ethylene or heated while of dry gas, thermal material is cooled, mixed material reaches reaction temperature, carries out alkylated reaction under the effect of catalyst again. The rest may be inferred for the situation of all the other each sections. The final reaction logistics goes out reactor and enters follow-up separation and recovery system by pipeline 12.
Among Fig. 2, A ' is alkylation reactor, and B ' is preseparator, and C ' is the benzene tower, and D ' is ethylbenzene tower, and E ' is for taking off the propyl benzene tower, and F ' is many ethylbenzene towers, and G ' is transalkylation reactor.
Among Fig. 2, the alkylation reactor A ' of six beds, above 3 layers catalyst I is housed, below 3 layers catalyst I I is housed. Main flow benzene more than 80% and part pure ethylene (or dry gas) enter the alkylation reactor top by pipeline 22 and 21, and all the other a small amount of benzene are divided into 5 strands of chilling benzene, enter reactor by pipeline A2, A4, A6, A8 and A10 respectively; Remainder pure ethylene (or dry gas) also is divided into 5 strands, enters reactor by pipeline A1, A3, A5, A7 and A9 respectively. Reaction effluent enters preseparator B ' by pipeline 23, and the liquid part of telling is by entering benzene tower C ' through pipeline 25 at the bottom of the tower. The following non-aromatics of a small amount of C8 through the pre-separation tower after, take device act as a fuel usefulness with tail gas by pipeline 24 from cat head. In the benzene tower, after unreacted benzene was circulated to alkylation reactor population and fresh benzene (pipeline 22) mixing from cat head by pipeline 26, a part was as the raw material of alkylated reaction, and another part is as the raw material of transalkylation reaction; Mainly be that ethylbenzene, many ethylbenzene and a small amount of impurity propyl benzene, isopropylbenzene and butylbenzene etc. and restructuring divide at the bottom of the benzene Tata, enter ethylbenzene tower D ' by pipeline 27. In ethylbenzene tower, product ethylbenzene is told from cat head, and its purity 99.8% is delivered to the tank field by pipeline 28, mainly is that propyl benzene, isopropylbenzene, butylbenzene, many ethylbenzene and restructuring divide at the bottom of its tower, enters by pipeline 29 and takes off the propyl benzene tower. In taking off the propyl benzene tower, propyl benzene, isopropylbenzene and butylbenzene etc. are told from cat head, are sent to out-of-bounds by pipeline 30, and diethylbenzene and triethylbenzene (TEB) enter many ethylbenzene towers F ' by pipeline 31 at the bottom of by tower. In many ethylbenzene towers, diethylbenzene and triethylbenzene (TEB) are told from cat head, deliver to the transalkylation reaction part by pipeline 32. Mainly be many ethylbenzene Residual oil at the bottom of its tower, take the device usefulness that acts as a fuel out of by pipeline 33. Many ethylbenzene enter transalkylation reactor G ' after mixing by pipeline 32 with from the recovery benzene (pipeline 34) of benzene tower, under the condition of liquid phase alkylation reaction, react, mainly contain benzene, ethylbenzene, many ethylbenzene and a small amount of toluene and dimethylbenzene etc. in the product, this material is delivered to pre-separation tower B ' by pipeline 35 and is separated recovery.
Give further instruction below by embodiment to the present invention.
Embodiment
[comparative example 1]
To be mixed with 1.8 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder
2/ Al
2O
3=60 moles/mole) catalyzer 60 grams were handled 4 hours at 520 ℃ with water vapour, obtained catalyzer finished product A.Get the above-mentioned catalyzer finished product that makes 8 grams, be positioned in one the four bed fixed-bed reactor.The employing pure ethylene is a raw material, and total benzene/ethylene molar ratio is 6.5/1, weight ethylene air speed 2.0 hours
-1, 49.7% benzene is entered by the top of reactor, and conversion of ethylene is 99.96%, and ethylbenzene selectivity is 91.60%.
Transalkylation reaction carries out in single bed reactor that 6 gram beta-molecular sieve catalyzer are housed, and is 7 in the mol ratio of 260 ℃ of temperature of reaction, reaction pressure 3.8MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 65.3%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.53%, and xylene content is 850ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.42%, detailed results sees Table 1.
[comparative example 2]
To be mixed with 1.8 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder
2/ Al
2O
3=160 moles/mole) catalyzer 60 grams were handled 4 hours at 530 ℃ with water vapour, obtained catalyzer finished product B.Get the above-mentioned catalyzer finished product that makes 8 grams, be positioned in one the four bed fixed-bed reactor.The employing pure ethylene is a raw material, and total benzene/ethylene molar ratio is 6.4/1, weight ethylene air speed 1.99 hours
-1, 49.8% benzene is entered by the top of reactor, and conversion of ethylene is 99.89%, and ethylbenzene selectivity is 92.50%.
Transalkylation reaction carries out in single bed reactor that 6 gram beta-molecular sieve catalyzer are housed, and is 8 in the mol ratio of 260 ℃ of temperature of reaction, reaction pressure 3.8MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 66.7%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.55%, and xylene content is 750ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.57%, detailed results sees Table 1.
[embodiment 1]
4 gram catalyst A are filled in above the four bed fixed-bed reactor 2 layers; 4 gram catalyst B are filled in below the four bed fixed-bed reactor 2 layers.The employing pure ethylene is a raw material, and total benzene/ethylene molar ratio is 6.5/1, weight ethylene air speed 2.0 hours
-180.6% benzene is entered by the top of reactor, conversion of ethylene is 99.92%, ethylbenzene selectivity is 93.80%, the temperature in of every section beds is low when all using with a kind of active catalyst, the level the when stability of the dimethylbenzene of generation and impurity equal size and catalyzer all will obviously be better than using with a kind of active catalyst.
Transalkylation reaction carries out in single bed reactor that 6 gram beta-molecular sieve catalyzer are housed, and is 8 in the mol ratio of 260 ℃ of temperature of reaction, reaction pressure 3.7MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 66.5%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.78%, and xylene content is 470ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.83%, detailed results sees Table 1.
[embodiment 2]
4 gram catalyst A are filled in above the four bed fixed-bed reactor 2 layers; 4 gram catalyst B are filled in below the four bed fixed-bed reactor 2 layers.The employing pure ethylene is a raw material, and total benzene/ethylene molar ratio is 6.5/1, weight ethylene air speed 2.0 hours
-1, 90.7% benzene is entered by the top of reactor, and conversion of ethylene is 99.93%, and ethylbenzene selectivity is 92.8%, the level the when stability of the dimethylbenzene of generation and impurity equal size and catalyzer also will obviously be better than using with a kind of active catalyst.
Transalkylation reaction carries out in single bed reactor that 6 gram beta-molecular sieve catalyzer are housed, and is 8 in the mol ratio of 260 ℃ of temperature of reaction, reaction pressure 3.8MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 67.3%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.82%, and xylene content is 490ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.72%, detailed results sees Table 1.
Table 1 four bed reactor pure ethylene alkylated reaction situations
[comparative example 3]
To be mixed with 1.8 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder
2/ Al
2O
3=150 moles/mole) catalyzer 60 grams were handled 5 hours at 510 ℃ with water vapour, obtained catalyzer finished product C.Get the above-mentioned catalyzer finished product that makes 8 grams, be positioned in one the four bed fixed-bed reactor.Used dry gas contains free-water 170ppm, H
2S7500 milligram/rice
3, CO
2(3.0 body) %, C
3 =And C
4 =0.7 (body) % and ethene 14.8% component do not need directly refining in advance and the benzene reaction; Total benzene/ethylene molar ratio is 6.5/1, weight ethylene air speed 0.7 hour
-1, conversion of ethylene is 99.78%.
Transalkylation reaction carries out in single bed reactor that 6 gram Y molecular sieve catalyzer are housed, and is 8 in the mol ratio of 160 ℃ of temperature of reaction, reaction pressure 2.8MPa, benzene/many ethylbenzene, total air speed 1.5 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 79.3%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.37%, and xylene content is 870ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.39%, detailed results sees Table 2.
[comparative example 4]
To be mixed with 1.8 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder
2/ Al
2O
3=250 moles/mole) catalyzer 60 grams were handled 4.5 hours at 525 ℃ with water vapour, obtained catalyzer finished product D.Get the above-mentioned catalyzer finished product that makes 8 grams, be positioned in one the four bed fixed-bed reactor.Used dry gas contains free-water 170ppm, H
2S7500 milligram/rice
3, CO
2(3.0 body) %, C
3 =And C
4 =(0.7 body) % and ethene 14.8% component, total benzene/ethylene molar ratio is 6.6/1, weight ethylene air speed 0.6 hour
-1, conversion of ethylene is 99.73%, ethylbenzene selectivity is 89.6%.
Transalkylation reaction carries out in single bed reactor that 6 gram Y molecular sieve catalyzer are housed, and is 7 in the mol ratio of 160 ℃ of temperature of reaction, reaction pressure 2.9MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 81.7%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.39%, and xylene content is 782ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.46%, detailed results sees Table 2.
[embodiment 3]
4 gram catalyzer C are filled in above the four bed fixed-bed reactor 2 layers; 4 gram catalyzer D are filled in below the four bed fixed-bed reactor 2 layers.The dry gas that adopts contains free-water 170ppm, H
2S7500 milligram/rice
3, CO
2(3.0 body) %, C
3 =And C
4 =0.7 (body) % and ethene 14.8% component do not need directly refining in advance and the benzene reaction, total benzene/ethylene molar ratio is 6.5/1, weight ethylene air speed 0.7 hour
-180.5% benzene is entered by the top of reactor, conversion of ethylene is 99.82%, ethylbenzene selectivity is 91.7%, the temperature in of every section beds is low when all using single catalyst, the level the when stability of the dimethylbenzene of generation and impurity equal size and catalyzer all will obviously be better than using single catalyst.
Transalkylation reaction carries out in single bed reactor that 6 gram Y molecular sieve catalyzer are housed, and is 8 in the mol ratio of 180 ℃ of temperature of reaction, reaction pressure 3.1MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 82.9%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.56%, and xylene content is 510ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.57%, detailed results sees Table 2.
[embodiment 4]
4 gram catalyzer C are filled in above the four bed fixed-bed reactor 2 layers; 4 gram catalyzer D are filled in below the four bed fixed-bed reactor 2 layers.The dry gas that adopts contains free-water 170ppm, H
2S7500 milligram/rice
3, CO
2(3.0 body) %, C
3 =And C
4 =0.7 (body) % and ethene 14.8% component do not need directly refining in advance and the benzene reaction, total benzene/ethylene molar ratio is 6.5/1, weight ethylene air speed 0.7 hour
-1100.0% benzene is entered by the top of reactor, conversion of ethylene is 99.80%, ethylbenzene selectivity is 92.6%, the temperature in of every section beds is low when all using single catalyst, the level the when stability of the dimethylbenzene of generation and impurity equal size and catalyzer all will obviously be better than using single catalyst.
Transalkylation reaction carries out in single bed reactor that 6 gram Y molecular sieve catalyzer are housed, and is 8 in the mol ratio of 180 ℃ of temperature of reaction, reaction pressure 3.2MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 83.7%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.56%, and xylene content is 516ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.58%, detailed results sees Table 2.
Table 2 four bed reactor dry gas alkylated reaction situations
[comparative example 5]
To be mixed with 1.8 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder
2/ Al
2O
3=80 moles/mole) catalyzer 60 grams were handled 4 hours at 530 ℃ with water vapour, obtained catalyzer finished product E.Get the above-mentioned catalyzer finished product that makes 12 grams, be positioned in one the six bed fixed-bed reactor.The employing pure ethylene is a raw material, and total benzene/ethylene molar ratio is 6.6/1, weight ethylene air speed 2.1 hours
-1, 50.2% benzene is entered by the top of reactor, and conversion of ethylene is 99.92%, and ethylbenzene selectivity is 92.5%.
Transalkylation reaction carries out in single bed reactor that 6 gram Y molecular sieve catalyzer are housed, and is 8 in the mol ratio of 170 ℃ of temperature of reaction, reaction pressure 3.0MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 82.5%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.67%, and xylene content is 700ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.58%, detailed results sees Table 3.
[comparative example 6]
To be mixed with 1.8 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder
2/ Al
2O
3=180 moles/mole) catalyzer 60 grams were handled 3 hours at 550 ℃ with water vapour, obtained catalyzer finished product F.Get the above-mentioned catalyzer finished product that makes 12 grams, be positioned in one the six bed fixed-bed reactor.The employing pure ethylene is a raw material, and total benzene/ethylene molar ratio is 6.5/1, weight ethylene air speed 2.0 hours
-1, 51.0% benzene is entered by the top of reactor, and conversion of ethylene is 99.83%, and ethylbenzene selectivity is 92.7%.
Transalkylation reaction carries out in single bed reactor that 6 gram Y molecular sieve catalyzer are housed, and is 8 in the mol ratio of 180 ℃ of temperature of reaction, reaction pressure 3.3MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 83.0%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.72%, and xylene content is 680ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.69%, detailed results sees Table 3.
[embodiment 5]
6 gram catalyzer E are filled in above the six bed fixed-bed reactor 3 layers; 6 gram catalyzer F are filled in below the six bed fixed-bed reactor 3 layers.The employing pure ethylene is a raw material, and total benzene/ethylene molar ratio is 6.5/1, weight ethylene air speed 2.1 hours
-180.0% benzene is entered by the top of reactor, conversion of ethylene is 99.85%, ethylbenzene selectivity is 93.8%, the temperature in of every section beds is low when all using with a kind of active catalyst, the level the when stability of the dimethylbenzene of generation and impurity equal size and catalyzer all will obviously be better than using with a kind of active catalyst.
Transalkylation reaction carries out in single bed reactor that 6 gram Y molecular sieve catalyzer are housed, and is 7 in the mol ratio of 170 ℃ of temperature of reaction, reaction pressure 3.0MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 82.6%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.82%, and xylene content is 310ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.81%, detailed results sees Table 3.
[embodiment 6]
6 gram catalyzer E are filled in above the six bed fixed-bed reactor 3 layers; 6 gram catalyzer F are filled in below the six bed fixed-bed reactor 3 layers.The employing pure ethylene is a raw material, and total benzene/ethylene molar ratio is 6.5/1, weight ethylene air speed 2.1 hours
-1100.0% benzene is entered by the top of reactor, conversion of ethylene is 99.86%, ethylbenzene selectivity is 93.6%, the temperature in of every section beds is low when all using with a kind of active catalyst, the level the when stability of the dimethylbenzene of generation and impurity equal size and catalyzer all will obviously be better than using with a kind of active catalyst.
Transalkylation reaction carries out in single bed reactor that 6 gram Y molecular sieve catalyzer are housed, and is 7 in the mol ratio of 170 ℃ of temperature of reaction, reaction pressure 3.1MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 84.3%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.85%, and xylene content is 350ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.80%, detailed results sees Table 3.
Table 3 six bed reactor pure ethylene alkylated reaction situations
[comparative example 7]
To be mixed with 1.8 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder
2/ Al
2O
3=85 moles/mole) catalyzer 60 grams were handled 4.5 hours at 530 ℃ with water vapour, obtained catalyzer finished product G.Get the above-mentioned catalyzer finished product that makes 12 grams, be positioned in one the six bed fixed-bed reactor.Used dry gas contains free-water 150ppm, H
27000 milligrams/meter of S
3, CO
2(2.5 body) %, C
3 =And C
4 =0.7 (body) % and ethene 18.5% component do not need directly refining in advance and the benzene reaction; Total benzene/ethylene molar ratio is 6.7/1, weight ethylene air speed 0.6 hour
-1, 51.1% benzene is entered by the top of reactor, and conversion of ethylene is 99.83%, and ethylbenzene selectivity is 89.8%.
Transalkylation reaction carries out in single bed reactor that 6 gram beta-molecular sieve catalyzer are housed, and is 8 in the mol ratio of 260 ℃ of temperature of reaction, reaction pressure 3.7MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 63.8%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.47%, and xylene content is 750ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.42%, detailed results sees Table 4.
[comparative example 8]
To be mixed with 1.8 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder
2/ Al
2O
3=210 moles/mole) catalyzer 60 grams were handled 4.0 hours at 540 ℃ with water vapour, obtained catalyzer finished product H.Get the above-mentioned catalyzer finished product that makes 12 grams, be positioned in one the six bed fixed-bed reactor.Used dry gas contains free-water 150ppm, H
2S7000 milligram/rice
3, CO
2(2.5 body) %, C
3 =And C
4 =(0.7 body) % and ethene 18.5% component, total benzene/ethylene molar ratio is 6.6/1, weight ethylene air speed 0.7 hour
-1, 50.3% benzene is entered by the top of reactor, and conversion of ethylene is 99.79%, and ethylbenzene selectivity is 90.3%4.
Transalkylation reaction carries out in single bed reactor that 6 gram beta-molecular sieve catalyzer are housed, and is 8 in the mol ratio of 260 ℃ of temperature of reaction, reaction pressure 3.7MPa, benzene/many ethylbenzene, total air speed 1.0 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 64.2%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.53%, and xylene content is 680ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.51%, detailed results sees Table 4.
[embodiment 7]
6 gram catalyzer G are filled in above the six bed fixed-bed reactor 3 layers; 6 gram catalyzer H are filled in below the six bed fixed-bed reactor 3 layers.Used dry gas contains free-water 150ppm, H
27000 milligrams/meter of S
3, CO
2(2.5 body) %, C
3 =And C
4 =0.7 (body) % and ethene 18.5% component do not need directly refining in advance and the benzene reaction, total benzene/ethylene molar ratio is 6.5/1, weight ethylene air speed 0.7 hour
-1, 85.0% benzene is entered by the top of reactor, and conversion of ethylene is 99.86%, and ethylbenzene selectivity is 91.6%, the level the when stability of the dimethylbenzene of generation and impurity equal size and catalyzer all will obviously be better than using with a kind of active catalyst.
Transalkylation reaction carries out in single bed reactor that 6 gram beta-molecular sieve catalyzer are housed, and is 7 in the mol ratio of 280 ℃ of temperature of reaction, reaction pressure 4.0MPa, benzene/many ethylbenzene, total air speed 1.1 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 66.8%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.78%, and xylene content is 330ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.65%, detailed results sees Table 4.
[embodiment 8]
6 gram catalyzer G are filled in above the six bed fixed-bed reactor 3 layers; 6 gram catalyzer H are filled in below the six bed fixed-bed reactor 3 layers.Used dry gas contains free-water 150ppm, H
27000 milligrams/meter of S
3, CO
2(2.5 body) %, C
3 =And C
4 =0.7 (body) % and ethene 18.5% component do not need directly refining in advance and the benzene reaction, total benzene/ethylene molar ratio is 6.5/1, weight ethylene air speed 0.7 hour
-1, 95.0% benzene is entered by the top of reactor, and conversion of ethylene is 99.87%, and ethylbenzene selectivity is 92.3%4.
Transalkylation reaction carries out in single bed reactor that 6 gram beta-molecular sieve catalyzer are housed, and is 7 in the mol ratio of 280 ℃ of temperature of reaction, reaction pressure 4.0MPa, benzene/many ethylbenzene, total air speed 1.2 hours
-1Condition under, once by the time diethylbenzene transformation efficiency be 67.2%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene are as the raw material of transalkylation reaction, according to the material balance data of alkylation and transalkylation, the product ethylbenzene that alkylation and transalkylation reaction are obtained mixes, the purity of measuring ethylbenzene is 99.78%, and xylene content is 337ppm, and ethene generates the overall selectivity of ethylbenzene, be that the ethyl selectivity is 99.63%, detailed results sees Table 4.
Table 4 six bed reactor dry gas alkylated reaction situations
Claims (9)
1. pure ethylene or dry gas and the benzene reaction method of producing ethylbenzene, comprise that with pure ethylene or dry gas and benzene be raw material, in alkylation reactor, carry out alkylated reaction, after reacted effluent was isolated benzene, ethylbenzene, propyl benzene and many ethylbenzene successively, many ethylbenzene entered transalkylation reactor and are converted into ethylbenzene again; It is characterized in that:
Described alkylation reactor is fixed-bed reactor, wherein is mounted with at least one section SiO
2/ Al
2O
3Mol ratio is ZSM-5 molecular sieve catalyst I and at least one section SiO of 50～150
2/ Al
2O
3Mol ratio is 160～300 ZSM-5 molecular sieve catalyst II; Reactant flow flow through the earlier catalyst I and then the catalyst I I that flows through;
Wherein, the operational condition of alkylation reactor is: 300～430 ℃ of temperature of reaction, reaction pressure 0.5～2.8MPa, weight ethylene air speed 0.2～5.0 hour
-1, total benzene/ethylene molar ratio 2～10; The pure ethylene of 30～70 weight % or dry gas enter the bed that is mounted with catalyst I, and remaining pure ethylene or dry gas enter the bed that is mounted with catalyst I I; The benzene of 80～100 weight % enters first section bed that catalyst I is housed by reactor head, remaining benzene segmentation enters following each section beds, with control every section beds temperature in and reactor head logistics temperature in differ be no more than ± 5 ℃.
2. the method that ethylbenzene is produced in pure ethylene according to claim 1 or dry gas and benzene reaction is characterized in that in the alkylation reactor SiO of catalyst I
2/ Al
2O
3Mol ratio is 60～140, the SiO of catalyst I I
2/ Al
2O
3Mol ratio is 170～280.
3. pure ethylene according to claim 2 or dry gas and benzene react the method for producing ethylbenzene, it is characterized in that the SiO of catalyst I
2/ Al
2O
3Mol ratio is 80～120, the SiO of catalyst I I
2/ Al
2O
3Mol ratio is 180～250.
4. the method that ethylbenzene is produced in pure ethylene according to claim 1 or dry gas and benzene reaction, 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.
5. the method that ethylbenzene is produced in pure ethylene according to claim 1 or dry gas and benzene reaction is characterized in that described alkylation reactor is divided into 4 or 6 layers, and catalyst I is loaded superincumbent 2 or 3 layers, and catalyst I I is seated in following 2 or 3 layers.
6. the method that ethylbenzene is produced in pure ethylene according to claim 1 or dry gas and benzene reaction 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 can react with benzene.
7. the method that ethylbenzene is produced in pure ethylene according to claim 1 or dry gas and benzene reaction is characterized in that transalkylation catalyst is selected from beta-molecular sieve or Y zeolite.
8. the method that ethylbenzene is produced in pure ethylene according to claim 1 or dry gas and benzene reaction, it is characterized in that transalkylation reaction is to carry out under liquid-phase condition, its operational condition is: 120～320 ℃ of temperature of reaction, reaction pressure 2.0～5.0MPa, the mol ratio 2～25 of benzene/many ethylbenzene, total air speed 0.5～6.0 hour
-1
9. the method that ethylbenzene is produced in the reaction of pure ethylene according to claim 8 or dry gas and benzene is characterized in that the operational condition of transalkylation reaction is: the mol ratio of 160～280 ℃ of temperature of reaction, reaction pressure 2.8～4.0Mpa, benzene/many ethylbenzene is 5～10, total air speed 0.8～3.0 hour
-1
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Cited By (7)
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| CN103664484A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene through benzene and ethylene gas-phase alkylation |
| CN106946643A (en) * | 2017-03-02 | 2017-07-14 | 中国科学院大连化学物理研究所 | A kind of method for improving ethene and benzene liquid phase alkylation reaction performance |
| CN106944129A (en) * | 2017-03-07 | 2017-07-14 | 中国科学院大连化学物理研究所 | Preparation method for dry gas and the molecular sieves of 11@Silicalite of benzene alkylation reaction nucleocapsid ZSM 2 |
| CN109351289A (en) * | 2018-10-18 | 2019-02-19 | 中石化广州工程有限公司 | A method of control alkylation reactor bed temperature rise |
| CN111514928A (en) * | 2020-04-29 | 2020-08-11 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing ethylbenzene from synthesis gas and benzene by one-step method |
| CN112675903A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Catalyst system and improved method for producing ethylbenzene by liquid phase alkylation of benzene and ethylene |
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| CN103664484A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene through benzene and ethylene gas-phase alkylation |
| CN103664484B (en) * | 2012-09-05 | 2016-04-06 | 中国石油化工股份有限公司 | The method of benzene and ethene gas phase hydrocarbonylation ethylbenzene |
| CN106946643A (en) * | 2017-03-02 | 2017-07-14 | 中国科学院大连化学物理研究所 | A kind of method for improving ethene and benzene liquid phase alkylation reaction performance |
| CN106946643B (en) * | 2017-03-02 | 2019-11-08 | 中国科学院大连化学物理研究所 | A method of improving ethylene and benzene liquid phase alkylation reaction performance |
| CN106944129A (en) * | 2017-03-07 | 2017-07-14 | 中国科学院大连化学物理研究所 | Preparation method for dry gas and the molecular sieves of 11@Silicalite of benzene alkylation reaction nucleocapsid ZSM 2 |
| CN109351289A (en) * | 2018-10-18 | 2019-02-19 | 中石化广州工程有限公司 | A method of control alkylation reactor bed temperature rise |
| CN112675903A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Catalyst system and improved method for producing ethylbenzene by liquid phase alkylation of benzene and ethylene |
| CN111514928A (en) * | 2020-04-29 | 2020-08-11 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing ethylbenzene from synthesis gas and benzene by one-step method |
| CN111514928B (en) * | 2020-04-29 | 2022-09-20 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing ethylbenzene from synthesis gas and benzene by one-step method |
| CN114426455A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Benzene and ethylene alkylation reaction |
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