CN102276412B - Method for producing ethylbenzene from ethanol and benzene - Google Patents
Method for producing ethylbenzene from ethanol and benzene Download PDFInfo
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Abstract
The invention relates to a method for producing ethylbenzene from ethanol and benzene. The method is used for mainly solving the problem that a method for producing the ethylbenzene from the ethanol and the benzene does not exist in the prior art. The problem is well solved by adopting the technical scheme as follows: the ethanol and the benzene are adopted as raw materials; the gas phase alkylation reaction is carried out in an alkylation reactor; after benzene, ethylbenzene and poly-ethylbenzene are sequentially separated from the effluence obtained after reacting, the poly-ethylbenzene enters an alkyl transfer reactor to carry out alkyl transfer reaction so as to form the ethylbenzene; the alkylation catalyst is characterized by comprising the following components in percentage by weight: (a) 40-90% of ZSM-5 molecular sieve with the silicon-to-aluminium mol ratio SiO2/Al2O3 of 30-400 and the grain diameter of 5-350nm; (b) 9-59% of binder alumina or silica; and (c) 0.1-10% of rare-earth oxide; and, before being used, the catalyst is treated through high-temperature steam and phosphoric acid. The method can be applied in the industrial production for producing the ethylbenzene from the ethanol and the benzene.
Description
Technical field
The present invention relates to a kind of ethanol and benzene and produce the method for ethylbenzene.
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, mainly contains traditional A1C13 liquid-phase alkylation method and the large class of molecular sieve alkylation process two, and wherein molecular sieve alkylation production technique has obtained very ten-strike.The eighties in 20th century, Mobil and Badger company have successfully released molecular sieve producing ethyl benzene through alkylation in gas phase technique, this process using ZSM-5 zeolite is catalyzer, have the simple and heat energy recovery rate advantages of higher of corrosion-free, pollution-free, flow process, US Patent No. 3751504, US3751506, US4016218 and US4547605 are all described in detail this.Early 1990s, Lummus and Uop Inc. have released molecular sieve preparing ethylbenzene by liquid phase alkylation technique, and this process using β and y-type zeolite are catalyzer, have that temperature of reaction is low, processing ease and an advantage such as by product is few.US4891458, US5227558 and ZL02151177.2 are all described in detail this.
As can be seen here, be no matter that traditional AiCl3 liquid-phase alkylation method or molecular sieve alkylation process all adopt that to take ethene and benzene be raw material.Along with socioeconomic, grow continuously and fast, people are to producing the demand expanding day of basic raw material one oil of ethene, cause oil to be the gesture of petering out.Along with the growing tension of world petroleum resource and the energy, people on the one hand advocate energetically and encourage frugality resource and the energy, actively seek and explore the utilization of renewable resources on the other hand.Biomass ethanol is green renewable raw materials, and along with continuous progress and the maturation of biology ethanol technology processed, the price of ethanol is expected to significantly decline.Therefore, adopt ethanol to substitute ethene operational path direct and benzene alkylation reaction production ethylbenzene and there is stronger competitive power.But the gordian technique of this operational path is catalyzer and Technology.The catalyzer of preparation not only will meet the needs of industrial production long-term operation, to there be longer regeneration period and work-ing life, and guaranteeing that on the basic basis all transforming of ethanol, catalyzer will have good selectivity, reduces the generation of the impurity such as dimethylbenzene as far as possible; It is simple that the technique adopting is not only wanted, and will give full play to the performance of catalyzer, reduces energy consumption and the material consumption of device, improves the ethylbenzene yield of device.At present, there is not yet relevant report both domestic and external.
Summary of the invention
Technical problem to be solved by this invention is the problem that prior art there is no the method for ethanol and benzene production ethylbenzene, provides a kind of new ethanol and benzene to produce the method for ethylbenzene.The method is usingd ethanol and is substituted ethene as alkylating agent directly and the benzene generation ethylbenzene that reacts, do not need to carry out the unit equipment of ethanol dehydration reaction, there is technical process simple, comprehensive energy consumption is low, plant investment expense greatly reduces, ethanol conversion is high, and ethyl selectivity is high, and the good feature of catalyst stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ethanol and benzene are produced the method for ethylbenzene, take ethanol and benzene as raw material, in alkylation reactor, carry out vapor phase alkylation, reacted effluent is isolated after benzene, ethylbenzene and many ethylbenzene successively, and many ethylbenzene enters transalkylation reactor to carry out transalkylation reaction and be converted into ethylbenzene; Wherein said alkylation catalyst, contains following component by weight percentage:
A) 40～90% silica alumina ratio SiO
2/ A1
2o
3be 30～400, crystal grain diameter is the ZSM-5 molecular sieve of 5～350 nanometers;
B) 9～59% binding agent aluminum oxide or silicon-dioxide;
C) 0.1～10% rare-earth oxide;
Described catalyzer is processed with water vapour and phosphoric acid successively, and then drying, roasting obtain required finished product; Wherein steam treatment condition is normal pressure, 400～800 ℃ of temperature, steam treatment 1～20 hour; Phosphoric acid treatment condition are for processing 1～20 hour at 5～95 ℃ of temperature with the phosphoric acid solution of concentration 0.05～15.0 mol/L, and the weight ratio of phosphoric acid solution and catalyzer is 1～20.
In technique scheme, the operational condition preferred version of alkylation reactor is: 300～460 ℃ of temperature of reaction, reaction pressure 0.5～2.8MPa, ethanol weight space velocity 0.1～5.0 hour
-1, benzene/ethanol mol ratio 2～10; More preferably scheme is: 380～420 ℃ of temperature of reaction, reaction pressure 0.8～1.6MPa, ethanol weight space velocity 0.2～1.5 hour
-1, benzene/ethanol mol ratio 5～8.Transalkylation catalyst preferred version is for being selected from ZSM-5, β or Y zeolite catalyzer.When transalkylation reaction carries out under gas phase condition, employing ZSM-5 molecular sieve is catalyzer, and the operational condition preferred version of transalkylation reactor is: 400～460 ℃ of temperature of reaction, reaction pressure 0.3～1.2MPa, the mol ratio 1～20 of benzene/many ethylbenzene, total liquid phase air speed 15～40 hours
-1; More preferably scheme is: the mol ratio 2～5 of 430～450 ℃ of temperature of reaction, reaction pressure 0.5～0.8MPa, benzene/many ethylbenzene, total liquid phase air speed 20～35 hours
-1.When transalkylation reaction carries out under liquid-phase condition, adopt beta-molecular sieve or Y zeolite catalyzer, the operational condition preferred version of transalkylation reactor is: 120～320 ℃ of temperature of reaction, reaction pressure 2.0～5.0MPa, the mol ratio 2～25 of benzene/many ethylbenzene, total liquid phase air speed 0.5～6.0 hour
-1; More preferably scheme is: the mol ratio of 160～280 ℃ of temperature of reaction, reaction pressure 2.8～4.0MPa, benzene/many ethylbenzene is 5～10, total liquid phase air speed 0.8～3.0 hour
-1.The crystal grain diameter preferable range of ZSM-5 molecular sieve is 10～250 nanometers, and more preferably scope is 20～200 nanometers.ZSM-5 molecular sieve silica alumina ratio SiO
2/ A1
2o
3preferable range is 50～200.The consumption preferable range of ZSM-5 molecular sieve is 55～85% by weight percentage, and the consumption preferable range of binding agent is 14～44%, and the consumption preferable range of rare-earth oxide is 0.1～2.0%.Described rare-earth oxide preferred version is for being selected from lanthanum trioxide, cerium oxide or Praseodymium trioxide, and more preferably scheme is for being selected from lanthanum trioxide.Steam treatment condition optimization scheme is normal pressure, 480～650 ℃ of temperature, steam treatment 3～10 hours.Phosphoric acid treatment condition preferred version is for being that the phosphoric acid solution of 0.1～2.5 mol/L is processed 3～16 hours at 30～95 ℃ of temperature by concentration, and the weight ratio of phosphoric acid solution and catalyzer is 2～10.
Ethanol described in the present invention, can be the ethanol of 95 % by weight, can be also dehydrated alcohol.
The alkylation catalyst using in the present invention is prepared in accordance with the following methods:
1) by silica alumina ratio SiO
2/ A1
2o
3the ZSM-5 molecular sieve that be 30～400, crystal grain diameter is 5～350 nanometers well known to a person skilled in the art that under condition, hydrochloric acid exchange, washing, oven dry and roasting obtain HZSM-5 molecular sieve.
2) molecular sieve carried rare earth oxide.The rare 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 ℃, the weight ratio of rare earth salt aqueous solution and HZSM-5 molecular sieve is 0.5～10, then oven dry, roasting, obtains the HZSM-5 molecular sieve containing rare earth.Immersion condition preferred version is that rare earth salt aqueous solution concentration is 0.05～1.0 mol/L, and the weight ratio of rare earth salt aqueous solution and HZSM-5 molecular sieve is 1～5, and dipping temperature is 20～40 ℃, and dipping time is 2～10 hours.
3) shaping of catalyst.By step 2) prepare containing HZSM-5 molecular sieve and aluminum oxide or the silicon sol moulding of rare earth, extrusion becomes the bar shaped catalyst of 1.8 millimeters of Φ.Above-mentioned catalyzer is dried and 550 ℃ of roastings in 4 hours through 110 ℃ for 10 hours again.
4) steam treatment.Preformed catalyst is through 400～800 ℃ of steam treatment 1～20 hour, to improve the hydrothermal stability of catalyzer.
5) phosphoric acid is processed.Catalyzer, after steam treatment, is that the phosphoric acid solution of 0.05～15.0 mol/L is acid treatment 1～20 hour at 5～95 ℃ in temperature by concentration, and the weight ratio of phosphoric acid solution and catalyzer is 1～20.After acid treatment, maturing temperature is 450～650 ℃, and roasting time is 1～10 hour.
In the catalytic reaction process of benzene and ethanol vapor phase alkylation ethylbenzene processed, first there is dehydration reaction and generate ethene and water in ethanol under the effect of catalyzer; Then there is alkylated reaction generation ethylbenzene in ethene and benzene under the effect of same catalyzer.Therefore, in reaction process, can produce a large amount of water, water can produce adverse influence to the activity stability of catalyzer under reaction conditions.In the present invention, adopting high-temperature vapor to process is exactly in order to improve the hydrothermal stability of catalyzer, improves the water repelling property of catalyzer under reaction conditions.In the present invention, adopting rare-earth element modified is also in order to improve hydrothermal stability and the selectivity of catalyzer, due to the stabilization of rare earth element to framework of molecular sieve aluminium, delay aluminium atom and from skeleton, come off under high-temperature vapor reaction conditions, can keep for a long time the acidity-chain carrier of catalyzer.In the present invention, use phosphoric acid solution to process catalyzer, on the one hand can be to the Acidity of molecular sieve catalyst, B acid, L is sour and certain regulating effect is played in the distribution of strong and weak acid, increases the total amount of B acid, reduces sour intensity.Can remove on the other hand amorphous substance in molecular sieve pore passage or remove from framework of molecular sieve the materials such as non-framework aluminum that get off, play the modification to molecular sieve pore passage; Meanwhile, can further increase the bonding force of alumina key in molecular sieve, thereby suppress the generation of framework of molecular sieve dealuminzation, improve the activity stability of catalyzer, reach the object in extending catalyst regeneration period and work-ing life.
Use the inventive method, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, ethanol weight space velocity (WHVS) 0.8 hour
-1, under the condition of benzene/ethanol mol ratio 6.5, carrying out alkylated reaction, ethanol conversion can reach 99.8%, and ethyl selectivity can reach 99.3%; Many ethylbenzene that alkylation produces, after transalkylation reaction, have improved the ethylbenzene yield of production equipment, and in product ethylbenzene, xylene content is below 800ppm, and the catalyst regeneration cycle has reached half a year, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
200 grams of silica alumina ratio SiO
2/ A1
2o
3be 100, crystal grain diameter is 2 liters 85 ℃ exchanges of the hydrochloric acid of 0.1 mol/L three times for ZSM-5 molecular sieve of 200 nanometers, with deionized water wash to without chlorine root, 110 ℃ of oven dry, more standby after 4 hours 580 ℃ of roastings.
The lanthanum nitrate aqueous solution of 20 grams and 35 milliliter 0.5 mol/L of above-mentioned molecular sieve is at room temperature flooded 4 hours, then 110 ℃ of oven dry, then 550 ℃ of roastings 2 hours.Itself 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.At 110 ℃, dry after 10 hours, then 550 ℃ of roastings 4 hours, the catalyzer obtaining was containing La
2o
32.0 % by weight.
Above-mentioned catalyzer with water steam is processed 2 hours 580 ℃ of normal pressures, with the phosphoric acid solution of 1.5 mol/L, at 50 ℃, process 5 hours again, the ratio of the weight of phosphoric acid solution and catalyzer is 3, dry after roasting 3 hours at 500 ℃, obtain finished product alkylation catalyst.
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 99.5%, ethylbenzene selectivity 91.5%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 80 ZSM-5 molecular sieve catalyzer, under gas phase condition, carry out.In the mol ratio of 430 ℃ of temperature of reaction, reaction pressure 0.6MPa, benzene/many ethylbenzene, be 3, total liquid phase air speed 30 hours
-1condition under, once by time diethylbenzene transformation efficiency be 57.8%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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 99.81%, xylene content is 780ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 99.60%.Detailed results is in Table 1.
[embodiment 2]
With [embodiment 1] identical preparation process, change the content of Rare Earth Lanthanum, the alkylation catalyst obtaining is containing La
2o
31.0 % by weight.
Pack above-mentioned catalyzer into alkylation reactor, 420 ℃ of temperature of reaction, reaction pressure 0.8MPa, benzene/ethanol 6.0 (moles/mole), ethanol weight space velocity 1.0 hours
-1condition under, ethanol conversion 99.7%, ethylbenzene selectivity 90.9%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 60 ZSM-5 molecular sieve catalyzer, under gas phase condition, carry out.In the mol ratio of 450 ℃ of temperature of reaction, reaction pressure 0.8MPa, benzene/many ethylbenzene, be 5, total liquid phase air speed 20 hours
-1condition under, once by time diethylbenzene transformation efficiency be 58.3%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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%, xylene content is 760ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 99.50%.Detailed results is in Table 1.
[embodiment 3]
With [embodiment 1] identical preparation process, change the content of Rare Earth Lanthanum, the alkylation catalyst obtaining is containing La
2o
30.5 % by weight.
Pack above-mentioned catalyzer into alkylation reactor, 380 ℃ of temperature of reaction, reaction pressure 1.6MPa, benzene/ethanol 8.0 (moles/mole), ethanol weight space velocity 1.5 hours
-1condition under, ethanol conversion 99.4%, ethylbenzene selectivity 92.6%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 150 ZSM-5 molecular sieve catalyzer, under gas phase condition, carry out.In the mol ratio of 440 ℃ of temperature of reaction, reaction pressure 0.7MPa, benzene/many ethylbenzene, be 4, total liquid phase air speed 35 hours
-1condition under, once by time diethylbenzene transformation efficiency be 55.9%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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%, xylene content is 720ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 99.40%.Detailed results is in Table 1.
[embodiment 4]
The silica alumina ratio SiO of alkylation catalyst molecular sieve
2/ A1
2o
3be 50, crystal grain diameter is 20 nanometers, La
2o
3content be 0.5%, catalyzer is containing the molecular sieve of 65% (weight), water vapour is processed 3 hours at 510 ℃, then at 85 ℃, processes 3 hours with the phosphoric acid solution of 1.5 mol/L, other preparation process are [embodiment 1] together.
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 99.8%, ethylbenzene selectivity 90.7%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 25 beta-molecular sieve catalyzer, under liquid-phase condition, carry out.In the mol ratio of 230 ℃ of temperature of reaction, reaction pressure 3.8MPa, benzene/many ethylbenzene, be 8, total liquid phase air speed 1.0 hours
-1condition under, once by time diethylbenzene transformation efficiency be 68.1%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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 99.89%, xylene content is 650ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 98.50%.Detailed results is in Table 1.
[embodiment 5]
Change the silica alumina ratio SiO of alkylation catalyst molecular sieve
2/ A1
2o
3be 150, other are with [embodiment 4].
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 98.7%, ethylbenzene selectivity 91.2%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 30 beta-molecular sieve catalyzer, under liquid-phase condition, carry out.In the mol ratio of 260 ℃ of temperature of reaction, reaction pressure 4.0MPa, benzene/many ethylbenzene, be 8, total liquid phase air speed 1.5 hours
-1condition under, once by time diethylbenzene transformation efficiency be 65.2%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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%, xylene content is 630ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 99.70%.Detailed results is in Table 1.
[embodiment 6]
Change the silica alumina ratio SiO of alkylation catalyst molecular sieve
2/ A1
2o
3be 200, other are with [embodiment 4].
Pack above-mentioned catalyzer into alkylation reactor, 360 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 97.3%, ethylbenzene selectivity 92.5%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 20 beta-molecular sieve catalyzer, under liquid-phase condition, carry out.In the mol ratio of 260 ℃ of temperature of reaction, reaction pressure 4.0MPa, benzene/many ethylbenzene, be 8, total liquid phase air speed 1.2 hours
-1condition under, once by 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 is as the raw material of transalkylation reaction, and 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 99.86%, xylene content is 650ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 99.80%.Detailed results is in Table 1.
[embodiment 7]
The silica alumina ratio SiO of alkylation catalyst molecular sieve
2/ A1
2o
3be 100, crystal grain diameter is 150 nanometers, La
2o
3content be 0.5%, catalyzer is containing the molecular sieve of 55% (weight), water vapour is processed 5 hours at 480 ℃, then at 95 ℃, processes 2 hours with the phosphoric acid solution of 1.5 mol/L, other preparation process are [embodiment 1] together.
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 99.5%, ethylbenzene selectivity 90.5%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 5 Y molecular sieve catalyzer, in the mol ratio of 170 ℃ of temperature of reaction, reaction pressure 3.0MPa, benzene/many ethylbenzene, be 8, total liquid phase air speed 1.0 hours
-1condition under, once by 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 is as the raw material of transalkylation reaction, and 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%, xylene content is 690ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 99.50%.Detailed results is in Table 1.
[embodiment 8]
Alkylation catalyst is containing the molecular sieve of 60% (weight), and other preparation process are with [embodiment 7].
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 99.6%, ethylbenzene selectivity 91.1%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 7 Y molecular sieve catalyzer, in the mol ratio of 180 ℃ of temperature of reaction, reaction pressure 3.3MPa, benzene/many ethylbenzene, be 8, total liquid phase air speed 1.0 hours
-1condition under, once by time diethylbenzene transformation efficiency be 84.8%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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 99.74%, xylene content is 700ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 99.40%.Detailed results is in Table 1.
[embodiment 9]
Alkylation catalyst is containing the molecular sieve of 75% (weight), and other preparation process are with [embodiment 7].
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 99.7%, ethylbenzene selectivity 91.8%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 5 Y molecular sieve catalyzer, in the mol ratio of 190 ℃ of temperature of reaction, reaction pressure 3.2MPa, benzene/many ethylbenzene, be 7, total liquid phase air speed 1.5 hours
-1condition under, once by time diethylbenzene transformation efficiency be 80.1%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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%, xylene content is 710ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 99.40%.Detailed results is in Table 1.
[embodiment 10]
Alkylation catalyst is containing the molecular sieve of 85% (weight), and other preparation process are with [embodiment 7].
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 99.8%, ethylbenzene selectivity 90.6%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 6 Y molecular sieve catalyzer, in the mol ratio of 220 ℃ of temperature of reaction, reaction pressure 3.4MPa, benzene/many ethylbenzene, be 7, total liquid phase air speed 2.0 hours
-1condition under, once by time diethylbenzene transformation efficiency be 78.6%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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 99.75%, xylene content is 690ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 99.20%.Detailed results is in Table 1.
[comparative example 1]
The HZSM-5 zeolite matrix identical with [embodiment 1] made catalyzer, but processes without lanthanum nitrate aqueous solution dipping, steam treatment and phosphoric acid, and all the other are all identical with [embodiment 1].
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 100.0%, ethylbenzene selectivity 86.7%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 80 ZSM-5 molecular sieve catalyzer, in the condition of gas phase, carry out.In the mol ratio of 435 ℃ of temperature of reaction, reaction pressure 0.7MPa, benzene/many ethylbenzene, be 3, total liquid phase air speed 33.0 hours
-1condition under, once by time diethylbenzene transformation efficiency be 57.9%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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 97.22%, xylene content is 1260ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 98.1%.Detailed results is in Table 1.
[comparative example 2]
The HZSM-5 molecular sieve identical with [embodiment 1] floods through 0.5 mol/L lanthanum nitrate aqueous solution, and the catalyzer obtaining is containing La
2o
32.0 % by weight, but not steam treatment and phosphoric acid processing, all the other are all identical with [embodiment 1].
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 99.3%, ethylbenzene selectivity 88.2%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 25 beta-molecular sieve catalyzer, under liquid-phase condition, carry out.In the mol ratio of 260 ℃ of temperature of reaction, reaction pressure 4.0MPa, benzene/many ethylbenzene, be 8, total liquid phase air speed 1.0 hours
-1condition under, once by time diethylbenzene transformation efficiency be 67.5%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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 99.06%, xylene content is 890ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 97.6%.Detailed results is in Table 1.
[comparative example 3]
The HZSM-5 zeolite matrix identical with [embodiment 1] made catalyzer, process, but without lanthanum nitrate aqueous solution dipping, all the other is all identical with [embodiment 1] through steam treatment and phosphoric acid.
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 99.9%, ethylbenzene selectivity 89.3%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 5 Y molecular sieve catalyzer, in the mol ratio of 180 ℃ of temperature of reaction, reaction pressure 3.2MPa, benzene/many ethylbenzene, be 8, total liquid phase air speed 1.0 hours
-1condition under, once by time diethylbenzene transformation efficiency be 81.5%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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 99.25%, xylene content is 850ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 98.5%.Detailed results is in Table 1.
[comparative example 4]
Identical with [embodiment 1], alkylation catalyst is containing La
2o
32.0 % by weight.Just ZSM-5 molecular sieve crystal grain diameter is 2 nanometers.
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 99.8%, ethylbenzene selectivity 85.3%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 100 ZSM-5 molecular sieve catalyzer, in the condition of gas phase, carry out.In the mol ratio of 435 ℃ of temperature of reaction, reaction pressure 0.7MPa, benzene/many ethylbenzene, be 3, total liquid phase air speed 33.0 hours
-1condition under, once by time diethylbenzene transformation efficiency be 56.3%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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 98.53%, xylene content is 1017ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 97.5%.Detailed results is in Table 1.
[comparative example 5]
Identical with [embodiment 1], catalyzer is containing La
2o
32.0 % by weight.Just ZSM-5 molecular sieve crystal grain diameter is 500 nanometers.
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 98.3%, ethylbenzene selectivity 87.1%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 70 ZSM-5 molecular sieve catalyzer, in the condition of gas phase, carry out.In the mol ratio of 435 ℃ of temperature of reaction, reaction pressure 0.7Mpa, benzene/many ethylbenzene, be 3, total liquid phase air speed 33.0 hours
-1condition under, once by time diethylbenzene transformation efficiency be 59.2%.Reaction product is through separation and recovery system, isolate benzene, ethylbenzene, many ethylbenzene and heavy constituent, many ethylbenzene is as the raw material of transalkylation reaction, and 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 99.76%, xylene content is 893ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 99.7%.Detailed results is in Table 1.
[embodiment 11]
Identical with [embodiment 1], just alkylation catalyst is containing Ce
2o
32.0 % by weight.
Pack above-mentioned catalyzer into alkylation reactor, 390 ℃ of temperature of reaction, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1condition under, ethanol conversion 97.2%, ethylbenzene selectivity 87.5%.
Transalkylation reaction adopts SiO
2/ A1
2o
3be 28 beta-molecular sieve catalyzer, under liquid-phase condition, carry out.In the mol ratio of 260 ℃ of temperature of reaction, reaction pressure 4.0MPa, benzene/many ethylbenzene, be 8, total liquid phase air speed 1.5 hours
-1condition under, once by 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 is as the raw material of transalkylation reaction, and 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 99.15%, xylene content is 580ppm, and ethanol generates the overall selectivity of ethylbenzene, and ethyl selectivity is 97.9%.Detailed results is in Table 1.
Table 1
Visible catalyzer ethanol conversion of the present invention reaches 99.8%, and selectivity is good, and xylene content is below 800ppm.
[embodiment 12]
On the pressurization static bed reaction unit of continuous flow, the activity stability of the alkylation catalyst that evaluation [embodiment 1～11], [comparative example 1～5] obtain, the i.e. regeneration period of catalyzer.Reaction conditions: 400 ℃ of temperature of reaction, reaction pressure 1.0MPa, benzene/ethanol=1.0 (moles/mole), ethanol weight space velocity (WHSV)=3.0 hour
-1, the reaction times is 100 hours.Reaction result is in Table 2.
Table 2
Visible catalyzer of the present invention has minimum deactivation rate, shows optimum activity stability, estimates that the regeneration period of catalyzer is greater than half a year, can meet industrial requirement completely.
Claims (8)
1. an ethanol and benzene are produced the method for ethylbenzene, take ethanol and benzene as raw material, in alkylation reactor, carry out vapor phase alkylation, reacted effluent is isolated after benzene, ethylbenzene and many ethylbenzene successively, and many ethylbenzene enters transalkylation reactor to carry out transalkylation reaction and be converted into ethylbenzene; Wherein said alkylation catalyst, contains following component by weight percentage:
A) 40～90% silica alumina ratio SiO
2/ A1
2o
3be 30～400, crystal grain diameter is the ZSM-5 molecular sieve of 5～350 nanometers;
B) 9～59% binding agent aluminum oxide or silicon-dioxide;
C) 0.1～10% rare-earth oxide;
Described catalyzer is processed with water vapour and phosphoric acid successively, and then drying, roasting obtain required finished product; Wherein steam treatment condition is normal pressure, 400～800 ℃ of temperature, steam treatment 1～20 hour; Phosphoric acid treatment condition are for processing 1～20 hour at 5～95 ℃ of temperature with the phosphoric acid solution of concentration 0.05～15.0 mol/L, and the weight ratio of phosphoric acid solution and catalyzer is 1～20; The operational condition of alkylation reactor is: 300～460 ℃ of temperature of reaction, reaction pressure 0.5～2.8MPa, ethanol weight space velocity 0.1～5.0 hour
-1, benzene/ethanol mol ratio 2～10; Transalkylation catalyst is selected from ZSM-5, β or Y zeolite catalyzer; When transalkylation reaction carries out under gas phase condition, the operational condition of transalkylation reactor is: 400～460 ℃ of temperature of reaction, reaction pressure 0.3～1.2MPa, the mol ratio 1～20 of benzene/many ethylbenzene, total liquid phase air speed 15～40 hours
-1; When transalkylation reaction carries out under liquid-phase condition, the operational condition of transalkylation reactor is: 120～320 ℃ of temperature of reaction, reaction pressure 2.0～5.0MPa, the mol ratio 2～25 of benzene/many ethylbenzene, total liquid phase air speed 0.5～6.0 hour
-1.
2. the method that ethanol and benzene are produced ethylbenzene according to claim 1, is characterized in that the operational condition of alkylation reactor is: 380～420 ℃ of temperature of reaction, reaction pressure 0.8～1.6MPa, ethanol weight space velocity 0.2～1.5 hour
-1, benzene/ethanol mol ratio 5～8; When transalkylation reaction carries out under gas phase condition, the operational condition of transalkylation reactor is: the mol ratio 2～5 of 430～450 ℃ of temperature of reaction, reaction pressure 0.5～0.8MPa, benzene/many ethylbenzene, total liquid phase air speed 20～35 hours
-1; When transalkylation reaction carries out under liquid-phase condition, the operational condition of transalkylation reactor is: the mol ratio of 160～280 ℃ of temperature of reaction, reaction pressure 2.8～4.0MPa, benzene/many ethylbenzene is 5～10, total liquid phase air speed 0.8～3.0 hour
-1.
3. the method that ethanol and benzene are produced ethylbenzene according to claim 1, the crystal grain diameter that it is characterized in that ZSM-5 molecular sieve is 10～250 nanometers.
4. the method that ethanol and benzene are produced ethylbenzene according to claim 3, the crystal grain diameter that it is characterized in that ZSM-5 molecular sieve is 20～200 nanometers.
5. the method that ethanol and benzene are produced ethylbenzene according to claim 1, is characterized in that ZSM-5 molecular sieve silica alumina ratio SiO
2/ A1
2o
3be 50～200; The consumption of ZSM-5 molecular sieve is 55～85% by weight percentage, and the consumption of binding agent is 14～44%, and the consumption of rare-earth oxide is 0.1～2.0%.
6. the method that ethanol and benzene are produced ethylbenzene according to claim 1, is characterized in that described rare-earth oxide is selected from lanthanum trioxide, cerium oxide or Praseodymium trioxide.
7. the method that ethanol and benzene are produced ethylbenzene according to claim 5, is characterized in that described rare-earth oxide is selected from lanthanum trioxide.
8. the method that ethanol and benzene are produced ethylbenzene according to claim 1, is characterized in that steam treatment condition is normal pressure, 480～650 ℃ of temperature, steam treatment 3～10 hours; Phosphoric acid treatment condition are for processing 3～16 hours at 30～95 ℃ of temperature with the phosphoric acid solution of concentration 0.1～2.5 mol/L, and the weight ratio of phosphoric acid solution and catalyzer is 2～10.
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| CN112844453B (en) * | 2019-11-12 | 2023-07-28 | 惠生工程（中国）有限公司 | ZSM-5 catalyst and preparation method and application thereof |
| CN115475653B (en) * | 2021-06-16 | 2024-03-29 | 中国石油化工股份有限公司 | Benzene and ethanol gas phase alkylation catalyst and preparation method and application thereof |
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| CN101085711A (en) * | 2007-07-13 | 2007-12-12 | 花尚元 | Method for synthesizing ethyl benzene and diethyl benzene |
| CN101450882A (en) * | 2007-12-06 | 2009-06-10 | 上海戊正工程技术有限公司 | Technique for producing ethyl benzene |
| CN101450888A (en) * | 2007-12-06 | 2009-06-10 | 上海戊正工程技术有限公司 | Method for preparing catalyst for synthesizing ethyl benzene |
| CN101618335A (en) * | 2009-08-06 | 2010-01-06 | 上海卓悦化工科技有限公司 | Method for preparing catalyst for compounding p-diethylbenzene by alkylation reaction of ethylbenzene and ethane or alcohol |
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| CN101085711A (en) * | 2007-07-13 | 2007-12-12 | 花尚元 | Method for synthesizing ethyl benzene and diethyl benzene |
| CN101450882A (en) * | 2007-12-06 | 2009-06-10 | 上海戊正工程技术有限公司 | Technique for producing ethyl benzene |
| CN101450888A (en) * | 2007-12-06 | 2009-06-10 | 上海戊正工程技术有限公司 | Method for preparing catalyst for synthesizing ethyl benzene |
| CN101618335A (en) * | 2009-08-06 | 2010-01-06 | 上海卓悦化工科技有限公司 | Method for preparing catalyst for compounding p-diethylbenzene by alkylation reaction of ethylbenzene and ethane or alcohol |
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