CN1285548C - Process for producing alkylbenzene - Google Patents
Process for producing alkylbenzene Download PDFInfo
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- CN1285548C CN1285548C CN 200410024736 CN200410024736A CN1285548C CN 1285548 C CN1285548 C CN 1285548C CN 200410024736 CN200410024736 CN 200410024736 CN 200410024736 A CN200410024736 A CN 200410024736A CN 1285548 C CN1285548 C CN 1285548C
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- benzene
- reaction
- alkylbenzene
- reactor
- alkene
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- 150000004996 alkyl benzenes Chemical class 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title abstract description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 148
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 150000001336 alkenes Chemical class 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 20
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 20
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- 238000002447 crystallographic data Methods 0.000 claims description 6
- 230000011218 segmentation Effects 0.000 claims description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 abstract description 31
- 230000029936 alkylation Effects 0.000 abstract description 29
- 239000000047 product Substances 0.000 abstract description 19
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 60
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 30
- 238000010555 transalkylation reaction Methods 0.000 description 15
- 238000011084 recovery Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000010792 warming Methods 0.000 description 8
- 239000006004 Quartz sand Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- -1 benzene hydrocarbon Chemical class 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000282346 Meles meles Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a production method of alkylbenzene, which mainly solves the problems existing in the prior art of high energy consumption and large circulation. In the present invention, in the existence of catalysts, raw material benzene is wholly or partly added from an alkyl transfer reactor to an alkylation reactor containing at least two segments, and olefin enters the alkylation reactor from the top of the alkylation reactor to react with the mixture of the alkylation reaction products and part of the alkyl transfer products to obtain alkylbenzene; the reaction liquor and the alkyl transfer products partly return to the alkylation reactor in an outside circulation manner. The present invention solves the problems well by adopting the technical scheme of an intermediate heat-exchanger segmented heating technique in each segment of the alkylation reactor, and can be used for the industrial production of alkylbenzene.
Description
Technical field
The present invention relates to the production method of alkylbenzene, particularly beyond the alkylbenzene production method of Recycle design heat-obtaining.
Background technology
Isopropyl benzene in the alkylbenzene, ethylbenzene, long-chain alkyl benzene all are important Organic Chemicals, wherein isopropyl benzene is an important intermediate raw material of producing phenol, acetone, mainly as the cinnamic raw material of preparation, long-chain alkyl benzene then is the main raw material of preparing washing agent to ethylbenzene.
Industrial traditional preparation isopropyl benzene, ethylbenzene and long-chain alkyl benzene all adopt solid phosphoric acid, aluminum chloride or hydrofluoric acid catalyst series, because it is serious to equipment corrosion, the three wastes are many, and along with the raising to environmental requirement, major part is replaced by novel sieve method.Produce the molecular sieve catalyst that alkylbenzene has turned to highly selective at present, comprise the ZSM series of large pore molecular sieve Y, beta, MCM series and mesopore etc.
A kind of method of producing ethylbenzene in industrial achieving success is to carry out vapor phase alkylation with ethene and benzene in the presence of solid acid ZSM-5 molecular sieve catalyst.Write at William R.Moser, Marcel Dekker, Inc. describes the technological process of the gas molecule in space sieve series ethylbenzene of Mobil/Badger in detail in " Catalysis of Organic Reaction " book that 1981 publish.The gas molecule in space sieve method has obtained huge market, but also exposes the high shortcoming of impurity xylene content in the product ethylbenzene.The alkylated reaction of ethylbenzene has the trend that is replaced by molecular sieve liquid-phase alkylation method gradually in recent years, and the characteristics of liquid-phase alkylation method are that the byproduct content that generates is little, operational condition is gentle, the catalyst regeneration cycle is long.
The major part that new isopropyl benzene production equipment adopts is the molecular sieve liquid-phase alkylation method of propylene and benzene.Because its reaction conditions gentleness, propylene conversion height, good product selectivity, pollution-free, no burn into by product polyisopropylbenzene can change isopropyl benzene into by transalkylation makes the isopropyl benzene productive rate up to more than 99%, is each institute of big industrial group company common concern of the world in recent years, an and cleaner technology of development research competitively.
The technical process of normal adopted production isopropyl benzene at present is that raw material propylene and new benzene feedstock of replenishing are passed through the interchanger preheating earlier before adding reactor, the material that reactor comes out enters flash distillation plant, most of recycle benzene is separated, enter depropanizing tower, the steam that then is rich in isopropyl benzene enters the benzene tower, isolates residual benzene at this.Remove a small amount of heavies of by-product in the removal of alkylation reaction then with the clay treatment isopropyl benzene.From the higher aromatics that benzene Tata still comes out, be mainly diisopropylbenzene(DIPB) (DIPB), DIPB reacts the generation isopropyl benzene again in transalkylation workshop section.Document WO 89/10910 and CN1217310C respectively provide a kind of production technique of alkylbenzene, in these two technical literatures, because the catalyzer that adopts can't adapt to low temperature, low benzene hydrocarbon than reaction, therefore there are reactive system working pressure height, internal circulating load is big, the heat of reaction utilization ratio is low, energy consumption is high problem.
Summary of the invention
Technical problem to be solved by this invention is to have the energy consumption height in the conventional art, and the problem that internal circulating load is big provides a kind of production method of new alkylbenzene.This method is used for the alkylbenzene production process and has heat of reaction utilization ratio height, and energy consumption is low, and internal circulating load is little, and throughput is big, transalkylation efficient height, the characteristics that product impurity is few.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of production method of alkylbenzene, with the alkene and the benzene that contain 2～12 carbon is raw material, crystal aluminosilicate is a catalyzer, temperature of reaction is 100～300 ℃, reaction pressure is 1.5～3.8MPa, and benzene/olefin molar ratio is 2～6, and the raw material olefin weight space velocity is 0.1～1.0 hour
-1Under the condition, raw material reacts in fixed-bed reactor and generates the product alkylbenzene, the fixed-bed reactor bed has two sections at least, each section is loading catalyst all, whole or the segmentation adding reactor of benzene feedstock, the alkene segmentation that contains 2～12 carbon adds reactor, and wherein the outer circulation of at least the second section beds product part is to first section bed of reactor, the outer circulation ratio is 0.1～6, and another part product enters subsequent handling; Described crystal aluminosilicate is the zeolite with following XRD diffraction data:
| 2 θ diffraction angle | Diffraction peak intensity (I/I 0×100) |
| 6.5° | 28.8±0.1 |
| 7.2° | 17.3±0.1 |
| 8.8° | 15.4±0.1 |
| 9.7° | 53.8±0.1 |
| 13.5° | 39.4±0.1 |
| 14° | 28.8±0.1 |
| 14.3° | 19.2±0.1 |
| 15.4° | 23.1±0.1 |
| 19.5° | 34.6±0.1 |
| 22.2° | 69.2±0.1 |
| 23.8° | 23.1±0.1 |
| 25.5° | 100±0.1 |
| 26.2° | 65.4±0.1 |
| 27.5° | 46.7±0.1 |
| 31° | 27.9±0.1 |
| 35.8° | 15.4±0.1 |
In the technique scheme, the temperature of reaction preferable range is 120～260 ℃, and the reaction pressure preferable range is 1.7～3.8MPa.
Fixed bed reactor catalyst bed preferred version is for dividing four sections, and outer circulation is 1～4 than preferred version; Preferred version is for adopting intermediate heat segmentation heat-obtaining respectively between each of fixed-bed reactor section bed.The alkene preferred version that contains 2～12 carbon is an ethene, and temperature of reaction is 230～260 ℃, and reaction pressure is 3.0～3.5MPa, and the weight ethylene air speed is 0.2～0.5 hour
-1, benzene/ethylene molar ratio is 2～4; Alkene second preferred version that contains 2～12 carbon is a propylene, and temperature of reaction is 130～160 ℃, and reaction pressure is 2.0～2.5MPa, and the propylene weight air speed is 0.6～1.2 hour
-1, benzene/propylene mol ratio is 2～3.5; Alkene the 3rd preferred version that contains 2～12 carbon is C
4～C
12A kind of in the alkene, temperature of reaction is 140～180 ℃, and reaction pressure is 1.7～2.2MPa, and the alkene weight space velocity is 0.1～0.3 hour
-1, benzene/olefin molar ratio is 4～6.
Alkylation reactor is an insulation fix bed reactor in the technique scheme, benzene feedstock can be recovery benzene or its miscellany of fresh benzene, follow-up workshop section, the all or part of adding transalkylation reactor of benzene feedstock, benzene feedstock can mix first section that enters alkylation reactor with alkene and recycle stock, also can enter the top of each section bed in the alkylation reactor respectively.Raw material olefin is preferably ethene and propylene, can be fresh alkene, also can be recovery alkene or its mixture of follow-up workshop section.The product of alkylation reactor can return the top of each bed that enters alkylation reactor respectively with external circulation mode, but returns first section the top that enters alkylation reactor at least.Recycle design is returned the top of alkylation reactor beyond the product of transalkylation, also can enter the top of each bed respectively, but the recycle stock of first section the top that enters alkylation reactor at least and alkene and alkylate mixes.The ratio of outer circulation is 0.1～6, and preferred version is 1～4, and the reaction hop count of alkylation reactor is preferably four sections.Fresh benzene can partly or entirely be used as the cooling fluid of the middle heat-obtaining of alkylation reactor.
Because the catalyzer that the present invention adopts can not only adapt to lower temperature of reaction, bigger alkene air speed and can adapt to lower benzene hydrocarbon ratio, therefore reduced the consumption of benzene in the material effectively, make the required energy consumption of reaction greatly reduce, the throughput of device is improved, and the vapor volume of consumption reduces.
Because the present invention adopts external circulation process, the outer circulation material has diluted the concentration of alkene effectively, and reaction pressure can be reduced, reduced the thermal insulation warming of bed simultaneously, also strengthen heat transfer in addition, reduced the heat transfer area of interchanger, obtained better technical effect.
The preparation method of crystal silicon-aluminate zeolite with above-mentioned XRD diffraction data is as follows:
With silicon source (silicon sol, water glass etc.), aluminium source (sodium aluminate, Tai-Ace S 150 etc.) and organic ammonium (hexanediamine, hexa-methylene imonium), caustic soda, water according to following mixed evenly after, under the effect of directed agents organic ammonium,, filter, washing, oven dry obtain finished product SHY crystal aluminosilicate in 140～180 ℃ of following crystallization 50～200 hours.Wherein material molar ratio is as follows: (molecular ratio, M refers to organic ammonium)
SiO
2∶Al
2O
3＝20～200
SiO
2∶Na
2O＝100～200
SiO
2∶H
2O＝0.01～0.1
SiO
2∶M＝2～8
The charging capacity of directed agents is 0.1%～10% of a silicon source weight.
Description of drawings
Fig. 1 is a process flow sheet of producing alkylbenzene in the document WO 89/10911.
Fig. 2 is a process flow sheet of producing alkylbenzene among the document CN1217310C.
Fig. 3 is a process flow sheet of the present invention.
Among Fig. 1 or Fig. 2: 1 is alkylation reactor, 2 is transalkylation reactor, 3 is the transalkylation reactor top discharge, 4 is the benzene recovery tower, 5 is the alkylbenzene treating tower, 6 is polyalkylbenzene benzene recovery tower, 7 for the benzene recovery tower ejects material, and 8 for the alkylbenzene treating tower ejects material, and 9 eject material for the polyalkylbenzene recovery tower, 10 is the discharging of polyalkylbenzene recovery tower still, 11 is fresh benzene, and 12,13,14 is raw material olefin, and 15 is the alkylation reactor top discharge, 16 is the alkylation reactor bottom feed, and 17 is alkylation reactor top outer circulation material.
Among Fig. 3: 1 benzene feedstock, 2 benzene recovery towers eject material, 3 benzene recovery towers, 4 cat head light constituents, 5 cut light tower, 6 product alkylbenzenes, 7 alkylbenzene treating towers, 8 alkylbenzene treating tower still dischargings, 9 transalkylation reactors, 10 alkylation reactors, 11 raw material olefins, 12 transalkylated product, 13 cut light tower still dischargings, 14 alkylates, 15 benzene recovery tower still dischargings, 16 transalkylation reactor chargings.
Fig. 3 is process chart of the present invention, enter the first paragraph reaction of alkylation reactor after the product of the raw material olefin of the first conversion zone and the portion of product of alkylation reactor and part transalkylation reactor is mixed, the product of first, second and third section of fresh feed benzene and alkylation reactor carries out making with extra care with the mixed cut light tower that enters of the recovery benzene at benzene recovery tower top after the heat exchange, then enter transalkylation reactor after mixed with the still liquid polyalkylbenzene of alkylbenzene treating column tower reactor and carry out transalkylation reaction, the product of transalkylation reactor returns the top of alkylation reactor, the product of alkylation reactor enters the benzene recovery tower and reclaims benzene, the still liquid of benzene recovery tower tower reactor mainly is that the mixture of alkylbenzene and polyalkylbenzene enters the rectifying of alkylbenzene treating column and goes out the product alkylbenzene, and the still liquid of alkylbenzene treating column enters transalkylation reactor again and carries out transalkylation reaction.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Press the technical process of accompanying drawing 3, getting 20 grams, to have the inertia quartz sand of same particle sizes of preformed catalyst (20～60 order) and equivalent of crystal silicon-aluminate zeolite of above-mentioned XRD diffraction data mixed, make the reaction of propylene and benzene generate isopropyl benzene, reaction solution outlet isopropyl benzene concentration is 45%, and propylene air speed (WHSV) is 0.8 hour
-1, every section 15 ℃ of thermal insulation warming of reaction, 145 ℃ of reactor inlet temperatures, 160 ℃ of temperature outs, reaction propyl group selectivity 99.1%, in the isopropyl benzene n-proplbenzene content less than 350ppm, reaction pressure 2.5MPa.Move 2000 hours altogether, do not observe the activity of such catalysts loss, steam consumption is 0.28 ton of/ton isopropyl benzene.
[embodiment 2]
Press the technical process of accompanying drawing 3, getting 20 grams, to have the inertia quartz sand of same particle sizes of preformed catalyst (20～60 order) and equivalent of crystal silicon-aluminate zeolite of above-mentioned XRD diffraction data mixed, make the reaction of ethene and benzene generate ethylbenzene, reaction solution outlet ethylbenzene concentration is 28%, and ethene air speed (WHSV) is 0.3 hour
-1, every section 17 ℃ of thermal insulation warming of reaction, 233 ℃ of reactor inlet temperatures, 250 ℃ of temperature outs, reaction ethyl selectivity 99.3%, in the ethylbenzene xylene content less than 50ppm, reaction pressure 3.5MPa.Move 2000 hours altogether, do not observe the activity of such catalysts loss, steam consumption is 0.26 ton of/ton ethylbenzene.
[embodiment 3]
Press the technical process of accompanying drawing 3, getting 20 grams, to have the inertia quartz sand of same particle sizes of preformed catalyst (20～60 order) and equivalent of crystal silicon-aluminate zeolite of above-mentioned XRD diffraction data mixed, make the reaction of propylene and benzene generate isopropyl benzene, reaction solution outlet isopropyl benzene concentration is 36%, and propylene air speed (WHSV) is 0.8 hour
-1, every section 15 ℃ of thermal insulation warming of reaction, 145 ℃ of reactor inlet temperatures, 160 ℃ of temperature outs, reaction propyl group selectivity 99.2%, in the isopropyl benzene n-proplbenzene content less than 350ppm, reaction pressure 2.5MPa.Move 2000 hours altogether, do not observe the activity of such catalysts loss, steam consumption is 0.30 ton of/ton isopropyl benzene.
[comparative example 1]
Press the technical process of accompanying drawing 2, the preformed catalyst (20～60 order) of getting 20 gram β zeolites is mixed with the inertia quartz sand of the same particle sizes of equivalent, make the reaction of propylene and benzene generate isopropyl benzene, reaction solution outlet isopropyl benzene concentration is 21%, and propylene air speed (WHSV) is 0.45 hour
-1, every section 30 ℃ of thermal insulation warming of reaction, 180 ℃ of reactor inlet temperatures, 210 ℃ of temperature outs, reaction propyl group selectivity 99.1%, in the isopropyl benzene n-proplbenzene content less than 650ppm, reaction pressure 3.0MPa.Move 1000 hours altogether, do not observe the activity of such catalysts loss, steam consumption is 0.37 ton of/ton isopropyl benzene.
[comparative example 2]
Press the technical process of accompanying drawing 2, the preformed catalyst (20～60 order) of getting 20 gram β zeolites is mixed with the inertia quartz sand of the same particle sizes of equivalent, make the reaction of propylene and benzene generate isopropyl benzene, reaction solution outlet isopropyl benzene concentration is 23%, and propylene air speed (WHSV) is 0.45 hour
-1, every section 12 ℃ of thermal insulation warming of reaction, 180 ℃ of reactor inlet temperatures, 192 ℃ of temperature outs, reaction propyl group selectivity 99.2%, in the isopropyl benzene n-proplbenzene content less than 650ppm, reaction pressure 3.0MPa.Move 1000 hours altogether, do not observe the activity of such catalysts loss, steam consumption is 0.32 ton of/ton isopropyl benzene.
[comparative example 3]
Press the technical process of accompanying drawing 1, the preformed catalyst (20～60 order) of getting 20 gram Y zeolite is mixed with the inertia quartz sand of the same particle sizes of equivalent, make the reaction of propylene and benzene generate isopropyl benzene, reaction solution outlet isopropyl benzene concentration is 14%, and propylene air speed (WHSV) is 0.3 hour
-1, every section 30 ℃ of thermal insulation warming of reaction, 180 ℃ of reactor inlet temperatures, 210 ℃ of temperature outs, reaction propyl group selectivity 99.2%, in the isopropyl benzene n-proplbenzene content less than 500ppm, reaction pressure 3.0MPa.Move 1000 hours altogether, do not observe the activity of such catalysts loss, steam consumption is 0.44 ton of/ton isopropyl benzene.
[comparative example 4]
Press the technical process of accompanying drawing 1, the preformed catalyst (20～60 order) of getting 20 gram Y zeolite is mixed with the inertia quartz sand of the same particle sizes of equivalent, makes the reaction of ethene and benzene generate ethylbenzene, and reaction solution outlet ethylbenzene concentration is 13%, and ethene air speed (WHSV) is 0.1 hour
-1, the outer circulation ratio is 2, every section 23 ℃ of thermal insulation warming of reaction, 230 ℃ of reactor inlet temperatures, 253 ℃ of temperature outs, reaction ethyl selectivity 99.3%, in the ethylbenzene xylene content less than 50ppm, reaction pressure 4.5MPa.Move 1000 hours altogether, do not observe the activity of such catalysts loss, steam consumption is 0.35 ton of/ton ethylbenzene.
Claims (6)
1, a kind of production method of alkylbenzene is a raw material with alkene and the benzene that contains 2～12 carbon, and crystal aluminosilicate is a catalyzer, temperature of reaction is 100～300 ℃, reaction pressure is 1.5～3.8MPa, and benzene/olefin molar ratio is 2～6, and the raw material olefin weight space velocity is 0.1～1.0 hour
-1Under the condition, raw material reacts in fixed-bed reactor and generates the product alkylbenzene, the fixed-bed reactor bed has two sections at least, each section is loading catalyst all, whole or the segmentation adding reactor of benzene feedstock, the alkene segmentation that contains 2～12 carbon adds reactor, it is characterized in that the outer circulation of at least the second section beds product part is to first section bed of reactor, the outer circulation ratio is 0.1～6, and another part product enters subsequent handling; Described crystal aluminosilicate is the zeolite with following XRD diffraction data:
2 θ diffraction angle Diffraction peak intensity (I/I
0×100)
6.5° 28.8±0.1
7.2° 17.3±0.1
8.8° 15.4±0.1
9.7° 53.8±0.1
13.5° 39.4±0.1
14° 28.8±0.1
14.3° 19.2±0.1
15.4° 23.1±0.1
19.5° 34.6±0.1
22.2° 69.2±0.1
23.8° 23.1±0.1
25.5° 100±0.1
26.2° 65.4±0.1
27.5° 46.7±0.1
31° 27.9±0.1
35.8° 15.4±0.1
2, according to the production method of the described alkylbenzene of claim 1, it is characterized in that the fixed bed reactor catalyst bed divides four sections, the outer circulation ratio is 1～4.
3,, it is characterized in that adopting intermediate heat segmentation heat-obtaining respectively between each section bed of fixed-bed reactor according to the production method of the described alkylbenzene of claim 1.
4, according to the production method of the described alkylbenzene of claim 1, the alkene that it is characterized in that containing 2～12 carbon is ethene, and temperature of reaction is 230～260 ℃, and reaction pressure is 3.0～3.5MPa, and the weight ethylene air speed is 0.2～0.5 hour
-1, benzene/ethylene molar ratio is 2～4.
5, according to the production method of the described alkylbenzene of claim 1, the alkene that it is characterized in that containing 2～12 carbon is propylene, and temperature of reaction is 130～160 ℃, and reaction pressure is 2.0～2.5MPa, and the propylene weight air speed is 0.6～1.2 hour
-1, benzene/propylene mol ratio is 2～3.5.
6, according to the production method of the described alkylbenzene of claim 1, the alkene that it is characterized in that containing 2～12 carbon is C
4～C
12A kind of in the alkene, temperature of reaction is 140～180 ℃, and reaction pressure is 1.7～2.2MPa, and the alkene weight space velocity is 0.1～0.3 hour
-1, benzene/olefin molar ratio is 4～6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410024736 CN1285548C (en) | 2004-05-28 | 2004-05-28 | Process for producing alkylbenzene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410024736 CN1285548C (en) | 2004-05-28 | 2004-05-28 | Process for producing alkylbenzene |
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| CN1285548C true CN1285548C (en) | 2006-11-22 |
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| US7576247B2 (en) * | 2007-02-12 | 2009-08-18 | Uop Llc | Processes for making detergent range alkylbenzenes |
| CN103030519B (en) * | 2011-09-29 | 2015-05-13 | 中国石油化工股份有限公司 | Production method for alkylbenzene |
| CN105585398B (en) * | 2014-10-24 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of alkylation |
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