CN1749227A - Energ ysaving method for producing ethyl benzene by benzene and dry gas hydrocarbonization - Google Patents
Energ ysaving method for producing ethyl benzene by benzene and dry gas hydrocarbonization Download PDFInfo
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- CN1749227A CN1749227A CNA2005100475247A CN200510047524A CN1749227A CN 1749227 A CN1749227 A CN 1749227A CN A2005100475247 A CNA2005100475247 A CN A2005100475247A CN 200510047524 A CN200510047524 A CN 200510047524A CN 1749227 A CN1749227 A CN 1749227A
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 335
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 273
- 238000004519 manufacturing process Methods 0.000 title description 9
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims description 55
- 238000005804 alkylation reaction Methods 0.000 claims description 30
- 241000282326 Felis catus Species 0.000 claims description 27
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000007600 charging Methods 0.000 claims description 24
- 238000010791 quenching Methods 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 15
- 230000011218 segmentation Effects 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000006872 improvement Effects 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000000875 corresponding effect Effects 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 13
- 230000029936 alkylation Effects 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- 210000000689 upper leg Anatomy 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 description 1
- 241000282346 Meles meles Species 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The energy saving method for dydrocarbonizing benzene and dry gas to produce ethyl benzene includes: improving the intersegmental chilling mode of dydrocarbonizing reactor for benzene and dry gas to participate the intersegmental chilling; extracting circulating benzene from side line of coarse separating tower to lower benzene tower load, improving the separation sequence of polyethyl benzene tower-biethyl benzene tower and increasing the theoretic plate number in propyl benzene tower to lower separation power consumption, adopting intermediate re-boiler to realize thermal integration of towers, and adopting double ethyl benzene tower process to obtain high grade ethyl benzene product; and optimizing heat exchange network. The present invention has obvious effect of reducing power consumption.
Description
Technical field
The invention belongs to refining of petroleum and petrochemical technology field, be specifically related to a kind of benzene and dry gas hydrocarbonylation system ethylbenzene power-economizing method.
Background technology
Ethylbenzene is mainly used in the production styrene monomer, and vinylbenzene can obtain by ethylbenzene dehydrogenation.Ethylbenzene is a kind of important industrial raw material, and market continues pulling ethylbenzene industrial scale to cinnamic solid demand.The ethylbenzene production method mainly contains benzene and the rare alkylation of second is synthetic, and refining of petroleum C
8Aromatic fraction separates two kinds, and wherein the former accounts for 90%, and the latter only accounts for 10%.Since nineteen thirties, developed the method for the multiple hydrocarbonylation system ethylbenzene that differs from one another, wherein majority uses high concentration ethylene to be raw material, causes the ethylbenzene raw materials cost higher.China ethylene raw source is subjected to the serious restriction of petroleum resources, and the approach of seeking cheap production ethylbenzene is significant.Along with the development of petrochemical industry, directly utilize the catalytic cracked dry gas of low-concentration ethane to be raw material, carry out ethylbenzene synthetic production technique and obtained extensive and deep research, these technology mainly are published in the patent of being correlated with both at home and abroad, foreign patent comprises: U.S. Pat 2,939,890; US3,691,245; US3,702,886; US3,848,012; US4,107,224; US4,459,026; English Patent BP827,830; BP1,162,481; German patent DE 2,756,221; And Romanian patent RO51,253 etc.Chinese patent comprises: Fushun petrochemical industry branch office of PetroChina Company Limited., Dalian Chemiclophysics Inst., Chinese Academy of Sciences and the CN90109803.5 of Luoyang Petrochemical engineering corporation of China Petrochemical Industry; CN92106016.5; CN93115960.1; CN96100371.5; CN97116471.1; CN98113847.0; CN98113983.3; CN03156679.0; CN200410021102.8, the CN93112744.0 of Mobil Oil Corporation, the CN93108241.2 of ELF Atochem S. A, Tianjin City XinTianJin Science Development Co., Ltd CN00131924.8, the CN02155114.6 of Shanghai Petroleum Chemical Engineering Institute, the CN99804925.5 of ABB Lummus Global Inc. etc.The reaction that more than relevant patent is set forth with separate, associated viscera such as energy-conservation and consumption reduction is important references of the present invention.
Benzene alkylation with ethylene technology has alchlor process, BF
3-Al
2O
3The branch of method and solid phosphoric acid method.With reaction phase branch, can be divided into two kinds of liquid-phase alkylation method and gas phase alkylation process.Traditional aluminum chloride liquid phase alkylation process is by the improvement alchlor process of U.S. Monsanto company exploitation, i.e. BF
3-Al
2O
3High pressure homogeneous phase alkylation process progressively replaces.The seventies, the common exploitation of Mobil and Badger two companies be that the alkylation process of catalyzer then is major transformation during ethylbenzene is produced with ZSM-5.Recently Kai Fa technology mainly is the Y zeolite catalyzer of the Unocal company exploitation eighties and relevant liquid phase alkylation process thereof; And the beginning of the nineties CD-Tech and the catalytic distillation system ethylbenzene technology of the common exploitation of Lummus two companies.
Chinese patent CN87105054 " process of ethylbenzene by alkylating low-density ethylene and relevant zeolite catalyst thereof " has disclosed the Preparation of Catalyst of benzene and catalytic cracked dry gas alkylation synthesizing ethyl benzene.Chinese patent CN93112744.0 " production of ethylbenzene " adopts the ZSM-5 molecular sieve catalyst, and ethene carries out the alkylated reaction synthesizing ethyl benzene to benzene in gas phase.Chinese patent CN99124797 " by the method and apparatus of benzene and oil refinery dry gas catalytic distillation process alkylation to prepare ethylbenzene ", the thick oil refinery dry gas of charging is carried out pre-treatment, in catalytic distillation tower, make benzene and ethene carry out gas-liquid-solid three-phase alkylated reaction then, make mixture of reaction products carry out fractionation by distillation simultaneously in solid catalyst surface.Chinese patent CN00131924.8 " technology of catalysis drying gas system ethylbenzene " adopts absorption agent that the ethene in the dry gas is absorbed and gets off to obtain fulvene solution, enters then in the reactor and carries out the liquid phase homogeneous reaction with benzene.
Fushun petrochemical industry branch office of PetroChina Company Limited., Dalian Chemiclophysics Inst., Chinese Academy of Sciences and Luoyang Petrochemical engineering corporation of China Petrochemical Industry once developed catalytic cracked dry gas process for preparing ethylbenzene technology jointly, and in 1993 Fushun petrochemical industry branch office of PetroChina Company Limited. Fushun second branch factory of oil build up first the cover throughput be 3 * 10
4The preparing ethylbenzene from dry gas device of t/a.The technological transformation of constantly save energy and reduce the cost of existing similar ethylbenzene production plants, up-to-date Chinese patent is CN200410021102.8 and CN03156679.0, finds through energy analysis, still has the space of further saving energy and reduce the cost.
Summary of the invention
The purpose of this invention is to provide a kind of benzene and dry gas hydrocarbonylation system ethylbenzene power-economizing method, adopt Quench between dry gas and recycle benzene fellowship reactor region, make full use of reaction heat, keep 30-50 ℃ of beds temperature rise, the reactor outlet temperature reaches peak value, need not the raw material preheating stove.Realize double-effect rectification by adjusting benzene tower and ethylbenzene tower pressure, benzene tower working pressure is 1.34MPa (absolute pressure), and the ethylbenzene tower working pressure is 0.73MPa (absolute pressure), and the benzene tower is provided with intermediate reboiler, and it is integrated that ethylbenzene tower condenser and benzene tower intermediate reboiler carry out heat.Tower is that the separation sequence processing technology routine is transformed and single tower operating parameters tuning rough segmentation tower side line extraction 10
4The kg/hr recycle benzene is improved many ethylbenzene towers-diethylbenzene tower separation sequence to reduce separating energy consumption to reduce benzene tower load, increases propyl benzene tower number of theoretical plate and increases to 30 by 20; Ethylbenzene tower adopts double-column process to obtain the top grade ethylbenzene product, and first ethylbenzene tower carries out the non-clear ethylbenzene top grade product that obtain of cutting apart, and second ethylbenzene tower carries out obtaining the ethylbenzene first grade clear cutting apart; Adopt of the distribution of hot pinch technology procurement process system heat flux, adjust the logistics coupling and finally obtain the heat exchange network optimization scheme along potential temperature.Same device energy consumption based on this conceptual design is domestic minimum level.
Technical scheme of the present invention comprises the alkylation reaction flow scheme improvements, and benzene tower-ethylbenzene tower heat is integrated, and process recovery of heat heat exchanger network improves three aspects.
(1) reactive moieties (referring to accompanying drawing 1)
(1) improves direct Quench mode between reactor region, adopt Quench between dry gas and recycle benzene fellowship reactor region.Dry gas and recycle benzene are divided into four bursts of chargings, and wherein dry gas and recycle benzene master incoming flow thigh enter reactor head, and dry gas and the charging of recycle benzene Quench divide three strands of side lines to enter reactor.
(2) dry gas and recycle benzene master incoming flow thigh all are preheated to suitable temperature of reaction 330-360 ℃, and dry gas and recycle benzene Quench feed stream all are preheated to suitable chilling temp 250-280 ℃.Owing to improved dry gas stream thigh potential temperature, thereby avoided causing high temperature circulation benzene to mix cooling, made full use of alkylation reaction hot reacting by heating logistics thigh and Quench incoming flow thigh because the dry gas temperature is low excessively.
(3) keep 30-50 ℃ of beds temperature rise, reactor outlet alkylation reaction product temperature reaches 390-400 ℃, can satisfy the needs of pre-hot drying gas and recycle benzene master charging, therefore need not the raw material preheating stove, save corresponding equivalent heating load 0.5~0.6GJ/ ton ethylbenzene.Reactant flow and Quench logistics all can be preheating to temperature required by reclaiming hydrocarbonylation product stream strand reaction heat.
(2) separate part
(1) referring to accompanying drawing 2, liquid phase side line extraction recycle benzene between the 5th~10 theoretical stage of rough segmentation tower, its produced quantity is 10
4~1.5 * 10
4Kg/hr, 114 ℃ of temperature, benzene content is more than 99.5% (Mass), satisfies the recycle benzene requirement.Column bottom temperature is 124.3 ℃.By the extraction of rough segmentation tower side line, the corresponding load that reduces the benzene tower makes the quantity of reflux of benzene tower reduce 14%, thereby has reduced benzene tower reboiler.
(2) referring to accompanying drawing 3, at first enter the propyl benzene tower from the material at the bottom of the ethylbenzene Tata, cat head distillates propyl benzene, and still liquid is mixtures such as diethylbenzene and high boiling material at the bottom of the tower.The propyl benzene tower bottoms enters the diethylbenzene tower, and cat head distillates diethylbenzene, and still liquid is high boiling material at the bottom of the tower.By changing many ethylbenzene towers → propyl benzene tower separation sequence into propyl benzene tower → diethylbenzene tower sequence, under the situation that guarantees propyl benzene and the diethylbenzene quality product and the rate of recovery since propyl benzene weak breathization, condensation each once, reduce this separation sequence energy consumption 23%.
(3) referring to accompanying drawing 4, increase propyl benzene tower number of theoretical plate to 30, guaranteeing that operating reflux ratio is reduced to 5~6 (Mass) under the product quality premise, propyl benzene tower reboiler reduces by 74%.
(4) referring to accompanying drawing 5, realize double-effect rectification by adjusting benzene tower and ethylbenzene tower pressure, the benzene tower is provided with intermediate reboiler, and it is integrated that ethylbenzene tower condenser and benzene tower intermediate reboiler carry out heat.Benzene column overhead pressure is 1.34MPa (absolute pressure), and benzene column overhead oil gas temperature is 192 ℃.The ethylbenzene tower tower top pressure is 0.73~0.78MPa (absolute pressure), and ethylbenzene tower overhead oil temperature degree is 229~233 ℃.Benzene tower intermediate reboiler is extracted out by the 46th theoretical stage liquid phase, returns in the 47th theoretical stage gas-liquid two-phase, and the stage casing material that refluxes is heated to 221 ℃ by 216 ℃.Ethylbenzene tower cat head oil gas is used for benzene tower intermediate reboiler thermal source, and saturation steam no longer takes place.Control intermediate reboiler thermal load is no more than 1/3rd of the total heating load of full tower, and the reboiler thermal load is fallen and reduced 30% at the bottom of the benzene Tata.
(5) referring to accompanying drawing 6.Because current technology ethylbenzene tower can't be realized separating of ethylbenzene and m-xylene and p-Xylol, if m-xylene and p-Xylol content height in the ethylbenzene tower charging then can not obtain the top grade product; Adopt double-column process can obtain the top grade ethylbenzene product.First ethylbenzene tower carries out the non-clear ethylbenzene top grade product that obtain of cutting apart, and second ethylbenzene tower carries out obtaining the ethylbenzene first grade clear cutting apart.The benzene tower bottoms is by compressing into into first ethylbenzene tower certainly, the first ethylbenzene tower feed entrance point is the 43rd theoretical stage, and part ethylbenzene (top grade product) distillates from the first ethylbenzene tower cat head, enters top grade product ethylbenzene storage tank, still liquid is ethylbenzene, many ethylbenzene and high boiling material mixture, by compressing into into second ethylbenzene tower certainly; The second ethylbenzene tower feed entrance point is the 30th theoretical stage, and the second ethylbenzene tower cat head distillates ethylbenzene product (first grade) and enters first grade ethylbenzene storage tank, and still liquid enters the propyl benzene tower and carries out later separation after pressurization.The first ethylbenzene tower cat head working pressure is 0.53~0.55MPa (absolute pressure), number of theoretical plate 100, and operating reflux ratio is 12~13 (Mass), 212~214 ℃ of tower top temperatures, the cat head ethylbenzene rate of recovery is 79.5%, and the ethylbenzene product xylene content can be controlled in below the 1000PPM, reaches top grade product standard.The second ethylbenzene tower cat head working pressure is 0.35~0.45MPa (absolute pressure), number of theoretical plate 100, the 30th theoretical stage of feed entrance point, operating reflux ratio is controlled at more than 20 (Mass), 190~202 ℃ of tower top temperatures, the cat head ethylbenzene rate of recovery is 99.5%, and the ethylbenzene product xylene content can be controlled in below the 1500PPM, reaches the first grade standard.
(3) heat exchanger network part (referring to accompanying drawing 7)
(1) alkylation reaction product stream thigh is used for pre-hot drying gas charging, recycle benzene charging, reverse alkylation charging and produces saturation steam, and the grade that steam takes place is risen to 1.0MPa (gauge pressure) by 0.4MPa (gauge pressure), and quantity of steam 0.55GJ/ ton ethylbenzene takes place.
(2) rough segmentation column overhead oil gas is used for pre-hot drying gas charging, and dry gas is heated to 90 ℃ from 40 ℃, fully reclaims tow taste heat, reclaims heat 0.15GJ/ ton ethylbenzene.
(3) at first preheating fresh benzene charging of ethylbenzene tower ethylbenzene product is heated to 140 ℃ with fresh benzene from 40 ℃, has fully reclaimed waste heat, reclaims heat 0.14GJ/ ton ethylbenzene.
Effect of the present invention and benefit are to reduce dry method system ethylbenzene unit consumption significantly, save energy, the grade of raising product; Based on the same device of above-mentioned serial conceptual design, energy consumption reduces significantly.Present technique has good controllability and stability, helps existing plant modification.
Description of drawings
Fig. 1: alkylation reaction device part process flow sheet.
Fig. 2: rough segmentation tower side line extraction process flow sheet.
Fig. 3: propyl benzene tower-diethylbenzene tower process schema.
Fig. 4: the propyl benzene tower operational condition figure of optimization.
Fig. 5: the hot integrated technique schema of benzene tower and ethylbenzene tower.
Fig. 6: ethylbenzene is made with extra care the double tower process schema.
Fig. 7: heat exchanger network process flow sheet.
Accompanying drawing 1~accompanying drawing 7 marks are as follows:
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.12. 13. 14. 15.- 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43.44. 45. 46. 47. 48. 49. 50. 51.52. 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. 65. 66. 67. 68. 69. 70. 71. 72. 73. 74. 75. 76.- 77.-No.278.- 79.-No.1 80.- 81.- 82.- 83. 84.。
Embodiment:
Be described in detail the specific embodiment of the invention below in conjunction with technical scheme and accompanying drawing.
With reference to throughput is 6 * 10
4The similar ethylbenzene device of t/a, this scheme device synthesis energy saving reaches 24GJ/h, and product energy unit consumption is from the previous level 3.2GJ/t (76 * 10 that descends
4Kcal/t).Optimized the matching structure of energy recovery, wherein 2t/h generation steam rank is increased to 1.0MPa (gauge pressure) by 0.4MPa (gauge pressure).Not only can produce the ethylbenzene first grade and also can produce the top grade product, ethylbenzene top grade product amount can reach 4.8 * 10
4T/a.The present invention is particularly suitable for existing benzene and dry gas hydrocarbonylation process for preparing ethylbenzene are carried out reducing energy consumption.
(1) details are as follows for reactive moieties:
Catalysis drying gas divides four the tunnel after entering Quench dry gas preheater heat exchange to 260 ℃ after the washing, wherein one the tunnel after main charging dry gas preheater is heated to 360 ℃, enter the alkylation reaction device by the top as main charging dry gas, other three the tunnel as the Quench dry gas from the intersegmental alkylation reaction device that enters; Recycle benzene is divided into four the tunnel after Quench recycle benzene preheater is heated to 260 ℃, one the tunnel enters the alkylation reaction device as main feed cycle benzene by the top after main feed cycle benzene preheater is heated to 360 ℃, other three the tunnel as the Quench recycle benzene from the intersegmental alkylation reaction device that enters; Each section of alkylation reaction device temperature in is controlled at 360-370 ℃, and corresponding temperature out maintains 390-400 ℃.
(2) details are as follows for separate part:
First point:
In the place's liquid phase side line extraction of rough segmentation tower 5-10 piece theoretical stage, the extraction product is mixed to the recycle benzene surge tank with benzene tower extraction recycle benzene after passing through pressurization, preheating as recycle benzene.Control side line produced quantity 10
4Kg/hr, the extraction temperature is 114-115 ℃, sideline product benzene content is 99.5% (Mass).Keep rough segmentation tower working pressure 0.55MPa (absolute pressure), after the side line extraction, column bottom temperature rises to 124.3 ℃.Because benzene tower inlet amount reduces 10
4Kg/hr, thus make the quantity of reflux of benzene tower reduce 7000kg/hr, and corresponding benzene tower reboiler reduces 3.2GJ/hr.
Second point:
Many ethylbenzene and high boiling material mixture are by compressing into into the propyl benzene tower certainly at the bottom of the ethylbenzene Tata, feed entrance point is the 7th theoretical stage, propyl benzene tower number of theoretical plate 20, control tower is pressed 0.43MPa (absolute pressure), reflux ratio 20 (Mass), tower top temperature are 225 ℃, and cat head distillates propyl benzene product purity 93% (Mass), the rate of recovery is 99.6% (Mass), and propyl benzene is as the product carrying device.The propyl benzene tower bottoms is by compressing into into the diethylbenzene tower certainly, feed entrance point is the 22nd theoretical stage, diethylbenzene tower number of theoretical plate 30, control tower is pressed 0.18MPa (absolute pressure), and reflux ratio 4 (Mass), tower top temperature are 209 ℃, it is 99% (Mass) that cat head distillates the diethylbenzene product purity, the rate of recovery is 99.5% (Mass), and diethylbenzene enters the absorption tower as absorption agent, and high boiling material is discharged system.Since all only gasifications of propyl benzene and diethylbenzene, condensation each once, propyl benzene tower and diethylbenzene tower reboiler are reduced to 9.51GJ/hr and 1.15GJ/hr respectively, this technology and current technology be its separating energy consumption reduction 3.1GJ/hr relatively.
Thirdly:
By theoretical analysis as can be known, propyl benzene tower number of theoretical plate and reflux ratio do not reach suitable coupling.Propyl benzene tower number of theoretical plate is increased to suitable number of theoretical plate 30 by 20, guaranteeing under the product quality premise, operating reflux ratio is corresponding reduces to suitable operating reflux ratio 5 (Mass) by 20 (Mass), has optimized the operational condition of propyl benzene tower, thereby can make propyl benzene tower reboiler reduce 6.84GJ/hr.
The 4th point:
The charging of benzene tower is from rough segmentation tower alkylation liquid and dealkylation reaction device reverse alkylation liquid, and feed entrance point is respectively the 45th and 49 theoretical stage place; Benzene column overhead pressure is 1.34MPa (absolute pressure); Benzene column overhead oil gas through recycle benzene vaporizer and the corresponding low-pressure steam of generation, enters benzene column overhead condensate cooler earlier then; Benzene column overhead condensate cooler gained liquid phase flows into benzene tower return tank, and the gained gas phase is after the cooling of topping benzene water cooler, and the gained liquid phase flows into benzene tower return tank, squeezes into the benzene cat head as backflow by benzene tower reflux pump, and the gained gas-phase transport is to the rough segmentation tower; A benzene tower bottoms part is returned in the tower through benzene tower reboiler heating and gasifying, and another part is delivered to the ethylbenzene tower charging stock tank from pressing; Recycle benzene is by the extraction of benzene tower side line.Derive liquid phase from the 46th theoretical stage of benzene tower and enter benzene tower intermediate reboiler, deriving liquidus temperature is 216 ℃, and flow is 7 * 10
4Kg/hr, the back gas-liquid mixed temperature of boiling again is 221 ℃, returns in the tower from the 47th theoretical stage; Benzene tower intermediate reboiler thermal load is about 7GJ/hr, and reboiler is 15.5GJ/hr at the bottom of the benzene Tata.The ethylbenzene tower charging divides two-way to proceed to ethylbenzene tower by the ethylbenzene tower charging stock tank, and feed entrance point is the 40th theoretical stage place; Ethylbenzene tower cat head oil gas is after the intermediate reboiler condensation, enter vapour generator 1.0MPa (absolute pressure) steam takes place, oil gas coagulates the rear section entirely and returns the ethylbenzene tower cat head as backflow, and another part enters the ethylbenzene product jar after cooling, and the ethylbenzene tower bottoms is by compressing into into the later separation operation certainly.The ethylbenzene tower tower top pressure is 0.73MPa (absolute pressure), and overhead oil temperature degree is 229 ℃, reboiler 24GJ/hr.Ethylbenzene cat head produced quantity is 7.556 * 10
3Kg/hr, the ethylbenzene rate of recovery is 99.5%, the ethylbenzene product xylene content can be controlled in below the 1500PPM, reaches the first grade standard.By adding intermediate reboiler, realize the hot integrated of benzene tower and ethylbenzene tower, save thermal barrier equivalent 5.5GJ/hr.
The 5th point:
The benzene tower bottoms is by entering first ethylbenzene tower from pressing from the 43rd theoretical stage, and part ethylbenzene (top grade product) distillates from the first ethylbenzene tower cat head, enters top grade product ethylbenzene storage tank, and still liquid is ethylbenzene, many ethylbenzene and high boiling material mixture, by compressing into into second ethylbenzene tower certainly; The second ethylbenzene tower feed entrance point is the 30th theoretical stage, and the second ethylbenzene tower cat head distillates ethylbenzene product (first grade) and enters first grade ethylbenzene storage tank, and still liquid enters the propyl benzene tower and carries out later separation after pressurization.The first ethylbenzene tower cat head working pressure is 0.53MPa (absolute pressure), number of theoretical plate 100, and operating reflux ratio is 13 (Mass), 212 ℃ of tower top temperatures, the cat head ethylbenzene rate of recovery is 79.5%, and the ethylbenzene product xylene content can be controlled in below the 1000PPM, reaches top grade product standard.The second ethylbenzene tower cat head working pressure is 0.35~0.45MPa (absolute pressure), number of theoretical plate 100, the 30th theoretical stage of feed entrance point, operating reflux ratio is 20 (Mass), 190~202 ℃ of tower top temperatures, the cat head ethylbenzene rate of recovery is 99.5%, and the ethylbenzene product xylene content can be controlled in below the 1500PPM, reaches the first grade standard.
(3) details are as follows for the heat exchanger network part:
At first, hydrocarbonylation product process reaction product-main feed cycle benzene interchanger, reaction product-main charging dry gas interchanger from the alkylation reaction device, main charging dry gas and main feed cycle benzene are preheated to 360 ℃ from 260 ℃, and hydrocarbonylation product temperature is corresponding reduces to 370 ℃.Then, the hydrocarbonylation product is through reaction product-reverse alkylation feed exchanger, and the reverse alkylation charging is heated to 260 ℃ from 185 ℃, and hydrocarbonylation product temperature is corresponding reduces to 348 ℃.Fresh benzene is preheated to 140 ℃ by ethylbenzene product-fresh benzene interchanger from 40 ℃ by ethylbenzene product stream strand, has made full use of ethylbenzene tower cat head ethylbenzene product heat, recyclable 1.05GJ/hr.Recycle benzene is heated to 181 ℃ by the recycle benzene vaporizer from 177 ℃ by benzene column overhead oil gas, is heated to 260 ℃ by reaction product-Quench recycle benzene interchanger recycle benzene that will gasify from 181 ℃ by the hydrocarbonylation product then, and hydrocarbonylation product temperature is corresponding reduces to 294 ℃.Then, the hydrocarbonylation product is preheated to 260 ℃ with the Quench dry gas from 120 ℃ by reaction product-Quench dry gas interchanger.Then, the hydrocarbonylation product is by reaction product-benzene tower charging No.2 interchanger, and the charging of benzene tower is preheated to 140 ℃ from 120 ℃, and hydrocarbonylation product temperature is corresponding reduces to 200 ℃.Then, the hydrocarbonylation product is by the saturation steam of reaction product-vapour generator generation 1.0MPa (absolute pressure), and hydrocarbonylation product temperature is corresponding reduces to 190 ℃.Then, the hydrocarbonylation product rises to 170 ℃ with benzene tower feeding temperature by 140 ℃ by reaction product-benzene tower charging No.1 interchanger, and hydrocarbonylation product temperature is corresponding reduces to 165 ℃.Dry gas is preheating to 90 ℃ through rough segmentation column overhead oil gas-dry gas interchanger from 40 ℃, and the dry gas preheater has made full use of the tow taste heat of rough segmentation column overhead hydrocarbon flow thigh, recyclable 1.17GJ/hr.The hydrocarbonylation product by reaction product-dry gas interchanger, is preheated to 120 ℃ with dry gas by 90 ℃ at last, and hydrocarbonylation product temperature is corresponding reduces to 140 ℃.
Claims (1)
1. benzene and dry gas hydrocarbonylation system ethylbenzene power-economizing method, comprise alkylation reaction flow scheme improvements, rough segmentation tower side line extraction recycle benzene, adopt propyl benzene tower-diethylbenzene tower separation sequence, the suitable number of theoretical plate of design propyl benzene tower, the benzene tower-ethylbenzene tower heat is integrated, ethylbenzene tower adopts double-column process, process recovery of heat heat exchanger network improves, it is characterized in that:
1). alkylation reaction flow scheme improvements: improve direct Quench mode between reactor region, adopt Quench between dry gas and recycle benzene fellowship reactor region, dry gas and recycle benzene master feeding temperature are 330-360 ℃, 250-280 ℃ of dry gas and recycle benzene Quench feed stream temperature, keep 30-50 ℃ of beds temperature rise, reactor outlet alkylation reaction product temperature reaches 390-400 ℃, need not the raw material preheating stove;
2). rough segmentation tower side line extraction recycle benzene: in the 5th~10 theoretical stage place of rough segmentation tower liquid phase side line extraction recycle benzene 10
4~1.5 * 10
4Kg/hr;
3). adopt propyl benzene tower-diethylbenzene tower separation sequence: adopt propyl benzene tower-diethylbenzene tower separation sequence, under the situation that guarantees propyl benzene and the diethylbenzene quality product and the rate of recovery;
4). the suitable number of theoretical plate of design propyl benzene tower: the suitable number of theoretical plate of design propyl benzene tower is 30, and the operating reflux ratio respective design is suitable reflux ratio 5~6 (Mass);
5). benzene tower-ethylbenzene tower heat is integrated: benzene column overhead pressure is 1.34MPa, and the ethylbenzene tower tower top pressure is 0.73~0.78MPa (absolute pressure), and ethylbenzene tower cat head oil gas is used for benzene tower intermediate reboiler thermal source; The benzene tower is extracted out by the 46th theoretical stage liquid phase, returns in the 47th theoretical stage gas-liquid two-phase through intermediate reboiler; Control intermediate reboiler thermal load is no more than 1/3rd of the total heating load of full tower;
6). ethylbenzene tower adopts double-column process: the refining double-column process that adopts of ethylbenzene, first ethylbenzene tower carries out the non-clear ethylbenzene top grade product that obtain of cutting apart, and second ethylbenzene tower carries out obtaining the ethylbenzene first grade clear cutting apart; The first ethylbenzene tower cat head working pressure is 0.53~0.55MPa (absolute pressure), and the cat head ethylbenzene rate of recovery is 79.5%, and the ethylbenzene product xylene content can be controlled in below the 1000PPM; The second ethylbenzene tower cat head working pressure is 0.35~0.45MPa (absolute pressure), and the cat head ethylbenzene rate of recovery is 99.5%, and the ethylbenzene product xylene content is controlled at below the 1500PPM;
7). process recovery of heat heat exchanger network improves: the grade of alkylation reaction product stream strand generation steam rises to 1.0MPa (gauge pressure) by 0.4MPa (gauge pressure); Rough segmentation column overhead oil gas is used for pre-hot drying gas charging, and dry gas is heated to 90 ℃ from 40 ℃; The ethylbenzene tower ethylbenzene product is the charging of preheating fresh benzene at first, and fresh benzene is heated to 140 ℃ from 40 ℃.
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