CN114456037B - Raw material gasification method for preparing styrene by ethylbenzene dehydrogenation - Google Patents
Raw material gasification method for preparing styrene by ethylbenzene dehydrogenation Download PDFInfo
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- CN114456037B CN114456037B CN202011134032.2A CN202011134032A CN114456037B CN 114456037 B CN114456037 B CN 114456037B CN 202011134032 A CN202011134032 A CN 202011134032A CN 114456037 B CN114456037 B CN 114456037B
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 668
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 74
- 239000002994 raw material Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000002309 gasification Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 248
- 238000000926 separation method Methods 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 59
- 239000007791 liquid phase Substances 0.000 claims abstract description 43
- 239000012071 phase Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 230000001502 supplementing effect Effects 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000006200 vaporizer Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 abstract description 27
- 230000008020 evaporation Effects 0.000 abstract description 25
- 238000005265 energy consumption Methods 0.000 abstract description 23
- 239000003054 catalyst Substances 0.000 abstract description 14
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 62
- 238000007599 discharging Methods 0.000 description 18
- 239000007858 starting material Substances 0.000 description 14
- YFPBWJDUUHCRBT-UHFFFAOYSA-N ethylbenzene;hydrate Chemical compound O.CCC1=CC=CC=C1 YFPBWJDUUHCRBT-UHFFFAOYSA-N 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 7
- 230000008016 vaporization Effects 0.000 description 5
- 238000009834 vaporization Methods 0.000 description 4
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- ZCCKUOITFYNSQG-UHFFFAOYSA-N styrene;hydrate Chemical compound O.C=CC1=CC=CC=C1 ZCCKUOITFYNSQG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a raw material gasification method for preparing styrene by ethylbenzene dehydrogenation, which comprises the steps of feeding a material flow VI comprising raw material ethylbenzene and raw material water into an ethylbenzene/water separation tank to obtain a liquid-phase ethylbenzene/water mixture; partially gasifying the liquid-phase ethylbenzene/water mixture through an azeotropic heat exchanger to obtain a material flow I, wherein the material flow I comprises a gas-phase ethylbenzene/water azeotropic material flow II and a gas-liquid mixture III; the raw material ethylbenzene IV and the gas-phase ethylbenzene/water azeotropic material flow II enter an ethylbenzene supplementing evaporator, and a material flow V is obtained after complete gasification and enters a subsequent reaction system. The method reduces the water distribution amount of the raw material ethylbenzene evaporation system by 25-35%, increases the main steam amount, ensures the use of the dehydrogenation catalyst with low water ratio, further reduces the water steam and circulating water consumption, improves the low-temperature heat recovery rate of the top of the ethylbenzene/styrene tower, and reduces the energy consumption of the device.
Description
Technical Field
The invention relates to a raw material gasification method for preparing styrene by ethylbenzene dehydrogenation.
Background
Styrene is one of the most important basic organic chemical raw materials, and is mainly used for manufacturing copolymer resins such as polystyrene PS and EPS, ABS and SAN, styrene/butadiene copolymer latex SB, styrene-butadiene rubber and latex SBR, unsaturated polyester and other materials such as styrene/methyl methacrylate latex, methyl methacrylate/butadiene/styrene copolymer MBS, ion exchange resins and medicines.
The technology for preparing styrene by ethylbenzene dehydrogenation mainly comprises an adiabatic dehydrogenation process, an isothermal dehydrogenation process, a selective oxidative dehydrogenation process and a propylene oxide co-oxidation process. The most widely applied and mature technology is the ethylbenzene negative pressure adiabatic dehydrogenation process, which accounts for about 85% of the worldwide styrene yield.
In the presence of catalyst and water vapor, ethylbenzene at 550-650 deg.c is dehydrogenated selectively to produce styrene. The reaction is a strong endothermic reaction, a large amount of superheated steam is added, on one hand, the superheated steam is a heat carrier for ethylbenzene dehydrogenation reaction, the heat required by the reaction is provided, on the other hand, the existence of the steam reduces the partial pressure of the reaction, which is beneficial to the generation of styrene, the steam can also react with carbon junctions indicated by the catalyst to generate water gas, the reduction of active components of the catalyst into metal can be prevented, the service life of the catalyst is prolonged, and the water ratio (the weight ratio of the steam to the ethylbenzene) adopted in industry is 1-1.6.
The production process of styrene requires a large amount of fuel and water vapor, and the process energy consumption is large. Along with the continuous rising of the prices of crude oil and raw materials, the adoption of an energy-saving technology becomes a key measure for reducing the cost of a styrene device. The energy saving problem of styrene device is widely studied at home and abroad, patent CN1007973B provides an improved dehydrogenation process for producing styrene from styrene, which comprises low-temperature heat recovery and an improved method for feeding styrene-water vapor, the heat of the top of an ethylbenzene/styrene separation tower is utilized to heat ethylbenzene and water, part of ethylbenzene raw material and water enter a reactor in an azeotropic way, and the energy consumption is saved by 10-20 percent.
The reduction of the water ratio can effectively reduce the energy consumption of the device, the research of the dehydrogenation catalyst with low water ratio is greatly advanced in recent years, the water ratio is reduced from 1.4-1.6 to 1-1.25, the water ratio is reduced from 1.4 to 1.1, the comprehensive energy consumption of the device is reduced by about 10 percent, and the economic benefit is considerable. If the low water ratio catalyst is used on the device built by the original azeotropic energy-saving styrene technology, the water quantity supplied to the ethylbenzene evaporation system cannot be reduced, the steam heat entering the heating furnace must be reduced by using the low water ratio dehydrogenation catalyst, the heat required by ethylbenzene dehydrogenation reaction is basically unchanged, the steam flow entering the heating furnace is reduced, and the outlet temperature of the corresponding heating furnace must be increased. When the water ratio is 1.4, the outlet temperatures of the steam heating furnaces A and B are 850 ℃ and 830 ℃ respectively. When the water ratio was reduced to 1.25, the outlet temperatures of the steam heating furnaces A and B were 890℃and 870℃respectively. When the water ratio was reduced to 1.0, the outlet temperatures of the steam heating furnaces A and B were 940℃and 930℃respectively. The catalyst cannot be directly used on an original azeotropic energy-saving styrene technology built device when the water ratio is less than or equal to 1.2 due to the upper limit of the use temperature of the heating furnace pipeline material. In order to solve the problem, CN103030522B proposes to separate an ethylbenzene/water azeotropic evaporation and ethylbenzene supplementary evaporation integrated system, and an independent ethylbenzene supplementary evaporation system is arranged, so that the problem of common use of sequential separation constant boiling and low water ratio catalysts is solved. The low temperature heat utilization rate of the ethylbenzene/styrene tower top is about 75%, the tower top cooling water and the chilled water consumption are increased, and the steam consumption is increased by partial ethylbenzene evaporation. In order to avoid accumulation of components such as styrene in ethylbenzene feed, the operating temperature of the ethylbenzene supplementing evaporator is controlled, and a small amount of water vapor is required to be added into the ethylbenzene evaporator, so that the water vapor consumption is further increased. The increased utility consumption of cooling water, chilled water, steam, etc. partially counteracts the reduced energy consumption associated with the use of low water ratio catalysts.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, an independent ethylbenzene evaporation system is arranged by adopting a low water ratio sequential azeotropic energy-saving process, and in order to avoid accumulation of components such as styrene in ethylbenzene, water vapor is required to be added into the independent ethylbenzene evaporation system, and the problems of insufficient low temperature utilization of a rectification system, high water vapor and circulating water consumption and high energy consumption of a device exist. Therefore, the invention provides a new raw material gasification method for preparing styrene by ethylbenzene dehydrogenation with low water ratio, which has the characteristics of further reducing water vapor and circulating water consumption and reducing energy consumption of a device when the azeotropic energy-saving process and a catalyst with low water ratio are simultaneously applied to the styrene device.
The first aspect of the invention provides a raw material gasification method for preparing styrene by ethylbenzene dehydrogenation, which comprises the following steps:
S1: feeding a material flow VI comprising raw material ethylbenzene and raw material water into an ethylbenzene/water separation tank to obtain a liquid-phase ethylbenzene/water mixture;
s2: partially gasifying the liquid-phase ethylbenzene/water mixture through an azeotropic heat exchanger to obtain a material flow I, wherein the material flow I comprises a gas-phase ethylbenzene/water azeotropic material flow II and a gas-liquid mixture III;
s3: the raw material ethylbenzene IV and the gas-phase ethylbenzene/water azeotropic material flow II enter an ethylbenzene supplementing evaporator, and a material flow V is obtained after complete gasification and enters a subsequent reaction system.
According to some embodiments of the invention, the method further comprises S4: and returning the gas-liquid mixture III to an ethylbenzene/water separation tank to obtain a gas-phase outlet material flow VII, wherein the material flow VII enters a subsequent reaction system.
According to a preferred embodiment of the invention, the stream V and the stream VII are mixed to obtain a stream VIII, which is fed to a subsequent reaction system.
According to some embodiments of the invention, the feed water in stream VI is 30-40% by weight, and may be, for example, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% and any value therebetween.
According to some embodiments of the invention, the gasification rate of stream I is 4% -20%, for example, may be 6%, 8%, 10%, 12%, 14%, 16%, 18% and any value therebetween.
According to some embodiments of the invention, the stream II comprises 5-15% of the mass of the feed ethylbenzene IV, which may be, for example, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% and any value in between.
According to some embodiments of the invention, the mass fraction of water in the stream V is 5-10%, which may be for example 6%, 7%, 8%, 9% and any value in between.
According to some embodiments of the invention, in S3, the gaseous ethylbenzene/water azeotrope stream II is fed to the ethylbenzene make-up evaporator multiple times, preferably 1-3 times.
According to some embodiments of the invention, the feed ethylbenzene IV comprises 10-35% of the total feed ethylbenzene mass and the ethylbenzene in stream VI comprises 65-90% of the total feed ethylbenzene mass.
According to some specific embodiments of the invention, the feedstock ethylbenzene IV comprises 15%, 20%, 25%, 30% and any value therebetween of the total feedstock ethylbenzene mass.
According to some embodiments of the invention, the ethylbenzene in stream VI comprises 70%, 75%, 80%, 85% and any value in between of the total feedstock ethylbenzene mass.
According to a preferred embodiment of the invention, the feed ethylbenzene IV comprises 12-30% of the total feed ethylbenzene mass; the ethylbenzene in stream VI represents 70-88% of the total feed ethylbenzene mass.
According to some embodiments of the invention, the ethylbenzene/water separation tank is operated at a pressure of 70-120kPaA and a temperature of 85-97 ℃.
According to some embodiments of the invention, the azeotropic heat exchanger is operated at a pressure of 70 to 120kPaA and a temperature of 85 to 97 ℃.
According to some embodiments of the invention, the ethylbenzene make-up evaporator is operated at a pressure of 80-120KPaA and a temperature of 100-140 ℃.
According to some embodiments of the invention, the stream VIII has a pressure of 80-120kPaA and a temperature of 85-130 ℃.
According to some embodiments of the invention, the azeotropic vaporizer uses an ethylbenzene/styrene separation column overhead gas as a heat source.
According to some embodiments of the invention, the ethylbenzene make-up evaporator is heated with steam.
According to some embodiments of the invention, the subsequent reaction system comprises a dehydrogenation reaction system, a steam heating system, or the like.
According to some embodiments of the invention, the dehydrogenation reaction system comprises a dehydrogenation reactor, preferably the dehydrogenation reactor comprises a first dehydrogenation reactor and a second dehydrogenation reactor.
According to some embodiments of the invention, the weight ratio of water to ethylbenzene in the dehydrogenation reactor is from 0.9 to 1.3:1.
According to some embodiments of the invention, the dehydrogenation reaction is operated at a pressure of 50-75kPaA and a temperature of 580-650 ℃.
According to some embodiments of the invention, the steam heating system comprises a steam heating furnace.
According to some embodiments of the invention, in the steam heating furnace, the outlet temperature of the A chamber of the steam heating furnace is 800-880 ℃, and the outlet temperature of the B chamber of the steam heating furnace is 800-860 ℃.
According to some specific embodiments of the invention, the method comprises the steps of: a) Feeding a material flow VI containing raw material ethylbenzene and water into an ethylbenzene/water separation tank, and partially vaporizing a separated liquid-phase ethylbenzene/water mixture through an ethylbenzene/styrene tower top azeotropic heat exchanger to obtain a material flow I, wherein the material flow I is subjected to vapor-liquid separation to obtain a gas-phase material flow II and a vapor-liquid mixture III, the vaporization rate of the material flow I is 4% -20%, and the gas-phase material flow II is an ethylbenzene/water azeotrope under the shell side operating pressure of the azeotropic heat exchanger; b) The raw material ethylbenzene IV enters an ethylbenzene supplementing evaporator, and 1-3 gas-phase ethylbenzene/water azeotropic material II enters the ethylbenzene supplementing evaporator and is completely vaporized to obtain a material flow V; c) The gas-liquid mixture III obtained in the step a) after partial vaporization is separated and returned to an ethylbenzene/water separation tank, so that a gas-phase outlet material flow VII is obtained, wherein the weight percentage of water in the material flow VI is 30-40%; d) And mixing the material flow V with the material flow VII to obtain a material flow VIII, and enabling the material flow VIII to enter a subsequent reaction system.
In a second aspect, the invention provides a system for implementing the method according to the first aspect, which comprises an azeotropic evaporation system, an ethylbenzene supplementary evaporation system, an ethylbenzene/water separation system, a steam heating system and a dehydrogenation reaction system, wherein the ethylbenzene/water mixture partially gasified by the azeotropic evaporation system separates out a gaseous ethylbenzene/water azeotrope stream II, and the gaseous ethylbenzene/water azeotrope stream II and raw material ethylbenzene IV enter the ethylbenzene supplementary evaporation system, and the gasified material V enters the dehydrogenation reaction system for reaction.
According to some embodiments of the invention, the ethylbenzene/water mixture partially gasified by the azeotropic evaporation system is separated into a gas-liquid mixture III, and the gas-liquid mixture III enters the ethylbenzene/water separation system to be gasified to obtain a gas-phase outlet material flow VII, and the gas-phase outlet material flow VII enters the dehydrogenation reaction system to be reacted.
According to some embodiments of the invention, the stream V and the stream VII are mixed and then fed into a dehydrogenation reaction system for reaction.
According to some embodiments of the invention, the azeotropic vaporization system comprises an azeotropic heat exchanger.
According to some embodiments of the invention, the ethylbenzene make-up vaporization system includes an ethylbenzene make-up vaporizer.
According to some embodiments of the invention, the ethylbenzene/water separation system comprises an ethylbenzene/water separation tank.
According to some embodiments of the invention, the dehydrogenation reaction system comprises a dehydrogenation reactor, preferably the dehydrogenation reactor comprises a first dehydrogenation reactor and a second dehydrogenation reactor.
According to some embodiments of the invention, the weight ratio of water to ethylbenzene in the dehydrogenation reactor is from 0.9 to 1.3:1.
According to some embodiments of the invention, the dehydrogenation reactor is operated at a pressure of 50-75kPaA and a temperature of 580-650 ℃.
According to some embodiments of the invention, the dehydrogenation reaction system further comprises an intermediate heat exchanger and/or a superheater.
According to some embodiments of the invention, the steam heating system comprises a steam heating furnace.
According to some embodiments of the invention, in the steam heating furnace, the outlet temperature of the A chamber of the steam heating furnace is 800-880 ℃, and the outlet temperature of the B chamber of the steam heating furnace is 800-860 ℃.
According to some embodiments of the invention, the system further comprises a tail gas cooler, a tail gas subcooler, and an ethylbenzene/styrene separation column.
A third aspect of the invention provides the use of a process according to the first aspect or a system according to the second aspect in the dehydrogenation of ethylbenzene to styrene.
In the invention, an independent ethylbenzene supplementary evaporation system is arranged, a part of gas-phase ethylbenzene/water azeotrope is separated from the ethylbenzene/water mixture gasified by the azeotropic heat exchanger, and the separated gas-phase ethylbenzene/water azeotrope and ethylbenzene enter the ethylbenzene supplementary evaporation system according to a certain proportion, and enter the dehydrogenation reaction system after evaporation is completed. The ethylbenzene and water azeotropic evaporation system maintains the original process condition, and the weight content of water in the ethylbenzene and water azeotropic evaporation system is about 33%, the water distribution amount of the ethylbenzene and water azeotropic evaporation system is reduced by 25-35%, the main steam amount is increased, the dehydrogenation catalyst with low water ratio is ensured to be used, the consumption of steam and circulating water is further reduced, the low-temperature heat recovery rate of the ethylbenzene and styrene tower top is improved, and the energy consumption of the device is reduced.
By adopting the technical scheme of the invention, when the azeotropic energy-saving process is applied, the water distribution amount can be reduced by 25-35%, the simultaneous use of the low-water-ratio dehydrogenation catalyst and the azeotropic energy-saving process is ensured, the ethylbenzene/water azeotrope and the ethylbenzene are jointly fed into the ethylbenzene complementary evaporation system, the water vapor consumption and the circulating water consumption are further reduced, the low-temperature heat recovery rate of the ethylbenzene/styrene tower top is improved, and the energy consumption of the device is reduced. When the water ratio is 1.0, the liquefaction rate of the ethylbenzene/styrene tower top gas through the azeotropic heat exchanger is improved to 0.82 from 0.75 of the independent ethylbenzene supplementary evaporation scheme in the prior art, the addition of water vapor into the ethylbenzene supplementary evaporator is not needed, the heating water vapor of the ethylbenzene supplementary evaporator is reduced by 15%, the circulating water consumption of the ethylbenzene/styrene separation tower top is reduced by 27%, the energy consumption of the device is reduced by 4.5kgoe/t.SM, the sequential separation energy-saving process effect is more outstanding, and the better technical effect is obtained.
Drawings
FIG. 1 is a flow chart of a prior art process for the dehydrogenation of ethylbenzene to styrene.
FIG. 2 is a flow chart of the process for the dehydrogenation of ethylbenzene to styrene in accordance with the present invention.
In fig. 1 and 2, a steam heating furnace 1, a first dehydrogenation reactor 2, a second dehydrogenation reactor 3, an intermediate heat exchanger 4, an ethylbenzene supplementary evaporator 5, an ethylbenzene/water separation tank 6, a superheater 7, an azeotropic heat exchanger 8, an off-gas cooler 9, an off-gas subcooler 10 and an ethylbenzene/styrene separation tower 11 are shown. 101 is steam entering a steam heating furnace A chamber, 102 is steam entering a steam heating furnace A chamber, 103 is steam entering a steam heating furnace B chamber, 104 is steam entering the steam heating furnace B chamber, 105 is water distribution, 106 is raw material ethylbenzene, 107 is ethylbenzene water mixture, 108 is ethylbenzene evaporator supplementing ethylbenzene, 109 is ethylbenzene evaporator discharging, 110 is first dehydrogenation reactor discharging, 111 is middle heat exchanger tube layer discharging, 112 is second dehydrogenation reactor discharging, 113 is ethylbenzene water mixture, 114 is superheater tube side discharging, 115 is ethylbenzene evaporator shell side feeding, 116 liquid phase water ethylbenzene/water separation tank, 118 liquid phase ethylbenzene out ethylbenzene/water separation tank, 122 is azeotropic heat exchanger tube side discharging, 123 is azeotropic heat exchanger tube side feeding, 124/styrene tower top gas phase discharging, 125 is gas phase ethylbenzene/water azeotrope entering ethylbenzene evaporator, 126 is tail gas cooler shell side discharging, 127 is tail gas subcooler shell side discharging, 128 is separated partial gas phase ethylbenzene/water azeotrope and then ethylbenzene/water azeotrope is returned, 129 is ethylbenzene to the ethylbenzene/water separation tank, 130 is water distribution to the ethylbenzene/styrene separation tank, 131 is water distribution to the evaporator.
In fig. 1, the raw material ethylbenzene 106 is divided into two strands 129 and 108, the water distribution 105 is also divided into 2 strands 130 and 131, part of ethylbenzene 129 and water distribution 130 are jointly fed into an ethylbenzene/water separation tank 6, the other part of ethylbenzene 108 and water distribution 131 are jointly fed into an ethylbenzene evaporator 5, the ethylbenzene/water separation tank separates liquid-phase ethylbenzene and liquid-phase water, the liquid-phase ethylbenzene 118 and the liquid-phase water 116 are fed into an azeotropic heat exchanger 8 for partial gasification, the heat source is the top gas of an ethylbenzene/styrene tower 11, the partially gasified gas-liquid mixture 122 is returned to the ethylbenzene/water separation tank 6, the water distribution 131 and the liquid-phase ethylbenzene 108 are mixed and fed into the ethylbenzene evaporator 5, the ethylbenzene is completely gasified in the ethylbenzene supplementing evaporator 5, the gasified material 109 and the gas-phase outlet material of the ethylbenzene/water separation tank 6 are mixed and fed into a superheater 7 for heating, and then the material 113 is fed into a first dehydrogenation reactor 2 for reaction.
In fig. 2, the raw material ethylbenzene 106 is divided into two parts, part of ethylbenzene 129 and steam distribution 105 are jointly fed into an ethylbenzene/water separation tank 6, the other part of ethylbenzene 108 is fed into an ethylbenzene evaporator 5, the ethylbenzene/water separation tank separates liquid phase ethylbenzene and liquid phase water, the liquid phase ethylbenzene 118 and the liquid phase water 116 are fed into an azeotropic heat exchanger 8 for partial gasification, the heat source is the top gas of the ethylbenzene/styrene tower 11, the gas-liquid mixture after partial gasification is divided into two parts, one part of gas phase ethylbenzene/water azeotrope 125 and the liquid phase ethylbenzene 108 are mixed and fed into the ethylbenzene evaporator 5, the other part of ethylbenzene/water mixture is fed back into the ethylbenzene/water separation tank 6, the top gas phase of the ethylbenzene/water separation tank 11 is fed into an overhead vacuum system through the azeotropic heat exchanger 8, a tail gas cooler 9 and a tail gas subcooler 10, and the gas phase discharged from the ethylbenzene/water separation tank 6 is fed into a first dehydrogenation reactor 2 for reaction through a material 113 heated by the superheater 7.
Detailed Description
The invention provides a gasification method for preparing styrene raw materials by ethylbenzene dehydrogenation with low water ratio, and the process flow is shown in figure 1.
In FIG. 1, 1 steam heating furnace, 2 first dehydrogenation reactor, 3 second dehydrogenation reactor, 4 intermediate heat exchanger, 5 ethylbenzene evaporator, 6 ethylbenzene/water separation tank, 7 superheater, 8 azeotropic heat exchanger, 9 tail gas cooler, 10 tail gas subcooler, 11 ethylbenzene/styrene separation column. 101 is steam entering a steam heating furnace A chamber, 102 is steam entering a steam heating furnace A chamber, 103 is steam entering a steam heating furnace B chamber, 104 is steam entering the steam heating furnace B chamber, 105 is water distribution, 106 is raw material ethylbenzene, 107 is ethylbenzene water mixture, 108 is ethylbenzene evaporator supplementing ethylbenzene, 109 is ethylbenzene evaporator discharging, 110 is first dehydrogenation reactor discharging, 111 is middle heat exchanger tube layer discharging, 112 is second dehydrogenation reactor discharging, 113 is ethylbenzene water mixture, 114 is superheater tube side discharging, 115 is ethylbenzene evaporator shell side feeding, 116 liquid phase water ethylbenzene/water separation tank, 118 liquid phase ethylbenzene out ethylbenzene/water separation tank, 122 is azeotropic heat exchanger tube side discharging, 123 is azeotropic heat exchanger tube side feeding, 124/styrene tower top gas phase discharging, 125 is gas phase ethylbenzene/water azeotrope entering ethylbenzene evaporator, 126 is tail gas cooler shell side discharging, 127 is tail gas subcooler shell side discharging, 128 is separated partial gas phase ethylbenzene/water azeotrope and then ethylbenzene/water azeotrope is returned, 129 is ethylbenzene to the ethylbenzene/water separation tank, 130 is water distribution to the ethylbenzene/styrene separation tank, 131 is water distribution to the evaporator.
In fig. 1, the raw material ethylbenzene 106 is divided into two strands 129 and 108, the water distribution 105 is also divided into 2 strands 130 and 131, part of ethylbenzene 129 and water distribution 130 are jointly fed into an ethylbenzene/water separation tank 6, the other part of ethylbenzene 108 and water distribution 131 are jointly fed into an ethylbenzene evaporator 5, the ethylbenzene/water separation tank separates liquid-phase ethylbenzene and liquid-phase water, the liquid-phase ethylbenzene 118 and the liquid-phase water 116 are fed into an azeotropic heat exchanger 8 for partial gasification, the heat source is the top gas of an ethylbenzene/styrene tower 11, the partially gasified gas-liquid mixture 122 is returned to the ethylbenzene/water separation tank 6, the water distribution 131 and the liquid-phase ethylbenzene 108 are mixed and fed into the ethylbenzene evaporator 5, the ethylbenzene is completely gasified in the ethylbenzene supplementing evaporator 5, the gasified material 109 and the gas-phase outlet material of the ethylbenzene/water separation tank 6 are mixed and fed into a superheater 7 for heating, and then the material 113 is fed into a first dehydrogenation reactor 2 for reaction.
In order that the invention may be readily understood, the invention will be described in detail with reference to the following examples, which are provided for illustrative purposes only and are not intended to limit the scope of the invention.
The starting materials or components used in the present invention may be prepared by commercial or conventional methods unless specifically indicated.
[ Example 1]
A certain 12-ten-thousand-ton/year styrene device (8000 hours in annual operation) adopts the technology of preparing styrene by ethylbenzene dehydrogenation shown in figure 2, the flow of raw material ethylbenzene is divided into two parts, the two parts enter an ethylbenzene/water separation tank for 17.8 tons/hour, the flow of the raw material ethylbenzene enters an ethylbenzene supplementing evaporator for 6.2 tons/hour, the total flow of water distribution is 8.8 tons/hour, and the raw material ethylbenzene is completely fed into the ethylbenzene/water separation tank. The ethylbenzene/water separation tank separates out liquid phase ethylbenzene and water, the liquid phase ethylbenzene and water enter an azeotropic heat exchanger through a circulating pump control, the gasification rate is 4.7%, the separated out gas phase ethylbenzene/water azeotrope is 2 tons/hour and 3 strands of liquid phase ethylbenzene/water azeotrope enter an ethylbenzene supplementing evaporator, the liquefaction rate of the top gas of the ethylbenzene/styrene separation tower is 0.82 after passing through the azeotropic heat exchanger, the circulating water consumption of a tail gas cooler is 176 tons/hour, the heating steam of the ethylbenzene supplementing evaporator is 1.2 tons/hour, and the water mass content of the outlet of the ethylbenzene supplementing evaporator is 8%. The azeotropic evaporator has an operating pressure of 100kPaA and an evaporating temperature of 91 ℃, and adopts the top gas of the ethylbenzene/styrene separation tower as a heat source, and the top pressure is 36kPaA and the temperature is 101 ℃. The ethylbenzene supplementing evaporator adopts a kettle type heat exchanger structure, the raw material ethylbenzene and the gas-phase ethylbenzene water azeotrope are completely gasified in a shell pass, 0.35MPa water vapor is adopted for heating in a tube pass, the operating pressure is 98kPaA, the temperature is 120 ℃, gasified materials are mixed with gas-phase outlet materials of an ethylbenzene/water separation tank, the temperature is 98 ℃ after mixing, the operating pressure is 98kPaA, the materials are heated to 520 ℃ through a heater, water vapor from a vapor heating furnace sequentially enters a first dehydrogenation reactor, an intermediate heat exchanger and a second dehydrogenation reactor, the mass flow rate of the water vapor entering the vapor heating furnace is 15.3 tons/hour, the outlet temperature of a chamber A of the vapor heating furnace is 878 ℃, and the outlet temperature of a chamber B of the vapor heating furnace is 872 ℃; the operating pressure of the first dehydrogenation reactor was 54kPaA; the reaction temperature was 623℃and the second dehydrogenation reactor operating pressure was 44kPaA, the reaction temperature was 623 ℃
The water ratio of the device is 1.0, the heating steam of the ethylbenzene supplementary evaporator is 1.2 tons/hour, the circulating water consumption of the tail gas cooler is 176 tons/hour, and the energy consumption of the device is 253kgoe/t.SM.
[ Example 2]
A certain 12-ten-thousand-ton/year styrene device (8000 hours in annual operation) adopts the technology of preparing styrene by ethylbenzene dehydrogenation shown in figure 2, the flow of raw material ethylbenzene is divided into two parts, the two parts enter an ethylbenzene/water separation tank 21.1 ton/hour, the flow of the raw material ethylbenzene enters an ethylbenzene supplementing evaporator 2.9 ton/hour, the total flow of water distribution is 10.6 ton/hour, and all the raw material ethylbenzene enters the ethylbenzene water separation tank. The ethyl benzene/water separation tank separates out liquid phase ethyl benzene and water, the liquid phase ethyl benzene and water enter an azeotropic heat exchanger through a circulating pump control, the gasification rate is 5%, the separated gas phase ethyl benzene/water azeotrope is 0.9 ton/hr and 2 strands of liquid phase ethyl benzene/water azeotrope enter an ethyl benzene supplementing evaporator, the liquefaction rate of the top gas of the ethyl benzene/styrene separation tower is 0.97 after passing through the azeotropic heat exchanger, the circulating water consumption of a tail gas cooler is 30 tons/hr, the heating steam of the ethyl benzene supplementing evaporator is 0.6 tons/hr, and the water mass content of an outlet of the ethyl benzene supplementing evaporator is 8%. The azeotropic evaporator has an operating pressure of 100kPaA and an evaporating temperature of 91 ℃, and adopts the top gas of the ethylbenzene/styrene separation tower as a heat source, and the top pressure is 36kPaA and the temperature is 101 ℃. The ethylbenzene supplementing evaporator adopts a kettle type heat exchanger structure, the raw material ethylbenzene and the gas-phase ethylbenzene water azeotrope are completely gasified in a shell side, the tube side is heated by 0.35MPa water vapor, the pressure after gasification is 98kPaA, the temperature is 120 ℃, the gasified material is mixed with the gas-phase outlet material of the ethylbenzene/water separation tank, the temperature after mixing is 98 ℃, the pressure is 98kPaA, the mixture is heated to 520 ℃ by a heater, the water vapor from a vapor heating furnace sequentially enters a first dehydrogenation reactor, an intermediate heat exchanger and a second dehydrogenation reactor, the mass flow rate of the water vapor entering the vapor heating furnace is 16.1 tons/hour, the outlet temperature of the vapor heating furnace A chamber is 878 ℃, the outlet temperature of the vapor heating furnace B chamber is 866 ℃, and the operating pressure of the first dehydrogenation reactor is 54kPaA; the reaction temperature was 623℃and the second dehydrogenation reactor was operated at a pressure of 44kPaA and a reaction temperature of 623 ℃.
The water ratio of the device is 1.1, the heating steam of the ethylbenzene supplementary evaporator is 0.6 ton/h, the circulating water consumption of the tail gas cooler is 30 tons/h, and the energy consumption of the device is 259kgoe/t.SM.
[ Example 3]
The difference from example 1 is that the flow of the raw material ethylbenzene is divided into two streams at 24 tons/hour, and the two streams enter the ethylbenzene/water separation tank at 2.4 tons/hour, enter the ethylbenzene make-up evaporator at 21.6 tons/hour, and enter the ethylbenzene water separation tank at 8.8 tons/hour in total flow of water distribution.
The water ratio of the device is 1.0, the heating steam of the ethylbenzene evaporator is 4.2 tons/hour, the circulating water consumption of the tail gas cooler is 850 tons/hour, and the energy consumption of the device is 300kgoe/t.SM.
[ Example 4]
The difference from example 1 is that the flow of the raw material ethylbenzene is divided into two streams at 24 tons/hour, and the two streams enter the ethylbenzene/water separation tank at 4.8 tons/hour, enter the ethylbenzene make-up evaporator at 19.2 tons/hour, and enter the ethylbenzene water separation tank at 8.8 tons/hour in total flow of water distribution.
The water ratio of the device is 1.0, the heating steam of the ethylbenzene evaporator is 3.7 tons/hour, the circulating water consumption of the tail gas cooler is 760 tons/hour, and the energy consumption of the device is 285kgoe/t.SM.
[ Example 5]
The difference from example 1 is that the flow of the raw material ethylbenzene is divided into two streams of 24 tons/hour, and the two streams are fed into an ethylbenzene/water separation tank for 8 tons/hour, and the flow of the raw material ethylbenzene is fed into an ethylbenzene supplementing evaporator for 16 tons/hour, and the total flow of water distribution is 8.8 tons/hour, and all the raw material ethylbenzene is fed into the ethylbenzene water separation tank.
The water ratio of the device is 1.0, the heating steam of the ethylbenzene evaporator is 3.1 tons/hour, the circulating water consumption of the tail gas cooler is 450 tons/hour, and the energy consumption of the device is 273kgoe/t.SM.
[ Example 6]
The difference from example 1 is that the flow of the raw material ethylbenzene is divided into two streams of 24 tons/hour, and the two streams are fed into an ethylbenzene/water separation tank for 12 tons/hour, an ethylbenzene supplementing evaporator for 12 tons/hour, and a total flow of 8.8 tons/hour of water distribution, and all the two streams are fed into the ethylbenzene water separation tank.
The water ratio of the device is 1.0, the heating steam of the ethylbenzene evaporator is 2.3 tons/hour, the circulating water consumption of the tail gas cooler is 380 tons/hour, and the energy consumption of the device is 265kgoe/t.SM.
[ Example 7]
The difference from example 1 is that the ethylbenzene/water separation tank separates liquid phase ethylbenzene and water, the liquid phase ethylbenzene and water enter the azeotropic heat exchanger through the control of a circulating pump, the gasification rate is 10%, and 3 parts of separated gas phase ethylbenzene/water azeotrope of 0.4 ton/hour enter the ethylbenzene make-up evaporator.
The water ratio of the device is 1.0, the heating steam of the ethylbenzene evaporator is 1.5 tons/hour, the circulating water consumption of the tail gas cooler is 200 tons/hour, and the energy consumption of the device is 260kgoe/t.SM. The device can be operated for a long time by the ethylbenzene evaporator, and the phenomenon that the polymer blocks the heat exchanger can occur.
[ Example 8]
The difference from example 1 is that the ethylbenzene/water separation tank separates out liquid phase ethylbenzene and water, the liquid phase ethylbenzene and water enter the azeotropic heat exchanger through the control of a circulating pump, the gasification rate is 12%, and 3 separated out liquid phase ethylbenzene/water azeotrope is 0.9 ton/hour and enters the ethylbenzene make-up evaporator.
The water ratio of the device is 1.0, the heating steam of the ethylbenzene evaporator is 1.45 tons/hour, the circulating water consumption of the tail gas cooler is 190 tons/hour, and the energy consumption of the device is 258kgoe/t.SM.
[ Example 9]
The difference from example 1 is that the ethylbenzene/water separation tank separates out liquid phase ethylbenzene and water, the liquid phase ethylbenzene and water enter the azeotropic heat exchanger through a circulating pump control, the gasification rate is 15%, and 3 separated out liquid phase ethylbenzene/water azeotrope is 2.7 tons/hour and enters the ethylbenzene make-up evaporator.
The water ratio of the device is 1.0, the heating steam of the ethylbenzene evaporator is 1.1 ton/hour, the circulating water consumption of the tail gas cooler is 180 tons/hour, the energy consumption of the device is 256kgoe/t.SM,
[ Example 10]
The difference from example 1 is that the ethylbenzene/water separation tank separates out liquid phase ethylbenzene and water, the liquid phase ethylbenzene and water are controlled by a circulating pump to enter an azeotropic heat exchanger, the gasification rate is 15%, and 3 separated out liquid phase ethylbenzene/water azeotrope is 3.6 tons/hour and 3 streams enter an ethylbenzene make-up evaporator.
The water ratio of the device is 1.1, the heating steam of the ethylbenzene evaporator is 0.5 ton/hour, the circulating water consumption of the tail gas cooler is 200 tons/hour, and the energy consumption of the device is 265kgoe/t.SM.
Comparative example 1
A10 ten thousand tons/year styrene device (8000 hours of annual operation time) adopts the low water ratio azeotropic energy-saving mode shown in the figure 1 of the prior art, an independent ethylbenzene evaporation system is arranged, the flow of raw material ethylbenzene is divided into two flows, the two flows enter an ethylbenzene/water separation tank 14.5 tons/hour, the flow of the ethylbenzene supplement evaporator is 6.5 tons/hour, the total flow of water distribution is 7.3 tons/hour, and all the raw material ethylbenzene flows enter the ethylbenzene/water separation tank. The weight content of water in the ethylbenzene/water separation tank is 33.4%, and 145 tons/hour of separated ethylbenzene and 73 tons/hour of separated water enter an azeotropic evaporator to be partially gasified. The operation pressure of the azeotropic evaporator is 100kPaA, the evaporation temperature is 91 ℃, the top gas of the ethylbenzene/styrene separation tower is used as a heat source, the top pressure is 38kPaA, the temperature is 102 ℃, and the partially gasified gas-liquid mixture is returned to the ethylbenzene/water separation tank. The ethylbenzene supplementing evaporator adopts a kettle type heat exchanger structure, the raw material ethylbenzene and the gas phase ethylbenzene water azeotrope are completely gasified in a shell side, 0.6MPaG water vapor is adopted for heating in a tube side, the pressure after gasification is 100kPaA, the temperature is 132 ℃, the gasified material is mixed with the gas phase outlet material of the ethylbenzene/water separation tank, the temperature after mixing is 104 ℃, the pressure is 98kPaA, the mixture is heated to 500 ℃ through a heater, the water vapor from a vapor heating furnace sequentially enters a first dehydrogenation reactor, an intermediate heat exchanger and a second dehydrogenation reactor, the mass flow rate of the water vapor entering the vapor heating furnace is 13.5 tons/hour, the outlet temperature of a vapor heating furnace A chamber is 880 ℃, the outlet temperature of a vapor heating B chamber is 860 ℃, and the operating pressure of the first dehydrogenation reactor is 54kPaA; the reaction temperature was 623℃and the second dehydrogenation reactor was operated at a pressure of 44kPaA and a reaction temperature of 623 ℃.
The water ratio of the device is 1.0, the heating steam of the ethylbenzene evaporator is 1.2 tons/hour, the supplementing steam of the ethylbenzene evaporator is 0.56 tons/hour, the circulating water consumption of the tail gas cooler is 200 tons/hour, and the energy consumption of the device is 265kgoe/t.SM.
Comparative example 2
A certain 12 ten thousand tons/year styrene device (8000 hours of annual operation time) adopts the low water ratio azeotropic energy-saving mode shown in the figure 1 of the prior art, an independent ethylbenzene evaporation system is arranged, the flow of raw material ethylbenzene is divided into two parts, the two parts enter an ethylbenzene/water separation tank, the flow of the ethylbenzene is 6.2 tons/hour, the total flow of water distribution is 8.8 tons/hour, and all the raw material ethylbenzene is fed into the ethylbenzene/water separation tank. The weight content of water in the ethylbenzene/water separation tank was 33.1%. The operation pressure of the azeotropic evaporator is 100kPaA, the evaporation temperature is 91 ℃, the top gas of the ethylbenzene/styrene separation tower is used as a heat source, the top pressure is 36kPaA, the temperature is 101 ℃, and the partially gasified gas-liquid mixture is returned to the ethylbenzene/water separation tank. The ethylbenzene supplementing evaporator adopts a kettle type heat exchanger structure, the raw material ethylbenzene and the gas-phase ethylbenzene water azeotrope are completely gasified in a shell side, 0.6MPaG water vapor is adopted for heating in a tube side, the pressure after gasification is 98kPaA, the temperature is 120 ℃, the gasified material is mixed with the gas-phase outlet material of the ethylbenzene/water separation tank, the temperature after mixing is 98 ℃, the pressure is 98kPaA, the mixture is heated to 520 ℃ through a heater, the water vapor from a vapor heating furnace sequentially enters a first dehydrogenation reactor, an intermediate heat exchanger and a second dehydrogenation reactor, the outlet temperature of a chamber A of the vapor heating furnace is 878 ℃, the outlet temperature of a chamber B of the vapor heating furnace is 872 ℃, and the operating pressure of the first dehydrogenation reactor is 54kPaA; the reaction temperature was 623℃and the second dehydrogenation reactor was operated at a pressure of 44kPaA and a reaction temperature of 623 ℃. The water ratio of the device is 1.1, the steam supplement of the ethylbenzene evaporator is 0.6 ton/hour, the circulating water consumption of the tail gas cooler is 120 ton/hour, and the energy consumption of the device is 285kgoe/t.SM.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (9)
1. A raw material gasification method for preparing styrene by ethylbenzene dehydrogenation comprises the following steps:
S1: feeding a material flow VI comprising raw material ethylbenzene and raw material water into an ethylbenzene/water separation tank to obtain a liquid-phase ethylbenzene/water mixture;
S2: partially gasifying the liquid-phase ethylbenzene/water mixture through an azeotropic evaporator to obtain a material flow I, wherein the material flow I comprises a gas-phase ethylbenzene/water azeotropic material flow II and a gas-liquid mixture III;
S3: the raw material ethylbenzene IV and the gas-phase ethylbenzene/water azeotropic material flow II enter an ethylbenzene supplementing evaporator, and a material flow V is obtained after complete gasification and enters a subsequent reaction system;
the operating pressure of the ethylbenzene/water separation tank is 70-120kPaA, and the temperature is 85-97 ℃;
the raw material ethylbenzene IV accounts for 10-35% of the total raw material ethylbenzene; the ethylbenzene in stream VI represents 65-90% of the total feed ethylbenzene mass.
2. The method according to claim 1, characterized in that the method further comprises S4: and returning the gas-liquid mixture III to an ethylbenzene/water separation tank to obtain a gas-phase outlet material flow VII, wherein the material flow VII enters a subsequent reaction system.
3. The process of claim 2, wherein the stream V and the stream VII are mixed to obtain a stream VIII, and wherein the stream VIII is fed to a subsequent reaction system.
4. A process according to any one of claims 1 to 3, wherein the feed water in stream VI is present in an amount of 30 to 40% by weight; and/or
The gasification rate of the material flow I is 4% -20%; and/or said stream II comprises 5-15% of the mass of the feed ethylbenzene IV; and/or
The mass fraction of water in the stream V is 5-10%.
5. A process according to any one of claims 1 to 3, wherein in S3 the gaseous ethylbenzene/water azeotrope stream II is fed to the ethylbenzene make-up evaporator in multiple passes.
6. A process according to any one of claims 1 to 3, wherein the feedstock ethylbenzene IV comprises from 12 to 30% of the total feedstock ethylbenzene mass; the ethylbenzene in stream VI accounts for 70-88% of the total feed ethylbenzene mass.
7. A process according to any one of claims 1 to 3, wherein the azeotropic vaporizer is operated at a pressure of from 70 to 120kPaA and a temperature of from 85 to 97 ℃; and/or
The operation pressure of the ethylbenzene supplementing evaporator is 80-120KPaA, and the temperature is 100-140 ℃; and/or
The pressure of stream VIII is 80-120kPaA and the temperature is 85-130 ℃.
8. A process according to any one of claims 1 to 3, wherein the azeotropic vaporizer employs ethylbenzene/styrene separation column overhead gas as a heat source; and/or the ethylbenzene make-up evaporator is heated with steam.
9. Use of a process according to any one of claims 1 to 8 in the dehydrogenation of ethylbenzene to styrene.
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| CN114436744A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Method and system for preparing styrene by ethylbenzene dehydrogenation |
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