WO2023050988A1 - 一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法 - Google Patents

一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法 Download PDF

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WO2023050988A1
WO2023050988A1 PCT/CN2022/108063 CN2022108063W WO2023050988A1 WO 2023050988 A1 WO2023050988 A1 WO 2023050988A1 CN 2022108063 W CN2022108063 W CN 2022108063W WO 2023050988 A1 WO2023050988 A1 WO 2023050988A1
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styrene
tower
ethylbenzene
pressure
reboiler
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English (en)
French (fr)
Inventor
张晶
和成刚
顾佳慧
周海燕
陈霞
徐志刚
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CHANGZHOU RUIHUA CHEMICAL ENGINEERING TECHNOLOGY Co Ltd
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CHANGZHOU RUIHUA CHEMICAL ENGINEERING TECHNOLOGY Co Ltd
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Priority to US18/009,541 priority Critical patent/US12121835B2/en
Priority to EP22818169.9A priority patent/EP4180102A4/en
Publication of WO2023050988A1 publication Critical patent/WO2023050988A1/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
    • B01D3/322—Reboiler specifications
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/007—Energy recuperation; Heat pumps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/42—Regulation; Control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • B01D5/006—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
    • Y02B30/52—Heat recovery pumps, i.e. heat pump based systems or units able to transfer the thermal energy from one area of the premises or part of the facilities to a different one, improving the overall efficiency
    • 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

Definitions

  • the invention belongs to the technical field of petrochemical industry, and in particular relates to a method for refining styrene in which a falling film reboiler and a heat pump technology are combined to provide a heat source required by a separation tower.
  • Styrene is the third largest polymer monomer after ethylene and propylene.
  • styrene is mainly used in the production of polystyrene and ABS/SAN resin.
  • expandable polystyrene (EPS) accounts for about 38% of the total consumption
  • non-expandable polystyrene (GPPS/HIPS)
  • ABS/SAN resin accounts for about 10%
  • unsaturated polyester UPR
  • SBR/SBL styrene-based copolymers
  • SBR/SBL styrene-based thermoplastic elastomers, methacrylic acid-butadiene-styrene copolymers resins, styrene-divinyl based ion exchange resins, etc.
  • the mainstream styrene production methods include ethylbenzene catalytic dehydrogenation method, styrene-propylene oxide co-production method (ie, ethylbenzene co-oxidation method), ethylbenzene dehydrogenation selective oxidation method, pyrolysis gasoline extraction distillation recovery method, etc.
  • the catalytic dehydrogenation method of ethylbenzene and the cogeneration method of styrene-propylene oxide that is, the co-oxidation method of ethylbenzene
  • the former accounts for around 85% of styrene production capacity.
  • Chinese patent CN 1163289C discloses a series reboil method of ethylbenzene/styrene towers. This patent needs to set up two thermally coupled high and low pressure towers. The feed sources of the two towers are the same, their composition and temperature are the same, and the products with the same composition are separated from the two tower bottoms, and they are used as the feed of the other tower at the same time.
  • this scheme only provides the thermal coupling of the high and low pressure ethylbenzene/styrene tower itself, and the utilization rate of heat energy is still at a relatively low level.
  • Chinese patent CN101602640B discloses an energy-saving separation method of ethylbenzene/styrene, which divides the ethylbenzene/styrene separation tower from a single tower into two towers for operation, wherein a part of the overhead steam of ethylbenzene/styrene separation tower A Or all of them are imported into the compressor, and the compressed process gas is used as the heat source of the ethylbenzene/styrene separation tower B reboiler.
  • This patent additionally uses compressor pressurization to ensure the thermal coupling effect between the high and low pressure towers.
  • This method has high energy consumption and poor economy, and can only carry out the heat pump cycle process between the high and low pressure ethylbenzene/styrene towers , energy utilization needs to be further improved.
  • Chinese patent CN105669354B discloses a method for separating ethylbenzene dehydrogenation reaction products, which separates the dehydrogenation mixed liquid through a crude styrene separation tower, and compresses the gas phase containing benzene, toluene and ethylbenzene at the top of the tower as a method for separating benzene from the top of the tower.
  • Toluene the heat source of the tower reboiler for the separation of ethylbenzene in the tower kettle and the heat source of the tower reboiler as a styrene product.
  • the separation of ethylbenzene/styrene is realized by only one tower, and the inlet gas of the compressor contains almost all the benzene and toluene brought in by the dehydrogenation mixture, so the inlet pressure and temperature of the compressor are relatively low, which will bring The problem of high consumption and poor economy.
  • the existing styrene refining process still has the problems of insufficient energy utilization, high energy consumption and poor economy, so it is necessary to further explore and improve the existing process.
  • the purpose of the present invention is to solve the deficiencies in the prior art, disclose a kind of falling film type reboiler and heat pump technology combination to provide the styrene refining method of the heat source required by the separation tower, mainly in the high and low pressure coupling ethylbenzene/styrene Based on the separation tower energy-saving technology, through open or closed heat pump circulation, combined with the arrangement and utilization of the falling film reboiler, the energy consumption in the styrene separation process can be further greatly reduced, the energy utilization rate can be improved, and the economical efficiency of the device can be improved.
  • the technical solution of the present invention is: a falling film reboiler and heat pump technology combined to provide a styrene refining method for the heat source required by the separation tower, the refining route includes a pre-separation tower, a high-pressure ethylbenzene/styrene tower from upstream to downstream , low-pressure ethylbenzene/styrene tower and styrene product tower, the total flow of the pre-separation tower kettle flowing out from the bottom of the pre-separation tower is divided into two streams and sent to the high and low pressure ethylbenzene/styrene tower respectively; the high and low pressure ethylbenzene/benzene
  • the ethylbenzene stream separated from the top of the ethylene tower is sent to the dehydrogenation unit as a raw material, and the corresponding column stream is sent to the styrene product tower; the tar from the
  • the pre-separation tower is equipped with a reboiler that uses the gas phase medium sent by the open or closed heat pump as the heat source;
  • the styrene product tower is equipped with a reboiler using the gas phase medium sent by an open or closed heat pump as a heat source;
  • the open heat pump cycle is to connect the ethylbenzene heat pump compressor to the top of the low-pressure ethylbenzene/styrene tower, and a part of the gaseous phase flowing out of the top of the tower is compressed by the ethylbenzene heat pump compressor and used as a pre-separation tower and/or product styrene tower Another part of the non-pressurized gas phase stream is sent to the low-pressure ethylbenzene/styrene column condenser for condensation, and the condensate is collected together with the stream condensed by the pre-separation column reboiler and/or styrene product column reboiler.
  • the pressurization is used as the total stream of condensate, a part of the total stream of condensate is used as the reflux of the low-pressure ethylbenzene/styrene tower, and the rest is sent to the ethylbenzene dehydrogenation unit as the production stream for recycling;
  • the closed heat pump cycle is to send the gaseous stream at the top of the low-pressure ethylbenzene/styrene tower as a heat source to the heat pump working fluid evaporator of the low-pressure ethylbenzene/styrene tower for evaporating the heat pump working fluid, and the uncondensed stream continues to be sent to the low-pressure ethylbenzene / Styrene tower after condenser condenses; the evaporated heat pump working fluid is pressurized by the working fluid heat pump compressor, and then sent to the pre-separation tower reboiler and/or the styrene product tower reboiler as a heat source, and passes through the pre-separation tower The heat pump working fluid condensed by the reboiler and/or the reboiler of the styrene product column is recycled to the heat pump working fluid evaporator of the low-pressure ethylbenzen
  • the ethylbenzene heat pump compressor and the working medium heat pump compressor can be set up jointly, and provide heat for the pre-separation tower and the styrene product tower reboiler at the same time; Compressors with different outlet pressures are set independently for different condensing pressures required on the heat source side of the boiler.
  • the reboiler on the pre-separation column, the reboiler on the styrene product column and the low-pressure ethylbenzene/styrene reboiler are all falling film reboilers.
  • both the falling film reboiler of the pre-separation tower and the falling film reboiler of the product styrene tower are equipped with circulation pumps to establish the circulation flow required by the falling film reboiler.
  • the top of the pre-separation tower is connected to the condenser of the pre-separation tower
  • the top of the styrene product tower is connected to the condenser of the styrene product tower
  • both condensers use circulating water as a cooling source.
  • the circulating water used in the styrene product tower condenser and the pre-separation tower condenser is connected in series with the circulating water used in the low-pressure ethylbenzene/styrene tower condenser, and the styrene product tower condenser and the pre-separation tower Condensers are placed at the front of the circulating water process;
  • the circulating water used in the condenser of the styrene product column and the condenser of the pre-separation column are connected in series with the circulating water used in the postcondenser of the low-pressure ethylbenzene/styrene column, and the condenser of the styrene product column and the pre-separation column Separation tower condensers are placed at the front of the circulating water process.
  • the operating pressure of the low-pressure ethylbenzene/styrene column is 7-17KPaA.
  • the operating pressure of the pre-separation tower is 12-19KPaA.
  • the operating pressure of the styrene product tower is 2-5KPaA.
  • the present invention further utilizes heat pump technology and in conjunction with the use of falling film reboiler to reduce the overhead energy of the low-pressure ethylbenzene/styrene tower
  • this design can make full use of the heat transfer temperature difference, further greatly reduce the energy consumption in the styrene separation process, and improve the production process accordingly and put it into production in a short period of time Cost recovery, significant long-term economic benefits;
  • the present invention can adopt the combination of open heat pump technology and falling film reboiler to realize the reuse of energy from the top of the low-pressure ethylbenzene/styrene tower, which mainly separates the top of the low-pressure ethylbenzene/styrene tower directly through the compressor
  • the high-concentration gas-phase ethylbenzene is pressurized, and the directly pressurized stream is sent to the falling film reboiler with small heat transfer temperature difference, which can be used as the heat source of the pre-separation tower in the styrene separation process and as the product styrene Tower heat source to achieve the purpose of saving energy and operating costs;
  • the present invention can also adopt closed-type heat pump technology and falling film reboiler to realize the reutilization of the tower top energy of low-pressure ethylbenzene/styrene tower in combination, and it mainly separates the high-energy by low-pressure ethylbenzene/styrene tower top Concentration gas phase ethylbenzene gasifies the heat pump working fluid, and pressurizes the gasified heat pump working fluid, and the indirect gasified and pressurized stream is sent to the falling film reboiler that requires a small heat transfer temperature difference to be used as benzene
  • the pre-separation tower and or product styrene tower heat source in the ethylene separation process achieves the purpose of saving energy and operating costs;
  • the present invention on the basis of selecting and utilizing heat pump technology and falling film reboiler, simultaneously uses the available circulating water condensation tower top gas phase as the tower pressure design bottleneck of pre-separation tower and styrene product tower, reduces pre-separation tower and /or the operating pressure of the two heated towers of the styrene product tower and the pressure difference between the top and the bottom of the tower to reduce the temperature of the tower kettle and achieve the effect of saving energy consumption of the compressor;
  • the present invention not only enables the heat input from the high-pressure ethylbenzene/styrene tower tank to be used three times, but also has the function of increasing the operating pressure at the top of the low-pressure ethylbenzene/styrene separation tower and reducing the pressure of the pre-separation tower and/or styrene product tower. Reduced heat pump compressor power advantage.
  • Fig. 1 is the styrene refining process roadmap that the combination of open heat pump technology and falling film reboiler provides the required heat source for pre-separation tower and styrene product tower disclosed in embodiment 1;
  • Fig. 2 is the styrene refining process roadmap that closed heat pump technology and falling film reboiler are combined to provide the required heat source of pre-separation tower and styrene product tower disclosed in embodiment two;
  • Fig. 3 is a styrene refining process roadmap that combines the open heat pump technology and the falling film reboiler to provide the heat source required for the styrene product tower disclosed in Application Example 1;
  • Fig. 4 is the process roadmap for refining styrene that combines the open heat pump technology and the falling film reboiler to provide the required heat source for the pre-separation tower disclosed in Application Example 2;
  • Fig. 5 is a styrene refining process roadmap that combines the closed heat pump technology and the falling film reboiler to provide the heat source required by the styrene product tower disclosed in Application Example 3;
  • T-101 Pre-separation tower
  • T-102 High pressure ethylbenzene/styrene tower
  • T-103 Low pressure ethylbenzene/styrene tower
  • T-104 Styrene product tower
  • E-101 Pre-separation tower falling film Reboiler
  • E-102 pre-separation tower condenser
  • E-103 high pressure ethylbenzene/styrene column reboiler
  • E-104 low pressure ethylbenzene/styrene column falling film reboiler
  • E-105 Low pressure ethylbenzene/styrene tower condenser
  • E-106 Styrene product tower falling film reboiler
  • E-107 Styrene product tower condenser
  • E-108 Low pressure ethylbenzene/styrene tower heat pump working fluid evaporation
  • E-109 low-
  • the dehydrogenation mixed liquid contains water, benzene, toluene, ethylbenzene, styrene, and tar components.
  • benzene, toluene and a small amount of water in the dehydrogenated mixed liquid are separated, and the tower is separated Ethylbenzene, styrene, and tar, so the temperature difference between the top and bottom of the tower is large.
  • the typical temperature at the top of the tower is 55.18°C
  • the typical temperature at the bottom of the tower is 91.9°C
  • the temperature difference between the top and the bottom is 36.72°C.
  • a heat pump for the reboiler is not economical.
  • the pressure drop at the top of the styrene product tower is 6KPaA
  • the gas-phase styrene temperature at the top of the tower is 63.56°C
  • the outlet temperature of the reboiler is 78.87°C.
  • the temperature difference between the top and the bottom of this tower is small, and a heat pump can be installed that uses the gas phase at the top of the tower as a heat source to heat its own tower kettle.
  • the heating steam grade of the pre-separation tower and the reboiler of the styrene product tower has adopted extremely low-pressure 0.04MPaG steam as the heat source, reducing the pre-separation tower and We have mature experience in controlling the temperature of the styrene product tower and ensuring the stable operation of the styrene separation process under high vacuum.
  • the pre-separation tower and styrene product tower have been tested to reduce the pressure of the top and bottom of the tower under low load conditions, and further through simulation calculations, it is judged that the pre-separation tower and styrene product tower pass through the falling film It is feasible and economical for the boiler to receive heat from the open or closed heat pump at the top of the low-pressure ethylbenzene/styrene column as a heat source.
  • Embodiment 1 The combination of falling film reboiler and open heat pump technology provides the styrene refining method for the heat source required by the separation tower
  • the present invention adds a heat pump to the existing rectification process device for separating ethylbenzene/styrene in the dehydrogenation mixed liquid with high and low pressure coupling towers cycle device.
  • the heat pump cycle that is, the reverse Carnot cycle, is to apply a small amount of high-grade energy to the low-temperature heat of the recovered tower top fluid through the compressor to raise its temperature level, which can be used as a heat source at the bottom of the tower, so as to achieve energy saving and economical operation purpose of the fee.
  • the heat pump process can be divided into open heat pump and closed heat pump; the open heat pump uses the compressor to directly compress the low-pressure ethylbenzene/styrene tower top high-concentration gas-phase ethylbenzene, which is used as a pre-separation tower and product styrene tower reboiler Heat source technology.
  • This example focuses on the styrene refining method in which the combination of the open heat pump technology and the falling film reboiler provides the heat source required by the pre-separation tower and the styrene product tower.
  • the combination of the open heat pump technology and the falling film reboiler provides the heat source required by the pre-separation tower and the styrene product tower.
  • the styrene refining operation line is equipped with four key columns in sequence from upstream to downstream, which are to separate the benzene and toluene components in the dehydrogenation mixed liquid from the top of the tower, and to separate the ethylbenzene and benzene components in the dehydrogenated mixed liquid.
  • Pre-separation tower T-101 that separates ethylene and tar components from the bottom of the tower; separates the ethylbenzene component from the top of the tower, separates the styrene and tar components from the bottom of the tower, and has the same effect and thermally coupled high-pressure ethylbenzene/benzene Ethylene tower T-102 and low-pressure ethylbenzene/styrene tower T-103; and styrene product tower T-104 that separates styrene products from the top of the tower and separates all tar and a small part of styrene entrained from the bottom of the tower;
  • the top of the pre-separation tower T-101 is connected to the pre-separation tower condenser E-102.
  • the condensed liquid phase is collected and pressurized by the reflux tank and used as reflux and recovery.
  • the pre-separation of the bottom of the pre-separation tower T-101 The total stream 11 of the tower kettle is divided into two shares (i.e.
  • Benzene/styrene tower T-103; the lower part of the pre-separation tower T-101 is connected with the falling film reboiler E-101 of the pre-separation tower.
  • the styrene product tower T-104 is connected with the falling film reboiler E-106 of the styrene product tower T-104, and the total stream 15 extracted from the bottom of the styrene product tower T-104 is divided into styrene recovery tower feed 17 and styrene
  • the product tower recycle stream 16 the styrene product tower recycle stream 16 flows through the styrene product tower falling film reboiler E-106, and the heated recycle stream is output and returns to the lower area of the styrene product tower T-104;
  • the top of the tower is connected to the styrene product tower condenser E-107, and the condensed liquid phase is collected and pressurized through the reflux tank and used as reflux and the product styrene.
  • the high-pressure ethylbenzene/styrene tower T-102 is connected with the high-pressure ethylbenzene/styrene tower reboiler E-103, and the high-pressure ethylbenzene/styrene tower T-102 bottom extracts mainly contain high-concentration styrene monomer
  • the high-pressure column product stream 21 is sent to the styrene product column T-104, and the gas phase distillate at the top of the tower mainly contains ethylbenzene, and the gas phase distillate at the top of the tower is used for the heat of the falling film reboiler of the low-pressure ethylbenzene/styrene column Supply, the gas phase stream is condensed after heat transfer to the falling film reboiler of the low-pressure ethylbenzene/styrene tower, part of it is used as reflux, and the other part is extracted as recycled e
  • the low-pressure ethylbenzene/styrene tower T-103 is connected with the falling-film reboiler E-104 of the low-pressure ethylbenzene/styrene tower.
  • the low-pressure column effluent 18 of the body is divided into a low-pressure column product stream 20 and a low-pressure column recycle stream 19, and the low-pressure column product stream 20 is sent to the styrene product tower T-104, and the low-pressure column recycle stream 19 flows through the low-pressure ethylbenzene/benzene
  • the falling film reboiler E-104 of the ethylene tower is partially vaporized after being heated by the gaseous stream from the top of the high-pressure ethylbenzene/styrene tower, and returns to the bottom of the low-pressure ethylbenzene/styrene tower T-103.
  • the overhead gas stream 1 of the low-pressure ethylbenzene/styrene tower T-103 is divided into two streams, and one stream can be divided into two streams after being pressurized by the ethylbenzene heat pump compressor C-101, and the first gas stream 2 is sent to the pre-
  • the falling film reboiler E-101 of the separation tower is used as the heat source of the pre-separation tower T-101, and the second gas phase stream 3 is sent to the falling film reboiler E-106 of the styrene product tower as the heat source of the styrene product tower T-104.
  • Another unpressurized gas phase flow 4 is sent to the low-pressure ethylbenzene/styrene tower condenser E-105 to condense, the condensate 5 and the first condensate flow 6 condensed by the falling film reboiler E-101/E-106 , the second condensate stream 7 are collected together and pressurized as the total stream 8 of the condensate, the total stream 8 of the condensate is sent to the ethylbenzene removal as the reflux 9 of the low-pressure ethylbenzene/styrene tower T-103 or as the total production stream 10 Hydrogen recycling.
  • the low-pressure ethylbenzene/styrene tower condenser E-105 plays an auxiliary role in adjusting the condensation load during startup and shutdown or fluctuating working conditions.
  • the falling film reboiler E-101 of the pre-separation tower needs a supporting circulation pump to establish the circulation stream 12 of the pre-separation tower.
  • the falling film reboiler E-106 of the styrene product tower needs a supporting circulation pump to establish the styrene product tower recycle stream 16.
  • the pre-separation tower condenser E-102, the low-pressure ethylbenzene/styrene tower condenser E-105, and the styrene product tower condenser E-107 in this embodiment are still the same as the aforementioned high and low pressure coupling sequential separation process, and are composed of circulating water as a cold source.
  • the circulating water used in the styrene product tower condenser E-107 and the pre-separation tower condenser E-102 is connected in series with the circulating water used in the low-pressure ethylbenzene/styrene tower condenser E-105, and the styrene product tower condenser E-107 and The pre-separation tower condenser E-102 is placed at the front of the circulating water process in order to save the consumption of circulating water.
  • the dehydrogenation liquid 23 first enters the pre-separation tower T-101, which is a high-efficiency packed rectification tower operated under negative pressure conditions.
  • the light components are separated from the top of the pre-separation tower T-101, and the total stream 11 of the pre-separation tower bottom is obtained at the bottom of the tower (mainly a mixture containing ethylbenzene, styrene, tar), and then the total stream 11 of the pre-separation tower Divided into two streams (i.e.
  • the main equipment of the ethylbenzene recovery and crude styrene separation system are two high-efficiency low-pressure drop packed towers T-102/T-103 coupled with high and low pressure; the ethylbenzene distilled from the tower is recycled back to the dehydrogenation reaction system as a reactor A part of feeding ethylbenzene;
  • the crude styrene obtained at the bottom of the tower is that the low-pressure tower product stream 20 and the high-pressure tower product stream 21 are collected into the total feed 22 of the styrene product tower and sent into the styrene product tower T-104 for separation to obtain qualified Styrene products;
  • Tower top gas stream 1 is divided into two streams, one stream is divided into two streams after being pressurized by ethylbenzene heat pump compressor C-101, and the first gas stream 2 is sent to pre-separation tower falling film reboiler E-101 As the pre-separation tower heat source, the second gas phase stream 3 is sent into the styrene product tower falling film reboiler E-106 as the styrene product tower T-104 heat source, and another unpressurized gas phase stream 4 is sent into the low-pressure ethylbenzene/ Styrene tower condenser E-105 condensation;
  • the main function of the styrene product tower T-104 is to produce styrene products at the top of the tower, and tar with a relatively high concentration of styrene in the bottom of the tower to form the feed 17 of the styrene recovery tower and send it to styrene recovery
  • the system recovers styrene, and produces tar with a styrene content of less than 6% in the styrene recovery system.
  • Embodiment 2 The combination of falling film reboiler and closed heat pump technology provides the styrene refining method for the heat source required by the separation tower
  • This example focuses on the styrene refining method in which the combination of closed heat pump technology and reboiler provides the heat source required for the separation tower. Refer to Figure 2 for the specific process route.
  • the evaporated heat pump working fluid 4' is pressurized by the working fluid heat pump compressor C-102, and is divided into the first heat pump working fluid gas stream 2' and the second heat pump working gas gas stream 3', and the two gas phase streams are respectively sent to
  • the falling film reboiler E-101 of the pre-separation tower and/or the falling film reboiler E-106 of the styrene product tower are used as heat sources, and the first condensing heat pump working fluid 6' and the second condensing heat pump condensed in E-101/106
  • the working fluid 7' is merged into the total condensing heat pump working fluid 5' and then circulated back to the low-pressure ethylbenzene/styrene tower heat pump working fluid evaporator E-108 to continue to be gasified and recycled.
  • the pre-separation tower falling film reboiler E-101 needs a supporting circulation pump to establish the pre-separation tower circulation stream 12 required by the falling film reboiler.
  • the falling film reboiler E-106 of the styrene product column needs a supporting circulation pump to establish the styrene product column circulation stream 16 required by the falling film reboiler.
  • the closed-type heat pump uses the high-concentration gas-phase ethylbenzene separated from the top of the low-pressure ethylbenzene/styrene tower T-103 to vaporize the heat pump working fluid, and pressurizes the gasified heat pump working fluid, which is indirectly gasified and pressurized
  • the working fluid of the heat pump is sent to the falling film reboiler with small heat transfer temperature difference as the heat source of the pre-separation tower T-101 and/or the styrene product tower T-104 in the styrene separation process.
  • Closed heat pump working fluid needs to be selected from the low-pressure ethylbenzene/styrene top gas phase vaporized medium, the pressure is suitable for compressor selection and the compressor power is low, such as: n-butane, isobutane, butene, pentane, cyclo Pentane, benzene, methanol, etc.
  • the pre-separation tower condenser E-102, the low-pressure ethylbenzene/styrene tower post-condenser E-109, and the styrene product tower condenser E-107 in this embodiment are still the same as the aforementioned high and low pressure coupling sequential separation process, and are formed by circulation Water acts as a cooling source.
  • the circulating water used in the condenser E-107 of the styrene product column and the condenser E-102 of the pre-separation column are connected in series with the circulating water used in the postcondenser E-109 of the low-pressure ethylbenzene/styrene column, and the condenser E-109 of the styrene product column
  • Both 107 and pre-separation tower condenser E-102 are placed at the front of the circulating water process in order to increase the heat exchange temperature difference between E-102 and E-107 and save circulating water consumption.
  • the pre-separation tower reboiler, the styrene product column reboiler and the low-pressure ethylbenzene/styrene reboiler used in the above-mentioned embodiments and the following application examples are all falling film reboilers, and the choice of falling film reboiler The reason is: falling film reboiler is one of the forms of reboiler, in addition to kettle reboiler, horizontal thermosiphon reboiler, vertical thermosiphon reboiler, forced circulation reboiler wait.
  • the falling film reboiler requires an additional liquid phase circulation pump and liquid phase distribution devices, such as distribution heads and liquid phase distribution plates.
  • the liquid phase is drawn into a film along the wall of the heat exchange tube through the above-mentioned distribution device, and the gas phase is evaporated along the film.
  • Other types of reboilers such as the thermosiphon type, do not need an additional circulation pump, and they circulate by the density difference of the heated liquid itself.
  • Falling film reboiler due to the circulation of the pump, its installation height relative to the tower body is generally not specially regulated, but the thermosiphon reboiler needs to be specially formulated according to its operating conditions and material properties.
  • the ratio of the material processed by the falling film reboiler to that of the thermosiphon reboiler is suitable for materials with high vacuum, strong heat sensitivity, and high viscosity. efficient.
  • the concentration of tar contained in the tower bottom and the gasification rate of the tower bottom reboiler are all related. It has more influence on the heat transfer effect of the reboiler. Therefore, it is necessary to use a falling film reboiler and reduce the heat transfer temperature difference between the tube and shell side of the falling film reboiler by increasing the styrene content in the styrene product column and reducing the gasification rate of the falling film reboiler.
  • Low-pressure ethylbenzene/styrene tower T-103 has a top pressure of 10KPaA and a temperature of 67.04°C.
  • the top of the tower contains high-concentration gas-phase ethylbenzene, which is boosted by ethylbenzene heat pump compressor C-101 and then sent to the styrene product tower to drop
  • the material flow of film reboiler E-106 is 78.86t/h;
  • the E-107 heat exchanger type BXM of the styrene product tower condenser is a through-flow heat exchanger with a diameter of 4000mm, a length of 7000mm, a heat exchange area of 3008m 2 and a weight of 101.8t.
  • the shell-side styrene gas is condensed by the tube-side circulating water, the pressure drop on the shell side is 0.4KPa, and the mass flow rate of uncondensed gas-phase styrene at the outlet of the heat exchanger is 725Kg/h;
  • the circulating water used in the overhead condenser E-107 of the styrene product is connected in series with the circulating water used in the low-pressure ethylbenzene/styrene tower condenser E-105, and E-107 is placed at the front of the circulating water process to increase the low-pressure ethylbenzene /Styrene tower condenser E-105 heat transfer temperature difference;
  • the heat load required by the falling film reboiler E-106 of the styrene product tower is 8059KW.
  • the falling film BEM heat exchanger has a diameter of 3800mm, a length of 8500mm, a heat exchange area of 3616m 2 , and a total volume of 129.5t.
  • the temperature difference is 7.2°C
  • the shell side temperature is 75.73°C-82.18°C
  • the tube side temperature is 67.5°C-70.66°C
  • the non-condensable gas volume at the shell side outlet is 1563Kg/h
  • the gasification rate is 7%;
  • Circulation pump for falling film reboiler of styrene product tower designed flow rate 1118m 2 /h (115% margin), head 36m, shaft power 132kw;
  • the styrene product tower T-104 has a tower diameter of 5000mm, a tower shell weight of 103.8t, and a packing volume of 353m 3 .
  • the styrene product tower uses 0.04MPaG steam as the heat source:
  • E-107 heat exchanger type BXM in the condenser of the styrene product tower, with a diameter of 2800mm, a heat exchange tube length of 6000mm, a heat exchange area of 1825m 2 and a weight of 56.7t.
  • the shell-side styrene gas is condensed by the tube-side circulating water, the pressure drop on the shell side is 0.9KPa, and the mass flow rate of uncondensed gas-phase styrene at the outlet of the heat exchanger is 356Kg/h;
  • the styrene product tower adopts a thermosyphon heat exchanger, and the required heat load is 8083KW. Need to consume 0.04PMPaG steam 12.89t/h. Two reboilers are required in parallel. The diameter of each reboiler is 2200mm, the length of the heat exchange tube is 3000mm, and the heat exchange area of each unit is 842m 2 . Each weighs 28.9t;
  • the styrene product tower T-104 has a tower diameter of 4200mm, a tower shell weight of 75.4t, and a packing volume of 249m 3 .
  • Low-pressure ethylbenzene/styrene tower T-103 has a top pressure of 10KPaA and a temperature of 67.04°C.
  • the high-concentration gas-phase ethylbenzene flowing out of the top of the tower is boosted by ethylbenzene heat pump compressor C-101 and then sent to the pre-separation tower
  • the material flow rate of falling film reboiler E-101 is 0.81t/h;
  • ethylbenzene heat pump compressor C-101 The inlet conditions of ethylbenzene heat pump compressor C-101 are: 10KPaA, temperature 67.04°C, material flow 50.81t/h; the outlet conditions of ethylbenzene heat pump compressor C-101 are: pressure 36KPaA; shaft power 657.8KW (compression Machine efficiency is calculated as 75%);
  • Pre-separation tower condenser E-102 heat exchanger type BXM diameter 2500mm, length 6000mm, heat exchange area 2238m 2 , weight 50.9t.
  • the shell-side styrene gas is condensed by the tube-side circulating water, the pressure drop on the shell side is 0.72KPa, and the flow rate of the uncondensed gas phase at the outlet of the heat exchanger is 3389Kg/h;
  • the circulating water used in the pre-separation tower condenser E-102 is connected in series with the circulating water used in the low-pressure ethylbenzene/styrene tower condenser E-105, and E-102 is placed at the front of the circulating water process to increase the heat transfer of E-105 temperature difference;
  • the heat load required by the pre-separation tower falling film reboiler E-101 is 4948KW
  • the falling film BEM heat exchanger has a diameter of 3000mm, a length of 6500mm, a heat exchange area of 3445m 2 , a total volume of 90.9t, a temperature difference of 8.5°C, and a shell side
  • the temperature is 91.33°C-98.79°C
  • the tube side temperature is 83.4°C-86.78°C
  • the non-condensable gas volume at the shell side outlet is 1316Kg/h
  • the gasification rate is 24.3%;
  • Circulating pump for falling film reboiler of styrene product tower design flow rate 276.8m 2 /h (115% margin), head 36m, shaft power 33kw;
  • the diameter of the pre-separation tower T-101 is 3400mm.
  • the pre-separation tower uses 0.04MPaG steam as the heat source:
  • the top pressure of the pre-separation tower T-101 is 20KPaA, the temperature is 55.18°C, the pressure in the bottom of the tower is 21.8KPaA, and the outlet temperature of the reboiler is 91.94°C;
  • the heat exchanger type of the pre-separation tower condenser E-102 is BXM, with a diameter of 2200mm, a heat exchange tube length of 6000mm, a heat exchange area of 1553m 2 and a weight of 38.5t.
  • the shell-side styrene gas is condensed by the tube-side circulating water, the pressure drop on the shell side is 0.58KPa, and the mass flow rate of uncondensed gas-phase styrene at the outlet of the heat exchanger is 1710Kg/h;
  • thermosiphon heat exchanger of the pre-separation tower The heat load required by the thermosiphon heat exchanger of the pre-separation tower is 4948KW. Need to consume 0.04PMPaG steam 7.92t/2h. Two reboilers are required to be connected in parallel. The diameter of each reboiler is 2000mm, the length of the heat exchange tube is 3000mm, and the heat exchange area of each unit is 712m 2 . Each weighs 26.1t;
  • the diameter of the pre-separation tower T-101 is 3800mm.
  • the application example 2 reduces the tower pressure compared with the traditional process, the weight of the tower, reboiler, and condenser of the application example 2 increases by almost 50%, and the investment increases by about 1 million yuan.
  • the application example 2 requires an additional investment of about 7.5 million yuan in compressors and falling film reboiler circulation pumps compared with the traditional process. Adding other supporting expenses, the increased investment cost of application example 2 can be recovered in about 4 years.
  • This application example uses a closed heat pump to send the overhead stream of the low-pressure ethylbenzene/styrene tower T-103 to the low-pressure ethylbenzene/styrene tower heat pump working fluid evaporator E-108, and the uncondensed stream continues to be sent to
  • the low-pressure ethylbenzene/styrene separation tower is condensed in the after-condenser E-109.
  • the vaporized heat pump working fluid 4' is pressurized by the working fluid heat pump compressor C-102, and the second heat pump working fluid gas phase stream 3' is sent to the falling film reboiler E-106 of the styrene product tower as a heat source. -106
  • the condensed second condensing heat pump working medium 7' is circulated back to the low-pressure ethylbenzene/styrene tower heat pump working medium evaporator E-108 to be continuously vaporized and recycled. See attached drawing 5 for details.
  • the inlet conditions of the working fluid heat pump compressor C-102 the medium is 1-butene, the pressure is 748KPaA, the temperature is 58°C, and the material flow rate is 88.5t/h; the outlet conditions of the working fluid heat pump compressor C-102 are: : Pressure 1150KPaA; shaft power 696.5KW (compressor efficiency is calculated as 65%);
  • the heat exchanger type of the condenser E-107 of the styrene product tower is BXM, with a diameter of 4000mm, a length of 7000mm, a heat exchange area of 3008m 2 and a weight of 101.8t.
  • the shell-side styrene gas is condensed by the tube-side circulating water, the pressure drop on the shell side is 0.4KPa, and the mass flow rate of uncondensed gas-phase styrene at the outlet of the heat exchanger is 725Kg/h;
  • the E-108 heat exchanger of the low-pressure ethylbenzene/styrene tower heat pump working fluid evaporator is BKM, with a diameter of 2500mm, a length of 7000mm, a heat exchange area of 2785m 2 and a weight of 71.98t.
  • the shell-side 1-butene gasification temperature is 57.99°C
  • the inlet temperature of the high-concentration gas phase ethylbenzene in the tube-side is 66.96°C
  • the outlet temperature of the tube-side is 60°C
  • the flow rate of uncondensed gas at the outlet of the tube-side is 1871Kg/h;
  • the circulating water used by the styrene product overhead condenser E-107 is connected in series with the circulating water used by the low-pressure ethylbenzene/styrene postcondenser E-109, and E-107 is placed at the front of the circulating water process to increase the E-109 heat transfer temperature difference;
  • the heat load required by the falling film reboiler E-106 of the styrene product tower is 8059KW.
  • the falling film BEM heat exchanger has a diameter of 4000mm, a length of 8500mm, a heat exchange area of 4019m 2 and a total volume of 156.8t.
  • the temperature difference is 6.2°C
  • the shell side temperature is 80.35°C-75.00°C
  • the tube side temperature is 67.5°C-70.16°C
  • the non-condensable gas volume at the shell side outlet is 0Kg/h
  • the gasification rate is 12%;
  • E-106 supporting circulating pump for styrene product tower falling film reboiler design flow rate 707m 2 /h (115% margin), head 36m, shaft power 85kw;
  • the diameter of the styrene product tower T-104 tower is 5000mm, the weight of the tower shell is 103.8t, and the packing volume is 353m 3 ;
  • the styrene product tower uses 0.04MPaG steam as the heat source:
  • the heat exchanger of the styrene product tower condenser E-107 is BXM, with a diameter of 2800mm, a heat exchange tube length of 6000mm, a heat exchange area of 1825m 2 and a weight of 56.7t.
  • the shell-side styrene gas is condensed by the tube-side circulating water, the pressure drop on the shell side is 0.9KPa, and the mass flow rate of uncondensed gas-phase styrene at the outlet of the heat exchanger is 356Kg/h;
  • thermosiphon heat exchanger of the styrene product tower 8083KW. Need to consume 0.04PMPaG steam 12.89t/h.
  • Two reboilers are required to be connected in parallel. The diameter of each reboiler is 2200mm, the length of the heat exchange tube is 3000mm, and the heat exchange area of each unit is 842m 2 . Each weighs 28.9t;
  • the diameter of the product styrene tower T-104 is 4200m 2 , the weight of the tower shell is 75.4t, and the packing volume is 249m 3 .
  • the application example 3 reduces the tower pressure compared with the traditional process, the weight of the tower, reboiler and condenser in the application example 3 is almost doubled, and the low-pressure ethylbenzene/styrene tower heat pump working fluid evaporator is added E-108.
  • the investment increased by about 4 million yuan.
  • the application example 3 requires an additional investment of about 8.5 million yuan in compressors and falling film reboiler circulating pumps compared with the traditional process. Adding other supporting expenses, the increased investment cost of Application Example 3 can be recovered in about 2.5 years.
  • the present invention realizes the connection between the low-pressure ethylbenzene/styrene tower T-103, the pre-separation tower T-101 and the styrene product tower T-104 by increasing the heat pump circulation process flow and combining the use of the falling film reboiler.
  • the energy consumption in the styrene separation process can be further greatly reduced, and the input cost can be recovered after several years of operation, and the long-term The economic and environmental benefits are obvious.

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Abstract

本发明公开一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，其是在现有的高低压耦合的乙苯/苯乙烯分离塔节能技术基础上，通过压缩机直接将低压乙苯/苯乙烯塔顶分离出的高浓度气相乙苯增压或利用低压乙苯/苯乙烯塔顶分离出的高浓度气相乙苯气化热泵工质，并将气化后的热泵工质增压，被直接增压后的气相物流或间接气化并增压后的物流送入传热温差需求小的降膜式再沸器作为苯乙烯分离流程中的预分离塔和或苯乙烯产品塔热源。该方案进一步大幅降低了苯乙烯分离过程中的能耗，对生产流程进行相应改进并投入生产后可在较短年限内收回成本，长期经济效益显著。

Description

一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法 技术领域
本发明属于石油化工技术领域，具体涉及一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法。
背景技术
苯乙烯是仅次于乙烯、丙烯的第三大聚合物单体，我国苯乙烯主要应用于聚苯乙烯、ABS/SAN树脂的生产。其中可发性聚苯乙烯(EPS)约占总消费量的38％，非可发性聚苯乙烯(GPPS/HIPS)约占31％，ABS/SAN树脂约占10％，不饱和聚酯(UPR)约占7％，丁苯橡胶/丁苯胶乳(SBR/SBL)约占7％，其他为苯乙烯系共聚物(苯乙烯系热塑性弹性体、甲基丙烯酸-丁二烯-苯乙烯共聚树脂、苯乙烯-二乙烯基本离子交换树脂等)。
目前主流的苯乙烯生产方法有乙苯催化脱氢法、苯乙烯-环氧丙烷联产法(即乙苯共氧化法)、乙苯脱氢选择性氧化法、裂解汽油抽提蒸馏回收法等，其中以乙苯催化脱氢法和苯乙烯-环氧丙烷联产法(即乙苯共氧化法)为主。前者约占苯乙烯生产能力的85％左右。联产法尽管工艺流程较复杂，投资较大，但由于能同时获得两种重要的基本有机原料，近年来发展迅速。到2020年为止，我国苯乙烯的主要生产企业有40多家，苯乙烯生产能力超过1000万吨/年。
李雪云在华东理工大学硕士学位论文《苯乙烯精馏阻聚剂研究》中，通过试验揭示了在不加入阻聚剂时，不同温度情况下纯苯乙烯聚合转化率同时间之间的关系，经实验分析得知，同一反应时间内，纯苯乙烯聚合反应的转化率随温度升高而增大，同一温度下，聚合反应的转化率随时间的推移而提高。通常情况下，温度每升高10℃，聚合转化率升高近一倍。
针对上述问题，本领域技术人员也提出了不同的改进方法，其中，高低压耦合塔分离脱氢混合液中的乙苯/苯乙烯的精馏流程是当今分离脱氢混合液中乙苯/苯乙烯的最先进节能流程。
中国专利CN 1163289C公开了一种乙苯/苯乙烯塔的串联重沸方法， 该专利需设置热耦合的高低压两个塔，用高压塔顶蒸汽作为低压塔釜再沸器热源，高低压两个塔的进料来源相同，其组成和温度都相同，且两个塔釜都分离出组成一致的产品，同时作为另外一个塔的进料。但是该方案只是提供了高、低压乙苯/苯乙烯塔自身热耦合，热能利用率还处在较低水平。
中国专利CN101602640B公开了一种乙苯/苯乙烯的节能分离方法，其将乙苯/苯乙烯分离塔由单塔分为两个塔操作，其中乙苯/苯乙烯分离塔A的塔顶蒸汽一部分或全部导入压缩机，压缩后的工艺气体作为乙苯/苯乙烯分离塔B再沸器热源使用的专利。该专利额外使用压缩机增压来保证高低压塔之间的热耦合效果，该方式的能耗高、经济性差，且也只能在高、低压乙苯/苯乙烯塔之间进行热泵循环过程，能源利用方面还有待进一步提升。
中国专利CN105669354B公开了一种乙苯脱氢反应产物分离方法，其将脱氢混合液经粗苯乙烯分离塔分离，塔顶含有苯、甲苯和乙苯的气相经压缩，作为从塔顶分离苯、甲苯，塔釜分离乙苯的塔再沸器热源和作为苯乙烯产品塔再沸器热源。该发明中乙苯/苯乙烯的分离只用一个塔实现，且压缩机入口气体含有脱氢混合液带入的几乎所有苯、甲苯，所以其压缩机入口压力和温度都较低，会带来耗高且经济性差的问题。
综上可知，现有的苯乙烯精制工艺还是存在能源利用不足、耗能高和经济性差的问题，因此有必要对现有工艺进行进一步地探索改进。
发明内容
本发明的目的在于解决现有技术中的不足，公开一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，主要是在高低压耦合的乙苯/苯乙烯分离塔节能技术基础上，通过开式或闭式热泵循环，结合降膜再沸器的布置利用，进一步大幅降低苯乙烯分离过程中的能耗、提高能源利用率、提升装置经济性。
本发明的技术方案为：一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，精制路线中从上游至下游包括预分离塔、高压乙苯/苯乙烯塔、低压乙苯/苯乙烯塔和苯乙烯产品塔，预分离塔底部流出的预分离塔釜总物流分为两股分别送入高、低压乙苯/苯乙烯塔；高、 低压乙苯/苯乙烯塔顶分离出的乙苯物流都送到脱氢单元作为原料使用，对应塔釜物流送入苯乙烯产品塔；苯乙烯产品塔塔釜未脱除干净苯乙烯的焦油送入苯乙烯回收系统；预分离塔顶分离出的苯、甲苯混合物可继续分离，得到可回用到乙苯单元作为原料使用的苯，以及副产品甲苯；低压乙苯/苯乙烯塔与低压乙苯/苯乙烯塔再沸器连接，低压乙苯/苯乙烯塔塔底采出的低压塔产物物流被送入苯乙烯产品塔、低压塔循环物流流经低压乙苯/苯乙烯塔再沸器并被高压乙苯/苯乙烯塔塔顶馏出的气相物流加热部分气化后再返回到低压乙苯/苯乙烯塔底部；高压乙苯/苯乙烯塔与高压乙苯/苯乙烯塔再沸器连接，高压乙苯/苯乙烯塔塔底流出的高压塔产物物流被送入苯乙烯产品塔，高压乙苯/苯乙烯塔塔顶馏出物与低压乙苯/苯乙烯塔再沸器连接；其特征在于，
在低压乙苯/苯乙烯塔的塔顶设置开式热泵循环或闭式热泵循环；
预分离塔上设有以开式或闭式热泵送来的气相介质作为热源的再沸器；
苯乙烯产品塔上设有以开式或闭式热泵送来的气相介质作为热源的再沸器；
开式热泵循环是在低压乙苯/苯乙烯塔的塔顶连接乙苯热泵压缩机，一部分塔顶流出的气相物流经乙苯热泵压缩机压缩后，作为预分离塔和/或产品苯乙烯塔的热源；另一部分未增压的气相物流送入低压乙苯/苯乙烯塔冷凝器冷凝，冷凝液以及被预分离塔再沸器和/或苯乙烯产品塔再沸器冷凝的物流一道收集并增压作为冷凝液总物流，冷凝液总物流一部分作为低压乙苯/苯乙烯塔的回流，剩余部分作为采出物流被送出到乙苯脱氢单元循环使用；
闭式热泵循环是将低压乙苯/苯乙烯塔的塔顶气相物流作为热源送入低压乙苯/苯乙烯塔热泵工质蒸发器用于蒸发热泵工质，未冷凝的物流继续送入低压乙苯/苯乙烯塔后凝器冷凝；被蒸发的热泵工质经工质热泵压缩机增压后，送入预分离塔再沸器和/或苯乙烯产品塔再沸器作为热源，经预分离塔再沸器和/或苯乙烯产品塔再沸器冷凝后的热泵工质循环回低压乙苯/苯乙烯塔热泵工质蒸发器。
进一步地，乙苯热泵压缩机和工质热泵压缩机可联合设置，并同时为 预分离塔和苯乙烯产品塔再沸器提供热量；也可根据预分离塔再沸器和苯乙烯产品塔再沸器热源侧所需冷凝压力的不同分别独立设置不同出口压力的压缩机。
进一步地，所述预分离塔上的再沸器、苯乙烯产品塔上的再沸器和低压乙苯/苯乙烯再沸器均为降膜式再沸器。
进一步地，预分离塔降膜再沸器和产品苯乙烯塔降膜再沸器均配有循环泵，以建立降膜再沸器所需循环物流。
进一步地，预分离塔塔顶与预分离塔冷凝器相连，苯乙烯产品塔塔顶与苯乙烯产品塔冷凝器相连，两个冷凝器均以循环水作为冷源。
进一步地，开式热泵循环中，苯乙烯产品塔冷凝器和预分离塔冷凝器所用循环水同低压乙苯/苯乙烯塔冷凝器所用循环水串联，且苯乙烯产品塔冷凝器和预分离塔冷凝器都置于循环水流程前部；
进一步地，闭式热泵循环中，苯乙烯产品塔冷凝器和预分离塔冷凝器所用循环水都同低压乙苯/苯乙烯塔后凝器所用循环水串联，且苯乙烯产品塔冷凝器和预分离塔冷凝器都置于循环水流程前部。
进一步地，低压乙苯/苯乙烯塔的操作压力为7～17KPaA。
进一步地，预分离塔的操作压力为12～19KPaA。
进一步地，苯乙烯产品塔的操作压力为2～5KPaA。
本发明的有益效果是：
1.本发明在现有的高低压耦合的乙苯/苯乙烯分离塔节能技术基础上，进一步利用热泵技术并结合降膜式再沸器的使用将低压乙苯/苯乙烯塔的塔顶能量作为预分离塔和/或苯乙烯产品塔热源，该设计可充分利用传热温差，进一步大幅降低苯乙烯分离过程中的能耗，对生产流程进行相应改进并投入生产后可在较短年限内收回成本，长期经济效益显著；
2.本发明可采用开式热泵技术和降膜式再沸器结合实现低压乙苯/苯乙烯塔塔顶能量的再利用，其主要通过压缩机直接将低压乙苯/苯乙烯塔顶分离出的高浓度气相乙苯增压，被直接增压后的物流送入传热温差需求小的降膜式再沸器，既可作为苯乙烯分离流程中的预分离塔热源又可作为产品苯乙烯塔热源，达到节能和节约操作费用的目的；
3.本发明还可采用闭式热泵技术和降膜式再沸器结合实现低压乙苯/ 苯乙烯塔的塔顶能量的再利用，其主要通过低压乙苯/苯乙烯塔顶分离出的高浓度气相乙苯气化热泵工质，并将气化后的热泵工质增压，间接气化并增压后的物流被送入传热温差需求小的降膜式再沸器即可作为苯乙烯分离流程中的预分离塔和或产品苯乙烯塔热源，达到节能和节约操作费用的目的；
4.本发明在选择利用热泵技术和降膜式再沸器的基础上，同时以可用循环水冷凝塔顶气相作为预分离塔和苯乙烯产品塔的塔压设计瓶颈，尽量降低预分离塔和/或苯乙烯产品塔这两个被加热塔的操作压力和塔的顶底压差，以降低塔釜温度，达到节约压缩机能耗的效果；
5.本发明不但使高压乙苯/苯乙烯塔釜输入的热量得以三次应用，还具有通过提升低压乙苯/苯乙烯分离塔顶操作压力、降低预分离塔和/或苯乙烯产品塔压力来降低热泵压缩机功率优势。
附图说明
图1是实施例一公开的将开式热泵技术与降膜再沸器组合提供预分离塔和苯乙烯产品塔所需热源的苯乙烯精制工艺路线图；
图2是实施例二公开的将闭式热泵技术与降膜再沸器组合提供预分离塔和苯乙烯产品塔所需热源的苯乙烯精制工艺路线图；
图3是应用例一公开的将开式热泵技术与降膜再沸器组合提供苯乙烯产品塔所需热源的苯乙烯精制工艺路线图；
图4是应用例二公开的将开式热泵技术与降膜再沸器组合提供预分离塔所需热源的苯乙烯精制工艺路线图；
图5是应用例三公开的将闭式热泵技术与降膜再沸器组合提供苯乙烯产品塔所需热源的苯乙烯精制工艺路线图；
其中，附图标记为：
T-101：预分离塔，T-102:高压乙苯/苯乙烯塔，T-103:低压乙苯/苯乙烯塔，T-104:苯乙烯产品塔，E-101:预分离塔降膜再沸器，E-102:预分离塔冷凝器，E-103:高压乙苯/苯乙烯塔再沸器，E-104:低压乙苯/苯乙烯塔降膜再沸器，E-105:低压乙苯/苯乙烯塔冷凝器，E-106:苯乙烯产品塔降膜再沸器，E-107:苯乙烯产品塔冷凝器，E-108:低压乙苯/苯乙烯塔热泵工质蒸发器，E-109:低压乙苯/苯乙烯塔后凝器，C-101：乙苯热泵压缩机，C-102： 工质热泵压缩机；
1：塔顶气相物流，2：第一气相物流，3：第二气相物流，4：未增压气相物流，5:冷凝液，6：第一冷凝物流，7：第二冷凝物流，8:冷凝液总物流，9：回流，10：总采出物流，11：预分离塔釜总物流，12：预分离塔循环物流，13：高压乙苯/苯乙烯塔进料，14：低压乙苯/苯乙烯塔进料，15：总物流，16：苯乙烯产品塔循环物流，17：苯乙烯回收塔进料，18：低压塔流出物，19：低压塔循环物流，20：低压塔产物物流，21：高压塔产物物流，22：苯乙烯产品塔总进料，23：脱氢液；
2'：第一热泵工质气相物流，3'：第二热泵工质气相物流，4'：被蒸发的热泵工质，5'：总冷凝热泵工质，6'：第一冷凝热泵工质，7'：第二冷凝热泵工质；
注：为简化流程，上图中实现流程所需的泵、回流罐没有显示。
具体实施方式
以下实施例进一步说明本发明的内容，但不应理解为对本发明的限制。在不背离本发明实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。
脱氢混合液中含有水、苯、甲苯、乙苯、苯乙烯、焦油组份，在预分离塔塔顶，脱氢混合液中的苯、甲苯及微量的水被分离出来，塔釜分离出乙苯、苯乙烯、焦油，故塔顶和塔底温差较大。以预分离塔塔顶压降为20KPaA为例，塔顶典型温度为55.18℃，塔釜典型温度为91.9℃，顶底温差相差36.72℃，显然，设置以该塔顶气相为热源加热自身塔釜再沸器的热泵不具有经济性。
在苯乙烯产品塔塔顶压降为6KPaA时，塔顶气相苯乙烯温度为63.56℃，对应塔釜压力为9KPaA、塔釜液苯乙烯含量70％时，再沸器出口温度为78.87℃。此塔的顶底温差较小，可设置以塔顶气相为热源加热自身塔釜的热泵。但同以温度相对产品苯乙烯塔顶较高的低压乙苯/苯乙烯分离塔顶气相为热源加热产品苯乙烯塔釜再沸器的热泵流程相比，经济性明显偏弱。
常州瑞华化工工程技术股份有限公司设计运行的苯乙烯装置中，预分离塔和苯乙烯产品塔再沸器的加热蒸汽等级已经采用压力极低的 0.04MPaG蒸汽为热源，在降低预分离塔和苯乙烯产品塔釜温度和保证苯乙烯分离流程在高真空下稳定运行方面具有成熟经验。已在现有装置基础上进行预分离塔和苯乙烯产品塔低负荷工况下的降低塔顶、塔釜压力试验，并进一步通过模拟计算，判断预分离塔和苯乙烯产品塔通过降膜再沸器接收低压乙苯/苯乙烯塔顶开式或闭式热泵送入热量作为热源具有可行性和经济性。
实施例一：降膜再沸器和开式热泵技术组合提供分离塔所需热源的苯乙烯精制方法
本发明为进一步降低操作能耗、提高乙苯/苯乙烯分离装置的经济性，在现有的高低压耦合塔分离脱氢混合液中的乙苯/苯乙烯的精馏流程装置中增设了热泵循环装置。
热泵循环，即逆向卡诺循环，它是将回收塔顶流体的低温热通过压缩机施加少量高品位能量后，使其温位升高，即可作为塔底热源使用，从而达到节能和节约操作费用的目的。
热泵流程具体又可分为开式热泵和闭式热泵；开式热泵是利用压缩机直接压缩低压乙苯/苯乙烯塔顶高浓度气相乙苯，作为预分离塔和产品苯乙烯塔釜再沸器热源的技术。
本实施例中重点陈述开式热泵技术与降膜再沸器组合提供预分离塔和苯乙烯产品塔所需热源的苯乙烯精制方法，具体工艺路线参考图1。
苯乙烯精制操作线上按照上游至下游的顺序依次设有四个关键塔，分别是将脱氢混合液中的苯、甲苯组分从塔顶分离，将脱氢混合液中的乙苯、苯乙烯、焦油组分从塔釜分离的预分离塔T-101；将乙苯组分从塔顶分离，苯乙烯及焦油组分从塔釜分离，具有相同作用且热耦合的高压乙苯/苯乙烯塔T-102和低压乙苯/苯乙烯塔T-103；以及将苯乙烯产品从塔顶分离，将全部焦油连同夹带的少部分苯乙烯从塔釜分离的苯乙烯产品塔T-104；
预分离塔T-101塔顶与预分离塔冷凝器E-102相连，冷凝后的液相通过回流罐收集和增压后作为回流和采出使用，预分离塔T-101底部流出的预分离塔釜总物流11分为两股(即高压乙苯/苯乙烯塔进料13和低压乙苯/苯乙烯塔进料14)后相应送入高压乙苯/苯乙烯塔T-102和低压乙苯/苯乙烯塔T-103；预分离塔T-101下部与预分离塔降膜再沸器E-101连接。
苯乙烯产品塔T-104与苯乙烯产品塔降膜再沸器E-106连接，苯乙烯产品塔T-104塔底采出的总物流15被分为苯乙烯回收塔进料17和苯乙烯产品塔循环物流16，苯乙烯产品塔循环物流16流经苯乙烯产品塔降膜再沸器E-106，被加热后的循环物流输出后重新返回到苯乙烯产品塔T-104的下部区域；塔顶连接苯乙烯产品塔冷凝器E-107，冷凝后的液相通过回流罐收集和增压后作为回流和采出产品苯乙烯使用。
高压乙苯/苯乙烯塔T-102与高压乙苯/苯乙烯塔再沸器E-103连接，高压乙苯/苯乙烯塔T-102塔底采出的主要含高浓度苯乙烯单体的高压塔产物物流21被送入苯乙烯产品塔T-104，塔顶的气相馏出物主要含有乙苯，塔顶气相馏出物用于低压乙苯/苯乙烯塔降膜再沸器的热量供给，该气相物流在传热给低压乙苯/苯乙烯塔降膜再沸器后被冷凝，一部分作为回流，另外一部分作为循环乙苯采出，送入脱氢单元循环使用。
低压乙苯/苯乙烯塔T-103与低压乙苯/苯乙烯塔降膜再沸器E-104连接，低压乙苯/苯乙烯塔T-103塔底采出的主要含高浓度苯乙烯单体的低压塔流出物18被分为低压塔产物物流20和低压塔循环物流19，低压塔产物物流20被送入苯乙烯产品塔T-104，低压塔循环物流19流经低压乙苯/苯乙烯塔降膜再沸器E-104，被高压乙苯/苯乙烯塔塔顶馏出的气相物流加热后部分气化，重新返回到低压乙苯/苯乙烯塔T-103底部。
低压乙苯/苯乙烯塔T-103的塔顶气相物流1分为两股，一股经乙苯热泵压缩机C-101增压后，可再分成二股物流，第一气相物流2送入预分离塔降膜再沸器E-101作为预分离塔T-101热源，第二气相物流3送入苯乙烯产品塔降膜再沸器E-106作为苯乙烯产品塔T-104的热源。另外一股未增压气相物流4送入低压乙苯/苯乙烯塔冷凝器E-105冷凝后，冷凝液5和被降膜再沸器E-101/E-106冷凝的第一冷凝物流6、第二冷凝物流7一道收集并增压作为冷凝液总物流8，冷凝液总物流8作为低压乙苯/苯乙烯塔T-103的回流9或作为总采出物流10被送出到乙苯脱氢循环使用。低压乙苯/苯乙烯塔冷凝器E-105起到开停车过程或波动工况调整冷凝负荷的辅助作用。
预分离塔降膜再沸器E-101需要配套循环泵，以建立预分离塔循环物流12。苯乙烯产品塔降膜再沸器E-106需要配套循环泵，以建立苯乙烯 产品塔循环物流16。
该实施例中的预分离塔冷凝器E-102、低压乙苯/苯乙烯塔冷凝器E-105、苯乙烯产品塔冷凝器E-107依然同前述高低压耦合循序分离流程一样，由循环水作为冷源。苯乙烯产品塔冷凝器E-107和预分离塔冷凝器E-102所用循环水同低压乙苯/苯乙烯塔冷凝器E-105所用循环水串联，且苯乙烯产品塔冷凝器E-107和预分离塔冷凝器E-102都置于循环水流程前部，以便节约循环水消耗量。
具体工作流程为：
(1)脱氢液23首先进入预分离塔T-101，它是一座在负压条件下操作的高效填料精馏塔，其作用是把脱氢液23中比乙苯沸点低的甲苯、苯等轻组分从预分离塔T-101的塔顶分离出去、塔底获得预分离塔釜总物流11(主要为含有乙苯、苯乙烯、焦油的混合物)，之后预分离塔釜总物流11分为两股(即高压乙苯/苯乙烯塔进料13和低压乙苯/苯乙烯塔进料14)，分别送入高压乙苯/苯乙烯塔T-102及低压乙苯/苯乙烯塔T-103进一步处理；
(2)乙苯回收及粗苯乙烯分离系统主要设备是二座高低压耦合的高效低压降填料塔T-102/T-103；塔顶馏出的乙苯循环返回脱氢反应系统，作为反应器进料乙苯的一部分；塔底得到的粗苯乙烯即低压塔产物物流20和高压塔产物物流21汇集成苯乙烯产品塔总进料22后送入苯乙烯产品塔T-104分离获得合格的苯乙烯产品；
(3)塔顶气相物流1分为两股，一股经乙苯热泵压缩机C-101增压后再分成二股物流，第一气相物流2送入预分离塔降膜再沸器E-101作为预分离塔热源，第二气相物流3送入苯乙烯产品塔降膜再沸器E-106作为苯乙烯产品塔T-104热源，另外一股未增压气相物流4送入低压乙苯/苯乙烯塔冷凝器E-105冷凝；
(4)苯乙烯产品塔T-104的主要作用是在其塔顶产出苯乙烯产品、塔釜产出含有较高浓度苯乙烯的焦油形成苯乙烯回收塔进料17，送到苯乙烯回收系统回收苯乙烯，并在苯乙烯回收系统产出苯乙烯含量低于6％的焦油。
实施例二：降膜再沸器和闭式热泵技术组合提供分离塔所需热源的苯乙烯精制方法
本实施例中重点陈述闭式热泵技术与再沸器组合提供分离塔所需热源的苯乙烯精制方法，具体工艺路线参考图2。
与开式热泵技术的不同之处在于：
将低压乙苯/苯乙烯塔T-103的塔顶气相物流1送入低压乙苯/苯乙烯塔热泵工质蒸发器E-108，未冷凝的物流继续送入低压乙苯/苯乙烯塔后凝器E-109冷凝。被蒸发的热泵工质4'经工质热泵压缩机C-102增压后，分为第一热泵工质气相物流2'和第二热泵工质气相物流3'，两股气相物流分别送入预分离塔降膜再沸器E-101和/或苯乙烯产品塔降膜再沸器E-106作为热源，在E-101/106冷凝的第一冷凝热泵工质6'、第二冷凝热泵工质7'汇合成总冷凝热泵工质5'后循环回低压乙苯/苯乙烯塔热泵工质蒸发器E-108继续被气化，循环使用。
预分离塔降膜再沸器E-101需要配套循环泵，以建立降膜再沸器所需预分离塔循环物流12。苯乙烯产品塔降膜再沸器E-106需要配套循环泵，以建立降膜再沸器所需苯乙烯产品塔循环物流16。
具体工作时：
闭式热泵利用低压乙苯/苯乙烯塔T-103塔顶分离出的高浓度气相乙苯气化热泵工质，并将气化后的热泵工质增压，被间接气化并增压后的热泵工质送入传热温差需求小的降膜式再沸器作为苯乙烯分离流程中的预分离塔T-101和/或苯乙烯产品塔T-104热源。
闭式热泵工质需选择被低压乙苯/苯乙烯塔顶气相蒸发后压力适合压缩机选型且压缩机功率低的介质，例如：正丁烷、异丁烷、丁烯、戊烷、环戊烷、苯、甲醇等。
该实施例中的预分离塔冷凝器E-102、低压乙苯/苯乙烯塔后凝器E-109、苯乙烯产品塔冷凝器E-107依然同前述高低压耦合循序分离流程一样，由循环水作为冷源。苯乙烯产品塔冷凝器E-107和预分离塔冷凝器E-102所用循环水都同低压乙苯/苯乙烯塔后凝器E-109所用循环水串联，且苯乙烯产品塔冷凝器E-107和预分离塔冷凝器E-102都置于循环水流程前部，以便增加E-102和E-107换热温差，并节约循环水消耗。
上述实施例和下述应用例中所用预分离塔再沸器、苯乙烯产品塔再沸器和低压乙苯/苯乙烯再沸器均为降膜式再沸器，选择降膜再沸器的理由 是：降膜再沸器是再沸器的形式之一，除此之外还有釜式再沸器、卧式热虹吸再沸器、立式热虹吸再沸器、强制循环再沸器等。降膜再沸器需额外配套液相循环泵和需液相分配装置，如分配头及液相分布盘等。液相通过上述分配装置沿换热管管壁拉成膜，并沿膜蒸发出气相。其它种类再沸器，像热虹吸式不需额外提供循环泵，其靠本身液体加热后的密度差来进行循环。降膜再沸器，由于有泵的循环，其相对于塔体的安装高度一般不作特别规定，但热虹吸式再沸器，需根据其操作工况，物料性质来进行特别制定相对与塔釜、气相、液相进出口的安装高度。一般来讲，降膜再沸器处理的物料与热虹吸再沸器比，适用于高真空、热敏性强、粘度大物料，且降膜式再沸器管壳程传热温度可缩小，换热效率高。
对于塔釜含有较高焦油含量的苯乙烯产品塔，除苯乙烯产品塔塔釜压力影响塔釜再沸器换热效果外，该塔釜所含焦油浓度、塔釜再沸器气化率都对再沸器换热效果有较多影响。故需选用降膜再沸器并通过增加苯乙烯产品塔塔釜物中的苯乙烯含量、降低降膜再沸器气化率来减少降膜再沸器管壳程传热温差。
应用例一
以50万吨乙苯脱氢制苯乙烯的苯乙烯分离单元为例。低压乙苯/苯乙烯塔T-103塔顶含高浓度气相乙苯，经过乙苯热泵压缩机C-101增压，仅为苯乙烯产品塔降膜再沸器E-106提供热源。具体工艺路线详见附图3。
a)低压乙苯/苯乙烯塔T-103的塔顶压力为10KPaA、温度67.04℃、塔顶含高浓度气相乙苯经乙苯热泵压缩机C-101增压后送入苯乙烯产品塔降膜再沸器E-106的物流量为78.86t/h；
b)苯乙烯产品塔T-104的塔顶压力为2.5KPaA、塔顶温度为45.45℃，塔釜压力为5.6KPaA、苯乙烯产品塔降膜再沸器出口温度67.5℃；
c)乙苯热泵压缩机C-101的入口条件：10KPaA、温度67.04℃、物流量78.86t/h；乙苯热泵压缩机C-101的出口条件：压力18KPaA；轴功率462.4KW(压缩机效率按75％计算)；若选用陕鼓轴流风机，则机型为ED160-2+2，功率539(最高出口压力可以达到25KPaA)，转速1485。
d)苯乙烯产品塔冷凝器E-107换热器型式BXM，为穿流式换热器，直径4000mm，长度7000mm，换热面积3008m 2，重量101.8t。壳程苯乙 烯气体被管程循环水冷凝，壳侧压降0.4KPa，换热器出口未冷凝气相苯乙烯质量流量725Kg/h；
e)苯乙烯产品塔顶冷凝器E-107所用循环水同低压乙苯/苯乙烯塔冷凝器E-105所用循环水串联，且E-107置于循环水流程前部，以便增加低压乙苯/苯乙烯塔冷凝器E-105传热温差；
f)苯乙烯产品塔降膜再沸器E-106所需热负荷8059KW。降膜式BEM换热器，直径为3800mm，长度为8500mm，换热面积为3616m 2，总量129.5t。温差7.2℃，壳侧温度为75.73℃-82.18℃，管侧温度为67.5℃-70.66℃，壳程出口不凝气量1563Kg/h，气化率7％；
g)苯乙烯产品塔降膜再沸器配套循环泵:设计流量1118m 2/h(115％余量)，扬程36m，轴功率为132kw；
h)苯乙烯产品塔T-104的塔直径为5000mm，塔壳体重量为103.8t，填料体积为353m 3。
对比例一
该对比例主要同应用例一进行对比：
以50万吨乙苯脱氢制苯乙烯的传统苯乙烯分离单元为例，苯乙烯产品塔使用0.04MPaG蒸汽为热源：
a)苯乙烯产品塔T-104的塔顶压力为6KPaA、温度为63.56℃，塔釜压力8.6KPaA、再沸器出口温度为77.74℃；
b)苯乙烯产品塔冷凝器E-107换热器型式BXM，直径为2800mm，换热管长度为6000mm，换热面积为1825m 2，重量56.7t。壳程苯乙烯气体被管程循环水冷凝，壳侧压降是0.9KPa，换热器出口未冷凝气相苯乙烯质量流量356Kg/h；
c)苯乙烯产品塔顶冷凝器E-107所用循环水同低压乙苯/苯乙烯塔冷凝器E-105所用循环水串联，且E-107置于循环水流程前部，以便增加E-105传热温差；
d)苯乙烯产品塔采用热虹吸式换热器，所需热负荷8083KW。需要消耗0.04PMPaG蒸汽12.89t/h。需要两台再沸器并联。每台再沸器直径2200mm，换热管长度换3000mm，每台换热面积842m 2。每台重量28.9t；
e)苯乙烯产品塔T-104的塔直径为4200mm，塔壳体重量为75.4t，填 料体积为249m 3。
将应用例一和对比例一进行比较：
1.应用例一无需使用蒸汽，仅增加乙苯热泵压缩机C-101和降膜再沸器循环泵电耗的轴功率总计：594.4kw。以0.7元每度电计价，花费416.08元/小时。每小时能耗为594.4*0.086＝51.1kg标油/小时。0.086为《苯乙烯单位产品能源消耗限额GB 32053》中的电折标油系数；注：应用列一、二、三的压缩机和降膜再沸器循环泵实际耗电量不超过轴功率的1.2倍。
2.对比例一中无需增加电耗，但需使用0.04MPaG蒸汽12.89t/h。以单价100元/吨计，需花费1289元/小时。每小时能耗为12.89*55＝708.95kg标油/小时。55为《苯乙烯单位产品能源消耗限额GB 32053》中的低低压蒸汽折标油系数；
3.因应用例一较传统工艺降低了塔压，导致应用例一的塔、再沸器、冷凝器的重量几乎增加了一倍，投资增加约300万元。另外应用例一相比传统工艺还需额外增加压缩机和降膜再沸器循环泵投资费用约950万元。加上其他配套费用，两年左右可以收回应用例一增加的投资成本。
应用例二
以50万吨乙苯脱氢制苯乙烯的苯乙烯分离单元为例。低压乙苯/苯乙烯塔T-103的塔顶馏出高浓度气相乙苯，经过乙苯热泵压缩机C-101增压，仅为预分离塔降膜再沸器E-101提供热源。具体工艺路线详见附图4。
a)低压乙苯/苯乙烯塔T-103的塔顶压力为10KPaA、温度为67.04℃、塔顶流出的高浓度气相乙苯经乙苯热泵压缩机C-101增压后送入预分离塔降膜再沸器E-101的物流量5为0.81t/h；
b)预分离塔T-101的塔顶压力为14KPaA、塔顶温度为46.6℃，塔釜压力为15.8KPaA、预分离塔降膜再沸器E-101的出口温度为83.25℃；
c)乙苯热泵压缩机C-101的入口条件为：10KPaA、温度67.04℃、物流量50.81t/h；乙苯热泵压缩机C-101的出口条件为：压力36KPaA；轴功率657.8KW(压缩机效率按75％计算)；
d)预分离塔冷凝器E-102换热器型式BXM，直径2500mm，长度6000mm，换热面积2238m 2，重量50.9t。壳程苯乙烯气体被管程循环水冷凝，壳侧压降0.72KPa，换热器出口未冷凝气相流量3389Kg/h；
e)预分离塔冷凝器E-102所用循环水同低压乙苯/苯乙烯塔冷凝器E-105所用循环水串联，且E-102置于循环水流程前部，以便增加E-105传热温差；
f)预分离塔降膜再沸器E-101所需热负荷4948KW，降膜式BEM换热器，直径3000mm，长度6500mm，换热面积3445m 2，总量90.9t，温差8.5℃，壳侧温度91.33℃-98.79℃，管侧温度83.4℃-86.78℃，壳程出口不凝气量1316Kg/h，气化率24.3％；
g)苯乙烯产品塔降膜再沸器配套循环泵:设计流量276.8m 2/h(115％余量)，扬程36m，轴功率33kw；
h)预分离塔T-101的塔直径为3400mm。
对比例二
该对比例主要同应用例二进行对比：
以50万吨乙苯脱氢制苯乙烯的传统苯乙烯分离单元为例，预分离塔使用0.04MPaG蒸汽为热源：
a)预分离塔T-101的塔顶压力为20KPaA、温度55.18℃，塔釜压力21.8KPaA、再沸器出口温度为91.94℃；
b)预分离塔冷凝器E-102的换热器型式为BXM，直径2200mm，换热管长度6000mm，换热面积1553m 2，重量为38.5t。壳程苯乙烯气体被管程循环水冷凝，壳侧压降0.58KPa，换热器出口未冷凝气相苯乙烯质量流量1710Kg/h；
c)预分离塔热虹吸式换热器所需热负荷4948KW。需要消耗0.04PMPaG蒸汽7.92t/2h。需两台再沸器并联。每台再沸器直径2000mm，换热管长度换3000mm，每台换热面积712m 2。每台重量26.1t；
d)预分离塔T-101的塔直径为3800mm。
将应用例二和对比例二进行比较：
1.应用例二无需使用蒸汽，仅增加乙苯热泵压缩机C-101和降膜再沸器循环泵电耗的轴功率总计：690.8kw。以0.7元每度电计价，花费483.56元/小时。每小时能耗为690.8*0.086＝59.4kg标油/小时。0.086为《苯乙烯单位产品能源消耗限额GB 32053》中的电折标油系数；
2.对比例二无需增加电耗，但需使用0.04MPaG蒸汽7.92t/h。以单价 100元/吨计，需花费792元/小时。每小时能耗为7.92*55＝435.6kg标油/小时。55为《苯乙烯单位产品能源消耗限额GB 32053》中的低低压蒸汽折标油系数；
3.因应用例二较传统工艺降低了塔压，导致应用例二的塔、再沸器、冷凝器的重量几乎增加了50％，投资增加约100万元。另外应用例二比传统工艺还需额外增加压缩机和降膜再沸器循环泵投资费用约750万元。加上其它配套费用，约4年可以收回应用例二增加的投资成本。
应用例三
以50万吨乙苯脱氢制苯乙烯的苯乙烯分离单元为例。该应用例采用的是闭式热泵，将低压乙苯/苯乙烯塔T-103的塔顶物流送入低压乙苯/苯乙烯塔热泵工质蒸发器E-108，未冷凝的物流继续送入低压乙苯/苯乙烯分离塔后冷凝器E-109冷凝。被蒸发的热泵工质4'经工质热泵压缩机C-102增压后的第二热泵工质气相物流3'，送入苯乙烯产品塔降膜再沸器E-106作为热源，在E-106经冷凝的第二冷凝热泵工质7'循环回低压乙苯/苯乙烯塔热泵工质蒸发器E-108继续被气化，循环使用。详见附图5。
a)低压乙苯/苯乙烯塔T-103的塔顶压力为9.99KPaA、温度为66.96℃、塔顶含高浓度气相乙苯送入低压乙苯/苯乙烯塔热泵工质蒸发器E-108物流量为69.3t/h；
b)苯乙烯产品塔T-104的塔顶压力为2.5KPaA、塔顶温度为45.45℃，塔釜压力为5.6KPaA、苯乙烯产品塔降膜再沸器E-106的出口温度为67.5℃；
c)工质热泵压缩机C-102的入口条件：介质为1-丁烯、压力为748KPaA、温度为58℃、物流量为88.5t/h；工质热泵压缩机C-102的出口条件为：压力1150KPaA；轴功率696.5KW(压缩机效率按65％计算)；
d)苯乙烯产品塔冷凝器E-107的换热器型式为BXM，直径4000mm，长度7000mm，换热面积3008m 2，重量101.8t。壳程苯乙烯气体被管程循环水冷凝，壳侧压降0.4KPa，换热器出口未冷凝气相苯乙烯质量流量725Kg/h；
e)低压乙苯/苯乙烯塔热泵工质蒸发器E-108换热器型式为BKM，直径2500mm，长度7000mm，换热面积2785m 2，重量71.98t。壳程1-丁 烯气化温度为57.99℃,管程高浓度气相乙苯入口温度66.96℃，管程出口温度60℃,管程出口未冷凝气体流量1871Kg/h；
f)苯乙烯产品塔顶冷凝器E-107所用循环水同低压乙苯/苯乙烯后凝器E-109所用循环水串联，且E-107置于循环水流程前部，以便增加E-109传热温差；
g)苯乙烯产品塔降膜再沸器E-106所需热负荷为8059KW。降膜式BEM换热器，直径4000mm，长度8500mm，换热面积4019m 2，总量156.8t。温差6.2℃，壳侧温度80.35℃-75.00℃，管侧温度67.5℃-70.16℃，壳程出口不凝气量0Kg/h，气化率12％；
h)苯乙烯产品塔降膜再沸器E-106配套循环泵：设计流量707m 2/h(115％余量)，扬程36m，轴功率85kw；
i)苯乙烯产品塔T-104塔的直径为5000mm，塔壳体重量103.8t，填料体积353m 3；
对比例三
以50万吨乙苯脱氢制苯乙烯的传统苯乙烯分离单元为例，苯乙烯产品塔使用0.04MPaG蒸汽为热源：
a)苯乙烯产品塔T104的塔顶压力为6KPaA、温度为63.56℃，塔釜压力8.6KPaA、塔釜再沸器出口温度77.74℃；
b)苯乙烯产品塔冷凝器E-107的换热器型式为BXM，直径2800mm，换热管长度为6000mm，换热面积1825m 2，重量56.7t。壳程苯乙烯气体被管程循环水冷凝，壳侧压降0.9KPa，换热器出口未冷凝气相苯乙烯质量流量356Kg/h；
c)苯乙烯产品塔热虹吸式换热器所需热负荷8083KW。需要消耗0.04PMPaG蒸汽12.89t/h。需两台再沸器并联。每台再沸器直径2200mm，换热管长度换3000mm，每台换热面积842m 2。每台重量28.9t；
d)产品苯乙烯塔T-104塔直径4200m 2，塔壳体重量75.4t，填料体积249m 3。
将应用例三和对比例三进行比较：
1.应用例三无需使用蒸汽，仅增加工质热泵压缩机C-102和降膜再沸器循环泵电耗的轴功率总计：781.5kw。以0.7元每度电计价，花费547.05 元/小时。每小时能耗为781.5*0.086＝67.21kg标油/小时。0.086为《苯乙烯单位产品能源消耗限额GB 32053》中的电折标油系数；
2.对比例三无需增加电耗，但需使用0.04MPaG蒸汽12.89t/h。以单价100元/吨计，需花费1289元/小时。每小时能耗为12.89*55＝708.95kg标油/小时。55为《苯乙烯单位产品能源消耗限额GB 32053》中的低低压蒸汽折标油系数；
3.因应用例三较传统工艺降低了塔压，导致应用例三的塔、再沸器、冷凝器的重量几乎增加了一倍，且增加了低压乙苯/苯乙烯塔热泵工质蒸发器E-108。投资增加约400万元。另外应用例三比传统工艺还需额外增加压缩机和降膜再沸器循环泵投资费用约850万元。加上其它配套费用，约2.5年可以收回应用例三增加的投资成本。
综上可知，本发明通过增加热泵循环工艺流程并结合降膜再沸器的使用实现了低压乙苯/苯乙烯塔T-103和预分离塔T-101以及苯乙烯产品塔T-104之间的热耦合，可在高低压耦合的乙苯/苯乙烯分离塔节能技术基础上，进一步大幅度降低苯乙烯分离过程中的能耗，且经过几年的运行操作后即可收回投入成本，长期经济和环境效益明显。
以上显示和描述了本发明的基本原理、主要特征及优点。但是以上所述仅为本发明的具体实施例，本发明的技术特征并不局限于此，任何本领域的技术人员在不脱离本发明的技术方案下得出的其他实施方式均应涵盖在本发明的专利范围之中。

Claims (10)

  1. 一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，精制路线中从上游至下游包括预分离塔、高压乙苯/苯乙烯塔、低压乙苯/苯乙烯塔和苯乙烯产品塔，预分离塔底部流出的预分离塔釜总物流分为两股分别送入高、低压乙苯/苯乙烯塔；高、低压乙苯/苯乙烯塔顶分离出的乙苯物流都送到脱氢单元作为原料使用，对应塔釜物流送入苯乙烯产品塔；苯乙烯产品塔塔釜未脱除干净苯乙烯的焦油送入苯乙烯回收系统；预分离塔顶分离出的苯、甲苯混合物可继续分离，得到可回用到乙苯单元作为原料使用的苯，以及副产品甲苯；低压乙苯/苯乙烯塔与低压乙苯/苯乙烯塔再沸器连接，低压乙苯/苯乙烯塔塔底采出的低压塔产物物流被送入苯乙烯产品塔、低压塔循环物流流经低压乙苯/苯乙烯塔再沸器并被高压乙苯/苯乙烯塔塔顶馏出的气相物流加热部分气化后再返回到低压乙苯/苯乙烯塔底部；高压乙苯/苯乙烯塔与高压乙苯/苯乙烯塔再沸器连接，高压乙苯/苯乙烯塔塔底流出的高压塔产物物流被送入苯乙烯产品塔，高压乙苯/苯乙烯塔塔顶馏出物与低压乙苯/苯乙烯塔再沸器连接；其特征在于，
    在低压乙苯/苯乙烯塔的塔顶设置开式热泵循环或闭式热泵循环；
    预分离塔上设有以开式或闭式热泵送来的气相介质作为热源的再沸器；
    苯乙烯产品塔上设有以开式或闭式热泵送来的气相介质作为热源的再沸器；
    开式热泵循环是在低压乙苯/苯乙烯塔的塔顶连接乙苯热泵压缩机，一部分塔顶流出的气相物流经乙苯热泵压缩机压缩后，作为预分离塔和/或产品苯乙烯塔的热源；另一部分未增压的气相物流送入低压乙苯/苯乙烯塔冷凝器冷凝，冷凝液以及被预分离塔再沸器和/或苯乙烯产品塔再沸器冷凝的物流一道收集并增压作为冷凝液总物流，冷凝液总物流一部分作为低压乙苯/苯乙烯塔的回流，剩余部分作为采出物流被送出到乙苯脱氢单元循环使用；
    闭式热泵循环是将低压乙苯/苯乙烯塔的塔顶气相物流作为热源送入低压乙苯/苯乙烯塔热泵工质蒸发器用于蒸发热泵工质，未冷凝的物流继 续送入低压乙苯/苯乙烯塔后凝器冷凝；被蒸发的热泵工质经工质热泵压缩机增压后，送入预分离塔再沸器和/或苯乙烯产品塔再沸器作为热源，经预分离塔再沸器和/或苯乙烯产品塔再沸器冷凝后的热泵工质循环回低压乙苯/苯乙烯塔热泵工质蒸发器。
  2. 如权利要求1所述的一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，其特征在于，乙苯热泵压缩机和工质热泵压缩机可联合设置，并同时为预分离塔和苯乙烯产品塔再沸器提供热量；也可根据预分离塔再沸器和苯乙烯产品塔再沸器热源侧所需冷凝压力的不同分别独立设置不同出口压力的压缩机。
  3. 如权利要求1所述的一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，其特征在于，所述预分离塔上的再沸器、苯乙烯产品塔上的再沸器和低压乙苯/苯乙烯再沸器均为降膜式再沸器。
  4. 如权利要求3所述的一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，其特征在于，预分离塔降膜再沸器和产品苯乙烯塔降膜再沸器均配有循环泵，以建立降膜再沸器所需循环物流。
  5. 如权利要求1所述的一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，其特征在于，预分离塔塔顶与预分离塔冷凝器相连，苯乙烯产品塔塔顶与苯乙烯产品塔冷凝器相连，预分离塔冷凝器和苯乙烯产品塔冷凝器均以循环水作为冷源。
  6. 如权利要求5所述的一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，其特征在于，开式热泵循环中，苯乙烯产品塔冷凝器和预分离塔冷凝器所用循环水同低压乙苯/苯乙烯塔冷凝器所用循环水串联，且苯乙烯产品塔冷凝器和预分离塔冷凝器都置于循环水流程前部。
  7. 如权利要求5所述的一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，其特征在于，闭式热泵循环中，苯乙烯产品塔冷凝器和预分离塔冷凝器所用循环水都同低压乙苯/苯乙烯塔后凝器所用循环水串联，且苯乙烯产品塔冷凝器和预分离塔冷凝器都置于循环水流程前部。
  8. 如权利要求1所述的一种降膜式再沸器和热泵技术组合提供分离塔 所需热源的苯乙烯精制方法，其特征在于，低压乙苯/苯乙烯塔的操作压力为7～17KPaA。
  9. 如权利要求1所述的一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，其特征在于，预分离塔的操作压力为12～19KPaA。
  10. 如权利要求1所述的一种降膜式再沸器和热泵技术组合提供分离塔所需热源的苯乙烯精制方法，其特征在于，苯乙烯产品塔的操作压力为2～5KPaA。
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CN113877227A (zh) 2022-01-04
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