WO2022083395A1 - 醋酸乙烯生产工艺及装置 - Google Patents

醋酸乙烯生产工艺及装置 Download PDF

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WO2022083395A1
WO2022083395A1 PCT/CN2021/119873 CN2021119873W WO2022083395A1 WO 2022083395 A1 WO2022083395 A1 WO 2022083395A1 CN 2021119873 W CN2021119873 W CN 2021119873W WO 2022083395 A1 WO2022083395 A1 WO 2022083395A1
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tower
acetic acid
gas
sent
gas separation
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English (en)
French (fr)
Chinese (zh)
Inventor
张敏华
余英哲
龚浩
董贺
王升
刘成
董秀芹
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Tianjin University
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Tianjin University
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Priority to US18/023,293 priority Critical patent/US20230312456A1/en
Priority to JP2022576528A priority patent/JP7486848B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds
    • C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
    • C07C69/15—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J7/00—Apparatus for generating gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives

Definitions

  • the invention belongs to the field of chemical reaction and separation, and relates to a process and a device for producing vinyl acetate, in particular to a production process and device for synthesizing vinyl acetate by an ethylene gas-phase method.
  • Vinyl acetate is a simple ester of saturated acid and unsaturated alcohol. It can be polymerized by itself or copolymerized with other monomers to generate polyvinyl alcohol (PVA), vinyl acetate-ethylene copolymer (EVA), polyvinyl acetate (PVAC), acetic acid Ethylene-vinyl chloride copolymer (EVC) and other polymers.
  • ethylene method ethylene production by ethylene method
  • acetylene method ethylene production currently dominates.
  • the production process of vinyl acetate by ethylene method is to send the raw material ethylene, oxygen and acetic acid gas into the reactor to contact with the catalyst, and react under the pressure of 0.5-1.4MPa (G) and the temperature of 130-220°C to generate VAC, water and a small amount of by-products.
  • the reaction gas enters the second gas separation tower after multi-stage cooling and condensation, so as to achieve the purpose of gas-liquid separation. Unreacted ethylene gas is returned to the compressor.
  • the condensed acetic acid and VAC mixture is sent to the rectification process for VAC purification.
  • the increase of vinyl acetate production is related to the concentration of oxygen in the system.
  • increasing the concentration of oxygen in the reactor can reduce the reaction temperature, prolong the service life of the catalyst, and improve the reaction selectivity.
  • the increase of oxygen concentration in the system is limited by the explosion limit.
  • the oxygen concentration is often controlled in a lower range, which will lead to the increase of reaction temperature and the decrease of vinyl acetate selectivity. Since the explosion limit of oxygen is a function of temperature, pressure and composition of the mixture, the explosion limit of oxygen can be changed by changing the temperature, pressure and composition of the mixture.
  • Carbon dioxide is a by-product generated during the synthesis of vinyl acetate by the ethylene method, and it can play this role very well. Therefore, the existing vinyl acetate technology often controls the degree of decarburization in the decarburization process, so that a certain concentration of carbon dioxide is maintained in the synthesis reaction gas to increase the lower explosion limit of oxygen, thereby expanding the stability zone.
  • the molecular weight of carbon dioxide is relatively large, and when the volume concentration of the stabilizer is reached, the work of the circulating compressor is consumed more, so the power consumption of the system and the production cost are increased.
  • the main composition of the discharged refined gas is ethylene.
  • the ethylene feedstock in the exhaust gas is recovered.
  • the current process mainly selects acetic acid as the absorbent.
  • ethane will also be absorbed by acetic acid, which will accumulate in the production cycle and affect the effect of emptying and removing impurities.
  • Patent ZL 201210385948.4 discloses a method for producing vinyl acetate, which clearly relates to the method for producing vinyl acetate.
  • the invention provides a method for producing vinyl acetate by gas-phase oxidation of ethylene, which comprises an optional ethylene preparation process, a vinyl acetate synthesis process and a vinyl acetate purification process.
  • the process described in this patent does not specify the oxygen content of the reaction gas, nor does it describe the stabilization process in the specific production process, which is very important to the process, that is, it is related to the safety of the production process, and also It directly determines the selectivity and conversion rate of the reaction.
  • the current process mainly has the following problems:
  • One object of the present invention is to provide the production process and device of vinyl acetate, by setting up stabilization process, acetic acid recovery system, desorption system and device, changing the composition of circulating gas, reducing the explosion range, under the same production load, the same catalyst conditions , the maximum allowable oxygen volume fraction at the inlet of the reactor is increased, the safety of the production process is increased, and the conversion rate per pass of the reaction is improved; at the same time, according to the actual production situation, the material separation sequence is reasonably cut, and the first gas separation tower is designed to recover the residual heat of the reaction gas. To achieve the purpose of pre-dehydration, reduce system energy consumption.
  • the vinyl acetate production process includes a circulating gas compressor, an acetic acid evaporator, a circulating ethylene preheater, an oxygen mixer, a synthesis reactor, the first heat exchanger at the reactor outlet, and the second cooling at the reactor outlet.
  • a circulating gas compressor for generating a gas separation column
  • first gas separation column condenser for separating a gas separation column
  • first gas separation column aftercooler for converting a gas separation column phase separator to the first gas separation column phase separator
  • second gas separation column degassing tank
  • recovery gas compressor water washing tower, absorption tower, ethylene recovery tower, acetic acid recovery system and desorption system.
  • reaction gas at the reactor outlet is subjected to heat exchange through the first heat exchanger at the reactor outlet and the second cooler at the reactor outlet, respectively, it is sent to the bottom of the first gas separation tower.
  • the dehydrated reaction liquid is obtained from the first gas separation tower still, and sent to the rectification section for purification treatment.
  • the top of the first gas separation tower obtains the top gas whose main components are vinyl acetate and water, and is sent to the first gas separation tower condenser for condensation, and the non-condensable gas of the first gas separation tower condenser is sent to the first gas separation tower.
  • the aftercooler is further cooled, and the condensed liquid of the first gas separation tower condenser and the first gas separation tower aftercooler enters the first gas separation tower phase separator for phase separation, and the oil phase after the phase separation is sent to the first gas separation tower as a reflux.
  • the water phase is sent to the rectification section for further processing.
  • the non-condensable gas behind the aftercooler of the first gas separation tower is sent to the bottom of the second gas separation tower, and after the reaction liquid and acetic acid are absorbed and separated, a certain amount of reaction liquid is continuously extracted from the tower reactor and sent to the degassing
  • the gas extracted from the degassing tank is compressed by the recovery gas compressor and sent to the water washing tower.
  • a mixed gas mainly composed of ethylene, carbon dioxide, ethane and oxygen is obtained, which is sent to the circulating gas compressor as a circulating gas.
  • the ethylene recovery tower tower top adds fresh acetic acid to reclaim the ethylene gas therein, the ethylene recovery tower tower still liquid is sent to the acetic acid evaporator tower top, and the ethylene recovery tower tower top is sent to incinerated.
  • the acetic acid recovery system includes an acetic acid flash tank, an acetic acid recovery tower, an acetic acid recovery tower condenser, and a vacuum unit; the acetic acid evaporator tower still liquid first enters the acetic acid flash tank, and the gas evaporated from the flash tank is sent to rectification.
  • the still liquid of the flash tank is sent to the acetic acid recovery tower.
  • the gas at the top of the acetic acid recovery tower is condensed by the condenser of the acetic acid recovery tower and then refluxed.
  • the uncondensed gas in the condenser of the acetic acid recovery tower is sent to the degassing tank after passing through the vacuum unit.
  • the condensate is sent to the acetic acid recovery tower for feed.
  • the desorption system includes a desorption tower and a desorption tower top condenser: the absorption tower still liquid is fed into the desorption tower from the top of the desorption tower, and two strands of materials are extracted from the top of the desorption column, one of which contains ethylene and sent to the desorption column.
  • the other main component is carbon dioxide. After being condensed by the condenser at the top of the desorption tower, the non-condensable carbon dioxide is sent out of the boundary area. sent back to the absorption tower together.
  • the circulating gas contains ethane gas, and the concentration of the ethane gas at the inlet of the reactor is 9-18 mol%.
  • the oxygen concentration at the inlet of the reactor is 6-12 mol%.
  • the present invention provides a vinyl acetate production device, as shown in Figure 2, comprising a circulating gas compressor (101), a circulating ethylene preheater (102), an acetic acid evaporator (103), and a first heat exchanger (104) at the reactor outlet ), the second heat exchanger (105) at the reactor outlet, the oxygen mixer (106), the synthesis reactor (107), the first gas separation column (108), the first gas separation column condenser (109), the first Gas separation column aftercooler (110), first gas separation column phase separator (111), second gas separation column (112), degassing tank (113), recovery gas compressor (114), water washing column (115) ), absorption tower (116), ethylene recovery tower (117), acetic acid flash tank (118), acetic acid recovery tower (119), acetic acid recovery tower condenser (120), vacuum unit (121), desorption tower (122) , the desorption tower condenser (123), and the matching heating and conveying equipment, the connection relationship is: the circulating gas compressor (101) is connected
  • the reactor outlet second heat exchanger (102) cooling side outlet is connected with the feed port at the bottom of the first gas separation tower (108); the top of the first gas separation tower (108) is sequentially connected with the first gas separation tower condenser (108).
  • the first gas separation column aftercooler (110) is connected; the first gas separation column condenser (109), the first gas separation column aftercooler (110) and the first gas separation column phase separator (111)
  • the water side of the phase separator (111) of the first gas separation tower is sent to the rectification section, and the oil side is connected to the return port of the first gas separation tower (108); the aftercooler (110) of the first gas separation tower is not condensable.
  • the outlet is connected with the feed port at the bottom of the second gas separation tower (112); the top of the second gas separation tower (112) is connected with the circulating gas compressor (101), and the outlet of the tower kettle of the second gas separation tower (112) is connected with the degassing
  • the tank (113) is connected; the gas phase outlet of the degassing tank (113) is connected with the recovery gas compressor (114); the recovery gas compressor (114) is connected with the inlet of the water washing tower (115); the top outlet of the water washing tower (115) is connected with the absorption
  • the bottom inlet of the tower (116) is connected; the top outlet of the absorption tower (116) is connected with the circulating gas compressor (101), the impurity outlet and the ethylene recovery tower (117) bottom inlet is connected, and ethylene recovery tower (117) tower kettle outlet is connected with acetic acid evaporator (103) top inlet; acetic acid evaporator (103) tower kettle outlet is connected with acetic acid flash tank (118), and acetic acid flash
  • the operating pressure of the acetic acid evaporator (103) is 1.0-1.2 bara, and the temperature at the top of the tower is 40-100°C.
  • the reaction temperature of the synthesis reactor (107) is 100-180° C., and the reaction pressure is 1.0-1.2 bara; the operating pressure of the first gas separation tower (108) is 6-9 bara, and the top temperature is 65-100 bara. °C; the operating pressure of the second gas separation column (112) is 6-9 bara, and the top temperature is 20-50 °C.
  • the operating pressure of the water washing tower (115) is 8-11bara, and the temperature at the top of the tower is 22-55°C;
  • the operating pressure of the absorption tower (116) is 8-11bara, and the temperature at the top of the tower is 92-112°C;
  • the operating pressure of the recovery column (117) is 7-8 bara, and the top temperature is 23-45°C.
  • the operating pressure of the acetic acid flash tank (118) is 1.0-1.2 bara, and the tower top temperature is 92-115 ° C; the operating pressure of the acetic acid recovery tower (119) is 1.0-1.2 bara, and the tower top temperature is 77 -91°C; the operating pressure of the desorption tower (122) is 1.0-1.3 bara, and the top temperature is 103-124°C.
  • the vinyl acetate synthesis reaction solution also contains acetic acid, water, low-boiling point components and high-boiling point components.
  • acetic acid water
  • low-boiling point components high-boiling point components.
  • the composition of the gas phase is different from that of the liquid phase, and the proportion of volatile substances in the gas phase is greater than that of the volatile substances in the liquid phase.
  • the ratio can be separated and purified by means of rectification.
  • the vinyl acetate rectification section (vinyl acetate refining process) includes an acetic acid column, a crude VAC column, a refined VAC column, a weight removal column, an aldehyde ester concentration column, an acetaldehyde column and an acetic acid recovery column.
  • Vinyl acetate rectification utilizes the difference in the relative volatility of each component in the reaction solution, separates each component through a series of rectification operations, and finally obtains high-purity vinyl acetate products and various by-products.
  • the oxygen concentration at the inlet and outlet of the reactor is increased, thereby increasing the selectivity at the same time and under the same catalyst conditions, and correspondingly increasing the production capacity, reducing the consumption of raw materials and increasing the output of products;
  • the pre-first gas separation tower is set to fully recover the heat of the reaction gas, reduce the energy consumption of the production process, and reduce the energy consumption of the whole production process; set up an acetic acid recovery system, and provide a negative pressure environment for the acetic acid recovery tower through the vacuum unit, to maximize the Acetic acid is recovered, and the accumulation of heavy components at the bottom of the acetic acid evaporator is avoided to ensure the stability of production; an ethylene recovery device is designed for the recovery of lye in the desorption tower, and the ethylene raw material in the recovered lye is reused.
  • Fig. 1 shows the production process flow chart of synthetic vinyl acetate according to the present invention
  • FIG. 2 shows a schematic diagram of a vinyl acetate production device and a flow chart according to the present invention.
  • the invention provides a production process and device for synthesizing vinyl acetate, including the following technical solutions:
  • reaction gas at the reactor outlet is subjected to heat exchange through the first heat exchanger at the reactor outlet and the second cooler at the reactor outlet, respectively, it is sent to the bottom of the first gas separation tower.
  • the dehydrated reaction liquid is obtained from the first gas separation tower still, and sent to the rectification section for purification treatment.
  • the top of the first gas separation tower obtains the top gas whose main components are vinyl acetate and water, and is sent to the first gas separation tower condenser for condensation, and the non-condensable gas of the first gas separation tower condenser is sent to the first gas separation tower.
  • the aftercooler is further cooled, and the condensed liquid of the first gas separation tower condenser and the first gas separation tower aftercooler enters the first gas separation tower phase separator for phase separation, and the oil phase after the phase separation is sent to the first gas separation tower as a reflux.
  • the water phase is sent to the rectification section for further processing.
  • the non-condensable gas behind the aftercooler of the first gas separation tower is sent to the bottom of the second gas separation tower, and after the reaction liquid and acetic acid are absorbed and separated, a certain amount of reaction liquid is continuously extracted from the tower reactor and sent to the degassing
  • the gas extracted from the degassing tank is compressed by the recovery gas compressor and sent to the water washing tower.
  • a mixed gas mainly composed of ethylene, carbon dioxide, ethane and oxygen is obtained, which is sent to the circulating gas compressor as a circulating gas.
  • the ethylene recovery tower tower top adds fresh acetic acid to reclaim the ethylene gas therein, the ethylene recovery tower tower still liquid is sent to the acetic acid evaporator tower top, and the ethylene recovery tower tower top is sent to incinerated.
  • the acetic acid recovery system includes a first-level flash tank, an acetic acid recovery tower, an acetic acid recovery tower condenser, and a vacuum unit; the acetic acid evaporator tower still liquid enters the acetic acid flash tank first, and the evaporated gas from the flash tank is sent to the refined In the distillation section, the still liquid of the flash tank is sent to the acetic acid recovery tower, the top gas of the acetic acid recovery tower is condensed by the condenser of the acetic acid recovery tower and then refluxed, the uncondensed gas is sent to the degassing tank after passing through the vacuum unit, and the condensed liquid of the vacuum unit is sent back to the acetic acid Recovery tower feed.
  • the acetic acid recovery system includes an acetic acid flash tank, an acetic acid recovery tower, an acetic acid recovery tower condenser, and a vacuum unit; the acetic acid evaporator tower still liquid first enters the acetic acid flash tank, and the gas evaporated from the flash tank is sent to rectification.
  • the still liquid of the flash tank is sent to the acetic acid recovery tower.
  • the gas at the top of the acetic acid recovery tower is condensed by the condenser of the acetic acid recovery tower and then refluxed.
  • the uncondensed gas in the condenser of the acetic acid recovery tower is sent to the degassing tank after passing through the vacuum unit.
  • the condensate is sent to the acetic acid recovery tower for feed.
  • the desorption system includes a desorption tower and a desorption tower overhead condenser: the desorption system includes a desorption tower and a desorption tower overhead condenser: the absorption tower still liquid is fed into the desorption tower from the top of the desorption tower, and extracted from the top of the desorption tower. Two strands of material, one of which contains ethylene, is sent to the degassing tank, and the other is mainly composed of carbon dioxide. The desorption tower tank liquid is mixed and sent back to the absorption tower together with the additional fresh lye.
  • the circulating gas contains ethane gas, and the concentration of the ethane gas at the inlet of the reactor is 9-18 mol%.
  • the oxygen concentration at the inlet of the reactor is 6-12 mol%.
  • the present invention provides a vinyl acetate production device, comprising a circulating gas compressor (101), a circulating ethylene preheater (102), an acetic acid evaporator (103), a reactor outlet first heat exchanger (104), a reactor outlet Second heat exchanger (105), oxygen mixer (106), synthesis reactor (107), first gas separation column (108), first gas separation column condenser (109), first gas separation column aftercooling (110), the first gas separation tower phase separator (111), the second gas separation tower (112), the degassing tank (113), the recovery gas compressor (114), the water washing tower (115), the absorption tower ( 116), ethylene recovery column (117), acetic acid flash tank (118), acetic acid recovery column (119), acetic acid recovery column condenser (120), vacuum unit (121), desorption column (122), desorption column condenser (123), and the supporting heating and conveying equipment, the connection relationship is: the circulating gas compressor (101) is connected to the inlet of the heating side of the second heat
  • heating side outlet is connected with acetic acid evaporator (103) bottom inlet; acetic acid vaporizer (103) top outlet is connected with reactor outlet first heat exchanger (105) (104) heating side inlet; reactor outlet first heat exchange The outlet (104) on the heating side of the reactor (105) is connected with the second heat exchanger (105) at the outlet of the reactor; the second heat exchanger (105) at the outlet of the reactor is connected with the oxygen mixer (106); the oxygen mixer (106) The outlet is connected to the inlet of the synthesis reactor (107); the outlet of the synthesis reactor (107) is connected to the cooling side of the reactor outlet first heat exchanger (104) and the reactor outlet second heat exchanger (102) in turn; the reactor outlet The outlet on the cooling side of the second heat exchanger (102) is connected to the feed port at the bottom of the first gas separation column (108); the top of the first gas separation column (108) is connected to the first gas separation column condenser (109), the first gas separation column The gas separation column aftercooler (110) is connected; the first gas separation column condenser (109)
  • ethylene recovery tower (117) tower kettle outlet is connected with acetic acid evaporator (103) top inlet; acetic acid evaporator (103) tower kettle outlet is connected with acetic acid flash tank (118), and acetic acid flash tank (118)
  • the bottom outlet is connected with the acetic acid recovery tower (119) feed port; the acetic acid recovery tower (119) top outlet is connected with the acetic acid recovery tower condenser (120), and the acetic acid condenser condensate outlet is refluxed with the acetic acid recovery tower (119) top
  • the ports are connected to each other, and the non-condensable gas port of the condenser (120) of the acetic acid recovery tower is connected to the vacuum unit (121);
  • the inlet of the degassing tank (113) is connected; the tower kettle of the absorption tower (116) is connected with the inlet of the top of the desorption tower (122);
  • the condensate outlet of the tower condenser (123) is connected
  • the operating pressure of the acetic acid evaporator (103) is 1.0-1.2 bara, and the temperature at the top of the tower is 40-100°C.
  • the reaction temperature of the synthesis reactor (107) is 100-180° C., and the reaction pressure is 1.0-1.2 bara; the operating pressure of the first gas separation tower (108) is 6-9 bara, and the top temperature is 65-100 bara. °C; the operating pressure of the second gas separation column (112) is 6-9 bara, and the top temperature is 20-50 °C.
  • the operating pressure of the water washing tower (115) is 8-11bara, and the temperature at the top of the tower is 22-55°C;
  • the operating pressure of the absorption tower (116) is 8-11bara, and the temperature at the top of the tower is 92-112°C;
  • the operating pressure of the recovery column (117) is 7-8 bara, and the top temperature is 23-45°C.
  • the operating pressure of the acetic acid flash tank (118) is 1.0-1.2 bara, and the tower top temperature is 92-115 ° C; the operating pressure of the acetic acid recovery tower (119) is 1.0-1.2 bara, and the tower top temperature is 77 -91°C; the operating pressure of the desorption tower (122) is 1.0-1.3 bara, and the top temperature is 103-124°C.
  • the vinyl acetate synthesis reaction solution also contains acetic acid, water, low-boiling point components and high-boiling point components.
  • acetic acid water
  • low-boiling point components high-boiling point components.
  • the composition of the gas phase is different from that of the liquid phase, and the proportion of volatile substances in the gas phase is greater than that of the volatile substances in the liquid phase.
  • the ratio can be separated and purified by means of rectification.
  • the vinyl acetate rectification section (vinyl acetate refining process) includes an acetic acid column, a crude VAC column, a refined VAC column, a weight removal column, an aldehyde ester concentration column, an acetaldehyde column and an acetic acid recovery column.
  • Vinyl acetate rectification utilizes the difference in the relative volatility of each component in the reaction solution, separates each component through a series of rectification operations, and finally obtains high-purity vinyl acetate products and various by-products.
  • the fresh ethylene and circulating gas are mixed and passed into the circulating gas compressor.
  • the second cooler at the reactor outlet exchanges heat with the reaction gas, it is passed into the bottom of the acetic acid evaporator.
  • the ethylene recovery tower still liquid is sprayed from the top of the acetic acid evaporator, the mixed gas of ethylene and acetic acid is drawn from the top of the evaporator, and the evaporator still liquid is sent to the acetic acid recovery system.
  • the operating pressure of the acetic acid evaporator is 1.0 bara, and the top temperature is 42°C
  • the mixed gas of ethylene and acetic acid comes out from the top of the acetic acid evaporator, it is heated through the first heat exchanger (105) at the reactor outlet and the circulating ethylene preheater, and then mixed with oxygen through an oxygen mixer.
  • the mixed gas from the oxygen mixer is fed into the synthesis reactor from the top.
  • the recycle gas contained ethane as an inert gas, and the reactor inlet ethane concentration was 9 mol%. After the gas is mixed with oxygen in an oxygen mixer, the oxygen concentration reaches 6 mol%.
  • the reaction gas at the reactor outlet was subjected to heat exchange through the first heat exchanger at the reactor outlet and the second cooler at the reactor outlet, respectively. sent to the bottom of the first gas separation tower.
  • the dehydrated reaction liquid is obtained from the first gas separation tower still, and sent to the rectification section for purification treatment.
  • the top of the first gas separation tower obtains the top gas whose main components are vinyl acetate and water, and is sent to the first gas separation tower condenser for condensation, and the non-condensable gas of the first gas separation tower condenser is sent to the first gas separation tower.
  • the aftercooler is further cooled, and the condensed liquid of the first gas separation tower condenser and the first gas separation tower aftercooler enters the first gas separation tower phase separator for phase separation, and the oil phase after the phase separation is sent to the first gas separation tower as a reflux.
  • the water phase is sent to the rectification section for further processing.
  • the operating pressure of the first gas separation column (108) was 6.2 bara and the top temperature was 67°C.
  • the non-condensable gas after the aftercooler of the first gas separation tower is sent to the bottom of the second gas separation tower.
  • a certain amount of reaction liquid is continuously extracted from the tower still and sent to the degassing tank for degassing.
  • the gas extracted from the gas tank is compressed by the recovery gas compressor and sent to the water washing tower.
  • a mixed gas mainly composed of ethylene, carbon dioxide, ethane and oxygen is obtained, which is sent to the circulating gas compressor as a circulating gas.
  • the operating pressure of the second gas separation tower is 6.1 bara, and the temperature at the top of the tower is 22°C;
  • the top gas is sent to the absorption tower to absorb the carbon dioxide in it with lye, most of the gas from the top of the absorption tower is sent to the circulating gas compressor, and the rest is sent to the ethylene recovery tower and At the outlet of impurity discharge, the liquid from the absorption tower is sent to the desorption system.
  • the operating pressure of the water scrubber was 8.3 bara, and the top temperature was 24°C.
  • the absorption tower top gas is sent to the ethylene recovery tower
  • fresh acetic acid is added to the top of the ethylene recovery tower to recover the ethylene gas therein
  • the ethylene recovery tower tower liquid is sent to the top of the acetic acid evaporator, and the top of the ethylene recovery tower is sent to incineration.
  • the operating pressure of the absorption tower was 8.1 bara, and the top temperature was 92°C; the operating pressure of the ethylene recovery tower was 7.0 bara, and the top temperature was 23°C.
  • the acetic acid recovery system includes an acetic acid flash tank, an acetic acid recovery tower, an acetic acid recovery tower condenser, and a vacuum unit; the acetic acid evaporator tower kettle liquid first enters the acetic acid flash tank, and the gas evaporated from the flash tank is sent to the rectification section, and flashes The liquid from the distillation tank is sent to the acetic acid recovery tower.
  • the gas at the top of the acetic acid recovery tower is condensed by the condenser of the acetic acid recovery tower and then refluxed.
  • the uncondensed gas in the condenser of the acetic acid recovery tower is sent to the degassing tank after passing through the vacuum unit.
  • the operating pressure of the acetic acid flash tank was 1.0 bara, and the top temperature was 93°C; the operating pressure of the acetic acid recovery column was 1.0 bara, and the top temperature was 77°C.
  • the desorption system includes a desorption tower and a desorption tower top condenser: the absorption tower liquid is sent to the desorption tower from the top of the desorption tower, and two materials are extracted from the top of the desorption tower, one of which is mainly composed of ethylene, which is sent to the degassing tower.
  • the other main component is carbon dioxide.
  • the non-condensable carbon dioxide is sent out of the boundary area.
  • the condensed liquid is mixed with the still liquid of the desorption tower and sent back together with the fresh lye added. absorption tower.
  • the operating pressure of the desorber was 1.1 bara, and the top temperature was 103°C.
  • ethane is used as the inert gas
  • the ethane concentration at the reactor inlet is 9 mol%
  • the oxygen concentration is 6 mol%.
  • the single-pass conversion rate of the reaction was 27%
  • the selectivity was 96%.
  • the fresh ethylene and circulating gas are mixed and passed into the circulating gas compressor.
  • the second cooler at the reactor outlet exchanges heat with the reaction gas, it is passed into the bottom of the acetic acid evaporator.
  • the ethylene recovery tower still liquid is sprayed from the top of the acetic acid evaporator, the mixed gas of ethylene and acetic acid is drawn from the top of the evaporator, and the evaporator still liquid is sent to the acetic acid recovery system.
  • the operating pressure of the acetic acid evaporator was 1.1 bara, and the top temperature was 60°C.
  • the mixed gas of ethylene and acetic acid comes out from the top of the acetic acid evaporator, it is heated through the first heat exchanger (105) at the reactor outlet and the circulating ethylene preheater, and then mixed with oxygen through an oxygen mixer.
  • the mixed gas from the oxygen mixer is fed into the synthesis reactor from the top.
  • the recycle gas contained ethane as an inert gas, the ethane concentration at the reactor inlet was 15 mol %, and after mixing with oxygen in the oxygen mixer, the oxygen concentration reached 10 mol %.
  • the reaction gas at the outlet of the reactor was subjected to heat exchange through the first heat exchanger at the reactor outlet and the second cooler at the reactor outlet, respectively. sent to the bottom of the first gas separation tower.
  • the dehydrated reaction liquid is obtained from the first gas separation tower still, and sent to the rectification section for purification treatment.
  • the top of the first gas separation tower obtains the top gas whose main components are vinyl acetate and water, and is sent to the first gas separation tower condenser for condensation, and the non-condensable gas of the first gas separation tower condenser is sent to the first gas separation tower.
  • the aftercooler is further cooled, and the condensed liquid of the first gas separation tower condenser and the first gas separation tower aftercooler enters the first gas separation tower phase separator for phase separation, and the oil phase after the phase separation is sent to the first gas separation tower as a reflux.
  • the water phase is sent to the rectification section for further processing.
  • the operating pressure of the first gas separation column (108) was 8.1 bara and the top temperature was 72°C.
  • the non-condensable gas after the aftercooler of the first gas separation tower is sent to the bottom of the second gas separation tower.
  • a certain amount of reaction liquid is continuously extracted from the tower still and sent to the degassing tank for degassing.
  • the gas extracted from the gas tank is compressed by the recovery gas compressor and sent to the water washing tower.
  • a mixed gas mainly composed of ethylene, carbon dioxide, ethane and oxygen is obtained, which is sent to the circulating gas compressor as a circulating gas.
  • the operating pressure of the second gas separation tower is 8.4 bara, and the temperature at the top of the tower is 30°C;
  • the top gas is sent to the absorption tower to absorb the carbon dioxide in it with lye, most of the gas from the top of the absorption tower is sent to the circulating gas compressor, and the rest is sent to the ethylene recovery tower and At the outlet of impurity discharge, the liquid from the absorption tower is sent to the desorption system.
  • the operating pressure of the water scrubber was 8.4 bara, and the top temperature was 33°C.
  • the absorption tower top gas is sent to the ethylene recovery tower, fresh acetic acid is added to the top of the ethylene recovery tower to recover the ethylene gas therein, the ethylene recovery tower tower liquid is sent to the top of the acetic acid evaporator, and the top of the ethylene recovery tower is sent to incineration.
  • the operating pressure of the absorption tower was 8.4 bara, and the top temperature was 97°C; the operating pressure of the ethylene recovery tower was 7.6 bara, and the top temperature was 36°C.
  • the acetic acid recovery system includes an acetic acid flash tank, an acetic acid recovery tower, an acetic acid recovery tower condenser, and a vacuum unit; the acetic acid evaporator tower kettle liquid first enters the acetic acid flash tank, and the gas evaporated from the flash tank is sent to the rectification section, and flashes The liquid from the distillation tank is sent to the acetic acid recovery tower.
  • the gas at the top of the acetic acid recovery tower is condensed by the condenser of the acetic acid recovery tower and then refluxed.
  • the uncondensed gas in the condenser of the acetic acid recovery tower is sent to the degassing tank after passing through the vacuum unit.
  • the operating pressure of the acetic acid flash tank is 1.1 bara, and the top temperature is 102°C; the operating pressure of the acetic acid recovery tower is 1.1 bara, and the top temperature is 85°C.
  • the desorption system includes a desorption tower and a desorption tower top condenser: the absorption tower liquid is sent to the desorption tower from the top of the desorption tower, and two materials are extracted from the top of the desorption tower, one of which is mainly composed of ethylene, which is sent to the degassing tower.
  • the other main component is carbon dioxide.
  • the non-condensable carbon dioxide is sent out of the boundary area.
  • the condensed liquid is mixed with the still liquid of the desorption tower and sent back together with the fresh lye added. absorption tower.
  • the operating pressure of the desorber was 1.2 bara and the top temperature was 119°C.
  • ethane is used as the inert gas
  • the ethane concentration at the reactor inlet is 15 mol%
  • the oxygen concentration is 10 mol%.
  • the single-pass conversion rate of the reaction was 35%
  • the selectivity was 99%.
  • the fresh ethylene and circulating gas are mixed and passed into the circulating gas compressor.
  • the second cooler at the reactor outlet exchanges heat with the reaction gas, it is passed into the bottom of the acetic acid evaporator.
  • the ethylene recovery tower still liquid is sprayed from the top of the acetic acid evaporator, the mixed gas of ethylene and acetic acid is drawn from the top of the evaporator, and the evaporator still liquid is sent to the acetic acid recovery system.
  • the operating pressure of the acetic acid evaporator was 1.2 bara and the top temperature was 98°C.
  • the mixed gas of ethylene and acetic acid comes out from the top of the acetic acid evaporator, it is heated through the first heat exchanger (105) at the reactor outlet and the circulating ethylene preheater, and then mixed with oxygen through an oxygen mixer.
  • the mixed gas from the oxygen mixer is fed into the synthesis reactor from the top.
  • the recycle gas contained ethane as an inert gas, and the reactor inlet ethane concentration was 18 mol%. After mixing with oxygen in an oxygen mixer, the oxygen concentration reached 12 mol%.
  • the reaction gas at the reactor outlet was subjected to heat exchange through the first heat exchanger at the reactor outlet and the second cooler at the reactor outlet, respectively. sent to the bottom of the first gas separation tower.
  • the dehydrated reaction liquid is obtained from the first gas separation tower still, and sent to the rectification section for purification treatment.
  • the top of the first gas separation tower obtains the top gas whose main components are vinyl acetate and water, and is sent to the first gas separation tower condenser for condensation, and the non-condensable gas of the first gas separation tower condenser is sent to the first gas separation tower.
  • the aftercooler is further cooled, and the condensed liquid of the first gas separation tower condenser and the first gas separation tower aftercooler enters the first gas separation tower phase separator for phase separation, and the oil phase after the phase separation is sent to the first gas separation tower as a reflux.
  • the water phase is sent to the rectification section for further processing.
  • the operating pressure of the first gas separation column (108) was 9 bara and the top temperature was 97°C.
  • the non-condensable gas after the aftercooler of the first gas separation tower is sent to the bottom of the second gas separation tower.
  • a certain amount of reaction liquid is continuously extracted from the tower still and sent to the degassing tank for degassing.
  • the gas extracted from the gas tank is compressed by the recovery gas compressor and sent to the water washing tower.
  • a mixed gas mainly composed of ethylene, carbon dioxide, ethane and oxygen is obtained, which is sent to the circulating gas compressor as a circulating gas.
  • the operating pressure of the second gas separation tower is 8.8 bara, and the temperature at the top of the tower is 47°C;
  • the top gas is sent to the absorption tower to absorb the carbon dioxide in it with lye, most of the gas from the top of the absorption tower is sent to the circulating gas compressor, and the rest is sent to the ethylene recovery tower and At the outlet of impurity discharge, the liquid from the absorption tower is sent to the desorption system.
  • the operating pressure of the water scrubber was 11 bara, and the top temperature was 55°C.
  • the absorption tower top gas is sent to the ethylene recovery tower, fresh acetic acid is added to the top of the ethylene recovery tower to recover the ethylene gas therein, the ethylene recovery tower tower liquid is sent to the top of the acetic acid evaporator, and the top of the ethylene recovery tower is sent to incineration.
  • the operating pressure of the absorption tower is 11 bara, and the top temperature is 110°C; the operating pressure of the ethylene recovery tower is 8 bara, and the top temperature is 45°C.
  • the acetic acid recovery system includes an acetic acid flash tank, an acetic acid recovery tower, an acetic acid recovery tower condenser, and a vacuum unit; the acetic acid evaporator tower kettle liquid first enters the acetic acid flash tank, and the gas evaporated from the flash tank is sent to the rectification section, and flashes The liquid from the distillation tank is sent to the acetic acid recovery tower.
  • the gas at the top of the acetic acid recovery tower is condensed by the condenser of the acetic acid recovery tower and then refluxed.
  • the uncondensed gas in the condenser of the acetic acid recovery tower is sent to the degassing tank after passing through the vacuum unit.
  • the operating pressure of the acetic acid flash tank is 1.2 bara, and the top temperature is 115°C; the operating pressure of the acetic acid recovery tower is 1.2 bara, and the top temperature is 90°C.
  • the desorption system includes a desorption tower and a desorption tower top condenser: the absorption tower liquid is sent to the desorption tower from the top of the desorption tower, and two materials are extracted from the top of the desorption tower, one of which is mainly composed of ethylene, which is sent to the degassing tower.
  • the other main component is carbon dioxide.
  • the non-condensable carbon dioxide is sent out of the boundary area.
  • the condensed liquid is mixed with the still liquid of the desorption tower and sent back together with the fresh lye added. absorption tower.
  • the operating pressure of the desorber was 1.3 bara, and the top temperature was 124°C.
  • ethane is used as the inert gas
  • the ethane concentration at the reactor inlet is 18 mol%
  • the oxygen concentration is 12 mol%.
  • the single-pass conversion rate of the reaction was 33%
  • the selectivity was 91%.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/CN2021/119873 2020-10-20 2021-09-23 醋酸乙烯生产工艺及装置 Ceased WO2022083395A1 (zh)

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CN113861026B (zh) * 2021-10-29 2022-09-06 天津大学 一种乙炔法合成的醋酸乙烯及醋酸的精制方法
CN116637567A (zh) * 2022-02-15 2023-08-25 中国石油化工股份有限公司 一种醋酸乙烯节能生产系统
CN115745794B (zh) * 2022-11-16 2023-06-20 天津大学 乙烯法醋酸乙烯生产工艺及装置
CN116924877A (zh) * 2023-07-26 2023-10-24 天津大学 醋酸乙烯合成过程循环气精制工艺及装置
CN119751195B (zh) * 2025-03-10 2025-07-01 华东理工大学 一种含密封油的乙烯气体中的乙烯的回收方法和回收装置

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JPS6287552A (ja) * 1985-10-11 1987-04-22 Nippon Synthetic Chem Ind Co Ltd:The 酢酸ビニル反応生成ガスの精製方法
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CN112299989A (zh) * 2020-10-20 2021-02-02 天津大学 醋酸乙烯生产工艺及装置

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