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CN110006216B - Separation and recovery process of non-condensable exhaust gas from ethylene cycle refrigeration system coupled with cryogenic and membrane - Google Patents

Separation and recovery process of non-condensable exhaust gas from ethylene cycle refrigeration system coupled with cryogenic and membrane Download PDF

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CN110006216B
CN110006216B CN201910247722.XA CN201910247722A CN110006216B CN 110006216 B CN110006216 B CN 110006216B CN 201910247722 A CN201910247722 A CN 201910247722A CN 110006216 B CN110006216 B CN 110006216B
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ethylene
refrigeration system
exhaust gas
cryogenic
membrane
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CN110006216A (en
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贺高红
杨晓航
阮雪华
代岩
郭明钢
肖红岩
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Dalian University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25BREFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B43/00Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat
    • F25B43/04Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat for withdrawing non-condensible gases
    • F25B43/043Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat for withdrawing non-condensible gases for compression type systems
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0295Start-up or control of the process; Details of the apparatus used, e.g. sieve plates, packings
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J5/00Arrangements of cold exchangers or cold accumulators in separation or liquefaction plants
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00Processes characterised by the type or other details of the product stream
    • F25J2215/62Ethane or ethylene

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

The invention provides a process for separating and recovering noncondensable exhaust gas of a cryogenic and membrane coupled ethylene circulating refrigeration system, belonging to the technical field of petrochemical industry. The process starts from the characteristics of an ethylene circulating refrigeration system, firstly, the non-condensable exhaust gas is liquefied and rectified by utilizing the cryogenic condition formed by ethylene throttling expansion, most of ethylene is recovered in a liquid state, then, residual ethylene in the enriched cryogenic tail gas is separated through a gas membrane, and low-pressure ethylene-rich gas obtained at a permeation side returns to a compressor of the ethylene circulating refrigeration system. Through the coupled treatment of deep cooling and membrane separation, the noncondensable exhaust gas can avoid the accumulation of oxygen and nitrogen and obviously reduce the loss of ethylene. By taking a butyl rubber device of 6 ten thousand tons per year as an example, the high-efficiency separation and recovery process of the noncondensable exhaust gas provided by the invention has the advantages that the content of ethylene in the tail gas discharged to a torch is lower than 5.0 vol%, the recovery rate of ethylene reaches 99%, about 210 tons of ethylene can be recovered every year, and the annual economic benefit exceeds 200 ten thousand yuan.

Description

Cryogenic and membrane coupled process for separating and recovering noncondensable exhaust gas of ethylene circulating refrigeration system
Technical Field
The invention relates to a process for separating and recovering noncondensable exhaust gas of a cryogenic and membrane coupled ethylene circulating refrigeration system, belonging to the technical field of petrochemical industry. The process comprises the steps of firstly liquefying and rectifying noncondensable exhaust gas by utilizing the cryogenic condition formed by ethylene throttling expansion, recovering most ethylene in a liquid state, then separating and enriching residual ethylene in cryogenic tail gas through a gas membrane, and returning low-pressure ethylene-rich gas obtained at a permeation side to a compressor of an ethylene circulating refrigeration system. Through the coupled treatment of deep cooling and membrane separation, the noncondensable exhaust gas can avoid the accumulation of oxygen and nitrogen and obviously reduce the loss of ethylene.
Background
Ethylene is an important basic chemical raw material and is widely applied to various fields. In the butyl unit, ethylene was used as a refrigerant to provide cold at-76, -97, and-110 ℃ at different throttling pressures. In order to meet the production requirement of a butyl rubber device and provide cold at the temperature of-110 ℃, an ethylene circulating refrigeration system needs to be operated under negative pressure, so that air enters the refrigeration system to form non-condensable gas. To ensure safe operation, the noncondensable gases must be periodically vented from the ethylene recycle refrigeration system. During the discharge process, a large amount of ethylene enters the flare system along with the non-condensable gas, causing huge waste. According to the production data of a 6-ten-thousand-ton butyl rubber device of a certain enterprise, if the noncondensable exhaust gas of an ethylene refrigeration system is directly discharged to a torch, about 212 tons of ethylene is lost every year, and the economic loss exceeds 200 ten thousand yuan/year.
The ethylene recovery methods commonly used at present mainly comprise cryogenic separation and gas membrane separation. Simple cryogenic separation has mainly the following limitations: the influence of the cryogenic temperature fluctuation is large, when the cryogenic temperature is not low enough, the recovery effect is not obvious, when the cryogenic temperature is too low, the full condensation phenomenon easily occurs, and the discharge of non-condensable gas is not facilitated. Simple gas membrane separation is also limited: the concentration of ethylene in the non-condensable exhaust gas reaches up to 97%, the membrane separation and enrichment effect is not obvious, and the phenomenon of obvious non-condensable gas accumulation also exists. Due to the defects of the prior art, a more reasonable and efficient noncondensable exhaust gas separation and recovery process is urgently needed for an ethylene circulating refrigeration system, so that the ethylene loss is obviously reduced while the accumulation of oxygen and nitrogen is avoided.
Disclosure of Invention
The invention relates to a process for separating and recovering noncondensable exhaust gas of a cryogenic and membrane coupled ethylene circulating refrigeration system. The process comprises the steps of firstly liquefying and rectifying noncondensable exhaust gas by utilizing the cryogenic condition formed by ethylene throttling expansion, recovering most ethylene in a liquid state, then separating and enriching residual ethylene in cryogenic tail gas through a gas membrane, and returning low-pressure ethylene-rich gas obtained at a permeation side to a compressor of an ethylene circulating refrigeration system.
The technical scheme of the invention is as follows:
a cryogenic and membrane coupled noncondensable exhaust gas separation and recovery process of an ethylene circulating refrigeration system, wherein the system used by the noncondensable exhaust gas separation and recovery process of the ethylene circulating refrigeration system comprises 1 an ethylene circulating refrigeration system 1, a rectifying tower 2, a heat exchanger 3 and a membrane separation unit 4;
noncondensable exhaust gas S-1 discharged from the ethylene circulating refrigeration system 1 firstly enters the rectifying tower 2 from the bottom of the rectifying tower 2 and is in countercurrent contact with the cryogenic condensate refluxed from the top of the rectifying tower, heavy component ethylene in a gas phase is cooled and liquefied, and oxygen and nitrogen of the noncondensable gas dissolved and absorbed in the cryogenic condensate are desorbed; the liquid ethylene S-2 obtained by separation in the rectifying tower 2 returns to the ethylene circulating refrigeration system 1 from the bottom of the tower;
the low-temperature liquid ethylene S-4 extracted from the ethylene circulating refrigeration system 1 enters a heat exchanger at the top of a rectifying tower 2, cold energy is provided by vaporization, the noncondensable exhaust gas S-1 rising in the rectifying tower 2 is partially liquefied, and the ethylene S-5 after low-temperature vaporization returns to a compressor of the ethylene circulating refrigeration system 1;
the cryogenic tail gas S-3 discharged from the top of the rectifying tower 2 exchanges heat with high-pressure normal-temperature ethylene S-7 output by a compressor in the ethylene circulating refrigeration system 1 in the heat exchanger 3, the high-pressure temperature-reducing liquefied ethylene S-8 is sent to a liquid ethylene tank of the ethylene circulating refrigeration system 1, and the cryogenic tail gas S-6 after heat exchange, the temperature of which is higher than the dew point, enters a membrane separation unit 4 as a raw material; the low pressure side of the membrane separation unit 4 obtains membrane separation permeation gas S-10 enriched with ethylene, the membrane separation permeation gas is sent to the inlet of a compressor of the ethylene circulating refrigeration system 1, the high pressure side of the membrane obtains membrane separation permeation residual gas S-9 without most of the ethylene, and the membrane separation permeation residual gas S-9 is discharged to a torch.
The invention has the beneficial effects that: the invention provides a high-efficiency cryogenic and membrane-coupled separation and recovery process for noncondensable exhaust gas of an ethylene circulating refrigeration system, which comprises the steps of firstly liquefying and rectifying the noncondensable exhaust gas by utilizing a cryogenic condition formed by throttling and expanding ethylene, recovering most of ethylene in a liquid state, then separating and enriching residual ethylene in cryogenic tail gas through a gas membrane, and returning low-pressure ethylene-rich gas obtained at a permeation side to a compressor of the ethylene circulating refrigeration system. By coupling cryogenic rectification and membrane separation, 99% of ethylene in the non-condensable exhaust gas can be recovered on the premise of avoiding the accumulation of oxygen and nitrogen. By taking a butyl rubber device of 6 ten thousand tons per year as an example, the high-efficiency separation and recovery process of the noncondensable exhaust gas provided by the invention can recover about 210 tons of ethylene every year, and the annual economic benefit exceeds 200 ten thousand yuan.
Drawings
FIG. 1 is a schematic flow diagram of the process for the separation and recovery of the non-condensed vent gas of a cryogenic membrane coupled ethylene cycle refrigeration system.
In the figure: 1 an ethylene circulating refrigeration system; 2, a rectifying tower; 3, a heat exchanger; 4 a membrane separation unit; s-1, noncondensable exhaust gas; s-2 liquid ethylene; s-3, deep cooling tail gas; s-4, low-temperature liquid ethylene; s-5 ethylene after low-temperature vaporization; s-6, carrying out heat exchange on the cryogenic tail gas; s-7, high-pressure normal-temperature ethylene; s-8, cooling liquefied ethylene under high pressure; s-9, separating the residual gas by a membrane; s-10 ethylene-enriched membrane separation permeate gas.
Detailed Description
The following detailed description of the invention refers to the accompanying drawings.
Examples
The separation and recovery process provided by the invention is used for treating noncondensable exhaust gas generated by an ethylene circulating refrigeration system of a 6 ten thousand ton/year butyl rubber device. The pressure of the uncondensed off-gas was 1.64MPaG, the temperature was-38 ℃ and the ethylene content was about 97 mol%, so that the amount of ethylene lost per year was about 212 tons of ethylene.
Noncondensable exhaust gas S-1 discharged from the ethylene circulating refrigeration system 1 firstly enters the bottom of a rectifying tower 2 and is in countercurrent contact with the cryogenic condensate refluxed from the top of the tower, heavy component ethylene in a gas phase is cooled and liquefied, and oxygen and nitrogen of the noncondensable gas dissolved and absorbed in the cryogenic condensate are desorbed; the liquid ethylene S-2 obtained by separation in the rectifying tower 2 returns to the ethylene circulating refrigeration system 1 from the bottom of the tower; the low-temperature liquid ethylene S-4 extracted from the ethylene circulating refrigeration system 1 enters a heat exchanger at the top of the rectifying tower 2, cold energy is provided by vaporization, the noncondensable exhaust gas rising in the rectifying tower 2 is partially liquefied, and the ethylene S-5 after low-temperature vaporization returns to a compressor of the ethylene circulating refrigeration system 1; the cryogenic tail gas S-3 discharged from the top of the rectifying tower 2 exchanges heat with high-pressure normal-temperature ethylene S-7 output by a compressor in the ethylene circulating refrigeration system 1 in a heat exchanger 3, the high-pressure normal-temperature ethylene S-8 is sent to a liquid ethylene tank of the ethylene circulating refrigeration system 1 after being cooled and liquefied, the cryogenic tail gas S-6 after heat exchange has the temperature higher than the dew point and is used as a raw material to enter a membrane separation unit 4, membrane separation permeation gas S-10 enriched with ethylene is obtained at the low-pressure side of a membrane and is sent to the compressor inlet of the ethylene circulating refrigeration system 1, and membrane separation permeation residual gas S-9 for removing most of ethylene is obtained at the high-pressure side of the membrane and is discharged to a torch.
The diameter of the rectifying tower 2 is 0.20 meter, the height of the filler is 0.8 meter, and the heat exchange area at the top of the tower is 0.3 square meter; the membrane area was 0.1 square meter.
Conditions of the rectifying tower 2: the pressure at the bottom of the tower is 1.64MPaG, and the temperature is-38 ℃; the overhead pressure was 1.61MPaG at-100 ℃.
Membrane separation conditions: the pressure of the raw material is 1.60MPaG, and the temperature is 30 ℃; osmotic pressure 5kPaG, temperature 27 ℃; residual pressure 1.58MPaG and temperature 29 ℃.
In this example, the membrane separation retentate discharged to the flare had an ethylene content of about 4.6 mol% and an ethylene recovery of 99.0%. 210 tons of ethylene can be recovered every year, and the annual economic benefit can reach 200 ten thousand yuan.

Claims (1)

1.一种深冷与膜耦合的乙烯循环制冷系统不凝排放气分离回收工艺,其特征在于,所述的乙烯循环制冷系统不凝排放气分离回收工艺所用的系统包括乙烯循环制冷系统(1)、精馏塔(2)、换热器(3)和膜分离单元(4);1. a non-condensable exhaust gas separation and recovery process of a cryogenic and membrane-coupled ethylene cycle refrigeration system is characterized in that, the used system of the non-condensable exhaust gas separation and recovery process of the described ethylene cycle refrigeration system comprises an ethylene cycle refrigeration system (1 ), rectification tower (2), heat exchanger (3) and membrane separation unit (4); 从乙烯循环制冷系统(1)排出的不凝排放气(S-1),首先从精馏塔(2)底部进入精馏塔(2)内,与塔顶回流的深冷凝液逆流接触,气相中的重组分乙烯降温液化、深冷凝液中溶解吸收的不凝气氧气和氮气解吸;在精馏塔(2)中分离获得的液态乙烯(S-2),从塔底返回乙烯循环制冷系统(1);The non-condensable exhaust gas (S-1) discharged from the ethylene circulation refrigeration system (1) first enters the rectifying column (2) from the bottom of the rectifying column (2), and is in countercurrent contact with the deep condensate refluxed at the top of the column. The heavy component ethylene in the ethylene is cooled and liquefied, and the non-condensable oxygen and nitrogen dissolved and absorbed in the deep condensate are desorbed; the liquid ethylene (S-2) obtained by separation in the rectifying tower (2) is returned to the ethylene circulation refrigeration system from the bottom of the tower. (1); 从乙烯循环制冷系统(1)采出的低温液态乙烯(S-4)进入精馏塔(2)顶部的换热器,通过汽化提供冷量,使精馏塔(2)中上升的不凝排放气(S-1)部分液化,低温汽化后的乙烯(S-5)返回乙烯循环制冷系统(1)的压缩机;The low-temperature liquid ethylene (S-4) extracted from the ethylene circulation refrigeration system (1) enters the heat exchanger at the top of the rectification tower (2), and provides cooling capacity through vaporization, so that the non-condensing liquid rising in the rectification tower (2) is not condensed. The exhaust gas (S-1) is partially liquefied, and the low-temperature vaporized ethylene (S-5) is returned to the compressor of the ethylene circulation refrigeration system (1); 精馏塔(2)顶部排出的深冷尾气(S-3),在换热器(3)中与乙烯循环制冷系统(1)中压缩机输出的高压常温乙烯(S-7)换热,高压降温液化的乙烯(S-8)送往乙烯循环制冷系统(1)的液态乙烯罐,换热后的深冷尾气(S-6),温度高于露点,作为原料进入膜分离单元(4);在膜分离单元(4)膜的低压侧获得乙烯富集的膜分离渗透气(S-10),送往乙烯循环制冷系统(1)的压缩机入口,再膜的高压侧获得脱除大部分乙烯的膜分离渗余气(S-9),排放至火炬。The cryogenic tail gas (S-3) discharged from the top of the rectification tower (2) exchanges heat with the high-pressure normal temperature ethylene (S-7) output by the compressor in the ethylene circulation refrigeration system (1) in the heat exchanger (3), The ethylene (S-8) liquefied by high pressure cooling is sent to the liquid ethylene tank of the ethylene circulation refrigeration system (1), and the cryogenic exhaust gas (S-6) after heat exchange, whose temperature is higher than the dew point, enters the membrane separation unit (4) as a raw material ); obtain ethylene-enriched membrane separation permeate gas (S-10) on the low-pressure side of the membrane separation unit (4), send it to the compressor inlet of the ethylene circulation refrigeration system (1), and then obtain the removal from the high-pressure side of the membrane. Most of the ethylene membranes separate the retentate (S-9), which is vented to the flare.
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