CN106588548B - A kind of alkene separation method - Google Patents
A kind of alkene separation method Download PDFInfo
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- CN106588548B CN106588548B CN201611035473.0A CN201611035473A CN106588548B CN 106588548 B CN106588548 B CN 106588548B CN 201611035473 A CN201611035473 A CN 201611035473A CN 106588548 B CN106588548 B CN 106588548B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
-
- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of alkene separation methods, it is characterized by comprising following step: hydrocarbon raw material and recycle hydrocarbons enter feed surge tank together, the material of tank bottom discharge enters heavy constituent knockout tower, obtain the heavy constituent of carbon atom number >=4, enter ice chest after the purification hydrocarbon raw material decompression obtained in the middle part of surge tank to exchange heat, provides the cooling capacity of different potential temperatures for ice chest；Heat exchange enters reactor, enters ice chest after obtained dehydrogenation product is cooling, gradually walks cooling by the material of different temperature sections in ice chest, and resulting vapour-liquid mixed phase, which is sent into liquid separation tank, carries out air-liquid separation；The gas phase isolated returns to ice chest and is condensed again, product gas is cooled down step by step by the LNG cryogen of different potential temperatures after product gas is cooled to -25~-40 DEG C, until the heavy constituent of three or more carbon all condenses in product gas, remaining tail gas discharge, the liquid phase that liquid separation tank is isolated successively is sent after entering ice chest recycling cooling capacity to light component knockout tower, rectifying column, obtains propylene product in the tower top of rectifying column.
Description
Technical field
The present invention relates to alkene separation methods.
Background technique
Separation of olefins usually requires processing hydrogen, methane, ethylene, ethane, carbon dioxide, carbon monoxide, water, propylene, third
The various ingredients such as alkane and heavy hydrocarbon.The component of different molecular weight need to be gradually isolated, especially light component, such as be separated not
It is good, it will seriously affect target product purity, and increase the energy consumption of downstream separation tower.According to the physicochemical property of each component, usually may be used
Light component is separated using the methods of oily absorption, cryogenic separation, UF membrane, pressure-variable adsorption and rectifying.Existing technique dress
In setting, propylene, ethylene cascading compression refrigerating method and reaction gas swell refrigeration method are mainly used.Propylene, ethylene cascade refrigeration process
There are cooling capacity classification is more, number of compressors and series are more, and process and control system are complicated, and heat exchange equipment is more, and investment is relatively high,
Land occupation is big.And the shortcomings that swell refrigeration is: process is complex, stability is poor, the manufacture difficulty of ice chest is big.
Summary of the invention
There is provided that a kind of process is simple, number of devices the technical problem to be solved by the present invention is to the status for the prior art
Less, the capacity usage ratio of device can be greatlyd improve, reduce plant energy consumption, the LNG cold energy to reduce investment and operating cost
Using method, to significantly improve economic benefit.
The technical scheme of the invention to solve the technical problem is: the alkene separation method, it is characterised in that packet
Include following step:
Pressure is content >=80wt% room temperature hydrocarbon raw material of 1.5~2.0MPaG propane and propylene and from product essence
The temperature for evaporating the tower reactor of tower is 50~80 DEG C, pressure is 1.5~3.0MPaG, propane content >=wt90% recycle hydrocarbons together into
Enter feed surge tank, the molar flow ratio of the hydrocarbon raw material and recycle hydrocarbons is 1:2~3；
The temperature of charge for buffering pot bottom discharge is 40~70 DEG C, 1.0~2.0MPaG of pressure, into heavy constituent knockout tower,
Obtain the heavy constituent of carbon atom number >=4 in the tower bottom of heavy constituent knockout tower, obtained in the middle part of surge tank propane content >=
The purification hydrocarbon raw material that 95wt%, temperature are 35~45 DEG C, pressure is 1.0~1.5MPaG；
Purification hydrocarbon raw material is decompressed to 0.05~0.1MPaG, -33 DEG C~-42 DEG C of temperature entrance ice chests heat exchange, is ice chest
The cooling capacity of different potential temperatures is provided；Vaporization hydrocarbon raw material after ice chest exchanges heat be pressurized to 0.2~0.6MPaG and exchanges heat to 550~
After 650 DEG C, into reactor, dehydrogenation reaction is carried out, obtains that temperature is 500~600 DEG C, pressure is -0.06~0.15MPaG, third
Alkene content is the product of 35~50wt%；
Product is cooled to 35~50 DEG C, is pressurized to 1.0~2.0MPaG and enters after dry to < -100 DEG C of water dew point cold
Case is gradually cooled down it by the raw material of different potential temperatures in ice chest, and the heavier component in product gas gradually condenses in ice chest, often
Heat exchange is primary, and resulting vapour-liquid mixed phase can be extracted out in the middle part of ice chest, and air-liquid separation is carried out in liquid separation tank；
The gas phase isolated returns to ice chest and is condensed again, and the liquid phase isolated is sent after cold recovery to light group of downstream
Knockout tower is divided to carry out gas-liquid separation；Again by the LNG cryogen of different potential temperatures p- 25~-40 after product is cooled to -25~-40 DEG C
DEG C product gas cooled down step by step, be finally cooled to -110~-130 DEG C, the heavy constituent of three or more carbon mistake herein in product gas
Cheng Jun is condensed, and the vapour that finally obtains, liquid mixture carry out gas-liquid separation in liquid separation tank；
Product gas sends to downstream from ice chest discharge tail gas after repeatedly cooling；The liquid phase that liquid separation tank is isolated enters ice chest work
It exchanges heat for cold source to sending to light component knockout tower after -45~-55 DEG C and further separates；
Light component separate column overhead be discharged tail gas, tower bottom obtain temperature be 0~30 DEG C, pressure 2.0MPaG, propylene content
It send for the logistics of 30~45wt% to rectifying column progress rectifying；
The materials at bottom of tower of rectifying column is recycled back to feed surge tank as raw material, the tower top of rectifying column obtain purity >=
99.5wt% propylene product.
It is preferred that by the material of different potential temperatures being respectively 0~-10 DEG C, -15~-25 DEG C and -30~-40 DEG C in the ice chest.
Preferably, the LNG cryogen of the different potential temperatures is respectively -80~-100 DEG C, -110~130 DEG C and -150~-162
℃；Accordingly, the product gas is cooled to -40~-60 DEG C, -80~-100 DEG C and -110~-130 DEG C step by step respectively.
Compared with prior art, the present invention is freezed using hydrocarbon raw material throttling expansion and is carried out using LNG cooling capacity to alkene
The method of cryogenic separation.It is simple using hydrocarbon raw material throttling expansion cooling flow, propylene compression refrigeration can be substituted；Made using LNG
For cryogen, alternative ethylene compression refrigeration, LNG refrigerant temperature adjustable range is big (minimum -162 DEG C), and separating effect is obvious.Using
Separation method process of the invention is simple, and number of devices is few, while the present invention can greatly improve the capacity usage ratio of device, drop
Low plant energy consumption can generate biggish economic benefit to reduce investment and operating cost.
Detailed description of the invention
Fig. 1 is schematic diagram of the embodiment of the present invention.
In Fig. 1 in Fig. 1,1- heavy constituent knockout tower, 2- throttle valve, 3- ice chest, 4- feed gas compressor, the heat exchange of 5- input and output material
Device, 6- feed heating furnace, 7- reactor, 8- waste heat boiler, the suction port of compressor 9- water cooler, 10- product air compressor, 11- production
Product Gas Cooler, 12- product gas drying tower, 13- gas-liquid separator, 14- light component knockout tower, 15- product rectifying column, 16- into
Expect surge tank.101- hydrocarbon raw material, 102- refine hydrocarbon raw material, 103- heavy constituent by-product, low temperature hydrocarbon after 104- pressure reducing valve
Raw material, hydrocarbon raw material after 105- gasification, hydrocarbon raw material after 106- pressurization, 107- feed heating furnace entrance hydrocarbon raw material, and 108- is anti-
Device entrance hydrocarbon raw material is answered, 109- goes out reactor product, the product gas after the heat exchange of 110- waste heat boiler, and 111- goes out input and output material heat exchange
The product gas of device, 112- product gas suction port of compressor material, 113- product gas compressor outlet material, 114- product after cooling
Gas, the product gas after 115- is dry, 116- material after ice chest condenses, the gaseous phase materials after 117- separation, 118- hydrogen rich gas,
Liquid phase stream after 119- separation, 120-C2 knockout tower tail gas, the charging of 121- product rectifying column, 122- product, 123- recycle hydrocarbons
Class raw material, 124-LNG, 125- natural gas.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
As shown in Fig. 1, pressure is 1.5~2.0MPaG, propane+propylene content >=80wt% room temperature hydrocarbon raw material 101
Temperature with the tower reactor from product rectifying column 15 is 50~80 DEG C, pressure is 1.5~3.0MPaG, propane >=wt90% is followed
Cyclic hydrocarbon 123 enters feed surge tank 16 together,
Hydrocarbon raw material 101 and 123 molar flow ratio of recycle hydrocarbons are 1:3.
40~70 DEG C of tank bottom part temperature of charge, the 1.0~2.0MPaG of pressure of surge tank 16 enter heavy constituent knockout tower 1,
Using each component boiling point difference, the operation temperature gradient of tower is different under certain operating pressure, heavy constituent is isolated, in tower bottom
Obtain heavy constituent C4+ byproduct 103 (four or more component of carbon >=90wt%), obtained in tower 35~45 DEG C of temperature, pressure 1.0~
1.5MPaG, propane >=95wt% purification hydrocarbon raw material 102；
Purification hydrocarbon raw material 102 is depressurized according to cryogenic separation institute chilling requirement grade, obtain temperature be respectively 0~-
The material of 10 DEG C, -15~-25 DEG C and -30~-40 DEG C three potential temperatures provides the cooling capacity of different potential temperatures for ice chest 3；It is changed through ice chest
Vaporization hydrocarbon raw material 105 after heat enters corresponding compression section in feed compressor 4.
Vapour phase hydrocarbon raw material by after compressor boost to 0.2~0.6MPaG, through the heat exchange of input and output material heat exchanger 5 to 300~
500 DEG C enter charging heating furnace 6.After charging heating furnace is heated to 550~650 DEG C of required temperature of reaction, into reactor 7,
Dehydrogenation reaction is completed, 109 temperature of product come out from reactor is 500~600 DEG C, pressure is -0.06~0.15MPaG, propylene
Content is 35~50wt%, sequentially enters waste heat boiler 8 and input and output material heat exchanger 5 recycles heat, then water cooled device 9 is cooled to
Enter product gas compressor 10 after 35~50 DEG C and be pressurized to 1.0~2.0MPaG, enters back into reactor product cooler 11 and be cooled to 35~50
DEG C, subsequently into entering ice chest 3 after dry to < -100 DEG C of water dew point of product gas drying tower 12.
The material of high temperature section part of the product gas in ice chest and above-mentioned purification hydrocarbon raw material decompression three obtained potential temperature
(0~-10 DEG C, -15~-25 DEG C, -30~-40 DEG C) exchange heat, and are gradually cooled to -25~-40 DEG C, heavier in product gas
Component gradually condenses in ice chest；Every heat exchange is primary, and resulting vapour-liquid mixed phase can be extracted out in the middle part of ice chest, into liquid separation tank 13
Carry out air-liquid separation；Gas returns to ice chest, and further cooling, condensation, liquid phase are sent to downstream light component after cold recovery and are separated
Tower (14) further separates.
After product gas is cooled to -25~-40 DEG C enter ice chest low-temperature zone part, successively with -80~-100 DEG C, -110
It is cooling that the LNG cryogen of~130 DEG C, -150~-162 DEG C three potential temperatures carries out stage-by-stage heat exchange, and product gas is successively cooled to -40~-
60 DEG C, -80~-100 DEG C and -110~-130 DEG C, heavier component is condensed in this process in product gas, every time after heat exchange
Liquid-vapor mixture enter liquid separation tank 13 carry out air-liquid separation.
118 pressure of tail gas that liquid separation tank 13 is isolated is 0.5~0.8MPaG, temperature is 35 DEG C~45 DEG C, hydrogen content >=
90v% is sent after recycling cooling capacity into ice chest to hydrogen purification device, such as Pressure Swing Adsorption device, or directly as fuel gas
It send to fuel gas pipe network；The low-temperature zone that the liquid phase that liquid separation tank 13 is isolated then enters ice chest is sent after recycling cooling capacity to downstream light component
Knockout tower 14 further separates.
121 temperature of logistics that the tower bottom of light component knockout tower 14 obtains is 0~30 DEG C, pressure 2.0MPaG, propylene contain
Amount is 30~45wt%, send to product rectifying column 15 and carries out rectifying；The tower top of rectifying column obtain propylene product temperature be 35~
45 DEG C, pressure be 1.5~2.0MPaG, propylene content >=99.5wt%, the materials at bottom of tower of rectifying column is returned as circulation hydro carbons 123
It returns and is used as raw material.
Claims (2)
1. a kind of alkene separation method, it is characterised in that include the following steps:
Pressure is content >=80wt% room temperature hydrocarbon raw material (101) of 1.5~2.0MPaG propane and propylene and from product essence
The temperature for evaporating the tower reactor of tower (15) is 50~80 DEG C, pressure is 1.5~3.0MPaG, propane content >=wt90% recycle hydrocarbons
(123) enter feed surge tank (16) together, the molar flow ratio of the hydrocarbon raw material (101) and recycle hydrocarbons (123) be 1:2~
3；
The temperature of charge of surge tank (16) bottom discharge is 40~70 DEG C, 1.0~2.0MPaG of pressure, into heavy constituent knockout tower
(1), the heavy constituent (103) of carbon atom number >=4 is obtained in the tower bottom of heavy constituent knockout tower, obtains third in the middle part of surge tank (16)
The purification hydrocarbon raw material (102) that alkane content >=95wt%, temperature are 35~45 DEG C, pressure is 1.0~1.5MPaG；
Purification hydrocarbon raw material (102) is decompressed to 0.05~0.1MPaG, -33 DEG C~-42 DEG C of temperature entrance ice chest (3) heat exchange, is
Ice chest (3) provides the cooling capacity of different potential temperatures；Vaporization hydrocarbon raw material (105) after ice chest exchanges heat is pressurized to 0.2~0.6MPaG simultaneously
Heat exchange, into reactor (7), carries out dehydrogenation reaction to after 550~650 DEG C, obtain temperature be 500~600 DEG C, pressure be-
0.06~0.15MPaG, the product (109) that propylene content is 35~50wt%；
Product (109) is cooled to 35~50 DEG C, is pressurized to 1.0~2.0MPaG and enters after dry to < -100 DEG C of water dew point cold
Case (3) is gradually cooled down in ice chest by the material of different potential temperatures, and the heavier component in product gradually condenses in ice chest, often changes
Hot primary, resulting vapour-liquid mixed phase can be extracted out in the middle part of ice chest, and air-liquid separation is carried out in liquid separation tank (13)；
The gas phase isolated returns to ice chest (3) and is condensed again, and the liquid phase isolated is sent after cold recovery to light group of downstream
Knockout tower (14) are divided to carry out gas-liquid separation；It is p- by the LNG cryogen of different potential temperatures after product (109) is cooled to -25~-40 DEG C
25~-40 DEG C of product gas is cooled down step by step, is finally cooled to -110~-130 DEG C, the heavy constituent of three or more carbon in product gas
Condensed in this process, the vapour that finally obtains, liquid mixture carry out air-liquid separation in liquid separation tank (13)；
Product gas sends to downstream from ice chest discharge tail gas (118) after repeatedly cooling；The liquid phase that liquid separation tank (13) is isolated enters
Ice chest exchanges heat to sending after -45~-55 DEG C to light component knockout tower (14) as cold source and further separates；
Light component knockout tower (14) tower top be discharged tail gas, tower bottom obtain temperature be 0~30 DEG C, pressure 2.0MPaG, propylene content
It send for the logistics (121) of 30~45wt% to rectifying column (15) progress rectifying；
The materials at bottom of tower of rectifying column is recycled back to feed surge tank as raw material, and the tower top of rectifying column obtains purity >=99.5wt% third
Alkene product；
It by the material of different potential temperatures is respectively 0~-10 DEG C, -15~-25 DEG C and -30~-40 DEG C in the ice chest.
2. alkene separation method according to claim 1, it is characterised in that it is described difference potential temperatures LNG cryogen be respectively-
80~-100 DEG C, -110~130 DEG C and -150~-162 DEG C；Accordingly, the product gas is cooled to -40~-60 step by step respectively
DEG C, -80~-100 DEG C and -110~-130 DEG C.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020076812A1 (en) * | 2018-10-09 | 2020-04-16 | Chart Energy & Chemicals, Inc. | Dehydrogenation separation unit with mixed refrigerant cooling |
| CN110173960A (en) * | 2019-06-28 | 2019-08-27 | 正和集团股份有限公司 | A kind of recycle device and technique of hydrogen-rich gas |
| CN114573415B (en) * | 2020-11-30 | 2024-03-19 | 惠生工程（中国）有限公司 | Separation method and device for coupled alkane catalytic dehydrogenation reaction products |
| CN113061071B (en) * | 2021-03-29 | 2024-02-13 | 上海睿碳能源科技有限公司 | Method and equipment for directly preparing olefin from synthesis gas based on slurry bed reactor |
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