CN104030875B - High yield highly purified catalytic cracked dry gas sharp separation process for purification and device - Google Patents
High yield highly purified catalytic cracked dry gas sharp separation process for purification and device Download PDFInfo
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Abstract
High yield highly purified catalytic cracked dry gas sharp separation process for purification, comprise the steps: that catalytic cracked dry gas pressurizes, separated by the first pressure-swing absorber and the second pressure-swing absorber, membrance separation after repressurization, enter cryogenic separation system after membrance separation, obtain hydrogen, ethylene, methane, ethane, propylene by said method.And high yield highly purified catalytic cracked dry gas sharp separation refining plant, including the first compressor, the second compressor, the first pressure-swing absorber, the second pressure-swing absorber, membrane separation device and cryogenic separation system.The present invention uses pressure-variable adsorption, membrance separation, the technology of cryogenic separation triplicity, compensate for the defect that three kinds of techniques are individually present, for the hydrogen in oil refinery dry gas, light alkane and each component of light olefin achieve sharp separation and reclaim, and substantially increase yield and the purity of each gas component of oil refinery dry gas.
Description
Technical field
The invention belongs to chemical field, relate to a kind of high yield highly purified catalytic cracked dry gas sharp separation process for purification and device.
Background technology
Useful constituent in oil refinery dry gas is mainly hydrogen, light olefin and light alkane etc..These components are all of great value in refinery, but they high amounts are still not carried out optimum use at present, but have been directly used as fuel, the even direct-fire torch emptying having.For the catalytic cracked dry gas that the amount of accounting in oil refinery dry gas is maximum, both contained hydrogen, possibly together with a large amount of light olefins and light alkane.These components can be separated and be utilized respectively, higher than the raw material benefit being directly used as fuel or reformation hydrogen production, synthesizing methanol.
At present, the comprehensive utilization technique research and development of refinery catalytic cracking (FCC) dry gas are concentrated mainly on three big fields: one is that dry gas purification refines, and two is the separation and purification of each component, and three is the technology such as the chemical process utilization of each component.Wherein, the complete sharp separation of each component of FCC dry gas is refined is dry gas comprehensive utilization economic benefit a kind of well method.
The technology of low-concentration hydrogen, light olefin and light alkane of reclaiming from FCC dry gas mainly have separation by deep refrigeration, in cold and shallow cold oil absorption process, membrane separation process, adsorption method of separation etc..
Adsorption method of separation is to utilize adsorbent different to the adsorptive selectivity of component each in mixed gas, is changed a kind of separation method realizing absorption with regeneration by pressure or temperature, has the features such as reproduction speed is fast, energy consumption is low, simple to operate, technical maturity is stable.The pressure-variable adsorption realizing separating by pressure change reclaims hydrogen technique relative maturity in dry gas, and can obtain purity is 98%(volume ratio) more than hydrogen product, but hydrogen recovery rate is typically at about 80-85%.Use existing PSA Technology to reclaim highly purified hydrogen, ethylene and ethane from containing the FCC dry gas such as low-concentration hydrogen, ethylene simultaneously, there is the problems such as yield is low, can not realize the FCC complete sharp separation of dry gas key component, investment occupation of land is huge.Such as, in middle petrochemical industry petrochemical industry FCC dry gas pressure-variable adsorption reclaims ethylene and hydrogen demonstration plant, ethylene, the yield of hydrogen are less than 75-80%, and cannot reclaim highly purified ethane propylene etc. simultaneously.
Membrane separation process is under a certain pressure, utilizes other each components difference of infiltration rate in film to carry out separating.Membrane separation process reclaims being installed on 1987 of hydrogen in FCC dry gas and builds up at U.S.'s Pang card city Okia, and hydrogen recovery rate is 80-90%.Membrane separation process hydrogen be applicable to dry gas with pressure, that hydrogen content is low reclaims, and has an advantage in that occupation of land is little, simple to operate, energy consumption is low.But, the hydrogen purity reclaimed by membrane separation process is the highest, generally 95-99%.And in terms of reclaiming ethylene, ethane, membrane separation technique is still in the development phase.
Cold separation technology just has development as far back as the fifties in last century, and this Technical comparing is ripe at present.It is the difference (boiling-point difference) utilizing each component relative volatility in raw material, by gas turbine swell refrigeration, component each in dry gas being condensed out by technological requirement at low temperatures, the hydrogen being difficult to condensation obtains at first, hydrogen recovery rate is 90-95%, and purity is 95-98%.Thereafter being separated one by one by all kinds of hydrocarbon therein with rectification method, yield of ethene is generally more than 85-90%.Cryogenic separation has can reclaim hydrogen and ethylene-ethane, technical maturity, the response rate relatively advantages of higher simultaneously, is generally adapted the occasion processing a large amount of dry gas, is particularly suitable for area of concentration, refinery.Cryogenic separation shortcoming is that product purity is the highest, investment is big, energy consumption is high, is not suitable for the oil refinery dry gas recovery etc. of middle and small scale.
The most individually reclaim the limitation of dry gas for pressure-variable adsorption separation, membrance separation and cryogenic separation, under current technology less mature condition, use process integration to contribute to improving separating effect and economy.
CN1085821A proposes a kind of membrance separation and combines with cryogenic separation technique, catalytic cracked dry gas carries out hydrogen hydrocarbon and separates and recovery.The hydrogen purity that this process integration obtains is more than 95%, and hydrogen yield is more than 85%；The ethylene obtained has higher purity, and yield is close to 98%.This process integration yet suffers from the shortcomings such as product purity is low, hydrogen yield is low, energy consumption is high.
CN101773765A proposes a kind of membrance separation and separates, with pressure-variable adsorption, the technique that combines, and separates and recovers the hydrogen in catalytic cracked dry gas.The hydrogen purity that this process integration obtains is 95-99.5%, hydrogen yield 80%.But this process integration is without reference to the recovery of ethylene, ethane etc..
Summary of the invention
For overcoming the separation of existing pressure-variable adsorption, membrance separation, and the technological deficiency that cryogenic separation exists when being used alone that product purity is the highest, yield is relatively low, can not to realize the dry gas complete sharp separation of each component refined, the invention discloses a kind of high yield highly purified catalytic cracked dry gas sharp separation process for purification and device.
Yield of the present invention highly purified catalytic cracked dry gas sharp separation process for purification, comprises the steps:
The catalytic cracked dry gas pressure that refinery catalytic cracking device comes is brought up to 0.7-1.2MPa by step 101.；
Dry gas after step 102. pressurization is separated into ethylene-rich dry gas and concentrated gas by the first pressure-swing absorber, and wherein ethylene-rich dry gas is the stripping gas of the first pressure-swing absorber, is mainly composed of carbon two component gas；Concentrated gas is mainly composed of hydrogen, methane and nitrogen；Described carbon two component gas is the olefines gas that molecular formula contains two and two or more carbon atom；
Described concentrated gas enters the second pressure-swing absorber, is separated into product hydrogen and the second stripping gas；Described second stripping gas completely or partially enters step 103, is introduced into part the second stripping gas emptying of step 103；
It is forced into 1.0-3.5MPa after the second stripping gas obtained in step 103. step 102 and the mixing of ethylene-rich dry gas, forms ethylene-rich mixing dry gas；
The ethylene-rich mixing dry gas obtained in step 104. step 103 is separated into infiltration gas and impermeable gas by membrane separating method, and described infiltration gas returns to input the first pressure-swing absorber in step 102, as the partial raw gas of the first pressure-swing absorber；Described infiltration gas is membrane separation device per-meate side effluent air, and impermeable gas is membrane separation device impermeable side effluent air；
The impermeable gas obtained in step 105. step 104 is separated by cryogenic separation system, respectively obtains ethane, ethylene, propylene and the combustion gas rich in methane；
Described it is mainly composed of the gas componant that molar ratio in gas is maximum.
Preferably, the step of the gas removal acidic components after also including pressurization in described step 101.
Further, after removing acidic components, also include that Dry gas treatment step, described Dry gas treatment step include the step of hydrogenation deoxidation and oxynitride, removal of mercaptans and cos, demercuration and arsenic.
Preferably, in described step 104, ethylene-rich mixing dry gas is before entering membrance separation step, also includes except mist dedusting deoiling step.
Preferably, in described step 105, to the separating step of combustion gas it is:
Impermeable gas in step 104 sends into domethanizing column after heat exchange, and domethanizing column top row goes out methane and nitrogen；Discharging carbon two component gas at the bottom of tower, described carbon two component gas is the olefines gas that molecular formula contains two and two or more carbon atom；
Methane domethanizing column top row gone out and nitrogen input cold recovery system swell refrigeration, export cold, discharges combustion gas from cold recovery system simultaneously.
Further, in described step 105, to ethane, ethylene, the separating step of propylene it is: the carbon two component pneumatic transmission discharged at the bottom of demethanizer is entered ethylene topping still, ethylene topping still tower top flows out material entrance ethylene rectifying column rectification and goes out ethylene, ethylene topping still bottom stream matter sends into propylene topping still, propylene coarse evaporates column overhead and flows out material ethane, and propylene topping still bottom stream matter is sent into propylene rectification tower rectification and gone out propylene.
The invention also discloses a kind of high yield highly purified catalytic cracked dry gas sharp separation refining plant, including the first compressor, the second compressor, the first pressure-swing absorber, the second pressure-swing absorber, membrane separation device and cryogenic separation system；
Import at the bottom of described first compressor output end and the first pressure-swing absorber tower connects, and described first pressure-variable adsorption column overhead connects import at the bottom of the second pressure-swing absorber tower；The tower bottom outlet of described first pressure-swing absorber and the second pressure-swing absorber is all connected with the second compressor input；
Described second compressor output end junctional membrane segregation apparatus feed side, the per-meate side of described membrane separation device be also connected with import at the bottom of the tower of the first pressure-swing absorber, the impermeable side of described membrane separation device is connected with described cryogenic separation system.
Preferably, deacidification gas tower it is also associated with between described first compressor and the first pressure-swing absorber.
Preferably, described cryogenic separation system includes that domethanizing column and cold recovery system, described domethanizing column entrance are connected with described membrane separation device impermeable gas side, and demethanizer column overhead outlet is connected with cold recovery system.
Further, described cryogenic separation system also includes ethylene topping still, ethylene rectifying column, propylene topping still, propylene rectification tower；
The import of described ethylene topping still is connected with the tower bottom outlet of domethanizing column, and the described tower top outlet of ethylene topping still is connected with the entrance of ethylene rectifying column；Described ethylene topping still tower bottom outlet and propylene topping still import connect；Described ethylene distillation column overhead flows out ethylene product, and tower bottom outlet returns to ethylene topping still；Described propylene coarse evaporates column overhead and flows out ethane product, tower bottom outlet and propylene rectification tower import connection.
Use high yield of the present invention highly purified catalytic cracked dry gas sharp separation process for purification and device, use pressure-variable adsorption, membrance separation, the technology of cryogenic separation triplicity, compensate for the defect that three kinds of techniques are individually present, for the hydrogen in oil refinery dry gas, light alkane and each component of light olefin achieve sharp separation and reclaim, and substantially increase yield and the purity of each gas component of oil refinery dry gas.
Accompanying drawing explanation
Fig. 1 illustrates a kind of detailed description of the invention schematic flow sheet of high yield of the present invention highly purified catalytic cracked dry gas sharp separation process for purification
Fig. 2 illustrates the another kind of detailed description of the invention schematic flow sheet of high yield of the present invention highly purified catalytic cracked dry gas sharp separation process for purification；
Fig. 3 illustrates the detailed description of the invention structural representation of the corresponding diagram 2 of high yield of the present invention highly purified catalytic cracked dry gas sharp separation refining plant；
In each figure, reference is entitled: 1-the first pressure-swing absorber 2-the second pressure-swing absorber 3-the first compressor 4-the second compressor 5-membrane separation device 6-deacidification gas tower 7-domethanizing column 8-ethylene topping still 9-propylene topping still 10-cold recovery system 11-ethylene rectifying column 12-propylene rectification tower 13-removes spray dust oil device 14-Dry gas treatment device.
Detailed description of the invention
Below in conjunction with the accompanying drawings, the detailed description of the invention of the present invention is described in further detail.
Yield of the present invention highly purified catalytic cracked dry gas sharp separation process for purification, comprises the steps:
The catalytic cracked dry gas pressure that refinery catalytic cracking device comes is brought up to 0.7-1.2MPa by step 101.；
Useful component in oil refinery dry gas is mainly hydrogen, light olefin and light alkane etc., but also has a small amount of oxygen, carbon dioxide, sulfur dioxide, nitrogen oxides, mercaptan, cos and hydrargyrum, arsenic etc..Preferably, step 101 can increase after pressurizeing oil refinery dry gas the deacidification jia bombardier to oil refinery dry gas rapid, i.e. use traditional amine to wash caustic wash tower, remove sour gas therein.Another kind of advantageous measure is after oil refinery dry gas pressurizes or after deacidification gas, increases Dry gas treatment step, so-called Dry gas treatment step, i.e. uses the hydrogenation deoxidation reactor of routine to carry out deoxidation, hydrogenation reduction device denitrogenation oxygen compound (NxOy), removal of mercaptans (RSH) and cos (COS), and the demercuration loading activated carbon and molecular sieve of routine/arsenic device composition.Both advantageous measure have purified oil refinery dry gas further, it is to avoid in subsequent step, the poison deactivation such as adsorbent, membrane module situation occurs, and improve the rate of departure and product yield.
Dry gas after step 102. pressurization is separated into ethylene-rich dry gas and concentrated gas by the first pressure-swing absorber, and wherein ethylene-rich dry gas is the stripping gas of the first pressure-swing absorber, is mainly composed of carbon two component gas；Concentrated gas is mainly composed of hydrogen, methane and nitrogen；Described carbon two component gas is the olefines gas that molecular formula contains two and two upper carbon atoms.
Described concentrated gas enters the second pressure-swing absorber, is separated into product hydrogen and the second stripping gas.Wherein, the second stripping gas can partly be vented.
After pressurization, dry gas is from the first pressure-variable adsorption tower bottom, from bottom to top by being filled with the bed of adsorbent, the component adsorbed by force, two and the hydrocarbon gas of two or more carbon atom is contained including molecular formula, i.e. carbon two component gas and a small amount of hydrogen, methane etc., be collectively referred to as ethylene-rich dry gas, desorbed by reverse pressure reduction from adsorbent, and discharge from the bottom of the first pressure-swing absorber tower, form ethylene-rich dry gas.The operation temperature of the first pressure-swing absorber could be arranged to 30 to 40 degrees Celsius.
Hydrogen, methane and the nitrogen etc. of not to be adsorbed dose of absorption go out from the first pressure-swing absorber overhead stream, enter from the second pressure-variable adsorption tower bottom, from bottom to top by being filled with the bed of adsorbent, adsorbed methane and a small amount of hydrogen, desorbed from adsorbent by reverse pressure reduction, discharge from the bottom of the second pressure-swing absorber, form the second resolution gas.Wherein, the second stripping gas part can be vented.The hydrogen of not to be adsorbed dose of absorption goes out from the second pressure-swing absorber overhead stream, obtains pressure 0.6-1.1MPa, temperature is the hydrogen product of room temperature.The operation temperature of the second pressure-swing absorber is set to 30 to 40 degrees Celsius.
Step 102 uses two-stage pressure swing absorption process, improves yield and the purity of hydrogen, after the resolution gas mixing of two pressure-swing absorbers, send into subsequent step, to continue the separation of subsequent olefin class.
It is forced into 1.0-3.5MPa after the second stripping gas obtained in step 103. step 102 and the mixing of ethylene-rich dry gas, forms ethylene-rich mixing dry gas.
The ethylene-rich mixing dry gas obtained in step 104. step 103 is separated into infiltration gas and impermeable gas by membrane separating method, and described infiltration gas returns to input the first pressure-swing absorber in step 102, as the partial raw gas of the first pressure-swing absorber；Described infiltration gas is membrane separation device per-meate side effluent air, and impermeable gas is membrane separation device impermeable side effluent air；Wherein infiltration gas is mainly composed of hydrogen, and impermeable gas is mainly composed of methane and carbon two component gas.
Ethylene-rich mixing dry gas enters after membrane separation device, and hydrogen flows out from the per-meate side of membrane separation device, flow back into the first pressure-swing absorber as unstripped gas, further increases the response rate to oil refinery dry gas hydrogen.Other components are mainly composed of various olefines, such as methane, ethylene, ethane, propylene etc., also include the nitrogen of certain content, are collectively referred to as ethylene-rich mixing and concentrate dry gas, flow out from impermeable side.The temperature of step 104 could be arranged to 30 to 40 degrees Celsius.
Membrane separation technique separation hydrogen is existing mature technology, and in step 104 of the present invention, membrane separation device can use polycarbonate membrane to separate hydrogen, preferable to Hydrogen Separation effect.
Can be before ethylene-rich mixing dry gas enters membrane separation device in step 104, preferably increase except mist dedusting deoiling step, by impurity removals such as trace water smoke, dust and the oil droplets in the ethylene-rich mixing dry gas of the 1.0-3.5MPa pressure obtained in step 103, avoid polluting membrane module in subsequent film separating step, extend membrane module service life.Except spray dust oil can use the equipment such as the loading activated carbon demister of routine, 50-200 mesh metal gauze oil droplet, dust catching device to realize.
The impermeable gas obtained in step 105. step 104 is separated by cryogenic separation system, respectively obtains ethane, ethylene, propylene and the combustion gas rich in methane.
Gas cryogenic separation is technology commonly used in the art, ultimate principle is to utilize gas component boiling point or condensation point difference to be separated one by one according to boiling point or condensation point temperature height by gas, the cold used in cryogenic separation can come from extraneous low-temperature receiver, it is also possible to utilizes high pressure feed swell refrigeration.
To step 105, wherein separating step rich in the combustion gas of methane is preferably by the present invention:
Impermeable gas in step 104, be namely mainly composed of various hydro carbons and nitrogen ethylene-rich mixing concentrate dry gas after heat exchange, send into domethanizing column, domethanizing column top row goes out methane and nitrogen；Discharging carbon two component gas at the bottom of tower, described carbon two component gas is that molecular formula contains two and the hydrocarbon gas of two or more carbon atom；
Methane domethanizing column top row gone out and nitrogen input cold recovery system swell refrigeration, export cold, discharges combustion gas from cold recovery system simultaneously.Cold recovery system can be made up of conventional decompressor and ice chest.
Use said method separation of methane, utilize methane that demethanizer column overhead discharges and nitrogen expansion to freeze and obtain cold, during for components such as later separation ethylene, ethane, propylene.
The carbon two component pneumatic transmission discharged at the bottom of demethanizer in above-mentioned steps is entered ethylene topping still, and ethylene topping still tower top flows out material sends into ethylene rectifying column, and ethylene distillation column overhead flows out ethylene product, and tower bottom outlet material returns ethylene topping still；Ethylene topping still bottom stream matter sends into propylene topping still, propylene coarse evaporates column overhead and flows out material ethane, can send into ethane cracking furnace as ethane product or ethane cracking raw material, propylene topping still bottom stream matter is sent into propylene rectification tower tower top rectification and is gone out propylene, and rectification at the bottom of tower goes out C3Above fraction.Cold needed for ethylene, propylene, ethane fractionation is from the cold obtained during above-mentioned swell refrigeration.
The invention also discloses a kind of high yield highly purified catalytic cracked dry gas sharp separation refining plant, to realize aforesaid method.Including the first compressor, the second compressor, the first pressure-swing absorber, the second pressure-swing absorber, membrane separation device and cryogenic separation system；Import at the bottom of described first compressor output end and the first pressure-swing absorber tower connects, and described first pressure-variable adsorption column overhead connects import at the bottom of the second pressure-swing absorber tower；The tower bottom outlet of described first pressure-swing absorber and the second pressure-swing absorber is all connected with the second compressor input；Described second compressor output end junctional membrane segregation apparatus, the per-meate side of described membrane separation device be also connected with import at the bottom of the tower of the first pressure-swing absorber, the impermeable side of described membrane separation device is connected with described cryogenic separation system.
The pressurization that first compressor and the second compressor are respectively used in step 101 and step 103, the first pressure-swing absorber and the second pressure-swing absorber correspondence realize step 102.Membrane separation device and cryogenic separation system are respectively used to realize step 104 and step 105.
Preferably, deacidification gas tower it is also associated with between described first compressor and the first pressure-swing absorber.Aforesaid preferably deacidification jia bombardier in a step 101 is realized rapid with correspondence.
Preferably, described cryogenic separation system includes that domethanizing column and cold recovery system, described domethanizing column entrance are connected with the infiltrating gas side of described membrane separation device, and demethanizer column overhead outlet is connected with cold recovery system.To realize separating rich in the combustion gas of methane the step freezed in abovementioned steps 105.
Further, described cryogenic separation system also includes ethylene topping still, ethylene rectifying column, propylene topping still, propylene rectification tower；To realize the separation of follow-up ethylene, ethane and propylene.
The import of wherein said ethylene topping still is connected with the tower bottom outlet of domethanizing column, and described ethylene topping still tower top outlet is connected with the entrance of ethylene rectifying column；Described ethylene topping still tower bottom outlet and propylene topping still import connect；Described ethylene distillation column overhead flows out ethylene product, and tower bottom outlet returns to ethylene topping still；Described propylene coarse evaporates column overhead and flows out ethane product, tower bottom outlet and propylene rectification tower import connection；Described propylene rectification tower tower top flows out propylene, flows out C3 fraction at the bottom of tower.
As Fig. 1 illustrates a kind of detailed description of the invention of high yield of the present invention highly purified catalytic cracked dry gas sharp separation process for purification.
Refinery's FCC dry gas enters the first pressure-swing absorber after pressurization and carries out pressure-variable adsorption dry gas concentration, discharges ethylene-rich dry gas.Hydrogen, methane and nitrogen etc. not to be adsorbed go out from the first pressure-swing absorber overhead stream, enter the second pressure-swing absorber carry out hydrogen psa refine, adsorbed methane and a small amount of hydrogen, desorbed from adsorbent by reverse pressure reduction, discharge from the bottom of the second pressure-swing absorber, form the second stripping gas.Wherein, the second stripping gas can partly be vented.The hydrogen of not to be adsorbed dose of absorption goes out from the second pressure-swing absorber overhead stream, obtains hydrogen product.
Pressurized mixing after second stripping gas and the mixing of ethylene-rich dry gas, the ethylene-rich mixing dry gas of formation enters membrance separation step and is separated into infiltration gas and impermeable gas, and infiltration gas is mainly composed of hydrogen, returns to pressure-variable adsorption dry gas concentration step as partial raw gas；Impermeable gas is mainly composed of olefines and methane, nitrogen, is separated into ethylene, propylene, ethane and the combustion gas rich in methane by cryogenic separation step.
The another kind of detailed description of the invention of high yield the most of the present invention highly purified catalytic cracked dry gas sharp separation process for purification, uses the high yield highly purified catalytic cracked dry gas sharp separation refining plant shown in corresponding diagram 3.
After refinery's FCC dry gas pressurizes through the first compressor 3, deacidification gas tower 6 deacidification gas, Dry gas treatment device 14 remove foreign gas, enter and carry out pressure-variable adsorption dry gas concentration at the bottom of the first pressure-swing absorber 1 tower, at the bottom of tower, discharge ethylene-rich dry gas.Hydrogen, methane and nitrogen etc. not to be adsorbed go out from the first pressure-swing absorber overhead stream, bottom the second pressure-swing absorber 2, carry out pressure-variable adsorption refine hydrogen, adsorbed methane, nitrogen and a small amount of hydrogen, desorbed from adsorbent by reverse pressure reduction, discharge from the bottom of the second pressure-swing absorber, form the second resolution gas.Wherein, the second stripping gas can partly be vented.The hydrogen of not to be adsorbed dose of absorption goes out from the second pressure-swing absorber overhead stream, obtains hydrogen product.
Pressurizeed mixing by the second compressor 4 after second stripping gas and the mixing of ethylene-rich dry gas, the ethylene-rich mixing dry gas formed is sent into membrane separation device 5 after removing steam dust therein and oil droplet except spray dust oil device 13 and is separated into infiltration gas and impermeable gas, infiltration gas is mainly composed of hydrogen, return to the first pressure-swing absorber 1, as the partial raw gas of the first pressure-swing absorber；Impermeable gas is mainly composed of olefines, methane and nitrogen, send into domethanizing column 7, demethanizer column overhead discharges methane and nitrogen, enter cold recovery system 10 swell refrigeration, flow out composition entrance ethylene topping still 8 at the bottom of demethanizer, ethylene topping still tower top flows out material entrance ethylene rectifying column 11 tower top rectification and goes out ethylene, and ethylene rectifying column bottom stream returns to ethylene topping still.Ethylene topping still bottom stream matter sends into propylene topping still 9, propylene coarse evaporates column overhead and flows out material ethane, ethane cracking furnace can be sent into by unstripped gas as product or as ethane cracking furnace, propylene topping still bottom stream matter is sent into propylene rectification tower 12 tower top rectification and is gone out propylene, and rectification at the bottom of tower goes out more than C3 fraction.Cold needed for ethylene, propylene, ethane fractionation is from the cold obtained during above-mentioned swell refrigeration.
Using the method flow shown in Fig. 2-3 and device, each component recovery and the purity that obtain under processing the different oil refinery dry gas of component and different reaction conditions are as follows:
Hydrogen content 57.9%, methane content 22.2%, ethane content 7.5%, ethylene contents 4.5%, propylene content 1.5%, nitrogen content 5.5%, CO in embodiment 1. unstripped gas2Content 0.1%, sulfur content 50ppm, oxygen content 0.65%, other components 0.15%, wherein content is volume ratio (V/V).
First compressor is forced into 0.7MPa, first pressure-swing absorber operation temperature is 30 degrees Celsius, the second pressure-swing absorber operation temperature is 30 degrees Celsius, the second compressor is forced into 2.0MPa, membrance separation operation temperature is 35 degrees Celsius, when the cryogenic temperature that cold recovery system provides is-120 degrees Celsius, hydrogen recovery rate and purity are respectively 90% and 99.9%, methane recovery and purity are respectively 85% and 92%, Recovery rate of ethylene and purity are respectively 92% and 99%, propylene recovery rate and purity are respectively 92% and 99%, and ethane recovery and purity are respectively 90% and 99%.
Hydrogen content 46.5%, methane content 20.0%, ethane content 12.4%, ethylene contents 6.0%, propylene content 0.6%, nitrogen content 9.5%, CO in embodiment 2. unstripped gas2Content 0.1%, CO content 0.5%, butane 2.0%, pentane 1.0%, other components 0.15%, wherein content is volume ratio (V/V).
First compressor is forced into 1.2MPa, first pressure-swing absorber operation temperature is 40 degrees Celsius, the second pressure-swing absorber operation temperature is 40 degrees Celsius, the second compressor is forced into 2.6MPa, membrance separation operation temperature is 50 degrees Celsius, when the cryogenic temperature that cold recovery system provides is-100 degrees Celsius
Hydrogen recovery rate and purity are respectively 93% and 99.9%, and methane recovery and purity are respectively 89% and 92%, and Recovery rate of ethylene and purity are respectively 94% and 99%, and propylene recovery rate and purity are respectively 94% and 99%, and ethane recovery and purity are respectively 94% and 99%.
Hydrogen content 18.5%, methane content 30.0%, ethane content 14.5%, ethylene contents 16.0%, propylene content 1.7%, nitrogen content 14.5%, CO in embodiment 3. unstripped gas2Content 1.7%, water content 0.02%, other components (3.08%), wherein content is volume ratio (V/V).
First compressor is forced into 1.0MPa, first pressure-swing absorber operation temperature is 35 degrees Celsius, the second pressure-swing absorber operation temperature is 35 degrees Celsius, the second compressor is forced into 3.2MPa, membrance separation operation temperature is 40 degrees Celsius, when the reaction temperature that cold recovery system provides is-105 degrees Celsius
Hydrogen recovery rate and purity are respectively 92% and 99.9%, and methane recovery and purity are respectively 90% and 92%, and Recovery rate of ethylene and purity are respectively 96% and 99.9%, and propylene recovery rate and purity are respectively 96% and 99%, and ethane recovery and purity are respectively 95% and 99%.
The above-mentioned response rate and purity are all measured with volume ratio.
Use high yield of the present invention highly purified catalytic cracked dry gas sharp separation process for purification and device, use pressure-variable adsorption, membrance separation, the technology of cryogenic separation triplicity, compensate for the defect that three kinds of techniques are individually present, for the hydrogen in oil refinery dry gas, light alkane and each component of light olefin achieve sharp separation and reclaim, substantially increase yield and the purity of each gas component of oil refinery dry gas, wherein hydrogen, ethylene, ethane, the recovery purity of propylene are all up 99%, also can reach 92% rich in methane concentration in the fuel gas of methane.
Further, add that deacidification jia bombardier is rapid and corresponding intrument, protect the normal operating of subsequent step and device service life.
Further, hydrogen is first separated and recovered in membrane separating process, make enrichment carbon two and the domethanizing column of carbon more than two component mixed gas entrance cryogenic system of impermeable side, the treating capacity of cryogenic separation can be reduced, it is substantially reduced domethanizing column refrigerant charge, improve demethanizer column overhead dew point so that cryogenic separation processing ease, be substantially reduced cryogenic separation equipment investment and running cost.
Further, during demethanation, gas expansion refrigeration is used to obtain cold for later separation, it is achieved that cold is self-produced, saves equipment and cost.
In sum, advantages of the present invention and having the beneficial effects that:
1. the present invention combines adsorption method of separation, membrane separation process and separation by deep refrigeration and processes oil refinery dry gas, highly purified hydrogen, ethylene, ethane, propylene etc. can be obtained, ensure that high yield, it is simultaneously achieved the sharp separation of hydrogen, ethylene, ethane, propylene, overcome pressure-variable adsorption separation, membrance separation, and the limitation that cryogenic separation is used alone, and yet suffer from when membrance separation is combined with cryogenic separation, membrance separation is used in combination with pressure-variable adsorption that product purity is the highest, yield is relatively low, the problem such as can not to realize the dry gas complete sharp separation of each component refined；
2. the present invention includes purifying step, it is possible to remove the sour gas in dry gas, it is possible to increase two sections of pressure-variable adsorption-regenerative systems and the service life of film separation system, reduces running cost, and improves hydrogen purity；
3. the present invention includes drying steps and except mist dedusting deoiling step, it is possible to remove trace water smoke, dust and the oil droplet in gas, improves the service life of film separation system further, reduces membrance separation running cost；
4. the present invention includes membrance separation step, enrichment C2 fraction, methane and a small amount of hydrogen that two sections of pressure-variable adsorptions-regeneration step regeneration obtains can be separated, hydrogen infiltration in the past, returns to two sections of pressure-variable adsorption-regeneration step so that the final response rate of hydrogen can reach more than 90%；
5. the present invention includes two sections of pressure-variable adsorption-regeneration step and membrance separation step, is first reclaimed by hydrogen, first, cryogenic separation system throughput can be made to greatly reduce so that domethanizing column refrigerant charge is substantially reduced；Second, the C such as ethylene in dehydrogenation gas, ethane2Above ends content increases, and the demethanation tower top dew point in cryogenic separation system increases so that cryogenic separation operation is more prone to, C2And C2Above fraction seperation efficiency increases so that the ethylene of recovery, ethane, propylene purity all can more than 99%, yield is more than 90-92%；3rd, little by the dehydrogenation gas pressure drop of membrance separation impermeable side, suitably reduce pressure so that cryogenic separation system effectiveness is higher；4th, investment and the running cost of cryogenic separation equipment can be reduced simultaneously；
6. the present invention includes cold recovery step, the cold of acquisition is used for cryogenic separation step, has so accomplished recycling of resource, thus reduced energy consumption, reduce the input of cost.
Previously described each preferred embodiment for the present invention, preferred implementation in each preferred embodiment is if not the most contradictory or premised on a certain preferred implementation, each preferred implementation can arbitrarily stack combinations use, design parameter in described embodiment and embodiment is merely to clearly state the invention proof procedure of inventor, and it is not used to limit the scope of patent protection of the present invention, the scope of patent protection of the present invention is still as the criterion with its claims, the equivalent structure change that the description of every utilization present invention and accompanying drawing content are made, in like manner should be included in protection scope of the present invention.
Claims (10)
- The highest yield highly purified catalytic cracked dry gas sharp separation process for purification, it is characterised in that comprise the steps:The catalytic cracked dry gas pressure that refinery catalytic cracking device comes is brought up to 0.7-1.2MPa by step 101.；Dry gas after step 102. pressurization is separated into ethylene-rich dry gas and concentrated gas by the first pressure-swing absorber, and wherein ethylene-rich dry gas is the stripping gas of the first pressure-swing absorber, is mainly composed of carbon two component gas；Concentrated gas is mainly composed of hydrogen, methane and nitrogen；Described carbon two component gas is the olefines gas that molecular formula contains two and two or more carbon atom；Described concentrated gas enters the second pressure-swing absorber, is separated into product hydrogen and the second stripping gas；Described second stripping gas completely or partially enters step 103, is introduced into part the second stripping gas emptying of step 103；It is forced into 1.0-3.5MPa after the second stripping gas obtained in step 103. step 102 and the mixing of ethylene-rich dry gas, forms ethylene-rich mixing dry gas；The ethylene-rich mixing dry gas obtained in step 104. step 103 is separated into infiltration gas and impermeable gas by membrane separating method, and described infiltration gas returns to input the first pressure-swing absorber in step 102, as the partial raw gas of the first pressure-swing absorber；Described infiltration gas is membrane separation device per-meate side effluent air, and impermeable gas is membrane separation device impermeable side effluent air；The impermeable gas obtained in step 105. step 104 is separated by cryogenic separation system, respectively obtains ethane, ethylene, propylene and the combustion gas rich in methane；Described it is mainly composed of the gas componant that molar ratio in gas is maximum.
- High yield the most as claimed in claim 1 highly purified catalytic cracked dry gas sharp separation process for purification, it is characterised in that the step of the gas removal acidic components after also including pressurization in described step 101.
- High yield the most as claimed in claim 2 highly purified catalytic cracked dry gas sharp separation process for purification, it is characterized in that, after removing acidic components, also include that Dry gas treatment step, described Dry gas treatment step include the step of hydrogenation deoxidation and oxynitride, removal of mercaptans and cos, demercuration and arsenic.
- High yield the most as claimed in claim 1 highly purified catalytic cracked dry gas sharp separation process for purification, it is characterised in that in described step 104, ethylene-rich mixing dry gas is before entering membrance separation step, also includes except mist dedusting deoiling step.
- High yield the most as claimed in claim 1 highly purified catalytic cracked dry gas sharp separation process for purification, it is characterised in that in described step 105, to the separating step of combustion gas be:Impermeable gas in step 104 sends into domethanizing column after heat exchange, and domethanizing column top row goes out methane and nitrogen；Discharging carbon two component gas at the bottom of tower, described carbon two component gas is the olefines gas that molecular formula contains two and two or more carbon atom；Methane domethanizing column top row gone out and nitrogen input cold recovery system swell refrigeration, export cold, discharges combustion gas from cold recovery system simultaneously.
- High yield the most as claimed in claim 5 highly purified catalytic cracked dry gas sharp separation process for purification, it is characterized in that, in described step 105, to ethane, ethylene, the separating step of propylene it is: the carbon two component pneumatic transmission discharged at the bottom of demethanizer is entered ethylene topping still, ethylene topping still tower top flows out material entrance ethylene rectifying column rectification and goes out ethylene, ethylene topping still bottom stream matter sends into propylene topping still, propylene coarse evaporates column overhead and flows out material ethane, and propylene topping still bottom stream matter is sent into propylene rectification tower rectification and gone out propylene.
- The highest yield highly purified catalytic cracked dry gas sharp separation refining plant, including the first compressor (3), the second compressor (4), the first pressure-swing absorber (1), the second pressure-swing absorber (2), membrane separation device (5) and cryogenic separation system；It is characterized in that,Import at the bottom of described first compressor output end and the first pressure-swing absorber tower connects, and described first pressure-variable adsorption column overhead connects import at the bottom of the second pressure-swing absorber tower；The tower bottom outlet of described first pressure-swing absorber and the second pressure-swing absorber is all connected with the second compressor input；Described second compressor output end junctional membrane segregation apparatus feed side, the per-meate side of described membrane separation device be also connected with import at the bottom of the tower of the first pressure-swing absorber, the impermeable side of described membrane separation device is connected with described cryogenic separation system.
- High yield the most as claimed in claim 7 highly purified catalytic cracked dry gas sharp separation refining plant, it is characterised in that be also associated with deacidification gas tower (6) between described first compressor and the first pressure-swing absorber.
- High yield the most as claimed in claim 7 highly purified catalytic cracked dry gas sharp separation refining plant, it is characterized in that, described cryogenic separation system includes domethanizing column (7) and cold recovery system (10), described domethanizing column entrance is connected with described membrane separation device (5) impermeable gas side, and demethanizer column overhead outlet is connected with cold recovery system.
- High yield the most as claimed in claim 9 highly purified catalytic cracked dry gas sharp separation refining plant, it is characterized in that, described cryogenic separation system also includes ethylene topping still (8), ethylene rectifying column (11), propylene topping still (9), propylene rectification tower (12)；The described import of ethylene topping still (8) is connected with the tower bottom outlet of domethanizing column, and the tower top outlet of described ethylene topping still (8) is connected with the entrance of ethylene rectifying column (11)；Described ethylene topping still (8) tower bottom outlet and propylene topping still (9) import connect；Described ethylene rectifying column (11) tower top flows out ethylene product, and tower bottom outlet returns to ethylene topping still (8)；Described propylene topping still (9) tower top flows out ethane product, tower bottom outlet and propylene rectification tower (12) import and connects.
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| RU2697800C2 (en) | 2015-06-15 | 2019-08-20 | Юоп Ллк | Methods and apparatus for extracting ethylene from hydrocarbons |
| CN106831304A (en) * | 2017-04-01 | 2017-06-13 | 天邦膜技术国家工程研究中心有限责任公司 | A kind of method and device for improving catalysis drying gas ethylbenzene efficiency |
| CN109022033A (en) * | 2017-06-09 | 2018-12-18 | 中石化广州工程有限公司 | A kind of group technology that oil refinery dry gas recycling is isolated |
| CN108011119B (en) * | 2017-12-18 | 2020-12-01 | 陕西省石油化工研究设计院 | Method and system for clean power generation and resource utilization of hydrogen-containing waste gas coupled fuel cell |
| CN109173580A (en) * | 2018-09-19 | 2019-01-11 | 苏州经贸职业技术学院 | A kind of pressure varying adsorption gas separating equipment energy-saving control device |
| CN110006216B (en) * | 2019-03-29 | 2020-01-24 | 大连理工大学 | Cryogenic and membrane coupled process for separating and recovering noncondensable exhaust gas of ethylene circulating refrigeration system |
| CN112374959B (en) * | 2020-12-02 | 2023-09-29 | 西南化工研究设计院有限公司 | Method for separating ethylene and ethane in catalytic dry gas |
| CN116036633B (en) * | 2023-02-13 | 2024-04-26 | 贵州威顿晶磷电子材料股份有限公司 | Environment-friendly energy-saving preparation method of electronic grade triethyl borate and matched equipment |
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