CN109652120A - By the method for mink cell focus production low-carbon alkene - Google Patents
By the method for mink cell focus production low-carbon alkene Download PDFInfo
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- CN109652120A CN109652120A CN201710940563.2A CN201710940563A CN109652120A CN 109652120 A CN109652120 A CN 109652120A CN 201710940563 A CN201710940563 A CN 201710940563A CN 109652120 A CN109652120 A CN 109652120A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/04—Thermal processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to petrochemical industry production fields, disclose a kind of method by mink cell focus production low-carbon alkene.Method includes the following steps: mink cell focus is contacted and separated with supercritical carbon dioxide by (1), the lighter fluid phase containing light oil and carbon dioxide, and the heavy fluid phase containing heavy oil are obtained；(2) component separation is mutually carried out with the lighter fluid of carbon dioxide containing light oil by described, obtains light oil and carbon dioxide；(3) light oil is subjected to throttled steam thermal cracking, obtains low-carbon alkene.This method can prepare in high yield low-carbon alkene by raw material of mink cell focus, and cracker can be with long-play.And carbon dioxide has been used, this not only avoids CO2 emissions, and greenhouse effects are caused into atmosphere, and the carbon dioxide can be recycled, and achieve the effect that synergy emission reduction.
Description
Technical field
The present invention relates to petrochemical industry production fields, and in particular, to by the method for mink cell focus production low-carbon alkene.
Background technique
Currently, mainly producing low-carbon alkene using steam thermal cracking process in the world.Lighter hydrocarbons, naphtha, hydrogenation tail oil etc.
Raw material and a certain proportion of dilution steam generation are blended in industrial pyrolysis furnace occurs cracking reaction under hot conditions, pyrolysis product warp
The processes final production such as over-quenching, compression, separation goes out the low-carbon alkenes such as ethylene, propylene, butadiene.
For a long time, China prepares low-carbon alkene product with naphtha, with the large size of petroleum chemical enterprise's process units scale
Change, the processing capacity that China singly covers oil refining apparatus alreadys exceed 10,000,000 tons/year, and the ethylene of matched ethylene unit is raw
Production capacity power has also reached 80~1,200,000 tons/year.As the ownership of electric car is continuously increased, people are to fossil fuel, such as vapour
Oily, diesel oil demand is increasingly reduced, however the demand of petrochemicals is growing, and tradition is by designing bigger rule
The mode of the refinery of the mould then corresponding scale of Aided design can not resolve that demand for fuel reduces and chemical products demand constantly increases
Long contradiction.
In recent years, with a large amount of exploitations of Middle East associated gas and U.S.'s shale gas, these cheap petroleum resources
It is largely used as ethylene raw, causes the sharply decline of ethylene Related product price.In order to cope with the impact of market competition, open up
The raw material sources of ethylene cracker are opened up, cost of material is reduced, becomes the effective means of conventional ethylene enterprise cost efficiency.
Heavy oil viscosity is big, boiling point is high, colloid, asphalt content are high, directly carries out steam hot tearing by raw material of mink cell focus
The main problem of solution is exactly that mink cell focus is difficult to be gasified totally in convection section, and coking is serious in reaction tube, and the short time will block.
Meanwhile it is low as the raw material progress resulting yield of light olefins relatively lightweight raw material of steam thermal cracking using mink cell focus.With China part
Oil field enters " three adopt " stage, and Chinese Crude Oils are increasingly heavier, and mink cell focus ratio is higher and higher in petrochemical production process, if
Mink cell focus can be made full use of, suitable cracking stock is transformed by certain method, it is tight to be conducive to alleviation cracking stock
, olefin production plant cost of material and energy consumption are reduced, the supply and demand variation of market cracking stock is rapidly adapted to, for maintaining
Petrochemical industry sustainable development is of great significance.
Summary of the invention
The purpose of the invention is to overcome coking in reaction tube of the existing technology serious, the short time will be blocked,
And the low problem of the resulting yield of light olefins of steam cracking is carried out by raw material of mink cell focus, it provides and low-carbon is produced by mink cell focus
The method of alkene, this method can make full use of mink cell focus, and prepare low-carbon alkene in high yield by raw material of mink cell focus.
To achieve the goals above, the present invention provides a kind of methods by mink cell focus production low-carbon alkene, wherein the party
Method the following steps are included:
(1) mink cell focus is contacted and is separated with supercritical carbon dioxide, obtained light containing light oil and carbon dioxide
Fluid phase, and the heavy fluid phase containing heavy oil；
(2) component separation is mutually carried out with the lighter fluid of carbon dioxide containing light oil by described, obtains light oil and titanium dioxide
Carbon；
(3) light oil is subjected to throttled steam thermal cracking, obtains low-carbon alkene.
Preferably, in step (3), the pressure of the throttled steam thermal cracking is absolute pressure 0.5-101kPa, preferably 1-
10kPa。
Preferably, the pressure of the supercritical carbon dioxide is 7MPa-50MPa, preferably 7MPa-20MPa；It is described super to face
The temperature of boundary's carbon dioxide is 30-70 DEG C.
Preferably, this method further includes that the mink cell focus is forced into 7MPa-50MPa before step (1), preferably
7MPa-20MPa；The mink cell focus is warming up to 30-70 DEG C.
Preferably, the mink cell focus is selected from the oil obtained through time processing, the oil, crude oil and the coal system that obtain through secondary operation
At least one of oil.
Preferably, the time processing is air-distillation and/or vacuum distillation.
Preferably, the secondary operation is catalytic cracking and/or is hydrocracked.
Preferably, in step (1), the mixed proportion of the mink cell focus and supercritical carbon dioxide is 1 by weight:
(0.5-20), preferably 1:(2-8).
Preferably, in step (2), the method for the component separation is temperature-raising method and/or voltage drop method.
Preferably, also contain modifying agent in the supercritical carbon dioxide；Preferably, the modifying agent is low-carbon alcohols；It is excellent
The weight ratio of selection of land, the supercritical carbon dioxide and modifying agent is 1:(0.001-0.15).
Preferably, in step (3), the condition of the steam cracking includes: that the weight ratio of water vapour and light oil is (0.1-
0.9): 1；Pyrolysis furnace is 500-750 DEG C across section temperature；Crack furnance radiation section furnace tube outlet temperature is 780-950 DEG C；When stop
Between be 1-500ms.
Preferably, in step (3), the condition of the steam cracking includes: that the weight ratio of water vapour and light oil is (0.4-
0.8): 1；Pyrolysis furnace is 540-700 DEG C across section temperature；Crack furnance radiation section furnace tube outlet temperature is 800-900 DEG C；When stop
Between be 10-400ms.
In the present invention, by utilize supercritical carbon dioxide, realize mink cell focus production low-carbon alkene, and by into
The throttled steam thermal cracking of one step, improves the yield of low-carbon alkene.Firstly because solvent solvability at supercritical conditions
It is few relative to liquid decline, and viscosity and diffusion coefficient are more preferable closer to gas, that is, mass-transfer performance, so overcritical pumping
Propose, high production capacity more faster than the speed of liquid extraction.Secondly as the physical property of solvent is in critical zone with temperature and pressure
Power variation is very sensitive, can adjust the solvability of solvent by adjusting the temperature, pressure of solvent, technology controlling and process is flexible.And
And carbon dioxide is the most common atmospheric emission and greenhouse gases, with carbon dioxide substitution low-carbon hydro carbons for mink cell focus
Visbreaking has not only saved valuable petrochemical material, while having decreased the discharge of greenhouse gases.Relative to supercritical propane, fourth
Alkane visbreaking, supercritical carbon dioxide low operation temperature will not cause heavy oil viscosity to further increase.Supercritical carbon dioxide is not
Excessive colloid can be proposed from mink cell focus.Therefore, in the present invention, mink cell focus is mixed with supercritical carbon dioxide, is separated into
Lighter fluid phase rich in light oil and carbon dioxide, and the heavy fluid phase rich in heavy oil.Lighter fluid mutually increases temperature or reduces pressure
So that carbon dioxide is separated with light oil, carbon dioxide can be recycled, and obtained light oil carries out throttled steam thermal cracking, from splitting
Isolated low-carbon alkene in product is solved, and the yield of product can be improved in decompression.In addition, being split using method of the invention
Solution boiler tube is not easy coking and blocking, can be realized long-term operation.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of methods by mink cell focus production low-carbon alkene, wherein method includes the following steps:
(1) mink cell focus is contacted and is separated with supercritical carbon dioxide, obtained light containing light oil and carbon dioxide
Fluid phase, and the heavy fluid phase containing heavy oil；
(2) component separation is mutually carried out with the lighter fluid of carbon dioxide containing light oil by described, obtains light oil and titanium dioxide
Carbon；
(3) light oil is subjected to throttled steam thermal cracking, obtains low-carbon alkene.
In throttled steam thermal cracking processes, yield of ethene can be 26.36-28.66%, and propene yield can be 14.28-
15.17%, butylene yield can be 10.25-10.61%, and butadiene yield can be 5.97-6.22%, and low-carbon alkene amounts to
56.86-60.66%.
In the present invention, in step (3), the pressure of the throttled steam thermal cracking is absolute pressure 0.5-101kPa, preferably
For 1-10kPa.The present invention improves the yield of low-carbon alkene by decompression, the decompression method, to produce low-carbon alkene by mink cell focus
Hydrocarbon provides more choices.
In the present invention, substance shows the state changes such as liquid, gas, solid, such as according to the difference of temperature and pressure
Fruit improves temperature and pressure to certain point or more, it may appear that the phenomenon that liquid and gas interface disappear, which is referred to as critical point, surpasses
Critical fluids (SCF) refer to the fluid in critical point temperatures above and pressure span, and phase at this time is referred to as overcritical
State is not liquefied non-condensed state improving pressure.In Near The Critical Point, it may appear that the density of fluid, viscosity, dissolution
There is a phenomenon where change dramaticallies for the physical property of all fluids such as degree, thermal capacity, dielectric constant.The physical property of supercritical fluid has both liquid
With gas double property, density is close to liquid, and diffusance is close to gas, and viscosity is between gas-liquid.In addition, according to pressure and temperature
The difference of degree, this physical property can change, therefore, extraction, purification, in terms of, be increasingly used as replacing
The novel dissolvent of original organic solvent uses.In short, being exactly that temperature and pressure is above the critical of solvent under super critical condition
Temperature and critical pressure.
In the present invention, light oil refers to the small oil of density ratio raw material mink cell focus.
In the present invention, the pressure of the supercritical carbon dioxide can be 7MPa-50MPa, preferably 7MPa-20MPa,
Such as in the range that can be made of any two in 7MPa, 15MPa, 20MPa, 35MPa, 50MPa and these numerical value
Arbitrary value.The temperature of the supercritical carbon dioxide can be 30-70 DEG C, such as can be 30 DEG C, 35 DEG C, 40 DEG C, 50 DEG C
With 70 DEG C etc..
In the present invention, this method further includes that the mink cell focus is forced into 7MPa-50MPa before step (1), preferably
It for 7MPa-20MPa, such as can be any two institute in 7MPa, 15MPa, 20MPa, 35MPa, 50MPa and these numerical value
Arbitrary value in the range of composition.The mink cell focus is warming up to 30-70 DEG C, such as can be 30 DEG C, 35 DEG C, 40 DEG C, 50 DEG C
With 70 DEG C etc..That is, the pressure limit that mink cell focus is mixed with supercritical carbon dioxide is in 7MPa-50MPa, preferably
7MPa-20MPa, temperature range maintain carbon dioxide in the supercritical state at 30-70 DEG C.
In the present invention, before contact, respective temperature can be different for mink cell focus and supercritical carbon dioxide, but not
It can differ too big, need to maintain carbon dioxide in tower, if differing too big, to influence whether the phase of carbon dioxide in supercriticality
State and density.
In the present invention, the mink cell focus can be selected from the oil obtained through time processing, the oil obtained through secondary operation, original
At least one of oil and coal oil.Preferably, the time processing can be air-distillation and/or vacuum distillation.Preferably,
The secondary operation can be catalytic cracking and/or be hydrocracked.
In the present invention, in step (1), the mixed weight ratio of the mink cell focus and supercritical carbon dioxide can be 1:
(0.5-20), preferably 1:(2-8).
In the present invention, in step (2), the method for the component separation is for the purpose of reducing density and realize separation, example
It such as can be temperature-raising method and/or voltage drop method.
In one embodiment of the present invention, heating can be used in the method that the supercritical carbon dioxide is separated with light oil
Method, such as pressure is maintained to be basically unchanged, the density of supercritical carbon dioxide substantially reduces at this time, loses the energy of dissolved oil substantially
Power specifically on the basis of temperature when contacting by mink cell focus and supercritical carbon dioxide, increases 30 DEG C -100 DEG C of temperature.
In another embodiment of the present invention, decompression is can be used in the method that the supercritical carbon dioxide is separated with light oil
Method, such as temperature are basically unchanged, reduce pressure so that carbon dioxide is changed into gaseous state from above-critical state, lose solvent power to
Light oil separation, specifically, pressure can be 0.01MPa-7MPa.
In another embodiment of the present invention, the method that the supercritical carbon dioxide is separated with light oil can use simultaneously
Voltage drop method and temperature-raising method, specific pressure limit are 0.01MPa-7MPa；When being contacted with mink cell focus and supercritical carbon dioxide
On the basis of temperature, temperature increases 10 DEG C -100 DEG C.Such as temperature is 50 DEG C when contact, then increases temperature to 60-150 DEG C.
In the present invention, modifying agent can also be contained in the supercritical carbon dioxide.Modifying agent can be but be not limited to:
Low-carbon alcohols.Preferably, the weight ratio of the supercritical carbon dioxide and modifying agent is 1:(0.001-0.15), preferably 1:
(0.1-0.15)。
In the present invention, in step (3), the condition of the throttled steam thermal cracking includes but is not limited to: water vapour with
The weight ratio of light oil is (0.1-0.9): 1；Pyrolysis furnace can be 500-750 DEG C across section temperature；Crack furnance radiation section furnace tube goes out
Mouth temperature can be 780-950 DEG C；Residence time can be 1-500ms.Preferably, the weight ratio of water vapour and light oil is
(0.4-0.8): 1；Pyrolysis furnace is 540-700 DEG C across section temperature；Crack furnance radiation section furnace tube outlet temperature is 800-900 DEG C；
Residence time is 10-400ms.
In the present invention, obtained from the carbon dioxide can collect industrial furnace discharge gas, to realize reduction
The purpose of greenhouse gas emission.
The present invention will be described in detail by way of examples below.
Embodiment 1-5 is for illustrating method of the invention.
Embodiment 1
It is 862.4kg/m by density3, carboloy residue 3.41%, colloid 9.1%, the crude oil (weight that asphalitine is 0.1%
Matter oil) it is pressurized to 20MPa, is preheating to 60 DEG C from top penetrating extraction tower.Supercritical carbon dioxide is pressurized to 20MPa, preheating
To 50 DEG C, enter extraction tower from lower part, the mixed weight ratio of crude oil and supercritical carbon dioxide into extraction tower is 1:2, is taken out
Stripper tower bottom obtains the heavy fluid phase rich in heavy oil, and extraction tower overhead extraction is mutually dropped rich in light oil with the lighter fluid of carbon dioxide
Low-pressure to 1MPa, temperature is 60 DEG C, the light oil and carbon dioxide separation subsequently into recovery tower, in lighter fluid phase；Knockout tower
Top is recycled back to extraction tower use, the light oil that recycling knockout tower tower bottom obtains after obtaining carbon dioxide boosting, heating.
In terms of crude oil feeding, light oil yield 60%, light oil, which is passed through steam cracking furnace and mixes with dilution steam generation, to be cracked,
The weight ratio of water vapour and light oil is 0.8:1, and pyrolysis furnace is 600 DEG C across section (coupling part of convection current and radiant section) temperature,
Crack furnance radiation section furnace tube outlet temperature is 850 DEG C, and cracking pressure is absolute pressure 5kPa, residence time 4.6ms.Pyrolysis product is through dividing
Obtain low-carbon alkene product from after, in throttled steam thermal cracking processes, yield of ethene 26.70%, propene yield is
14.58%, butylene yield 10.55%, butadiene yield 6.10%, low-carbon alkene total 57.93%.Operation 30 days, splits
Solve device normal operation.
Embodiment 2
It is 862.4kg/m by density3, carboloy residue 3.41%, colloid 9.1%, the crude oil pressurization that asphalitine is 0.1%
To 15MPa, 50 DEG C are preheating to from top penetrating extraction tower.Supercritical carbon dioxide is pressurized to 15MPa, is preheating to 40 DEG C, from
Lower part enters extraction tower, and the crude oil and the mixed weight ratio of supercritical carbon dioxide into extraction tower are 1:4, and extraction tower tower bottom obtains
To the heavy fluid phase for being rich in heavy oil, extraction tower overhead extraction mutually reduces pressure extremely with the lighter fluid of carbon dioxide rich in light oil
0.1MPa, temperature are 40 DEG C, the light oil and carbon dioxide separation subsequently into recovery tower, in lighter fluid phase；Separation tower top obtains
Extraction tower use, the light oil that recycling knockout tower tower bottom obtains are recycled back to after carbon dioxide boosting, heating.
In terms of crude oil feeding, light oil yield 42%, light oil, which is passed through steam cracking furnace and mixes with dilution steam generation, to be cracked,
The weight ratio of water vapour and light oil is 0.4:1, and pyrolysis furnace is 540 DEG C across section (coupling part of convection current and radiant section) temperature,
Crack furnance radiation section furnace tube outlet temperature be 800 DEG C, cracking pressure be absolute pressure 10kPa, the residence time 0.2 second.Pyrolysis product warp
Obtain low-carbon alkene product after separation, in throttled steam thermal cracking processes, yield of ethene 26.91%, propene yield is
14.86%, butylene yield 10.59%, butadiene yield 6.13%, low-carbon alkene total 58.49%.Operation 30 days, splits
Solve device normal operation.
Embodiment 3
It is 862.4kg/m by density3, carboloy residue 3.41%, colloid 9.1%, the crude oil pressurization that asphalitine is 0.1%
To 8MPa, 50 DEG C are preheating to from top penetrating extraction tower.Supercritical carbon dioxide is pressurized to 8MPa, is preheating to 35 DEG C, under
Portion enters extraction tower, and the crude oil and the mixed weight ratio of supercritical carbon dioxide into extraction tower are 1:8, and extraction tower tower bottom obtains
Heavy fluid phase rich in heavy oil, extraction tower overhead extraction mutually increase temperature to 100 with the lighter fluid of carbon dioxide rich in light oil
DEG C, pressure 8MPa, light oil and carbon dioxide separation subsequently into recovery tower, in lighter fluid phase；Separation tower top obtains dioxy
Extraction tower use, the light oil that recycling knockout tower tower bottom obtains are recycled back to after changing carbon boosting, heating.
In terms of crude oil feeding, light oil yield 34%, light oil, which is passed through steam cracking furnace and mixes with dilution steam generation, to be cracked,
The weight ratio of water vapour and light oil is 0.6:1, and pyrolysis furnace is 700 DEG C across section (coupling part of convection current and radiant section) temperature,
Crack furnance radiation section furnace tube outlet temperature be 900 DEG C, cracking pressure be absolute pressure 1kPa, the residence time 0.2 second.Pyrolysis product is through dividing
Obtain low-carbon alkene product from after, in throttled steam thermal cracking processes, yield of ethene 28.66%, propene yield is
15.17%, butylene yield 10.61%, butadiene yield 5.97%, low-carbon alkene total 60.41%.Operation 30 days, splits
Solve device normal operation.
Embodiment 4
It is 862.4kg/m by density3, carboloy residue 3.41%, colloid 9.1%, the crude oil pressurization that asphalitine is 0.1%
To 50MPa, 50 DEG C are preheating to from top penetrating extraction tower.Supercritical carbon dioxide is pressurized to 50MPa, is preheating to 35 DEG C, from
Lower part enters extraction tower, and the mixed weight ratio of crude oil and supercritical carbon dioxide into extraction tower is 1:0.5, extraction tower tower bottom
The heavy fluid phase rich in heavy oil is obtained, extraction tower overhead extraction mutually increases temperature extremely with the lighter fluid of carbon dioxide rich in light oil
100 DEG C, pressure 2MPa, light oil and carbon dioxide separation subsequently into recovery tower, in lighter fluid phase；Separation tower top obtains two
Extraction tower use, the light oil that recycling knockout tower tower bottom obtains are recycled back to after carbonoxide boosting, heating.
In terms of crude oil feeding, light oil yield 71%, light oil, which is passed through steam cracking furnace and mixes with dilution steam generation, to be cracked,
The weight ratio of water vapour and light oil is 0.1:1, and pyrolysis furnace is 500 DEG C across section (coupling part of convection current and radiant section) temperature,
Crack furnance radiation section furnace tube outlet temperature be 780 DEG C, cracking pressure be absolute pressure 0.1kPa, the residence time 0.2 second.Pyrolysis product warp
Obtain low-carbon alkene product after separation, in throttled steam thermal cracking processes, yield of ethene 26.41%, propene yield is
14.34%, butylene yield 10.34%, butadiene yield 5.99%, low-carbon alkene total 57.08%.Operation 30 days, splits
Solve device normal operation.
Embodiment 5
It is 862.4kg/m by density3, carboloy residue 3.41%, colloid 9.1%, the crude oil pressurization that asphalitine is 0.1%
To 7MPa, 30 DEG C are preheating to from top penetrating extraction tower.Supercritical carbon dioxide is pressurized to 7MPa, is preheating to 30 DEG C, under
Portion enters extraction tower, and the crude oil and the mixed weight ratio of supercritical carbon dioxide into extraction tower are 1:20, and extraction tower tower bottom obtains
To the heavy fluid phase for being rich in heavy oil, extraction tower overhead extraction mutually increases temperature to 40 with the lighter fluid of carbon dioxide rich in light oil
DEG C, pressure 2MPa, light oil and carbon dioxide separation subsequently into recovery tower, in lighter fluid phase；Separation tower top obtains dioxy
Extraction tower use, the light oil that recycling knockout tower tower bottom obtains are recycled back to after changing carbon boosting, heating.
In terms of crude oil feeding, light oil yield 31%, light oil, which is passed through steam cracking furnace and mixes with dilution steam generation, to be cracked,
The weight ratio of water vapour and light oil is 0.9:1, and pyrolysis furnace is 750 DEG C across section (coupling part of convection current and radiant section) temperature,
Crack furnance radiation section furnace tube outlet temperature be 950 DEG C, cracking pressure be absolute pressure 101kPa, the residence time 0.2 second.Pyrolysis product warp
Obtain low-carbon alkene product after separation, in throttled steam thermal cracking processes, yield of ethene 26.36%, propene yield is
14.28%, butylene yield 10.25%, butadiene yield 6.22%, low-carbon alkene total 57.11%.Operation 30 days, splits
Solve device normal operation.
Comparative example 1
It is 862.4kg/m by density3, carboloy residue 3.41%, colloid 9.1%, asphalitine be 0.1% crude oil be passed through
Steam cracking furnace is mixed with dilution steam generation and is cracked, and the weight ratio of water vapour and light oil is 0.8:1, and pyrolysis furnace is (right across section
Stream and the coupling part of radiant section) temperature is 600 DEG C, crack furnance radiation section furnace tube outlet temperature is 850 DEG C, the residence time 0.2
Second.Pyrolysis product obtains low-carbon alkene product after separation, and in steam thermal cracking processes, yield of ethene 22.65%, propylene is received
Rate is 13.58%, butylene yield 8.22%, butadiene yield 4.66%, and low-carbon alkene amounts to 49.11%.It is small to run 10
When, cracking furnace pipe is blocked because of coking.
Comparative example 2
According to the method for embodiment 1, unlike, without throttled steam thermal cracking, steam thermal cracking has been carried out.
Pyrolysis product obtains low-carbon alkene product after separation, in steam thermal cracking processes, yield of ethene 23.52%,
Propene yield is 11.48%, butylene yield 7.92%, butadiene yield 3.57%, and low-carbon alkene amounts to 46.49%.Fortune
Row 20 days, cracker normal operation.
It can be seen that by the result of embodiment and comparative example and do not cracked using method long-term operation of the invention
The problem of boiler tube is blocked because of coking does not use method of the invention, will block because of coking within 10 hours, by using this hair
Bright method can well be run 20 days or more.
And the present invention by using decompression thermal cracking method, realize prepared in high yield using mink cell focus as raw material it is low
Carbon olefin, low-carbon alkene amount to from 46.49% and are increased to 57.93%.
Supercritical carbon dioxide can be recycled in the method for the present invention, achieved the effect that synergy emission reduction.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method by mink cell focus production low-carbon alkene, which is characterized in that method includes the following steps:
(1) mink cell focus is contacted and is separated with supercritical carbon dioxide, obtain the lighter fluid containing light oil and carbon dioxide
Phase, and the heavy fluid phase containing heavy oil；
(2) component separation is mutually carried out with the lighter fluid of carbon dioxide containing light oil by described, obtains light oil and carbon dioxide；
(3) light oil is subjected to throttled steam thermal cracking, obtains low-carbon alkene.
2. according to the method described in claim 1, wherein, in step (3), the pressure of the throttled steam thermal cracking is absolute pressure
0.5-101kPa, preferably 1-10kPa.
3. according to the method described in claim 1, wherein, the pressure of the supercritical carbon dioxide is 7MPa-50MPa, preferably
For 7MPa-20MPa；The temperature of the supercritical carbon dioxide is 30-70 DEG C.
4. according to the method described in claim 1, wherein, this method further includes that the mink cell focus pressurizes before step (1)
To 7MPa-50MPa, preferably 7MPa-20MPa；The mink cell focus is warming up to 30-70 DEG C.
5. according to the method described in claim 1, wherein, the mink cell focus is selected from the oil obtained through time processing, adds through secondary
At least one of oil, crude oil and coal oil that work obtains；
Preferably, the time processing is air-distillation and/or vacuum distillation；
Preferably, the secondary operation is catalytic cracking and/or is hydrocracked.
6. according to the method described in claim 1, wherein, in step (1), the mink cell focus and supercritical carbon dioxide it is mixed
Composition and division in a proportion example is 1:(0.5-20 by weight), preferably 1:(2-8).
7. according to the method described in claim 1, wherein, in step (2), the method for the component separation be temperature-raising method and/
Or voltage drop method.
8. according to the method described in claim 1, wherein, also containing modifying agent in the supercritical carbon dioxide；
Preferably, the modifying agent is low-carbon alcohols；
Preferably, the weight ratio of the supercritical carbon dioxide and modifying agent is 1:(0.001-0.15).
9. according to the method described in claim 1, wherein, in step (3), the condition of the throttled steam cracking includes: water
The weight ratio of steam and light oil is (0.1-0.9): 1；Pyrolysis furnace is 500-750 DEG C across section temperature；Crack furnance radiation section furnace tube
Outlet temperature is 780-950 DEG C；Residence time is 1-500ms.
10. according to the method described in claim 9, wherein, in step (3), the condition of the throttled steam cracking includes: water
The weight ratio of steam and light oil is (0.4-0.8): 1；Pyrolysis furnace is 540-700 DEG C across section temperature；Crack furnance radiation section furnace tube
Outlet temperature is 800-900 DEG C；Residence time is 10-400ms.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4235702A (en) * | 1977-12-20 | 1980-11-25 | Imperial Chemical Industries Limited | Hydrocarbon processing |
-
2017
- 2017-10-11 CN CN201710940563.2A patent/CN109652120A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4235702A (en) * | 1977-12-20 | 1980-11-25 | Imperial Chemical Industries Limited | Hydrocarbon processing |
Non-Patent Citations (3)
| Title |
|---|
| [美]J.H.加里 等著，王加玮 等译: "《石油炼制技术与经济（第二版）》", 30 September 1991, 中国石化出版社 * |
| 北京石油化工总厂北京化工研究院情报室译: "《石油化工译文集 第六集 石油烃的裂解（之二）》", 31 July 1976, 石油化学工业出版社 * |
| 闫立峰编著: "《绿色化学》", 30 April 2007, 中国科学技术大学出版社 * |
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