CN109207199A - The method of low-carbon olefines high-output and system for low-carbon olefines high-output - Google Patents
The method of low-carbon olefines high-output and system for low-carbon olefines high-output Download PDFInfo
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- CN109207199A CN109207199A CN201710536598.XA CN201710536598A CN109207199A CN 109207199 A CN109207199 A CN 109207199A CN 201710536598 A CN201710536598 A CN 201710536598A CN 109207199 A CN109207199 A CN 109207199A
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
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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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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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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- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to wax oils to utilize field, disclose a kind of method of low-carbon olefines high-output and the system for low-carbon olefines high-output, hydrocracking reaction is carried out this method comprises: wax oil raw material is introduced into fixed bed hydrogenation cracking reaction area, hydrocracking reaction effluent is separated, hydrogen wax oil fraction will be added successively to be introduced into first reactor and second reactor and carry out catalytic cracking reaction, and the first light naphthar is introduced into the third reactor in catalytic cracking reaction area and carries out catalytic cracking reaction；The catalytic pyrolysis product obtained in the second reactor in catalytic cracking reaction area and third reactor is separated, recycle oil is recycled back to fixed bed hydrogenation cracking reaction area.The present invention organically combines fixed bed wax oil hydrogenation technique and Deep Catalytic Cracking process, can significantly improve the high-value products yield such as propylene in group technology, ethylene.
Description
Technical field
The present invention relates to hydrocarbon ils manufacture fields, and in particular, to a kind of fixed bed hydrogenation cracking and catalytic pyrolysis combine work
The method of skill low-carbon olefines high-output and system for low-carbon olefines high-output.
Background technique
Traditional petrochemical industry is based on preparing ethylene by steam cracking.In China, steam cracking primary raw material is stone brain
Oil, however in recent years, oil price constantly surging and shale gas exploitation technology continuous maturation, using shale gas as raw material
Extensive use of the steam cracking device in North America is constantly squeezed using naphtha as the economy of ethylene cracking material technique.Relatively
Ethylene product market, propylene is smaller by the impact of shale gas revolution, and market is still larger to the notch of propylene.Therefore, in crude oil
Price develops the technology of producing more propylene with respect to the downturn period, will have wide practical use in future.
Currently, oil-refining chemical enterprise production propylene main device first is that cat-cracker.Cat-cracker
Primary raw material includes wax oil and wax oil, wherein wax oil raw material through hydrogenated processing after, propylene is reachable in the yield of catalyst cracking unit
To 20% or even 30% or more.However, lower as the cat-cracker productivity of propylene of raw material using wax oil.Therefore, pass through selection
Suitable process route, improving wax catalysis cracking propene yield has biggish growth space.
CN101045884A discloses the method for a kind of residual oil and heavy distillate production cleaning diesel oil and low-carbon alkene, the party
In method, residual oil and optional catalytic cracking slurry oil enter Solvent deasphalting unit, resulting deasphalted oil and optional heavy distillat
Oil enters hydrogenation unit, carries out hydrocracking reaction in the presence of hydrogen gas, and separation reaction product obtains light, heavy naphtha and evaporates
Point, diesel oil distillate and hydrogenation tail oil；Hydrogenation tail oil enters catalyst cracking unit, carries out catalytic cracking reaction, and separation product obtains
Low-carbon alkene, gasoline fraction, diesel oil distillate and slurry oil.Whole catalytic pyrolysis diesel oil distillates are recycled back to catalytic cracking reaction device,
All or part of catalytic cracking slurry oil returns to Solvent deasphalting unit.This method by residual oil solvent deasphalting, be hydrocracked, urge
Change cracking organic assembling, improves the utilization rate of heavy oil, fecund part low-carbon alkene, but to Hydrocracking unit and catalysis
The light naphthar of unit is cracked not in the further cracking of catalyst cracking unit, therefore productivity of low carbon olefin hydrocarbon increase rate is limited.
CN101063047A discloses a kind of method of dense raw material hydrotreatment-catalytic cracking for improving productivity of propylene,
Heavy distillate and the optional light cycle oil from catalyst cracking unit can also can exist respectively jointly in a reaction zone
It is reacted in the hydroconversion reaction zone of the different hydrogenation catalysts of two fillings, after reaction effluent is cooled and separated and is fractionated,
Resulting heavy liquid phase fraction removes catalyst cracking unit, and separator catalytic cracking reaction products obtain final products.The present invention mentions
The method of confession improves the property of catalyst cracking unit wax oil raw material by the method for hydrotreating, but hydroprocessing technique is to wax
Oily feedstock property improves limited extent, therefore catalyst cracking unit productivity of propylene increase rate is limited, and to light naphtha fraction
Freshening is not carried out, further reduced the yield of low-carbon alkene.
CN102453543A discloses a kind of residue fixed-bed hydrotreating and catalytic cracking combination process, this method
Using wax oil as raw material, the light component generated after fixed bed hydrogenation is handled is directly entered catalytic cracking riser reactor, recombination
Divide and enter catalytic cracking fractionating tower, is fractionated together with catalytic cracking reaction effluent, isolates dry gas, liquefied gas, gasoline
Fraction, diesel oil distillate, recycle oil and slurry oil, wherein recycle oil is fed as the riser reactor second level, and slurry oil is as delay
Coker feedstock composition.This method significantly improves catalytic cracking unit petrol and diesel oil yield, reduces recycle oil and slurry oil yield, but
Productivity of propylene increase rate is limited.
Summary of the invention
The purpose of the present invention is improve the yield of the high-value products such as low-carbon alkene, especially propylene, ethylene.
To achieve the goals above, in a first aspect, the present invention provides a kind of method of low-carbon olefines high-output, this method packet
It includes:
(1) wax oil raw material is introduced into fixed bed hydrogenation cracking reaction area and carries out hydrocracking reaction, be hydrocracked
Reaction effluent；
(2) the hydrocracking reaction effluent is separated, obtains the first light naphthar, the first heavy naphtha, bavin
Oil distillate and plus hydrogen wax oil fraction；
(3) described plus hydrogen wax oil fraction is successively introduced into the first reactor and second reactor in catalytic cracking reaction area
Catalytic cracking reaction is carried out, and first light naphthar is introduced into the third reactor in catalytic cracking reaction area and is urged
Change cracking reaction；
(4) by the catalytic pyrolysis product obtained in the second reactor in the catalytic cracking reaction area and third reactor into
Row separation, obtains low-carbon alkene, the second light naphthar, the second heavy naphtha, recycle oil and catalytic cracking slurry oil；
(5) second light naphthar is sent into the third reactor in the catalytic cracking reaction area, and will be described
Recycle oil is sent into fixed bed hydrogenation cracking reaction area.
Second aspect, the present invention provide a kind of system for low-carbon olefines high-output, which includes:
Fixed bed hydrogenation cracking reaction area, for wax oil raw material to be carried out hydrocracking reaction；
First Disengagement zone, by the reaction effluent in fixed bed hydrogenation cracking reaction area in first Disengagement zone into
Row separation obtains the first light naphthar, the first heavy naphtha, diesel oil distillate and adds hydrogen wax oil fraction；
Catalytic cracking reaction area, the catalytic cracking reaction area include first reactor, second reactor and third reaction
Device, from first Disengagement zone plus hydrogen wax oil fraction is by adding hydrogen wax oil fraction line to be introduced in the first reactor
Catalytic cracking reaction is carried out, and the material in the first reactor is introduced to described second instead by first reactor pipeline
It answers and carries out catalytic cracking reaction in device, and the first light naphthar from first Disengagement zone passes through the first light naphthar pipe
Line is introduced into the third reactor and carries out catalytic cracking reaction；
Second Disengagement zone, the catalytic pyrolysis product from the second reactor and the third reactor are split by catalysis
Solution product line, which is introduced in second Disengagement zone, to be separated, and low-carbon alkene, the second light naphthar, the second scheelite brain are obtained
Oil, recycle oil and catalytic cracking slurry oil, and by the second light naphthar pipeline by second Disengagement zone obtains second gently
Naphtha is recycled to the third reactor, and is recycled by the recycle oil that recycle oil pipeline obtains second Disengagement zone
Go back to fixed bed hydrogenation cracking reaction area.
In the method for the invention, the process of fixed bed hydrogenation process includes: wax oil raw material and catalyst cracking unit
Recycle oil mixing after with hydrogen be mixed into fixed bed hydrogenation cracking reaction area, urged with Hydrobon catalyst and being hydrocracked
Hydrogenation reaction occurs for agent contact, and hydrogenation reaction effluent carries out gas-liquid separation, and the first light naphthar that liquid phase fractionates out is into urging
The third reactor for changing cracking unit, adds hydrogen wax oil fraction to enter the first reactor of catalyst cracking unit.
The present invention by fixed bed wax oil hydrogenation technique and is catalyzed according to the property feature of fixed bed wax oil hydrogenation cracked product
Cracking technology organically combines, and can significantly improve the high-value products yield such as propylene in group technology, ethylene.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the process flow chart of the method for low-carbon olefines high-output of the invention.
Fig. 2 is the process flow chart in comparative example 1 of the invention for the method for low-carbon olefines high-output.
Description of symbols
1, wax oil raw material 2, catalytic pyrolysis recycle oil
3, fixed bed hydrogenation cracking reaction area 4, hydrocracking reaction effluent
5, high-pressure separator 6, circulating hydrogen compressor
7, new hydrogen 8, mixing hydrogen are supplemented
9, fractionating column 10, dry gas liquefied gas are hydrocracked
11, the first light naphthar 12, the first heavy naphtha
13, diesel oil distillate 14 plus hydrogen wax oil fraction
15, the first and second light naphthar miscellas 16, first reactor
17, second reactor 18, third reactor
19, settler 20, cyclone separator
21, regenerator 22, catalytic pyrolysis separative unit
23, low-carbon alkene 24, the second light naphthar
25, the second heavy naphtha 26, catalytic cracking slurry oil
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
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.
In a first aspect, the present invention provides a kind of methods of low-carbon olefines high-output, this method comprises:
(1) wax oil raw material is introduced into fixed bed hydrogenation cracking reaction area and carries out hydrocracking reaction, be hydrocracked
Reaction effluent；
(2) the hydrocracking reaction effluent is separated, obtains the first light naphthar, the first heavy naphtha, bavin
Oil distillate and plus hydrogen wax oil fraction；
(3) described plus hydrogen wax oil fraction is successively introduced into the first reactor and second reactor in catalytic cracking reaction area
Catalytic cracking reaction is carried out, and first light naphthar is introduced into the third reactor in catalytic cracking reaction area and is urged
Change cracking reaction；
(4) by the catalytic pyrolysis product obtained in the second reactor in the catalytic cracking reaction area and third reactor into
Row separation, obtains low-carbon alkene, the second light naphthar, the second heavy naphtha and recycle oil；
(5) second light naphthar is recycled in the third reactor in the catalytic cracking reaction area, and by institute
Recycle oil is stated to be recycled back in fixed bed hydrogenation cracking reaction area.
In the present invention, the reaction carried out in fixed bed hydrogenation cracking reaction area further includes hydrodesulfurization, hydrodenitrogeneration, aromatic hydrocarbons
Hydrogen saturation, hydrodemetallization etc. is added to react.
Preferably, Hydrobon catalyst and hydrocracking catalyst are successively loaded in fixed bed hydrogenation cracking reaction area
Agent, by volume, the filling ratio of Hydrobon catalyst and hydrocracking catalyst are 2:8~8:2.
Preferably, the active metal member in the Hydrobon catalyst containing carrier and load on the carrier
Element, the carrier are selected from least one of aluminium oxide, aluminium oxide-silicon oxide and titanium oxide, and the active metallic element is selected from
At least one of nickel, cobalt, molybdenum and tungsten；Preferably, in Hydrobon catalyst, with the total weight of Hydrobon catalyst
Meter, the content of nickel and/or cobalt in terms of oxide are 1~30 weight %, the content of molybdenum and/or tungsten in terms of oxide is 5~
35 weight %；
Preferably, the active metal member in the hydrocracking catalyst containing carrier and load on the carrier
Element, the carrier contain molecular sieve and selected from least one of aluminium oxide, aluminium oxide-silicon oxide and titanium oxide, the activity
Metallic element is selected from least one of nickel, cobalt, molybdenum and tungsten；Preferably, in hydrocracking catalyst, with hydrocracking catalyst
The total weight of agent, molecular sieve content are 3~40 weight %, and the content of nickel and/or cobalt in terms of oxide is 1~30%, with
The molybdenum of oxide meter and/or the content of tungsten are 5~40 weight %.
The shape of the fixed bed hydrogenation catalyst for refining and hydrocracking catalyst can be in extrudate or spherical shape, and heap is close
Degree is 0.4~1.3g/cm3, catalyst average particle diameter (spherical diameter or bar shaped diameter) is 0.08~1.2mm, specific surface
Product is 100~300m2/g。
Preferably, it is 6~30MPa, reaction that the reaction condition in fixed bed hydrogenation cracking reaction area, which includes: reaction pressure,
Temperature is 320~490 DEG C, and volume space velocity is 0.1~5.0h when liquid-1, hydrogen to oil volume ratio is 200~2000.It is highly preferred that described
The reaction condition in fixed bed hydrogenation cracking reaction area includes: that reaction pressure is 13~15MPa, and reaction temperature is 350~410 DEG C,
Volume space velocity is 0.5~2.0h when liquid-1, hydrogen to oil volume ratio is 400~1200.
It is further preferred that the reaction condition in fixed bed hydrogenation cracking reaction area is controlled, so that described be hydrocracked instead
The yield for answering the first light naphthar in effluent is 5~12%.
The hydrocracking reaction effluent, which carries out separation, can obtain the first light naphthar, the first heavy naphtha, diesel oil
Fraction and plus hydrogen wax oil fraction, and obtain dry gas and liquefied gas.Wherein, the first light naphthar enters catalytic cracking reaction area
Catalytic cracking reaction is carried out in third reactor, the first heavy naphtha goes out device as product as reformer feed, diesel oil distillate,
Add hydrogen wax oil fraction to be successively introduced into the first reactor and second reactor in catalytic cracking reaction area and carries out catalytic cracking reaction.
Preferably, in step (3), described plus hydrogen wax oil fraction is successively introduced to first reaction in catalytic cracking reaction area
The step of cracking reaction is carried out in device and second reactor includes: that described plus hydrogen wax oil fraction is first introduced catalytic cracking reaction area
The first reactor containing catalytic cracking catalyst in carry out catalytic cracking reaction, then will be obtained in the first reactor
Oil gas and reaction after catalytic cracking catalyst be introduced into the second reactor and carry out catalytic cracking reaction.
Preferably, the raw material for entering first reactor is preheated, the temperature of the preheating is 250~450 DEG C.And
Preferably, the raw material for entering third reactor is preheated, the temperature of the preheating is 100~250 DEG C.
Preferably, it is 500~650 DEG C that the reaction condition in the first reactor, which includes: reaction temperature, and weight (hourly) space velocity (WHSV) is
0.1~750h-1, reaction pressure is 0.10~1.0MPa (absolute pressure), oil plant in catalytic cracking catalyst and the first reactor
Weight ratio be 2~100:1.It is highly preferred that it is 540~600 that the reaction condition in the first reactor, which includes: reaction temperature,
DEG C, weight (hourly) space velocity (WHSV) is 1~500h-1, reaction pressure is 0.10~1.0MPa (absolute pressure), and catalytic cracking catalyst is anti-with described first
The weight ratio for answering oil plant in device is 5~50:1.
In case of no particular description, the pressure of the invention is gauge pressure；It is special if having special instruction
Illustrate the pressure indicated.
Preferably, the reaction temperature of the second reactor is 10~100 DEG C higher than the temperature of the first reactor；It is more excellent
Selection of land, the reaction temperature of the second reactor are 20~60 DEG C higher than the temperature of the first reactor.
Preferably, in the second reactor, the weight of oil plant in catalytic cracking catalyst and the second reactor
Than for 5~50:1.
Preferably, the ratio between weight (hourly) space velocity (WHSV) of the second reactor and the first reactor is 1:1.1~750；It is more excellent
Select the ratio between weight (hourly) space velocity (WHSV) of the second reactor and the first reactor for 1:1.1~300.
Preferably, it is 600~750 DEG C that the reaction condition of the third reactor, which includes: reaction temperature, and weight (hourly) space velocity (WHSV) is
0.1~100h-1, reaction pressure is 0.1~1.0MPa (absolute pressure), oil plant in catalytic cracking catalyst and the third reactor
4~100:1 of weight ratio.It is highly preferred that it is 600~700 DEG C that the reaction condition of the third reactor, which includes: reaction temperature, weight
When air speed be 0.5~75h-1, reaction pressure is 0.1~1.0MPa (absolute pressure), catalytic cracking catalyst and the third reactor
5~80:1 of weight ratio of middle oil plant.
Preferably, the reaction temperature of the third reactor is higher than the reaction temperature of the second reactor.It is highly preferred that
The reaction temperature of the third reactor is 30~100 DEG C higher than the reaction temperature of the second reactor, particularly preferably high by 40~
80℃.The reaction temperature for controlling the third reactor is higher than the reaction temperature of the second reactor, especially high by 30~100
DEG C, at preferably high 40~80 DEG C, the yield of the low-carbon alkene obtained by method of the invention can be made higher.
In the present invention, the material (including oil gas and reclaimable catalyst) obtained after third reactor reaction is introduced to separation
It is separated in equipment, it is preferable that reclaimable catalyst obtained after separation is introduced into the second reactor and is reacted.
In the present invention, the material (including oil gas and reclaimable catalyst) obtained after second reactor is reacted is introduced to separation
The reclaimable catalyst for being separated in equipment, and being obtained after being isolated, which is introduced in catalyst regeneration units, to be regenerated,
The regenerated catalyst obtained after regeneration is recycled back in the first reactor and the third reactor.
The catalytic pyrolysis product obtained in the second reactor in the catalytic cracking reaction area and third reactor is carried out
Isolated method may include urging respectively by what is obtained in the second reactor in the catalytic cracking reaction area and third reactor
Change pyrolysis product to be separated, or is urged what is obtained in the second reactor in the catalytic cracking reaction area and third reactor
It is separated together after changing pyrolysis product mixing.In the present invention, the catalytic pyrolysis product be do not include catalyst, only indicate
Carry out the oil gas obtained after catalytic cracking reaction.
In the present invention, the catalytic pyrolysis that will be obtained in the second reactor in the catalytic cracking reaction area and third reactor
Product is separated, and low-carbon alkene, the second light naphthar, the second heavy naphtha, recycle oil and catalytic cracking slurry oil are obtained,
In, the second light naphthar is sent into the third reactor in the catalytic cracking reaction area and second heavy naphtha can
Device is as aromatics extraction raw material out.
Low-carbon alkene of the invention includes ethylene and propylene.
Preferably, in the catalytic cracking catalyst in the catalytic cracking reaction area containing zeolite, inorganic oxide and
Optionally contain clay, with the total weight of the catalytic cracking catalyst, the content of the zeolite is 10~50 weight %, inorganic
The content of oxide is 5~90 weight %, and the content of clay is 0~70 weight %.It is described optionally to be indicated containing clay, it is described to urge
Clay can be contained by changing in catalyst for cracking, can also not contain clay, and therefore, when not containing clay, the content of clay is 0
Weight %, when containing clay, the content of the clay is greater than 0 to less than equal to 70 weight %.
Preferably, the active component in the catalytic cracking catalyst be selected from Y type with or without rare earth or HY type zeolite,
At least one of ultrastable with or without rare earth, zeolite with MFI structure.
Preferably, the wax oil raw material is at least one of normal pressure wax oil, decompressed wax oil, deasphalted oil.
Preferably, described plus hydrogen wax oil fraction boiling range is 300~580 DEG C.
Preferably, first light naphthar and second light naphthar are identical or different, and boiling range range is 65~135
℃。
Preferably, the boiling range range of first heavy naphtha and second heavy naphtha is 130~175 DEG C, circulation
The boiling range range of oil is 175~450 DEG C.
Preferably, the first reactor and the third reactor are riser reactor；The second reactor is
Fluidized-bed reactor.
In the first reactor, the atomizing steam amount for preferably playing castering action be account for the reactor feed amount 5~
50 weight %, preferably 10~25 weight %.
In the present invention, the material wait enter fixed bed hydrogenation cracking reaction area and catalytic cracking reaction area can be carried out
The temperature of preheating, the preheating can be for not higher than in fixed bed hydrogenation cracking reaction area and catalytic cracking reaction area to be entered
The temperature of the reaction of generation.
Second aspect, the present invention provides a kind of system for low-carbon olefines high-output, which includes:
Fixed bed hydrogenation cracking reaction area, for wax oil raw material to be carried out hydrocracking reaction；
First Disengagement zone, by the reaction effluent in fixed bed hydrogenation cracking reaction area in first Disengagement zone into
Row separation obtains the first light naphthar, the first heavy naphtha, diesel oil distillate and adds hydrogen wax oil fraction；
Catalytic cracking reaction area, the catalytic cracking reaction area include first reactor, second reactor and third reaction
Device, from first Disengagement zone plus hydrogen wax oil fraction is by adding hydrogen wax oil fraction line to be introduced in the first reactor
Catalytic cracking reaction is carried out, and the material in the first reactor is introduced to described second instead by first reactor pipeline
It answers and carries out catalytic cracking reaction in device, and the first light naphthar from first Disengagement zone passes through the first light naphthar pipe
Line is introduced into the third reactor and carries out catalytic cracking reaction；
Second Disengagement zone, the catalytic pyrolysis product from the second reactor and the third reactor are split by catalysis
Solution product line, which is introduced in second Disengagement zone, to be separated, and the second light naphthar, the second heavy naphtha, recycle oil are obtained
And catalytic cracking slurry oil, and respectively obtained second Disengagement zone by the second light naphthar pipeline and recycle oil pipeline
Second light naphthar and recycle oil are recycled to the third reactor and the fixed bed hydrogenation cracking reaction area respectively.
Preferably, fixed bed hydrogenation cracker is contained in fixed bed hydrogenation cracking reaction area.
Preferably, the first heavy naphtha pipeline and diesel fraction line, first weight are contained in first Disengagement zone
Naphtha and the diesel oil distillate lead to system by the first heavy naphtha pipeline and the diesel fraction line respectively
Outside.
Preferably, contain the second heavy naphtha pipeline and catalytic cracking slurry oil pipeline in second Disengagement zone, described the
The second heavy naphtha and catalytic cracking slurry oil that two Disengagement zone obtain pass through the second heavy naphtha pipeline respectively and described urge
Change cracking slurry oil pipeline to lead to outside system.
According to a kind of preferred embodiment, the method for low-carbon olefines high-output of the invention is using shown in Fig. 1
Process flow carry out, specifically:
Wax oil raw material 1, recycle oil 2 (carrying out autocatalytic cleavage separative unit 22) and recycle hydrogen 8 are concomitantly introduced into fixed bed
In hydrocracking reaction area 3, the fixed bed hydrogenation cracking of wax oil raw material 1, recycle oil 2 in fixed bed hydrogenation cracking reaction area 3 is anti-
It answers and carries out hydrocracking reaction in device, obtain hydrocracking reaction effluent 4；
The hydrocracking reaction effluent 4 is introduced in high-pressure separator 5 through pipeline and is separated, it is isolated
The hydrogen-rich gas in gas-phase product at the top of high-pressure separator is mixed to get after the processing of circulating hydrogen compressor 6 with the new hydrogen 7 of supplement
Hydrogen 8 is mixed, the mixing hydrogen 8 is for being recycled back in fixed bed hydrogenation cracking reaction area 3.The isolated liquid phase of high-pressure separator 5
Product is introduced in fractionating column 9 through pipeline and is fractionated, and obtains dry gas and liquefied gas 10, the first light naphthar 11, the first heavy naphtha
12, diesel oil distillate 13 plus hydrogen wax oil fraction 14；
Described plus hydrogen wax oil fraction 14 is introduced in the first reactor 16 in catalytic cracking reaction area, and carrys out self-catalysis
A part of regenerated catalyst of agent regeneration unit 21 enters through pipeline to be participated in reacting in first reactor 16；First reactor 16 goes out
Mouthful material (including oil gas and catalyst) obtained, which enters in second reactor 17, carries out catalytic cracking reaction, and will be from the
The reclaimable catalyst of three reactors 18, which is introduced in second reactor 17, participates in catalytic cracking reaction.And by first pumice
Cerebrol 11, which is introduced in the third reactor 18 in catalytic cracking reaction area, carries out catalytic cracking reaction, and comes from catalyst regeneration
Another part regenerated catalyst of unit 21 is introduced in the third reactor 18 and participates in catalytic cracking reaction；Then third is anti-
The material (including oil gas and catalyst) for answering 18 exit of device to obtain, which is introduced in settler 19, to be separated, and oil gas is respectively obtained
And reclaimable catalyst, the isolated reclaimable catalyst is introduced in second reactor 17 and carries out catalytic cracking reaction.
And the material (including oil gas and catalyst) for obtaining second reactor exit and the oil in third reactor 18
Gas is introduced in settler 20 and is separated, and respectively obtains oil gas and reclaimable catalyst, the isolated reclaimable catalyst
It is introduced in catalyst regeneration units 21 and is regenerated, and isolated oil gas is introduced to further catalytic pyrolysis separation list
It is separated in member 22, obtains low-carbon alkene 23, the second light naphthar 24, the second heavy naphtha 25, recycle oil 2 and catalytic pyrolysis
Slurry oil 26.The recycle oil 2 is recycled in fixed bed hydrogenation cracking reaction area 3.
It should be strongly noted that can be respectively obtained after being separated by catalytic pyrolysis separative unit dry gas, ethylene,
Propylene etc., the present invention indicate the ethylene, propylene etc. in above-mentioned preferred embodiment, with low-carbon alkene.
The above method of the invention also has the advantages that following specific:
1, in the present invention, using fixed bed wax oil hydrogenation process, wax oil feed stock conversion is higher, one of product
Raw material of first light naphthar as catalyst cracking unit third reactor can generate more low-carbon alkene product；
2, different reactor and technique item is arranged for the cracking performance difference of different fractions hydro carbons in catalyst cracking unit
Part increases substantially setting up for the cracking performance of each hydro carbons, especially third reactor, compares Conventional catalytic cracking reactor,
Light naphtha fraction can be completely converted into small molecule hydrocarbon especially low-carbon alkene class product.
The present invention will be described in detail by way of examples below.
Below in case of no particular description, the various raw materials used are all from commercially available.
The reaction of following embodiment be in catalytic pyrolysis middle- scale device and fixed bed wax oil hydrogenation cracking Chinese style device into
Capable.
Feedstock oil used below is Middle East decompressed wax oil, and property is shown in Table 1.
Fixed bed hydrogenation catalyst for refining used in embodiment and comparative example is identical, be bar shaped with aluminium oxide for carry
The nickel-molybdenum catalyst of body, wherein on the basis of the total amount of fixed bed hydrogenation catalyst for refining, fixed bed hydrogenation catalyst for refining
In the MoO containing 24.5 weight %3, 4.50 weight % NiO and surplus be carrier.Used in embodiment and comparative example
Fixed bed Cracking catalyst is identical, on the basis of the total amount of fixed bed hydrogenation Cracking catalyst, fixed bed hydrogenation Cracking catalyst
In the MoO containing 26.0 weight %3, 4.0 weight % NiO, Y type molecular sieve content be 28 weight %, surplus is carrying alumina
Body.
The type of catalytic cracking catalyst used in embodiment and comparative example is identical, is MMC-2, and the catalyst is in
The production of asphalt in Shenli Refinery of petrochemical industry limited liability company of state, catalyst property are shown in Table 2.
Table 1: wax oil feedstock property
| Property | |
| Density (20 DEG C), g/cm3 | 0.9326 |
| Carbon residue, weight % | 0.3 |
| Sulfur content, weight % | 2.53 |
| Nitrogen content, weight % | 0.13 |
| (Ni+V) content, μ g/g | 2 |
| Asphalitine, weight % | 0.02 |
Table 2: catalytic cracking catalyst property
Embodiment 1
The present embodiment is carried out using process flow chart shown in FIG. 1, specifically:
The wax oil raw material of property shown in table 1 is introduced in fixed bed hydrogenation cracking reaction area and carries out hydrocracking reaction,
Obtain hydrocracking reaction effluent；
The hydrocracking reaction effluent is separated, in the gas-phase product at the top of isolated high-pressure separator
Hydrogen-rich gas obtain recycle hydrogen after circulating hydrogen compressor is handled, the recycle hydrogen is mixed to get with supplement hydrogen mix hydrogen and recycles
It returns in fixed bed hydrogenation cracking reaction area, isolated liquid product, which is led in fractionating column, to be fractionated, and the first dry gas and the are obtained
One liquefied gas (note: the low-carbon alkene content in first liquefied gas is seldom, therefore, the receipts of the low-carbon alkene in embodiment result
In rate include this at the first liquefied gas in low-carbon alkene content, similarly hereinafter), the first light naphthar, the first scheelite brain
Oil, diesel oil distillate and plus hydrogen wax oil fraction；
Described plus hydrogen wax oil fraction is introduced in the first reactor in catalytic cracking reaction area, and again from catalyst
A part of regenerated catalyst of raw unit, which enters, participates in reaction in first reactor；Material (the packet that first reactor outlet obtains
Include oil gas and catalyst) enter in second reactor and carries out catalytic cracking reaction, and it will be urged from the to be generated of third reactor
Agent, which is introduced in second reactor, participates in catalytic cracking reaction.And that first light naphthar is introduced to catalytic pyrolysis is anti-
It answers and carries out catalytic cracking reaction in the third reactor in area, and another part regenerated catalyst from catalyst regeneration units
It is introduced in the third reactor and participates in catalytic cracking reaction；Then material (including oil third reactor exit obtained
Gas and catalyst) it is introduced in cyclone separator and is separated, oil gas and reclaimable catalyst are respectively obtained, by isolated institute
It states reclaimable catalyst and is introduced in second reactor and carry out catalytic cracking reaction.And the object for obtaining second reactor exit
Material (including oil gas and catalyst) and the oil gas in third reactor are introduced in settler and are separated, and respectively obtain
Oil gas and reclaimable catalyst, the isolated reclaimable catalyst, which is introduced in catalyst regeneration units, to be regenerated, and is divided
It is introduced in further catalytic pyrolysis separative unit and is separated from obtained oil gas, obtain low-carbon alkene gaseous mixture (wherein
Contain the low-carbon alkene including ethylene and propylene), the second light naphthar, the second heavy naphtha, recycle oil and catalytic cracking slurry oil.
Second light naphthar is recycled back in first reactor；And the recycle oil is recycled to the fixed bed hydrogenation cracking
In reaction zone.
The reaction condition in the fixed bed hydrogenation cracking reaction area product distribution is as shown in table 3 in the present embodiment, and urges
The reaction condition for changing pyrolysis reaction zone is as shown in table 4.The product distribution that the method for the present embodiment obtains is as shown in table 4.
Table 3: the reaction condition in fixed bed hydrogenation cracking reaction area
Table 4: the reaction condition and product distribution in catalytic cracking reaction area
Comparative example 1
Comparative example cracks group technology using wax oil fixed bed hydrogenation and conventional catalyst, and the process flow chart of comparative example 1 is shown in
Fig. 2 is not provided with third reactor with embodiment 1 the difference is that in comparative example 1 in catalytic cracking reaction area.Specifically:
It is anti-that fixed bed hydrogenation cracking is introduced to after the wax oil raw material 1 of property shown in table 1 is mixed with catalytic pyrolysis recycle oil 2
It answers and carries out hydrocracking reaction in area 3, obtain hydrocracking reaction effluent；
The hydrocracking reaction effluent 4 is introduced into high-pressure separator 5, the gas at the top of isolated high-pressure separator
Hydrogen-rich gas in phase product, which is mixed to get after the processing of circulating hydrogen compressor 6 with supplement hydrogen 7, mixes hydrogen 8, the mixing hydrogen 8
It is recycled back in fixed bed hydrogenation cracking reaction area 3, isolated liquid product is introduced in fractionating column 9 and is fractionated, and obtains dry gas
With liquefied gas 10, the first light naphthar of wax oil hydrogenation cracking 11, the first heavy naphtha of wax oil hydrogenation 12, diesel oil distillate 13 plus hydrogen
Wax oil fraction 14；
Described plus hydrogen wax oil fraction 14 is introduced in the first reactor 15 in catalytic cracking reaction area, and carrys out self-catalysis
The regenerated catalyst of agent regeneration unit 18, which enters, participates in reaction in first reactor 15；The material that the outlet of first reactor 15 obtains
(including oil gas and catalyst), which enters in second reactor 16, carries out catalytic cracking reaction.
Then the material (including oil gas and catalyst) that 16 exit of second reactor obtains is introduced to cyclone separator
It is separated in 17, respectively obtains oil gas and reclaimable catalyst, the isolated reclaimable catalyst is introduced to catalyst again
It is regenerated in raw unit 18, and isolated oil gas is introduced in further catalytic pyrolysis separative unit 19 and is divided
From obtaining low-carbon alkene 20, the second light naphthar 21, the second heavy naphtha 22, recycle oil 2 and catalytic cracking slurry oil 23.By institute
Recycle oil 2 is stated to be recycled in fixed bed hydrogenation cracking reaction area 3.
The reaction condition in fixed bed hydrogenation cracking reaction area and product distribution are as shown in table 3 in this comparative example, and urge
The reaction condition for changing pyrolysis reaction zone is as shown in table 4.The product distribution that the method for this comparative example obtains is as shown in table 4.
From the results shown in Table 4, method propylene provided in this embodiment compares comparative example with yield of ethene, mentions respectively
High 5.3 percentage points and 1.4 percentage points.
Embodiment 2-3
Embodiment 2-3 is carried out using process flow same as Example 1, the difference is that the fixed bed of embodiment 2-3
The reaction condition and product distribution in hydrocracking reaction area be as shown in table 3 and the reaction condition in catalytic cracking reaction area such as
Shown in table 4.The product distribution that the method for embodiment 2-3 obtains is as shown in table 4.
Embodiment 4
The present embodiment is carried out using method similar to Example 1, the difference is that the catalytic cracking reaction of the present embodiment
Reaction temperature in the third reactor in area is 30 DEG C higher than the reaction temperature in second reactor, and specifically, the present embodiment is consolidated
The reaction condition and product distribution in fixed bed hydrocracking reaction area be as shown in table 3 and the reaction item in catalytic cracking reaction area
Part is as shown in table 4.The product distribution that the method for the present embodiment obtains is as shown in table 4.
From the above results of the invention it can be seen that method of the invention is according to the property of fixed bed wax oil hydrogenation cracked product
Matter feature organically combines fixed bed wax oil hydrogenation technique and Deep Catalytic Cracking process, can significantly improve propylene in group technology,
The high-value products yield such as ethylene.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (18)
1. a kind of method of low-carbon olefines high-output, this method comprises:
(1) wax oil raw material is introduced into fixed bed hydrogenation cracking reaction area and carries out hydrocracking reaction, obtain hydrocracking reaction
Effluent；
(2) the hydrocracking reaction effluent is separated, obtains the first light naphthar, the first heavy naphtha, diesel oil and evaporates
Divide and add hydrogen wax oil fraction；
(3) described plus hydrogen wax oil fraction is successively introduced into the first reactor and second reactor in catalytic cracking reaction area and is carried out
Catalytic cracking reaction, and first light naphthar is introduced into the third reactor in catalytic cracking reaction area be catalyzed and is split
Solution reaction；
(4) the catalytic pyrolysis product obtained in the second reactor in the catalytic cracking reaction area and third reactor is divided
From obtaining low-carbon alkene, the second light naphthar, the second heavy naphtha, recycle oil and catalytic cracking slurry oil；
(5) second light naphthar is sent into the third reactor in the catalytic cracking reaction area, and by the circulation
Oil is sent into fixed bed hydrogenation cracking reaction area.
2. according to the method described in claim 1, wherein, the fixed bed hydrogenation cracking reaction successively loads hydrofinishing in area
Catalyst and hydrocracking catalyst, by volume, the filling ratio of Hydrobon catalyst and hydrocracking catalyst are 2:8
~8:2.
3. according to the method described in claim 2, wherein, in the Hydrobon catalyst containing carrier and being supported on described
Active metallic element on carrier, the carrier are selected from least one of aluminium oxide, aluminium oxide-silicon oxide and titanium oxide, institute
It states active metallic element and is selected from least one of nickel, cobalt, molybdenum and tungsten；Preferably, in Hydrobon catalyst, to add hydrogen smart
The total weight of catalyst processed, the content of nickel and/or cobalt in terms of oxide are 1~30 weight %, molybdenum in terms of oxide and/
Or the content of tungsten is 5~35 weight %；
Active metallic element in the hydrocracking catalyst containing carrier and load on the carrier, the carrier contain
There is molecular sieve and selected from least one of aluminium oxide, aluminium oxide-silicon oxide and titanium oxide, the active metallic element is selected from
At least one of nickel, cobalt, molybdenum and tungsten；Preferably, in hydrocracking catalyst, with the total weight of hydrocracking catalyst
Meter, molecular sieve content are 3~40 weight %, and the content of nickel and/or cobalt in terms of oxide is 1~30%, in terms of oxide
The content of molybdenum and/or tungsten is 5~40 weight %.
4. method according to claim 1 or 2, wherein the reaction condition in fixed bed hydrogenation cracking reaction area includes:
Reaction pressure is 6~30MPa, and reaction temperature is 320~490 DEG C, and volume space velocity is 0.1~5.0h when liquid-1, hydrogen to oil volume ratio is
200~2000；Preferably,
The reaction condition in fixed bed hydrogenation cracking reaction area includes: that reaction pressure is 13~17MPa, reaction temperature 350
~410 DEG C, volume space velocity is 0.5~2.0h when liquid-1, hydrogen to oil volume ratio is 400~1200.
5. method described in any one of -4 according to claim 1, wherein control fixed bed hydrogenation cracking reaction area
Reaction condition, so that the yield of the first light naphthar in the fixed bed hydrogenation cracking reaction effluent is 5~12%.
6. according to the method described in claim 1, wherein, in step (3), described plus hydrogen wax oil fraction is successively introduced catalysis
The step of cracking reaction is carried out in the first reactor and second reactor of pyrolysis reaction zone includes: first to evaporate described plus hydrogen wax oil
It separates and carries out catalytic cracking reaction in the first reactor containing catalytic cracking catalyst in catalytic cracking reaction area, then will
Catalytic cracking catalyst after the oil gas obtained in the first reactor and reaction is introduced into the second reactor and carries out
Catalytic cracking reaction.
7. according to the method described in claim 6, wherein, the reaction condition in the first reactor includes: that reaction temperature is
500~650 DEG C, weight (hourly) space velocity (WHSV) is 0.1~750h-1, reaction pressure is 0.10~1.0MPa, catalytic cracking catalyst and described the
The weight ratio of oil plant is 2~100:1 in one reactor；Preferably,
Reaction condition in the first reactor includes: that reaction temperature is 540~600 DEG C, and weight (hourly) space velocity (WHSV) is 1~500h-1, instead
Answering pressure is 0.10~1.0MPa, and the weight ratio of oil plant is 5~50:1 in catalytic cracking catalyst and the first reactor.
8. method according to claim 1 or 6, wherein the reaction temperature of the second reactor is than first reaction
The temperature of device is 10~100 DEG C high；It is preferred that 20~60 DEG C high；
And the ratio between the second reactor and the weight (hourly) space velocity (WHSV) of the first reactor are 1:1.1~750；Preferably 1:1.1
~300.
9. according to the method described in claim 1, wherein, the reaction condition of the third reactor includes: that reaction temperature is 600
~750 DEG C, weight (hourly) space velocity (WHSV) is 0.1~100h-1, reaction pressure is 0.1~1.0MPa, and catalytic cracking catalyst and the third are anti-
Answer 4~100:1 of weight ratio of oil plant in device；Preferably,
The reaction condition of the third reactor includes: that reaction temperature is 600~700 DEG C, and weight (hourly) space velocity (WHSV) is 0.5~75h-1, instead
Answering pressure is 0.1~1.0MPa, 5~80:1 of weight ratio of oil plant in catalytic cracking catalyst and the third reactor.
10. according to claim 1 or method described in 9, wherein the reaction temperature of the third reactor is than second reaction
The temperature of device is 30~100 DEG C high；It is preferred that 40~80 DEG C high.
11. according to the method described in claim 1, wherein, containing in the catalytic cracking catalyst in the catalytic cracking reaction area
There are zeolite, inorganic oxide and optionally contain clay, with the total weight of the catalytic cracking catalyst, the zeolite contains
Amount is 10~50 weight %, and the content of inorganic oxide is 5~90 weight %, and the content of clay is 0~70 weight %；It is preferred that
Ground,
Active component in the catalytic cracking catalyst is selected from Y type with or without rare earth or HY type zeolite, with or without dilute
Ultrastable, at least one of the zeolite with MFI structure of soil.
12. according to the method described in claim 1, wherein, the wax oil raw material is normal pressure wax oil, decompressed wax oil, deasphalted oil
At least one of.
13. according to the method described in claim 1, wherein, the boiling range of first light naphthar and second light naphthar
Range is 65~135 DEG C.
14. according to the method described in claim 1, wherein, the boiling range of first heavy naphtha and second heavy naphtha
Range is 130~175 DEG C, and the boiling range range of recycle oil is 175~450 DEG C.
15. according to the method described in claim 1, wherein, the first reactor and the third reactor are that riser is anti-
Answer device；The second reactor is fluidized-bed reactor.
16. a kind of system for low-carbon olefines high-output, the system include:
Fixed bed hydrogenation cracking reaction area, for wax oil raw material to be carried out hydrocracking reaction；
First Disengagement zone is divided the reaction effluent in fixed bed hydrogenation cracking reaction area in first Disengagement zone
From, obtain the first light naphthar, the first heavy naphtha, diesel oil distillate and add hydrogen wax oil fraction；
Catalytic cracking reaction area, the catalytic cracking reaction area include first reactor, second reactor and third reactor, are come
Hydrogen wax oil fraction is added to carry out by adding hydrogen wax oil fraction line to be introduced in the first reactor from first Disengagement zone
Catalytic cracking reaction, and the material in the first reactor is introduced to the second reactor by first reactor pipeline
Middle carry out catalytic cracking reaction, and the first light naphthar from first Disengagement zone are drawn by the first light naphthar pipeline
Enter in the third reactor and carries out catalytic cracking reaction；
Second Disengagement zone, the catalytic pyrolysis product from the second reactor and the third reactor are produced by catalytic pyrolysis
Property management line is introduced in second Disengagement zone and is separated, obtain low-carbon alkene, the second light naphthar, the second heavy naphtha,
Recycle oil and catalytic cracking slurry oil, and pass through the second light naphthar pipeline and recycle oil pipeline respectively for second Disengagement zone
The second light naphthar and recycle oil obtained is recycled to the third reactor and fixed bed hydrogenation cracking reaction area respectively.
17. system according to claim 16, wherein contain the first heavy naphtha pipeline and bavin in first Disengagement zone
Oil distillate pipeline, first heavy naphtha and the diesel oil distillate pass through the first heavy naphtha pipeline and the bavin respectively
Oil distillate pipeline is led to outside system.
18. system according to claim 16 or 17, wherein contain the second heavy naphtha pipeline in second Disengagement zone
Second heavy naphtha and catalytic cracking slurry oil obtained with catalytic cracking slurry oil pipeline, second Disengagement zone passes through respectively
The second heavy naphtha pipeline and the catalytic cracking slurry oil pipeline are led to outside system.
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| CN115784830A (en) * | 2021-09-10 | 2023-03-14 | 北京石油化工工程有限公司 | Coupling process method and coupling process system for improving yield of low-carbon olefins |
| CN116554927A (en) * | 2022-01-28 | 2023-08-08 | 中国石油化工股份有限公司 | Method and system for producing low-carbon olefin and aromatic hydrocarbon by heavy oil |
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| CN101210198A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Hydrogenation method for producing high grade diesel oil and high grade reforming raw material |
| CN101747935A (en) * | 2008-12-18 | 2010-06-23 | 中国石油化工股份有限公司 | Method for producing light olefins and monocyclic aromatic hydrocarbons from heavy hydrocarbons |
| CN103059990A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Efficient catalytic conversion method for petroleum hydrocarbon |
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| CN101210198A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Hydrogenation method for producing high grade diesel oil and high grade reforming raw material |
| CN101747935A (en) * | 2008-12-18 | 2010-06-23 | 中国石油化工股份有限公司 | Method for producing light olefins and monocyclic aromatic hydrocarbons from heavy hydrocarbons |
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| CN115784830A (en) * | 2021-09-10 | 2023-03-14 | 北京石油化工工程有限公司 | Coupling process method and coupling process system for improving yield of low-carbon olefins |
| CN116554927A (en) * | 2022-01-28 | 2023-08-08 | 中国石油化工股份有限公司 | Method and system for producing low-carbon olefin and aromatic hydrocarbon by heavy oil |
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