CN108329944A - Utilize the method for catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products - Google Patents
Utilize the method for catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products Download PDFInfo
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- 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
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
-
- 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
-
- 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
-
- 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
- C10G2400/02—Gasoline
-
- 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
-
- 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
- C10G2400/30—Aromatics
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a kind of method using catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products.The method of the present invention includes following steps：Pre-add hydrogen is carried out to catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking gasoline；Pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat；Centering fraction carries out solvent extraction, obtains the raffinate oil rich in alkene and the extraction oil rich in aromatic hydrocarbons；At least partly light fraction and/or at least partly raffinate oil are carried out to mitigate aromatisation or catalytic pyrolysis, obtain chemical products；Light olefin recycling is carried out to extraction oil, obtains light olefin and sulfur-rich oil；At least partly light olefin it will be back to and carry out carrying out backwash in solvent-extracted system；Selective hydrodesulfurization is carried out to heavy distillat and sulfur-rich oil, obtains desulfurization heavy distillat.The low alkene gasoline component of desulfurization that catalytically cracked gasoline can be efficiently converted to the chemical products of high value, while be capable of coproduction high quality by the method for the present invention.
Description
Technical field
The invention belongs to technical field of petrochemical industry, and in particular to a kind of to utilize the low alkene vapour of catalytically cracked gasoline coproduction desulfurization
The method of oil and chemical products.
Background technology
Increasingly exacerbation with the heaviness increasingly and motor vehicle exhaust emission of petroleum resources to atmosphere environment impact, in the world
Requirement in range to motor petrol quality is further harsh.The automobile-used vapour of state VI that China will come into effect on January 1st, 2019
Oil ga(u)ge alignment request content of sulfur in gasoline is less than 10ppm, and olefin(e) centent is less than 15v%, and octane number maintains 93 or more.Therefore, it produces
The mark of premium-type gasoline is to improve octane number in the case of sulfur content and olefin(e) centent while reduction.
Currently, for the production of low-sulfur, low alkene, high-knock rating gasoline, developed country is mainly by producing kinds of processes
Gasoline allocated to reach corresponding quality standard；In general, the catalytically cracked gasoline of general olefin-containing account for about 1/3 hereinafter,
Reformed Gasoline containing aromatic hydrocarbons but non-olefin-containing accounts for about 1/3 or more, other neither olefin-containings aromatic free alkylation, isomery again
The clean gasolines components such as change, etherificate account for about 1/3, and the sulfur content and olefin(e) centent of above-mentioned formulated gasolines are low, and octane number is high.
Catalytically cracked gasoline (i.e. FCC gasoline) is the chief component of China's motor petrol, and 75% is accounted in gasoline pool
Left and right.Catalytically cracked gasoline has the characteristics that high alkene (30-45v%), high sulfur content (150-1000ppm).It is reported that China quotient
The alkene of the sulphur of 85-95wt% and 95v% come from catalytically cracked gasoline in product gasoline, are that China's motor petrol is caused to be difficult to
Meet the main reason for sulfur content is less than 15-18v% less than 10ppm, olefin(e) centent.
China depends on hydrodesulfurization technology for the processing of catalytically cracked gasoline, which disclosure satisfy that sulfur content
Less than the requirement of 10ppm and reduction alkene, however olefin(e) centent is reduced in a manner of adding hydrogen to be saturated as alkane, to cause
The reduction of gasoline products octane number cannot not only meet the target that desulfurization drop alkene protects octane number, seriously affect enterprise in addition
Economic benefit.
In hydrodesulfurization, can not have by modes such as the catalyst of optimization hydrodesulfurization or process conditions
Effect inhibits loss of octane number caused by due to alkene is saturated, and olefin component is avoided to enter hydrodesulfurizationunit unit from hydrogenating materials,
It is the basic method for protecting alkene.Currently, correlative study both domestic and external is concentrated mainly on the distillation cutting of FCC gasoline and to height
The hydrotreating of sulphur component can not be converted into height although which can avoid high octane olefins from being hydrogenated saturation
The aromatic hydrocarbons of octane number.
Meanwhile the market demand pole of the chemical products such as ethylene, propylene and benzene, toluene and dimethylbenzene (referred to as BTX)
Greatly.Wherein, ethylene and propylene are very important organic chemical industry's base stock, and ethylene is mainly for the production of polyethylene, the third rubber of second
Glue, polyvinyl chloride etc., propylene can be used for generating synthetic resin, synthetic rubber and a variety of fine chemicals etc.；BTX can directly make
For Chemical Manufacture raw material, there is great market value.However, existing research is mainly to produce based on gasoline blend component,
The various chemical products of market in urgent need can not be converted into.
Therefore, how the production of high-knock rating gasoline fraction and the preparation of large chemical products to be efficiently combined,
As urgent problem to be solved.
Invention content
The present invention provides a kind of method using catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products, this method
The low alkene vapour of desulfurization that catalytically cracked gasoline can be efficiently converted to the chemical products of high value, while capableing of coproduction high quality
Oil ingredient.
The present invention provides a kind of method using catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products, including such as
Lower step：
Pre-add hydrogen is carried out to catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking gasoline；
The pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat；
Solvent extraction is carried out to the middle fraction, obtains the raffinate oil rich in alkene and the extraction oil rich in aromatic hydrocarbons；
At least partly described light fraction and/or at least partly described raffinate oil are carried out to mitigate aromatisation or catalytic pyrolysis,
Obtain chemical products；
Light olefin recycling is carried out to the extraction oil, obtains light olefin and sulfur-rich oil；
At least partly described light olefin is back to and carries out carrying out backwash in the solvent-extracted system；
Selective hydrodesulfurization is carried out to the heavy distillat and sulfur-rich oil, obtains desulfurization heavy distillat.
The present invention does not limit catalytically cracked gasoline (i.e. FCC gasoline) strictly, can be that the conventional catalysis of the present invention is split
Change gasoline.In the present invention, unless otherwise specified, pressure refers to that gauge pressure, content refer to mass content.
The present invention carries out pre-add hydrogen to catalytically cracked gasoline, is used for the trechmannite compound and alkadienes in catalytically cracked gasoline
Effect forms high boiling sulfide, situations such as to avoid alkadienes from generating coking during subsequent technique, to ensure
The longtime running of heavy fractioning hydrogenation desulfurization；During pre-add hydrogen, the alkene in catalytically cracked gasoline is not saturated.
The present invention does not limit pre- hydrogenation technique strictly, for example, may be used this field routine alkali-free sweetening technique or
The pre- hydrogenation techniques of Prime-G+.
In the concrete scheme of the present invention, the pre-add hydrogen is carried out in the presence of catalyst for pre-hydrogenation；Wherein, pre-add hydrogen is urged
Agent is Ni-Mo/Al2O3(nickel molybdenum bimetallic catalyst), composition for example can be (mass content %)：Al2O3(carrier)
90.5%, Ni 6%, Mo 3.5%；Pre- hydrogenation process conditions can be：Hydrogen partial pressure is 2.2MPa, volume space velocity 3.0h-1, hydrogen
Oil volume ratio is 10: 1, and reaction temperature is 110 DEG C.
In the present invention, the cutting be pre- hydrogenation catalyst cracking gasoline is cut into from low to high according to boiling range it is light, in,
Weigh three fractions；This field conventional method may be used and carry out the cutting, such as distillation cutting may be used etc..
In the concrete scheme of the present invention, the cutting temperature of the light fraction and middle fraction is 35-65 DEG C, further for
50-60℃；The middle fraction and the cutting temperature of heavy distillat are 100-160 DEG C.At this point, the boiling range of middle fraction be 35-65 DEG C extremely
100-160℃。
In the present invention, chemical products include BTX (including benzene, toluene and dimethylbenzene), ethylene, propylene etc.；Wherein, it mitigates
Aromatisation can produce BTX, and catalytic pyrolysis can produce ethylene, propylene.Furthermore, it is possible to carry out technique tune according to actual needs
It is whole；If chemical products need to be produced maximumlly, can all light fractions and whole raffinate oil be subjected to mitigation aromatization
Change or catalytic pyrolysis；It, can be by all light fractions and whole raffinates if the low alkene gasoline of desulfurization need to be produced maximumlly
Oil is reconciled with desulfurization heavy distillat；If the chemical products that need to get both and the low alkene gasoline of desulfurization, optionally described to part can gently evaporate
Divide and/or the part raffinate oil carries out mitigating aromatisation or catalytic pyrolysis.Further, it is also possible to optionally be carried out to part BTX
It reconciles.
In the concrete scheme of the present invention, mitigation aromatization is carried out to a part of light fraction and a part of raffinate oil
Change or catalytic pyrolysis, and raffinate oil described in light fraction described in another part and another part and the desulfurization heavy distillat are carried out
It reconciles, forms the low alkene gasoline of desulfurization；Wherein, it carries out mitigating the part of aromatisation or catalytic pyrolysis in light fraction and is reconciled
Partial volume ratio is (0.5-4)：1, carry out mitigating the part of aromatisation or catalytic pyrolysis and the portion reconciled in raffinate oil
The volume ratio divided is (0.5-3)：1.The solvent-extracted system is carried out in addition, can also optionally be back to part light fraction
Middle carry out backwash.
It is possible to further which the part light olefin to be back to carry out instead in the solvent-extracted system
It washes, while light olefin described in another part is carried out to mitigate aromatisation or catalytic pyrolysis；Wherein, to coming back for the solvent
The amount of the light olefin of extraction does not limit strictly, comes back for the amount of the solvent-extracted light olefin and can account for and recycle
The 20-100% (volume content, 100% is all to come back for the solvent extraction) of the amount of the light olefin arrived, further
Can be 40-60%.
In the present invention, solvent extraction mainly utilizes aromatic hydrocarbons and alkene, alkane and cycloalkane in fraction in solvent realization
Directional separation；The present invention does not limit solvent used by solvent extraction strictly, as long as above-mentioned directional separation can be realized
, such as diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, dimethyl sulfoxide, sulfolane, N- N-formyl morpholine Ns, N- crassitudes may be used
The double solvents that a kind of solvent or two or more combinations in ketone, polyethylene glycol, propene carbonate etc. are formed.In particular, above-mentioned
The water content of solvent preferred by weight percentage ＜ 1.0%, further preferably 0.5-0.8%.
In the concrete scheme of the present invention, solvent extraction is carried out using the double solvents of sulfolane and N-Methyl pyrrolidone
(i.e. using the double solvents as solvent), wherein volume content of the N-Methyl pyrrolidone in the double solvents are 5-
40%, it is further 5-20%.
Research shows that：When carrying out solvent extraction using above-mentioned double solvents, the alkene mass content in raffinate oil is 40-
45%, the aromatics quality content in extraction oil is 60-70%；And when sulfolane being used to carry out solvent extraction, the alkene in raffinate oil
Hydrocarbon mass content is 35-40%, and the aromatics quality content in extraction oil is 50-55%.It is indicated above that the present invention's is above-mentioned compound
The high selectivity of solvent, when carrying out solvent extraction using the double solvents, the alkene mass content in raffinate oil increases by 5 percentages
Point or so, the aromatics quality content in extraction oil increases 10-15 percentage points or so, to be conducive to aromatic hydrocarbons and alkene in middle fraction
The directional separation of hydrocarbon.
In the present invention, the usual manner that this field may be used carries out solvent extraction；Specifically, the solvent extraction can
To include：
The middle fraction is set to enter from extraction tower middle and lower part, solvent enters from extraction tower top, controls the tower top of extraction tower
Temperature is 50-105 DEG C, and column bottom temperature is 35-80 DEG C, and tower top pressure (absolute pressure) is 0.2-0.8MPa, solvent and middle fraction
Charge ratio be 1.0-5.0.
Further, the tower top temperature of extraction tower is preferably 50-70 DEG C, and tower top pressure (absolute pressure) is preferably 0.5-
The charge ratio of 0.6MPa, solvent and middle fraction are preferably controlled in 2.0-3.0.
In the present invention, it is the aromatisation that (low temperature, normal pressure) carries out under conditions of opposite mitigation to mitigate aromatisation, mainly
For converting alkene to aromatic hydrocarbons.
Specifically, mitigation aromatisation of the invention can carry out in the presence of aromatized catalyst；The Aromatizatian catalytic
Agent is obtained by carrier loaded active constituent.Further, the carrier of the aromatized catalyst include zeolite molecular sieve and
Boehmite, active constituent include first composition, second composition, third ingredient and the 4th ingredient, and the first composition is Na
Or K, the second composition are P, the third ingredient is Zn, and the 4th ingredient is La, and the load capacity of first composition is
The load capacity of 0.2-0.5%, second composition are 1-3%, and ternary load capacity is 5-8%, and the load capacity of the 4th ingredient is
0-3%.
Further, the mass ratio of zeolite molecular sieve and boehmite can be in the carrier of the aromatized catalyst
(1-9)：1；Wherein, zeolite molecular sieve is such as can be HZSM-5 molecular sieves.In addition, the load capacity of the 4th ingredient is further
1.5-3%.
In the present invention, the preparation method of above-mentioned aromatized catalyst, including following sequence carry out step：
Zeolite molecular sieve is mixed with boehmite, obtains catalyst precarsor；
Ion-exchanged is carried out to the catalyst precarsor, first composition is made to be supported on catalyst precarsor；
First modification is carried out to the catalyst precarsor, second composition or the 4th ingredient is made to be supported on catalyst precarsor
On；
Reactive metal modified is carried out to the catalyst precarsor, third ingredient is made to be supported on catalyst precarsor；
Second modification is carried out to the catalyst precarsor, second composition is made to be supported on catalyst precarsor.
Further, the ion-exchanged may include：
Using the salting liquid or aqueous slkali for containing sodium ion or potassium ion as ion exchanged soln, before the catalyst
Body implements ion-exchanged, and control ion-exchanged continues at least 30 minutes at 60-120 DEG C, then at 60-280 DEG C
Lower drying at least 3 hours finally roasts at 450-700 DEG C at least 1 hour.
The first modification of the present invention couple, reactive metal modified, the mode of the second modification do not limit strictly, can be with
Using the conventional method of this field, such as equi-volume impregnating etc.；In addition, modified condition can be the normal condition of this field.
In the present invention, it is 280-330 DEG C that can control the temperature for mitigating aromatisation, and pressure is normal pressure, and volume is empty
Speed is 1.0-2.0h-1.It mitigates aromatisation and fixed bed reactors progress may be used, it in addition can be under conditions of facing hydrogen with non-hydrogen
It carries out；It is preferred that being carried out under conditions of non-hydrogen.
The above-mentioned mitigation aromatisation of the present invention is easily achieved using above-mentioned aromatized catalyst and aromatization conditions, to
Alkene is set to be converted into aromatic hydrocarbons.
The mitigation aromatisation of the present invention is carried out using above-mentioned aromatized catalyst, which has high aromatisation
Activity can make aromatization at the temperature (especially not greater than 330 DEG C) and the temperate condition of normal pressure not higher than 400 DEG C
Carry out, and alkene select it is higher to the selectivity for being converted into aromatic hydrocarbons, selectivity ensure liquid yield be higher than 98.5% the case where
Under can reach 60% or more, and the aromatic hydrocarbons generated has reached 90% or so, while the production rate of benzene based on C7-C9 aromatic hydrocarbons
It is relatively low；In addition, the aromatized catalyst has good carbon accumulation resisting ability, therefore there is longer service life and stability,
Its one way activity is 8-10 days (olefin conversion maintains 50% or more activity) and liquid yield maintains 98.5% or more, from
And it effectively prevents oil product and loses and long-period stable operation can be kept.
The mitigation aromatisation of the present invention can not only effectively be such that the olefin(e) centent in aromatization products significantly reduces, aromatic hydrocarbons
Content, especially C7-C9 arene contents significantly improve and benzene content is relatively low, have reached low alkene, high-octane rating and low benzene content
Effect, to be conducive to obtain the high-quality gasoline for meeting state's VI standards, while also helping saving energy consumption, have it is non-
Often good industry amplification adaptability, can veritably be used in actual industrial production.
In the present invention, fluidized reactor progress may be used in catalytic pyrolysis；In addition, catalytic pyrolysis can be in catalytic pyrolysis
Carried out in the presence of catalyst, catalytic cracking catalyst includes ZSM-5 molecular sieve and RE-USY molecular sieves, and ZSM-5 molecular sieve with
The mass ratio of RE-USY molecular sieves is (1-3)：1；Temperature it is possible to further control the catalytic pyrolysis is 600-700 DEG C,
The mass ratio of water and raw material is (0.5-2)：1, the mass ratio of the catalytic cracking catalyst and raw material is 1：(2-5).
In the present invention, usual manner may be used, light olefin (referred to as light alkene) recycling is carried out to extraction oil；Wherein, it returns
The light olefin of receipts includes mainly C5 alkene.
Specifically, the light olefin recycling can be carried out in recovery tower, wherein the tower top temperature of recovery tower can be controlled
Degree is 80-95 DEG C, tower top pressure 0.05-0.2MPa, and column bottom temperature is 150-180 DEG C, tower bottom pressure 0.05-0.2MPa.
In the present invention, at least partly described light olefin is back to and carried out instead in the solvent-extracted system
It washes and (is stripped), for making macromolecular alkene from displacement to raffinate oil in extraction oil, to be flowed out from extraction tower tower top.Tool
Body, the light olefin can enter from the lower part of extraction tower.At this point, middle fraction carries out multistage with solvent in extraction tower epimere
After counter current contacting, raffinate oil (fraction in desulfurization) is flowed out from tower top；Meanwhile the light olefin of recycling is contacted with solvent in bottom of tower,
It to be replaced macromolecular alkene into raffinate oil from extraction oil, and then flows out, and contains from tower top together with fraction in desulfurization
There is the sulfur-rich oil (i.e. sulfur-rich middle fraction) of sulfide, aromatic hydrocarbons, cycloolefin to be flowed out from bottom of tower.
Research shows that：In solvent extraction process, the smaller then solvent of homologous series of hydrocarbon carbon number is higher to its solubility, and carbon number is bigger
Then opposite (i.e. low-carbon alkene has the solubility of bigger in a solvent)；Light olefin is back to solvent extraction by the present invention
In be stripped, higher olefins separation displacement can be made in raffinate oil, to obtain the higher raffinate oil of olefin(e) centent and
The higher extraction oil of arene content significantly improves separating effect of the solvent to alkene and aromatic hydrocarbons.
The result shows that：After carrying out backwash using light olefin, the mass content of alkene is 45-50% in raffinate oil；Not
When carrying out backwash using light olefin, the mass content of alkene is 40-45% in raffinate oil.Backwash is carried out using light olefin,
The mass content of alkene in raffinate oil can be made to improve 5 percentage points or so, the separating effect of alkene and aromatic hydrocarbons further obtains
It improves.
In the present invention, conventional achievable mode in the prior art may be used and carry out selective hydrodesulfurization, such as
S-zorb, RSDS, OCT-M, Prime-G may be used+, the selective desulfurizations technology such as CODS and other selective deep desulfuration skills
Any one of art or two or more combinations.
In the concrete scheme of the present invention, it is de- that the selective hydrogenation is carried out in the presence of catalyst for selectively hydrodesulfurizing
Sulphur, the present invention do not make considered critical to catalyst for selectively hydrodesulfurizing, can be the catalyst of this field routine, such as disclose
Number for the catalyst etc. disclosed in the Chinese patent of CN104673376A.
Specifically, the catalyst for selectively hydrodesulfurizing can be obtained by carrier loaded active metal components；Wherein, institute
It can be molecular sieve (such as X-type, Y types or ZSM-5 types) or metal oxide (such as alundum (Al2O3)), the activity to state carrier
Metal may include Co and Mo, and the gross mass content of Co and Mo in catalyst for selectively hydrodesulfurizing can be 5-20%.More
Further, the mass ratio of the Co and Mo of supported on carriers can be (0.2-0.8)：1.
In the present invention, the selective hydrodesulfurization can carry out in fixed bed reactors.Further, the choosing
The temperature of selecting property hydrodesulfurization is 200-305 DEG C, pressure 1.5-3.0MPa, volume space velocity 1-5h-1, hydrogen to oil volume ratio is
300-600.The desulfurization heavy distillat obtained through above-mentioned selective hydrodesulfurization, sulfur content are 10ppm hereinafter, gasoline tune can be used as
It is used with component.
Since sulfide, aromatic hydrocarbons, cycloolefin are the main components for constituting sulfur-rich oil, in chosen property hydrodesulfurization,
Sulfide is decomposed removing, and aromatic hydrocarbons is not involved in reaction, and cycloolefin adds hydrogen saturation that can improve octane number, therefore octane number does not lose.
The present invention is by forming distribution to Sulfur Content in Catalytic Cracking Gasoline, olefin(e) centent and arene content isofamily and narrow evaporating
The research of point octane Distribution value, by the catalytically cracked gasoline through pre-add hydrogen be divided into it is light, in, weigh three fractions, for each fraction
Impurity content distribution and octane Distribution value concrete condition, catalytically cracked gasoline is carried out using specific processing mode comprehensive
Quality upgrading and product restructuring, not only realize deep desulfuration, the gasoline fraction sulfur content that makes that treated drops to small
Be down to 18v% hereinafter, the octane number of gasoline products also greatly improved in 10ppm, while by olefin(e) centent, realize sulfur reduction,
Drop alkene puies forward high-octane target；In addition, the high price such as method also by-product benzene,toluene,xylene, ethylene and propylene of the present invention
The chemical products of value, have a good application prospect.
Description of the drawings
Fig. 1 is the work using catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products of an embodiment of the present invention
Skill flow chart；
Fig. 2 is that the present invention another embodiment utilizes the low alkene gasoline of catalytically cracked gasoline coproduction desulfurization and chemical products
Process flow chart.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, the attached drawing below in conjunction with the present invention and implementation
Example, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention
A part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
The every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
Embodiment 1
1, aromatized catalyst is prepared
1) catalyst precarsor is prepared
Under room temperature environment, by silica alumina ratio be 25, nano level HZSM-5 molecular sieves and boehmite are according to 4：1 ratio
Example physical mixed is uniform, obtains catalyst precarsor.
2) ion-exchanged
Using thermostatic water-bath method to catalyst precarsor carry out ion-exchange treatment, specifically by sodium hydroxide be dissolved in from
In sub- water, and mixes with catalyst precarsor and to be placed on 90 DEG C of water baths and stir 2 hours, it is about 0.2wt% to make the load capacity of sodium,
Then it dries 8 hours or so at about 120 DEG C, roasted 4 hours or so at about 540 DEG C successively.
3) the first modification
Using equi-volume impregnating, the first modification is carried out to the catalyst precarsor through ion-exchange treatment, specifically
Ammonium dihydrogen phosphate is dissolved in deionized water, then catalyst precarsor is impregnated, control the aqueous solution of ammonium dihydrogen phosphate with
The mass ratio of catalyst precarsor is (1.0 ± 0.2)：1, it is 1wt% or so to make the load capacity of phosphorus；After the completion of dipping, successively 20
DEG C or so at a temperature of be aged at 6 hours or so, about 120 DEG C it is 8 hours or so, about 540 DEG C dry at roast 4 hours or so.
4) reactive metal modified
The catalyst precarsor of the first modification will be implemented at a temperature of 300 DEG C or so, in 100% vapor atmosphere
About 6 hours of hydro-thermal process are carried out, equi-volume impregnating is then used, activity gold is carried out to the catalyst precarsor after hydro-thermal process
Belong to load：Zinc nitrate is dissolved in the citric acid solution that concentration is about 0.1mol/L, obtains maceration extract；Control maceration extract and catalysis
Mass ratio between agent precursor is (1.0 ± 0.2)：1, dipping temperature is about 20 DEG C, dip time is about 10 hours, makes the negative of zinc
Carrying capacity is about 5wt%；After the completion of dipping, about 120 DEG C of dryings 10 hours through being aged 4 hours at about 25 DEG C, under air atmosphere successively
Roasting or so 4 hours at left and right and 540 DEG C.
5) the second modification
Using equi-volume impregnating, the catalyst precarsor to implementing active metal load carries out the second modification, tool
Body technology obtains aromatized catalyst with reference to step 3).
Above-mentioned aromatized catalyst includes zeolite molecular sieve (HZSM-5 molecular sieves) and boehmite, wherein zeolite molecules
The mass ratio of sieve and boehmite is 4：1；Active constituent includes Na, P and Zn, and the wherein load capacity of Na is 0.2wt%, P's
Load capacity is 2wt%, and the load capacity of Zn is 5wt%.
2, aromatisation experiment is mitigated
The C 5 fraction stage catalytic cracking gasoline (race, which form, is shown in Table 1) produced using North China petrochemical industry by catalytic cracking is as former
Material carries out mitigation aromatisation experiment using above-mentioned aromatized catalyst under conditions of non-hydrogen.
In the presence of aromatized catalyst, mitigation aromatization is carried out to above-mentioned C 5 fraction stage catalytic cracking gasoline in fixed bed
Change, wherein the temperature that control mitigates aromatisation is 290 DEG C, pressure is normal pressure, volume space velocity 1.5h-1；Mitigate aromatisation result
It is shown in Table 2.
1 C 5 fraction stage catalytic cracking gasoline family of table forms
2 C 5 fraction section of table mitigates aromatization products race composition
The result shows that：
Mitigation aromatisation is carried out to C 5 fraction stage catalytic cracking gasoline by the way of the present embodiment, liquid yield is
99.5%, olefin conversion 58%, arene content increases by 12%.
In addition, it is 8-10 days (alkene that above-mentioned aromatized catalyst, which has longer service life and stability, one way activity,
Hydrocarbon conversion rate maintains 50% or more activity) and liquid yield maintain 98.5% or more, can effectively avoid oil product loss simultaneously
And long-period stable operation can be kept.
Embodiment 2
1, aromatized catalyst is prepared
1) catalyst precarsor is prepared
Under room temperature environment, by silica alumina ratio be 25, nano level HZSM-5 molecular sieves and boehmite are according to 9：1 ratio
Example physical mixed is uniform, obtains catalyst precarsor.
2) ion-exchanged
Using thermostatic water-bath method to catalyst precarsor carry out ion-exchange treatment, specifically by sodium hydroxide be dissolved in from
In sub- water, and mixes with catalyst precarsor and to be placed on 90 DEG C of water baths and stir 2 hours, it is about 0.5wt% to make the load capacity of sodium,
Then it dries 8 hours or so at about 120 DEG C, roasted 4 hours or so at about 540 DEG C successively.
3) the first modification
Using equi-volume impregnating, the first modification is carried out to the catalyst precarsor through ion-exchange treatment, specifically
Lanthanum nitrate is dissolved in deionized water, then catalyst precarsor is impregnated, it is 2wt% to make the load capacity of lanthanum；23 DEG C of left sides
It is aged 6 hours or so at right temperature；Then 8 hours or so dry at about 120 DEG C, finally roasted at a temperature of 540 DEG C or so
It burns 8 hours or so.
4) reactive metal modified and the second modification
The catalyst precarsor for implementing the first modification is carried out at a temperature of 300 DEG C or so, in 100% vapor atmosphere
About 6 hours of hydro-thermal process.
Using equi-volume impregnating, the catalyst precarsor after hydro-thermal process is carried out at active metal load and the second modification
Reason：Ammonium dihydrogen phosphate and zinc nitrate are all dissolved in the citric acid solution that concentration is about 0.1mol/L, obtain maceration extract；Control
Mass ratio between maceration extract and catalyst precarsor is (1.0 ± 0.2)：1, dipping temperature is about 30 DEG C, dip time is about 15
Hour, make the load capacity of phosphorus be about 1wt%, the load capacity of zinc is about 8wt%；After the completion of dipping, successively through being aged 6 at about 28 DEG C
Or so 4 hours of roasting at about 120 DEG C of dryings 8 hours or so and 540 DEG C, obtain aromatized catalyst under hour, air atmosphere.
Above-mentioned aromatized catalyst includes zeolite molecular sieve (HZSM-5 molecular sieves) and boehmite, wherein zeolite point
The mass ratio of son sieve and boehmite is 9：1；Active constituent includes Na, La, Zn and P, and the wherein load capacity of Na is
The load capacity of 0.5wt%, La are 2wt%, and the load capacity of Zn is 8wt%, and the load capacity of P is 1wt%.
2, aromatisation experiment is mitigated
The C6/7 fraction sections catalytically cracked gasoline (race, which forms, is shown in Table 3) produced using North China petrochemical industry by catalytic cracking as
Raw material carries out mitigation aromatisation experiment using above-mentioned aromatized catalyst under conditions of non-hydrogen.
In the presence of aromatized catalyst, mitigation aromatization is carried out to above-mentioned C 5 fraction stage catalytic cracking gasoline in fixed bed
Change, wherein the temperature that control mitigates aromatisation is 310 DEG C, pressure is normal pressure, volume space velocity 1.0h-1；Mitigate aromatisation result
It is shown in Table 4.
3 C6/7 fraction section catalytically cracked gasolines race of table forms
4 C6/7 fraction sections of table mitigate aromatization products race composition
The result shows that：
Mitigation aromatisation is carried out to C6/7 fraction sections catalytically cracked gasoline by the way of the present embodiment, liquid yield is
99.5%.
In addition, it is 8-10 days (alkene that above-mentioned aromatized catalyst, which has longer service life and stability, one way activity,
Hydrocarbon conversion rate maintains 50% or more activity) and liquid yield maintain 98.5% or more, can effectively avoid oil product loss simultaneously
And long-period stable operation can be kept.
Embodiment 3
As shown in Figure 1, the method using catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products of the present embodiment,
Include the following steps：
1, pre-add hydrogen
The composition of the catalytically cracked gasoline raw material of the present embodiment is shown in Table 5.
The composition of 5 catalytically cracked gasoline raw material of table
In the presence of catalyst for pre-hydrogenation, pre-add hydrogen is carried out to above-mentioned catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking
Gasoline；Wherein, catalyst for pre-hydrogenation Ni-Mo/Al2O3, consisting of (mass content %)：Al2O390.5%, Ni 6%,
Mo 3.5%；Pre- hydrogenation process conditions are：Hydrogen partial pressure is 2.2MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10: 1, instead
It is 110 DEG C to answer temperature.
After above-mentioned pre-add hydrogen, the trechmannite compound in catalytically cracked gasoline acts on forming high boiling vulcanization with alkadienes
Object, alkene are not saturated.
2, it cuts
Above-mentioned pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat, wherein gently, middle fraction cuts
It is 60 DEG C to cut temperature, in, the cutting temperature of heavy distillat be 130 DEG C, i.e.,：The boiling range of middle fraction is 60 DEG C to 130 DEG C.
3, solvent extraction
Solvent used by solvent extraction is the mixed solvent of sulfolane and N-Methyl pyrrolidone, wherein N- methylpyrroles
Alkanone is 10% in the volume content of in the mixed solvent.
Make among the above fraction from extraction tower middle and lower part enter, above-mentioned mixed solvent from extraction tower top enter, wherein controlling
The tower top temperature of extraction tower is 70 DEG C, and column bottom temperature is 45 DEG C, and tower top pressure (gauge pressure) is 0.5MPa, mixed solvent and middle fraction
Charge ratio be 2.0, obtain rich in alkene raffinate oil and the extraction oil rich in aromatic hydrocarbons.
4, light olefin recycling and backwash
Extraction oil is sent into recovery tower and carries out light olefin recycling, wherein the tower top temperature of control recovery tower is 88 DEG C,
Tower top pressure is 0.07MPa, and column bottom temperature is 168 DEG C, and tower bottom pressure 0.095MPa obtains light olefin and sulfur-rich oil.
40% light olefin is back in extraction tower and carries out backwash, remaining light olefin and part light fraction and part
Raffinate oil carries out mitigation aromatisation.
5, aromatisation is mitigated
Using the aromatized catalyst of embodiment 1 under conditions of non-hydrogen to part light fraction, part raffinate oil and its
Remaining light olefin carries out mitigation aromatisation.
Specifically, mitigation aromatisation is carried out in the presence of the aromatized catalyst of embodiment 1, wherein control mitigates aromatisation
Temperature be 290 DEG C, pressure is normal pressure, volume space velocity 1.5h-1, the reaction time is about 200 hours, obtains aromatization products
BTX。
6, selective hydrodesulfurization
First use CoSO4Solution carries out incipient impregnation, washed, dry and roasting to type ZSM 5 molecular sieve (carrier)
Afterwards, then using (NH4)6Mo7O24.4H2The aqueous solution of O is to having impregnated CoSO4The type ZSM 5 molecular sieve of solution is soaked in equal volume
Catalyst for selectively hydrodesulfurizing is made after washed, dry and roasting in stain；After testing, selective hydrodesulfurization obtained is urged
Total specific surface of agent is 168m2/ g or so, total pore volume are 0.378mL/g or so, and load capacity of the Co on carrier is about
The load capacity of 7%, Mo on carrier is about 10%, and the mass ratio of the Co and Mo of supported on carriers are 0.7：1.
In the presence of above-mentioned catalyst for selectively hydrodesulfurizing, it is de- that selective hydrogenation is carried out to above-mentioned heavy distillat and sulfur-rich oil
Sulphur, the wherein temperature of control selections hydrodesulfurization are 260 DEG C, pressure 1.8MPa, volume space velocity 3.0h-1, hydrogen oil volume
It is 500 than (i.e. hydrogen volume and the ratio between heavy distillat and sulfur-rich oily total volume), obtains desulfurization heavy distillat.
7, oil product reconciles
Another part in above-mentioned light fraction, another part in raffinate oil and desulfurization heavy distillat are reconciled, wherein：
The volume ratio that the part and the part reconciled of mitigating aromatisation are carried out in light fraction is 1：1, it carries out in raffinate oil mitigating virtue
The volume ratio of the part of structure and the part reconciled is 2：1, obtain high-quality gasoline product；The group of aromatization products BTX
It is shown in Table 6 respectively at the composition of alkene gasoline low with desulfurization.
Embodiment 4
As shown in Figure 1, the method using catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products of the present embodiment,
Include the following steps：
1, pre-add hydrogen
The composition of the catalytically cracked gasoline raw material of the present embodiment is same as Example 3.
In the presence of catalyst for pre-hydrogenation, pre-add hydrogen is carried out to above-mentioned catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking
Gasoline；Wherein, catalyst for pre-hydrogenation Ni-Mo/Al2O3, consisting of (mass content %)：Al2O390.5%, Ni 6%,
Mo 3.5%；Pre- hydrogenation process conditions are：Hydrogen partial pressure is 2.2MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10: 1, instead
It is 110 DEG C to answer temperature.
After above-mentioned pre-add hydrogen, the trechmannite compound in catalytically cracked gasoline acts on forming high boiling vulcanization with alkadienes
Object, alkene are not saturated.
2, it cuts
Above-mentioned pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat, wherein gently, middle fraction cuts
It is 50 DEG C to cut temperature, in, the cutting temperature of heavy distillat be 130 DEG C, i.e.,：The boiling range of middle fraction is 50 DEG C to 130 DEG C.
3, solvent extraction
Solvent used by solvent extraction is the mixed solvent of sulfolane and N-Methyl pyrrolidone, wherein N- methylpyrroles
Alkanone is 5% in the volume content of in the mixed solvent.
Make among the above fraction from extraction tower middle and lower part enter, above-mentioned mixed solvent from extraction tower top enter, wherein controlling
The tower top temperature of extraction tower is 50 DEG C, and column bottom temperature is 35 DEG C, and tower top pressure (gauge pressure) is 0.6MPa, mixed solvent and middle fraction
Charge ratio be 3.0, obtain rich in alkene raffinate oil and the extraction oil rich in aromatic hydrocarbons.
4, light olefin recycling and backwash
Extraction oil is sent into recovery tower and carries out light olefin recycling, wherein the tower top temperature of control recovery tower is 80 DEG C,
Tower top pressure is 0.05MPa, and column bottom temperature is 150 DEG C, and tower bottom pressure 0.08MPa obtains light olefin and sulfur-rich oil.
50% light olefin is back in extraction tower and carries out backwash, remaining light olefin and part light fraction and part
Raffinate oil carries out mitigation aromatisation.
5, aromatisation is mitigated
Using the aromatized catalyst of embodiment 2 under conditions of non-hydrogen to part light fraction, part raffinate oil and its
Remaining light olefin carries out mitigation aromatisation.
Specifically, mitigation aromatisation is carried out in the presence of the aromatized catalyst of embodiment 2, wherein control mitigates aromatisation
Temperature be 290 DEG C, pressure is normal pressure, volume space velocity 1.5h-1, the reaction time is about 200 hours, obtains aromatization products
BTX。
6, selective hydrodesulfurization
Catalyst for selectively hydrodesulfurizing is prepared according to 3 method of embodiment, unlike, loads of the control Co on carrier
Amount is about that load capacity of 4%, the Mo on carrier is about 10%, and the mass ratio of the Co and Mo of supported on carriers are 0.4：1.
In the presence of above-mentioned catalyst for selectively hydrodesulfurizing, it is de- that selective hydrogenation is carried out to above-mentioned heavy distillat and sulfur-rich oil
Sulphur, the wherein temperature of control selections hydrodesulfurization are 300 DEG C, pressure 2.5MPa, volume space velocity 2.0h-1, hydrogen oil volume
It is 400 than (i.e. hydrogen volume and the ratio between heavy distillat and sulfur-rich oily total volume), obtains desulfurization heavy distillat.
7, oil product reconciles
Another part in above-mentioned light fraction, another part in raffinate oil and desulfurization heavy distillat are reconciled, wherein：
The volume ratio that the part and the part reconciled of mitigating aromatisation are carried out in light fraction is 2：1, it carries out in raffinate oil mitigating virtue
The volume ratio of the part of structure and the part reconciled is 1：1, obtain high-quality gasoline product；The group of aromatization products BTX
It is shown in Table 6 respectively at the composition of alkene gasoline low with desulfurization.
Embodiment 5
As shown in Fig. 2, the method using catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products of the present embodiment,
Include the following steps：
1, pre-add hydrogen
The composition of the catalytically cracked gasoline raw material of the present embodiment is same as Example 3.
In the presence of catalyst for pre-hydrogenation, pre-add hydrogen is carried out to above-mentioned catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking
Gasoline；Wherein, catalyst for pre-hydrogenation Ni-Mo/Al2O3, consisting of (mass content %)：Al2O390.5%, Ni 6%,
Mo 3.5%；Pre- hydrogenation process conditions are：Hydrogen partial pressure is 2.2MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10: 1, instead
It is 110 DEG C to answer temperature.
After above-mentioned pre-add hydrogen, the trechmannite compound in catalytically cracked gasoline acts on forming high boiling vulcanization with alkadienes
Object, alkene are not saturated.
2, it cuts
Above-mentioned pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat, wherein gently, middle fraction cuts
It is 50 DEG C to cut temperature, in, the cutting temperature of heavy distillat be 160 DEG C, i.e.,：The boiling range of middle fraction is 50 DEG C to 160 DEG C.
3, solvent extraction
Solvent used by solvent extraction is the mixed solvent of sulfolane and N-Methyl pyrrolidone, wherein N- methylpyrroles
Alkanone is 15% in the volume content of in the mixed solvent.
Make among the above fraction from extraction tower middle and lower part enter, above-mentioned mixed solvent from extraction tower top enter, wherein controlling
The tower top temperature of extraction tower is 105 DEG C, and column bottom temperature is 80 DEG C, and tower top pressure (gauge pressure) is 0.4MPa, and mixed solvent is evaporated in
The charge ratio divided is 3.0, obtains the raffinate oil rich in alkene and the extraction oil rich in aromatic hydrocarbons.
4, light olefin recycling and backwash
Extraction oil is sent into recovery tower and carries out light olefin recycling, wherein the tower top temperature of control recovery tower is 95 DEG C,
Tower top pressure is 0.08MPa, and column bottom temperature is 180 DEG C, and tower bottom pressure 0.09MPa obtains light olefin and sulfur-rich oil.
60% light olefin is back in extraction tower and carries out backwash, remaining light olefin and part light fraction and part
Raffinate oil carries out catalytic pyrolysis.
5, catalytic pyrolysis
To part light fraction, part raffinate oil and remaining light olefin, (part gently evaporates in the presence of catalytic cracking catalyst
Divide, part raffinate oil and remaining light olefin are the catalytic pyrolysis raw material constituted) carry out catalytic pyrolysis；Wherein, catalytic pyrolysis is urged
Agent is made of ZSM-5 molecular sieve and RE-USY molecular sieves, and the mass ratio of ZSM-5 molecular sieve and RE-USY molecular sieves is 2：1；
The temperature for controlling catalytic pyrolysis is 650 DEG C, and the mass ratio of water and raw material is 2：1, the mass ratio of catalytic cracking catalyst and raw material
It is 1：4, obtain catalytic pyrolysis product ethylene, propylene.
6, selective hydrodesulfurization
Selective hydrodesulfurization is carried out using the catalyst for selectively hydrodesulfurizing of embodiment 3.
In the presence of catalyst for selectively hydrodesulfurizing, selective hydrodesulfurization is carried out to above-mentioned heavy distillat and sulfur-rich oil,
Wherein the temperature of control selections hydrodesulfurization is 250 DEG C, pressure 2.0MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio
(i.e. hydrogen volume and the ratio between heavy distillat and sulfur-rich oily total volume) is 300, obtains desulfurization heavy distillat.
7, oil product reconciles
Another part in above-mentioned light fraction, another part in raffinate oil and desulfurization heavy distillat are reconciled, wherein：
The volume ratio of part and the part reconciled that catalytic pyrolysis is carried out in light fraction is 1：1, catalytic pyrolysis is carried out in raffinate oil
Part and the part reconciled volume ratio be 1：1, obtain high-quality gasoline product；The composition of catalytic pyrolysis product and de-
The composition of the low alkene gasoline of sulphur is shown in Table 6 respectively.
Embodiment 6
As shown in Fig. 2, the method using catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products of the present embodiment,
Include the following steps：
1, pre-add hydrogen
The composition of the catalytically cracked gasoline raw material of the present embodiment is same as Example 3.
In the presence of catalyst for pre-hydrogenation, pre-add hydrogen is carried out to above-mentioned catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking
Gasoline；Wherein, catalyst for pre-hydrogenation Ni-Mo/Al2O3, consisting of (mass content %)：Al2O390.5%, Ni 6%,
Mo 3.5%；Pre- hydrogenation process conditions are：Hydrogen partial pressure is 2.2MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10: 1, instead
It is 110 DEG C to answer temperature.
After above-mentioned pre-add hydrogen, the trechmannite compound in catalytically cracked gasoline acts on forming high boiling vulcanization with alkadienes
Object, alkene are not saturated.
2, it cuts
Above-mentioned pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat, wherein gently, middle fraction cuts
It is 60 DEG C to cut temperature, in, the cutting temperature of heavy distillat be 130 DEG C, i.e.,：The boiling range of middle fraction is 60 DEG C to 130 DEG C.
3, solvent extraction
Solvent used by solvent extraction is the mixed solvent of sulfolane and N-Methyl pyrrolidone, wherein N- methylpyrroles
Alkanone is 10% in the volume content of in the mixed solvent.
Make among the above fraction from extraction tower middle and lower part enter, above-mentioned double solvents from extraction tower top enter, wherein controlling
The tower top temperature of extraction tower is 80 DEG C, and column bottom temperature is 60 DEG C, and tower top pressure (gauge pressure) is 0.3MPa, double solvents and middle fraction
Charge ratio be 2.0, obtain rich in alkene raffinate oil and the extraction oil rich in aromatic hydrocarbons.
4, light olefin recycling and backwash
Extraction oil is sent into recovery tower and carries out light olefin recycling, wherein the tower top temperature of control recovery tower is 88 DEG C,
Tower top pressure is 0.07MPa, and column bottom temperature is 168 DEG C, and tower bottom pressure 0.095MPa obtains light olefin and sulfur-rich oil.
50% light olefin is back in extraction tower and carries out backwash, remaining light olefin and part light fraction and part
Raffinate oil carries out catalytic pyrolysis.
5, catalytic pyrolysis
To part light fraction, part raffinate oil and remaining light olefin, (part gently evaporates in the presence of catalytic cracking catalyst
Divide, part raffinate oil and remaining light olefin are the catalytic pyrolysis raw material constituted) carry out catalytic pyrolysis；Wherein, catalytic pyrolysis is urged
Agent is made of ZSM-5 molecular sieve and RE-USY molecular sieves, and the mass ratio of ZSM-5 molecular sieve and RE-USY molecular sieves is 3：1；
The temperature for controlling catalytic pyrolysis is 700 DEG C, and the mass ratio of water and raw material is 1：1, the mass ratio of raw material and catalytic cracking catalyst
It is 3：1, obtain catalytic pyrolysis product ethylene, propylene.
6, selective hydrodesulfurization
Selective hydrodesulfurization is carried out using the catalyst for selectively hydrodesulfurizing of embodiment 4.
In the presence of catalyst for selectively hydrodesulfurizing, selective hydrodesulfurization is carried out to above-mentioned heavy distillat and sulfur-rich oil,
Wherein the temperature of control selections hydrodesulfurization is 250 DEG C, pressure 2.0MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio
(i.e. hydrogen volume and the ratio between heavy distillat and sulfur-rich oily total volume) is 300, obtains desulfurization heavy distillat.
7, oil product reconciles
Another part in above-mentioned light fraction, another part in raffinate oil and desulfurization heavy distillat are reconciled, wherein：
The volume ratio of part and the part reconciled that catalytic pyrolysis is carried out in light fraction is 3：1, catalytic pyrolysis is carried out in raffinate oil
Part and the part reconciled volume ratio be 2：1, obtain high-quality gasoline product；The composition of catalytic pyrolysis product and de-
The composition of the low alkene gasoline of sulphur is shown in Table 6 respectively.
Reference examples 1
Except the mitigation aromatisation of this reference examples divided by conventional aromatisation alternate embodiment 3, remaining is same as Example 3.
Specifically, the preparation method for the aromatized catalyst that this reference examples uses, specific steps are substantially the same manner as Example 1, and difference exists
In：Ion-exchange treatment of the catalyst precarsor without step 2), direct implementation steps 3), step 4) and step 5).
Conventional aromatisation is carried out in the presence of above-mentioned aromatized catalyst, wherein the temperature of conventional aromatisation is 450 DEG C, pressure
Power is normal pressure, volume space velocity 1.0h-1, the reaction time is about 200 hours, obtains aromatization products.
It is computed, the liquid yield of above-mentioned routine aromatisation is 70% or so, and selectivity is 20% or so；One way activity is only
3-4 days (one way activity is the activity that olefin conversion is maintained at 50% or more).
The composition of 6 product system of table
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of method using catalytically cracked gasoline coproduction desulfurization low alkene gasoline and chemical products, which is characterized in that including such as
Lower step：
Pre-add hydrogen is carried out to catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking gasoline；
The pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat；
Solvent extraction is carried out to the middle fraction, obtains the raffinate oil rich in alkene and the extraction oil rich in aromatic hydrocarbons；
At least partly described light fraction and/or at least partly described raffinate oil are carried out to mitigate aromatisation or catalytic pyrolysis, obtained
Chemical products；
Light olefin recycling is carried out to the extraction oil, obtains light olefin and sulfur-rich oil；
At least partly described light olefin is back to and carries out carrying out backwash in the solvent-extracted system；
Selective hydrodesulfurization is carried out to the heavy distillat and sulfur-rich oil, obtains desulfurization heavy distillat.
2. according to the method described in claim 1, it is characterized in that, the cutting temperature of the light fraction and middle fraction is 35-65
DEG C, the cutting temperature of the middle fraction and heavy distillat is 100-160 DEG C.
3. according to the method described in claim 1, it is characterized in that, the solvent extraction uses sulfolane and N- crassitudes
The double solvents of ketone carries out, and wherein volume content of the N-Methyl pyrrolidone in the double solvents is 5-40%.
4. method according to claim 1 or 3, which is characterized in that the solvent extraction includes：
The middle fraction is set to enter from extraction tower middle and lower part, solvent enters from extraction tower top, controls the tower top temperature of extraction tower
It it is 50-105 DEG C, column bottom temperature is 35-80 DEG C, tower top pressure 0.2-0.8MPa, and the charge ratio of solvent and middle fraction is 1.0-
5.0。
5. according to the method described in claim 1, it is characterized in that, carrying out the mitigation aromatization in the presence of aromatized catalyst
Change, the carrier of the aromatized catalyst includes zeolite molecular sieve and boehmite, and active constituent includes first composition, second
Ingredient, third ingredient and the 4th ingredient, the first composition are Na or K, and the second composition is P, and the third ingredient is Zn,
4th ingredient is La, and the load capacity of first composition is 0.2-0.5%, and the load capacity of second composition is 1-3%, third at
The load capacity divided is 5-8%, and the load capacity of the 4th ingredient is 0-3%.
6. method according to claim 1 or 5, which is characterized in that the temperature that control mitigates aromatisation is 280-330 DEG C,
Pressure is normal pressure, volume space velocity 1.0-3.0h-1。
7. according to the method described in claim 1, being split it is characterized in that, carrying out the catalysis in the presence of catalytic cracking catalyst
Solution, wherein the catalytic cracking catalyst includes ZSM-5 molecular sieve and RE-USY molecular sieves, and ZSM-5 molecular sieve and RE-USY
The mass ratio of molecular sieve is (1-3)：1, the temperature for controlling the catalytic pyrolysis is 600-700 DEG C, and the mass ratio of water and raw material is
(0.5-2)：1, the mass ratio of the catalytic cracking catalyst and raw material is 1：(2-5).
8. according to the method described in claim 1, it is characterized in that, carry out the light olefin recycling in recovery tower, control
The tower top temperature of recovery tower is 80-95 DEG C, tower top pressure 0.05-0.2MPa, and column bottom temperature is 150-180 DEG C, tower bottom pressure
For 0.05-0.2MPa.
9. according to the method described in claim 1, it is characterized in that, described in being carried out in the presence of catalyst for selectively hydrodesulfurizing
Selective hydrodesulfurization, the catalyst for selectively hydrodesulfurizing are obtained by carrier loaded active metal components；Wherein, the load
Body is molecular sieve or metal oxide, and the active metal includes Co and Mo, and Co and Mo are in catalyst for selectively hydrodesulfurizing
In gross mass content be 5-20%.
10. according to the method described in claim 1, it is characterized in that, the temperature of the selective hydrodesulfurization is 200-305
DEG C, pressure 1.5-3.0MPa, volume space velocity 1-5h-1, hydrogen to oil volume ratio 300-600.
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