CN108485702A - The method for maximizing production aromatic hydrocarbons using catalytically cracked gasoline - Google Patents
The method for maximizing production aromatic hydrocarbons using catalytically cracked gasoline 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a kind of method maximizing production aromatic hydrocarbons using catalytically cracked gasoline.The method of the present invention, includes the following steps：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；Mitigation aromatisation is carried out to the light fraction and raffinate oil, obtains aromatization products；Light olefin recycling is carried out to the extraction oil, obtains light olefin and sulfur-rich oil；Selective hydrodesulfurization is carried out to the heavy distillat and sulfur-rich oil, obtains desulfurization heavy distillat；Aromatics Extractive Project or extracting rectifying are carried out to the aromatization products and desulfurization heavy distillat.The method of the present invention can maximumlly produce aromatic hydrocarbons while carrying out drop alkene, desulfurization to catalytically cracked gasoline and improving octane number processing.
Description
Technical field
The invention belongs to technical field of petrochemical industry, and in particular to a kind of to maximize production aromatic hydrocarbons using catalytically cracked gasoline
Method.
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 raw and benzene, toluene and dimethylbenzene (referred to as BTX)
Greatly, there can be great market value directly as Chemical Manufacture raw material.However, existing research is mainly to produce vapour
Based on oily blend component, the various chemical products of market in urgent need can not be converted into.Therefore, how to be dropped to gasoline stocks
The chemical products such as aromatic hydrocarbons are maximumlly produced while alkene, desulfurization, become urgent problem to be solved.
Invention content
The present invention provides a kind of method maximizing production aromatic hydrocarbons using catalytically cracked gasoline, and this method is to catalytic cracking
Gasoline can maximumlly produce aromatic hydrocarbons while carrying out drop alkene, desulfurization.
The present invention provides a kind of method maximizing production aromatic hydrocarbons using catalytically cracked gasoline, includes the following steps：
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；
Mitigation aromatisation is carried out to the light fraction and raffinate oil, obtains aromatization products；
Light olefin recycling is carried out to the extraction oil, obtains light olefin and sulfur-rich oil；
Selective hydrodesulfurization is carried out to the heavy distillat and sulfur-rich oil, obtains desulfurization heavy distillat；
Aromatics Extractive Project or extracting rectifying are carried out to the aromatization products and desulfurization heavy distillat.
In the present invention, to catalytically cracked gasoline carry out pre-add hydrogen, for by catalytically cracked gasoline trechmannite compound with
Alkadienes acts on forming high boiling sulfide, situations such as to avoid alkadienes from generating coking during subsequent technique；
During pre-add hydrogen, the alkene in catalytically cracked gasoline is not saturated.
The present invention does not limit pre- hydrogenation technique strictly, such as the Prime-G+ pre-add hydrogen of this field routine may be used
Technique.
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 can be the nickel molybdenum bimetallic catalyst of this field routine.Specifically, the composition of nickel molybdenum bimetallic catalyst for example can be with
For (mass content %)：Al2O3(carrier) 90.5%, nickel 6%, molybdenum 3.5%；Pre- hydrogenation process conditions are not limited strictly, example
The temperature that pre-add hydrogen can such as be controlled is 130 DEG C or so, and hydrogen-oil ratio is 5 or so, volume space velocity 3h-1Left and right.
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 40-60 DEG C, the middle fraction
Cutting temperature with heavy distillat is 100-160 DEG C；That is, the boiling range of middle fraction is 40-60 DEG C to 100-160 DEG C.
It has been investigated that the distribution of hydrocarbon in catalytically cracked gasoline has the characteristics that：1) light fraction mainly contains low-carbon
The alkene and alkane of (such as C5), the wherein mass content of alkene are more than 50%；2) fraction mainly contains the alkene of C6-C8 in,
Contain aromatic hydrocarbons, alkane etc. simultaneously, is the minimum part of octane number, RON (fraction is even below 70) below 80；3) double distilled
Divide the high-carbon aromatic hydrocarbons and polycyclic aromatic hydrocarbon for mainly containing C9 or more, olefin(e) centent is relatively low and the content of aromatic hydrocarbons and sulphur is higher；4) it urges
The octane Distribution value of change cracking gasoline narrow fraction is first significantly reduced to minimum point with the increase of carbon number or boiling range, then most of
Go up.
Based on the studies above as a result, the present invention method will distill cutting, solvent extraction, mitigate aromatisation, selectivity add
Hydrogen desulfurization and Aromatics Extractive Project or extracting rectifying are combined；Wherein, for the distribution of alkene, aromatic hydrocarbons and sulfide in middle fraction
Rule takes solvent-extracted method to realize the directional separation of alkene and aromatic hydrocarbons；Also, mitigating aromatisation can be by light fraction
It is efficiently converted into high-octane aromatic hydrocarbons with the alkene in raffinate oil；In addition, olefin(e) centent is relatively low in heavy distillat, it is carried out
Selective hydrodesulfurization loss of octane number is less；In particular, after selective hydrodesulfurization, according to aromatic hydrocarbons and other substances it
Between the difference of solubility or relative volatility, aromatic hydrocarbons is detached using Aromatics Extractive Project or extracting rectifying, realizes aromatic hydrocarbons
Efficient and directional separation, to obtain the chemical products such as BTX and ethylene raw/gasoline component.
In the present invention, ethylene raw/gasoline component refers to same component, can both be used as chemical products ethylogen
Material, can also be used as gasoline component, can be applied according to actual needs.
The present invention said combination mode, can maximumlly convert catalytically cracked gasoline to BTX (including benzene, toluene,
Dimethylbenzene), the chemical products of the high values such as ethylene raw, to overcome the changes such as BTX that can not prepare or get both in the prior art
The drawbacks such as chemical product realize the target that production aromatic hydrocarbons is maximized using catalytically cracked gasoline.
In the present invention, solvent extraction is mainly the orientation point for realizing aromatic hydrocarbons with alkene, alkane and cycloalkane using solvent
From to be conducive to a series of chemical products of subsequent production.The present invention does not limit solvent used by solvent extraction strictly, only
Want to realize above-mentioned directional separation, for example, may be used diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, dimethyl sulfoxide, sulfolane,
N- N-formyl morpholine Ns, N-Methyl pyrrolidone, polyethylene glycol, propene carbonate etc..
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 single solvent being used to carry out solvent extraction, extraction
Alkene mass content in excess oil is 35%-40%, and the aromatics quality content in extraction oil is 50%-55%.The present invention's is upper
The high selectivity for stating double solvents, when carrying out solvent extraction using the double solvents, the alkene mass content in raffinate oil increases by 5
Percentage point or so, the aromatics quality content in extraction oil increases 10-15 percentage points or so, fragrant in middle fraction to be conducive to
The directional separation of hydrocarbon and alkene.
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 55-100 DEG C, and column bottom temperature is 40-80 DEG C, and tower top pressure (gauge pressure) is 0.2-0.7MPa, solvent and middle fraction into
Material is 1.0-5.0 than (i.e. the input material volume ratio of mixed solvent and middle fraction).
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 the alkene in the light fraction and raffinate oil 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
The alkene in light fraction and raffinate oil 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, usual manner may be used, light olefin recycling is carried out to extraction oil；Wherein, the lightweight alkene of recycling
Hydrocarbon 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, a part of light olefin is come back for into the solvent extraction, i.e.,：It will be at least partly described
Light olefin, which is back to, to carry out carrying out backwash (back extraction) in the solvent-extracted system；Meanwhile to light described in another part
Matter alkene carries out the mitigation aromatisation, i.e.,：After light olefin described in another part is merged with the light fraction and raffinate oil
Carry out mitigation aromatisation.The present invention does not limit the amount for coming back for the solvent-extracted light olefin strictly, return into
The amount of the row solvent-extracted light olefin can account for the 40-60% (volume content) of the amount for the light olefin that recycling obtains.
Research is found：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, it can make in higher olefins separation displacement to raffinate oil, to obtain the higher raffinate oil of olefin(e) centent and arene content more
High extraction oil can improve the purity of output C5 alkene after repeatedly recycling repeatedly, both significantly improve solvent to alkene and virtue
The separating effect of hydrocarbon, simultaneously effective protects olefin component.
Research shows that：After light olefin is come back for solvent extraction, the mass content of alkene is 45%- in raffinate oil
50%；When without light olefin being come back for solvent extraction, the mass content of alkene is 40%-45% in raffinate oil.It will be light
Matter alkene comes back for solvent extraction, can make 5 percentage points or so of the mass content raising of alkene in raffinate oil, alkene and virtue
The separating effect of hydrocarbon is further enhanced.
In the present invention, conventional achievable mode in the prior art may be used and carry out selective hydrodesulfurization, such as
The selective desulfurizations such as S-zorb, RSDS, OCT-M, Prime-G+, CODS technology or other selective deep desulfuration skills may be used
Art.
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
The carrier of sulphur, the catalyst for selectively hydrodesulfurizing is selected from least one of molecular sieve and metal oxide, active constituent
Including Co and Mo, and the gross mass content of Co and Mo in catalyst for selectively hydrodesulfurizing is 5-20%；The selectivity adds
The temperature of hydrogen desulfurization is 200-300 DEG C, pressure 1.5-2.5MPa, volume space velocity 1-5h-1, hydrogen to oil volume ratio (i.e. hydrogen
Product and the ratio between heavy distillat and sulfur-rich oily total volume) it is 300-600.The desulfurization heavy distillat obtained through above-mentioned selective hydrodesulfurization,
Sulfur content is 10ppm or less.
In the present invention, Aromatics Extractive Project and extracting rectifying are used to detach the aromatic hydrocarbons in aromatization products and desulfurization heavy distillat；
When carrying out Aromatics Extractive Project and extracting rectifying to aromatization products and desulfurization heavy distillat, may be used identical with solvent extraction molten
Agent；It is preferred that carrying out extracting rectifying using the mixed solvent of sulfolane and N-Methyl pyrrolidone, wherein N-Methyl pyrrolidone exists
The volume content of in the mixed solvent can be 5-40%, to be conducive to the separation of aromatic hydrocarbons and alkene.
Specifically, the usual manner that this field may be used carries out Aromatics Extractive Project, such as Publication No. CN may be used
The method of 104694158A carries out.
In addition, extracting rectifying may include：Make the aromatization products and desulfurization heavy distillat from extractive distillation column top into
Enter, solvent enters from extractive distillation column lower part；Wherein, the theoretical cam curve of the extractive distillation column is 20-25, and bottom temperature is
140-160 DEG C, charge ratio (oil ratio, i.e. solvent volume and aromatization products of solvent and aromatization products and desulfurization heavy distillat
The ratio between with desulfurization heavy distillat total volume) it is 1.0-5.0, reflux ratio 0.1-4.0.
Extract it is possible to further be obtained to extracting rectifying carries out light olefin (including mainly C5 alkene) recycling,
And the light olefin that recycling obtains is come back for into the mitigation aromatisation or comes back for the extracting rectifying；Specifically, exist
When light olefin is come back for the mitigation aromatisation, the yield of BTX can improve 2-4 percentage points；By light olefin
When coming back for the extracting rectifying, the yield of ethylene raw can improve 1-2 percentage points.
It is limited in view of the solvability of solvent, light olefin is come back for mitigate aromatisation or extracting rectifying, can be incited somebody to action
The higher olefins displacement of dissolving in a solvent to the purity in the light component of tower top, further improving ethylene raw and BTX and
Yield.
Specifically, the light olefin recycling can be carried out in recovery tower, and can control the tower top temperature of recovery tower
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, unless otherwise specified, pressure refers to gauge pressure；Content refers to mass content.
The present invention is by grinding hydrocarbon composition, sulfide and narrow fraction octane number equal distribution rule in catalytically cracked gasoline
Study carefully, by catalytically cracked gasoline be divided into it is light, in, weigh three fractions；For the distribution rule of alkene, aromatic hydrocarbons and sulfide in middle fraction
Rule is taken solvent-extracted mode to realize directional separation, while being improved to the light alkene recycling of extraction oil progress and Returning utilization
The separative efficiency of alkene and the yield of aromatic hydrocarbons；It, can be with by mitigating aromatisation for light fraction and the oil of the raffinate rich in alkene
It is converted into the higher aromatic hydrocarbons of octane number, which can not only meet the requirement of VI standard Olefin decrease of state, but also can be pungent in guarantor
BTX products are produced while alkane value；In addition, according to the difference of solubility or relative volatility between aromatic hydrocarbons and other substances, adopt
Aromatic hydrocarbons is detached with Aromatics Extractive Project or extracting rectifying, realizes the efficient and directional separation of aromatic hydrocarbons.The method of the present invention is dropping
The chemical products for producing the high values such as BTX on the basis of sulphur, drop alkene using catalytically cracked gasoline, before there is good application
Scape.
Description of the drawings
Fig. 1 is the process flow chart that production aromatic hydrocarbons is maximized using catalytically cracked gasoline of an embodiment of the present invention；
Fig. 2 is the process flow chart that production aromatic hydrocarbons is maximized using catalytically cracked gasoline of another embodiment of the present invention；
Fig. 3 is the process flow chart that production aromatic hydrocarbons is maximized using catalytically cracked gasoline of a further embodiment of the present invention.
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 for maximizing production aromatic hydrocarbons using catalytically cracked gasoline of the present embodiment, including walk as follows
Suddenly：
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 is nickel molybdenum bimetallic catalyst, consisting of (mass content %)：Al2O390.5%, Ni
6%, Mo 3.5%；Pre- hydrogenation process conditions are：Controlling reaction temperature is 130 DEG C, hydrogen-oil ratio 5, volume space velocity 3h-1。
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 40 DEG C to cut temperature, in, the cutting temperature of heavy distillat be 100 DEG C, i.e.,：The boiling range of middle fraction is 40 DEG C to 100 DEG C.
3, solvent extraction and light olefin recycling
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 80 DEG C, and column bottom temperature is 60 DEG C, and tower top pressure (gauge pressure) is 0.3MPa, mixed solvent and middle fraction
Charge ratio be 2.0, obtain rich in alkene raffinate oil and the extraction oil rich in aromatic hydrocarbons.
Extraction oil is sent into recovery tower and carries out light olefin (including mainly C5 alkene) recycling, wherein control recovery tower
Tower top temperature is 88 DEG C, tower top pressure 0.07MPa, and column bottom temperature is 168 DEG C, and tower bottom pressure 0.095MPa obtains lightweight
Alkene and sulfur-rich oil.
Wherein, 40% light olefin is subsequently returned to carry out solvent extraction in extraction tower, remaining light olefin with gently evaporate
Divide and raffinate oil carries out mitigation aromatisation together.
4, aromatisation is mitigated
Mitigation aromatisation is carried out under conditions of non-hydrogen using the aromatized catalyst of embodiment 1.
Specifically, in the presence of the aromatized catalyst of embodiment 1, to above-mentioned light fraction, raffinate oil and remaining lightweight alkene
Hydrocarbon carries out mitigation aromatisation, wherein the temperature that control mitigates aromatisation is 290 DEG C, pressure is normal pressure, volume space velocity 1.5h-1,
Reaction time is about 200 hours, obtains aromatization products.
It is computed, the liquid yield of above-mentioned mitigation aromatisation is 99.3%, and (i.e. olefine selective is converted into aromatic hydrocarbons to selectivity
Ratio) it is 64.36%.
5, 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.
6, Aromatics Extractive Project
Solvent used by Aromatics Extractive Project 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.
Solvent using above-mentioned mixed solvent as Aromatics Extractive Project, with the Chinese patent of Publication No. CN 104694158A
Disclosed method carries out Aromatics Extractive Project to above-mentioned aromatization products and desulfurization heavy distillat, obtain ethylene raw/gasoline component and
BTX products.
After above-mentioned processing, the composition of entire product systems is shown in Table 6.
Embodiment 4
As shown in Fig. 2, the method for maximizing production aromatic hydrocarbons using catalytically cracked gasoline of the present embodiment, including walk as follows
Suddenly：
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 is nickel molybdenum bimetallic catalyst, consisting of (mass content %)：Al2O390.5%, Ni
6%, Mo 3.5%；Pre- hydrogenation process conditions are：Controlling reaction temperature is 130 DEG C, hydrogen-oil ratio 5, volume space velocity 3h-1。
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 40 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 40 DEG C to 130 DEG C.
3, solvent extraction and light olefin recycling
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 55 DEG C, and column bottom temperature is 40 DEG C, and tower top pressure (gauge pressure) is 0.7MPa, mixed solvent and middle fraction
Charge ratio be 1.0, obtain rich in alkene raffinate oil and the extraction oil rich in aromatic hydrocarbons.
Extraction oil is sent into recovery tower and carries out light olefin (including mainly C5 alkene) recycling, wherein control recovery tower
Tower top temperature is 88 DEG C, tower top pressure 0.07MPa, and column bottom temperature is 168 DEG C, and tower bottom pressure 0.095MPa obtains lightweight
Alkene and sulfur-rich oil.
Wherein, 50% light olefin is subsequently returned to carry out solvent extraction in extraction tower, remaining light olefin with gently evaporate
Divide and raffinate oil carries out mitigation aromatisation together.
4, aromatisation is mitigated
Mitigation aromatisation is carried out under conditions of non-hydrogen using the aromatized catalyst of embodiment 2.
Specifically, in the presence of aromatized catalyst, above-mentioned light fraction, raffinate oil and remaining light olefin are mitigated
Aromatisation, wherein the temperature that control mitigates aromatisation is 330 DEG C, pressure is normal pressure, volume space velocity 2.0h-1, the reaction time is about
It is 200 hours, obtains aromatization products.
It is computed, the liquid yield of above-mentioned mitigation aromatisation is 99.5%, and selectivity is 64.61%.
5, 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 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.
6, extracting rectifying and light olefin recycling
Solvent used by extracting rectifying 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.
The theoretical cam curve of extractive distillation column is 21, makes above-mentioned aromatization products and desulfurization heavy distillat from extractive distillation column
18th block of plate enters, and above-mentioned mixed solvent enters from the 3rd block of plate of extractive distillation column, and control bottom temperature is 150 DEG C, solvent with
(oil ratio, i.e. solvent volume and aromatization products and desulfurization heavy distillat are overall for aromatization products and the charge ratio of desulfurization heavy distillat
The ratio between product) it is 1.0, reflux ratio 1.0.
The extract that extracting rectifying is obtained, which is sent into recovery tower, carries out light olefin (predominantly C5 alkene) recycling, wherein
The tower top temperature for controlling recovery tower is 88 DEG C, tower top pressure 0.07MPa, and column bottom temperature is 168 DEG C, and tower bottom pressure is
0.095MPa will obtain light olefin and come back for above-mentioned extracting rectifying, obtains ethylene raw/gasoline component and BTX products.
After above-mentioned processing, the composition of entire product systems is shown in Table 6.
Embodiment 5
As shown in figure 3, the method for maximizing production aromatic hydrocarbons using catalytically cracked gasoline of the present embodiment, including walk as follows
Suddenly：
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 is nickel molybdenum bimetallic catalyst, consisting of (mass content %)：Al2O390.5%, Ni
6%, Mo 3.5%；Pre- hydrogenation process conditions are：Controlling reaction temperature is 130 DEG C, hydrogen-oil ratio 5, volume space velocity 3h-1。
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 40 DEG C to cut temperature, in, the cutting temperature of heavy distillat be 140 DEG C, i.e.,：The boiling range of middle fraction is 40 DEG C to 140 DEG C.
3, solvent extraction and light olefin recycling
Solvent used by solvent extraction is the mixed solvent of sulfolane and N-Methyl pyrrolidone, wherein N- methylpyrroles
Alkanone is 20% 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 100 DEG C, 70 DEG C of column bottom temperature, and tower top pressure (gauge pressure) is 0.2MPa, mixed solvent and middle fraction
Charge ratio be 5.0, obtain rich in alkene raffinate oil and the extraction oil rich in aromatic hydrocarbons.
Extraction oil is sent into recovery tower and carries out light olefin (predominantly C5 alkene) recycling, wherein the tower of control recovery tower
It is 90 DEG C, tower top pressure 0.06MPa to push up temperature, and column bottom temperature is 170 DEG C, and tower bottom pressure 0.09MPa obtains light olefin
With sulfur-rich oil.
Wherein, 60% light olefin is subsequently returned to carry out solvent extraction in extraction tower, remaining light olefin with gently evaporate
Divide and raffinate oil carries out mitigation aromatisation together.
4, aromatisation is mitigated
Mitigation aromatisation is carried out under conditions of non-hydrogen using the aromatized catalyst of embodiment 1.
Specifically, in the presence of aromatized catalyst, above-mentioned light fraction, raffinate oil and remaining light olefin are mitigated
Aromatisation, wherein the temperature that control mitigates aromatisation is 280 DEG C, pressure is normal pressure, volume space velocity 1.5h-1, the reaction time is about
It is 200 hours, obtains aromatization products.
It is computed, the liquid yield of above-mentioned mitigation aromatisation is 99.2%, and selectivity is 62.57%.
5, 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 300 DEG C, pressure 2.5MPa, volume space velocity 2.0h-1, hydrogen to oil volume ratio is
400, obtain desulfurization heavy distillat.
6, extracting rectifying and light olefin recycling
Solvent used by extracting rectifying is the mixed solvent of sulfolane and N-Methyl pyrrolidone, wherein N- methylpyrroles
Alkanone is 20% in the volume content of in the mixed solvent.
The theoretical cam curve of extractive distillation column is 21, makes above-mentioned aromatization products and desulfurization heavy distillat from extractive distillation column
18th block of plate enters, and above-mentioned mixed solvent enters from the 3rd block of plate of extractive distillation column, and control bottom temperature is 160 DEG C, solvent with
(oil ratio, i.e. solvent volume and aromatization products and desulfurization heavy distillat are overall for aromatization products and the charge ratio of desulfurization heavy distillat
The ratio between product) it is 2.0, reflux ratio 2.0.
The extract that extracting rectifying is obtained, which is sent into recovery tower, carries out light olefin (predominantly C5 alkene) recycling, wherein
The tower top temperature for controlling recovery tower is 88 DEG C, tower top pressure 0.07MPa, and column bottom temperature is 168 DEG C, and tower bottom pressure is
0.095MPa will obtain light olefin and come back for above-mentioned mitigation aromatisation, obtains ethylene raw/gasoline component and BTX products.
After above-mentioned processing, the composition of entire product systems is shown in Table 6.
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).
In the presence of above-mentioned aromatized catalyst, conventional aromatisation is carried out to raffinate oil, wherein the temperature of conventional aromatisation
It it is 450 DEG C, pressure 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 each embodiment product systems 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 method of maximizing production aromatic hydrocarbons using catalytically cracked gasoline, which is characterized in that include the following steps：
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；
Mitigation aromatisation is carried out to the light fraction and raffinate oil, obtains aromatization products；
Light olefin recycling is carried out to the extraction oil, obtains light olefin and sulfur-rich oil；
Selective hydrodesulfurization is carried out to the heavy distillat and sulfur-rich oil, obtains desulfurization heavy distillat；
Aromatics Extractive Project or extracting rectifying are carried out to the aromatization products and 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 40-60
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, Aromatics Extractive Project and extracting rectifying use
The mixed solvent of sulfolane and N-Methyl pyrrolidone carries out, wherein volume of the N-Methyl pyrrolidone in the in the mixed solvent
Content 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 55-100 DEG C, column bottom temperature is 40-80 DEG C, tower top pressure 0.2-0.7MPa, 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 control temperature for mitigating aromatisation is 280-330
DEG C, pressure is normal pressure, volume space velocity 1.0-2.0h-1。
7. according to the method described in claim 1, it is characterized in that, a part of light olefin is come back for the solvent
Extraction, and the mitigation aromatisation is carried out to light olefin described in another part.
8. 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 carrier of the catalyst for selectively hydrodesulfurizing in molecular sieve and metal oxide at least one
Kind, active constituent includes Co and Mo, and the gross mass content of Co and Mo in catalyst for selectively hydrodesulfurizing is 5-20%；Institute
The temperature for stating selective hydrodesulfurization is 200-300 DEG C, pressure 1.5-2.5MPa, volume space velocity 1-5h-1, hydrogen to oil volume ratio
For 300-600.
9. according to the method described in claim 1, it is characterized in that, being extracted to the aromatization products and desulfurization heavy distillat
Rectifying carries out light olefin recycling to the extract that extracting rectifying obtains, the light olefin that recycling obtains is come back for described
It mitigates aromatisation or comes back for the extracting rectifying.
10. the method according to claim 1 or 9, which is characterized in that the light olefin recycling is carried out in recovery tower,
The tower top temperature for controlling recovery tower is 80-95 DEG C, tower top pressure 0.05-0.2MPa, and column bottom temperature is 150-180 DEG C, bottom of tower
Pressure is 0.05-0.2MPa.
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| CN114181737A (en) * | 2020-09-15 | 2022-03-15 | 中国石油化工股份有限公司 | Method for producing light aromatic hydrocarbon and clean gasoline component from inferior gasoline |
| CN115261057A (en) * | 2022-07-17 | 2022-11-01 | 中国石油化工股份有限公司 | Method for directly producing olefin and aromatic hydrocarbon by catalytically cracking gasoline |
| CN116515524A (en) * | 2022-07-25 | 2023-08-01 | 中国石油化工股份有限公司 | Method for producing light aromatic hydrocarbon by secondary hydrogenation of inferior diesel oil |
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| CN116515524A (en) * | 2022-07-25 | 2023-08-01 | 中国石油化工股份有限公司 | Method for producing light aromatic hydrocarbon by secondary hydrogenation of inferior diesel oil |
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