CN107903943A - The method and high-knock rating gasoline or high-knock rating gasoline blend component that catalytic cracking diesel oil utilizes - Google Patents
The method and high-knock rating gasoline or high-knock rating gasoline blend component that catalytic cracking diesel oil utilizes Download PDFInfo
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- CN107903943A CN107903943A CN201711066955.7A CN201711066955A CN107903943A CN 107903943 A CN107903943 A CN 107903943A CN 201711066955 A CN201711066955 A CN 201711066955A CN 107903943 A CN107903943 A CN 107903943A
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- catalytic cracking
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- cracking diesel
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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
- C10G67/04—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 solvent extraction as the refining step in the absence of hydrogen
- C10G67/0409—Extraction of unsaturated hydrocarbons
- C10G67/0445—The hydrotreatment being a hydrocracking
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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
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- 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 relates to PETROLEUM PROCESSING field, specifically, there is provided the method and high-knock rating gasoline or high-knock rating gasoline blend component that a kind of catalytic cracking diesel oil utilizes.The method that the catalytic cracking diesel oil utilizes comprises the following steps：(a) catalytic cracking diesel oil is formed and property analysis, determines cut point；(b) fractionation cutting, isolated light fraction and heavy distillat are carried out to catalytic cracking diesel oil；(c) heavy distillat is subjected to solvent pairs liquid-liquid extraction, obtains the extraction oil rich in aromatic hydrocarbons and the raffinate oil rich in saturated hydrocarbons；(d) catalytic cracking production high-knock rating gasoline or high-knock rating gasoline blend component are carried out to the raffinate oil rich in saturated hydrocarbons and light fraction.This method craft science is reasonable, and gasoline yield is high, and slurry oil, coke and dry gas yied are low, and technique is simple, cost is low.
Description
Technical field
The present invention relates to PETROLEUM PROCESSING FIELD OF THE INVENTIONThe, a kind of method utilized in particular to catalytic cracking diesel oil and
High-knock rating gasoline or high-knock rating gasoline blend component.
Background technology
The current country refinery FCC (catalytic cracking) devices LCO (light cycle oil) Cetane number is generally relatively low, and derv fuel
Cetane number requirement is being continuously improved, and on January 1st, 2017, the automobile-used 0# diesel oil standards of state V of implementation then require Cetane number not
Less than 51, hence in so that some catalytic cracking diesel oils are also difficult to meet refinery's reconciliation production car after hydrogenated refined or modify
With the demand of diesel oil, and hydro-upgrading needs to consume substantial amounts of hydrogen and extremely low reaction velocity, plant construction and operating cost
It has not been economically feasible route with very high.
LCO is first subjected to hydrofinishing, FCC apparatus charging is re-used as, produces high-knock rating gasoline or its blend component, be
It is more in line with the economically viable route of existing market situation.
US5944982 discloses the group technology of a kind of FCC techniques and hydrogenation technique, and wherein FCC techniques are using double
Riser technique, heavy charge isolate relatively light component and heavier group after FCC apparatus first lifts tube reaction
Point, for lighter component (heavy naphtha and LCO) after hydrotreating, it is anti-that hydrogenation products freshening to the second riser carries out cracking
Should.The technique purpose is production low-carbon alkene and high-knock rating gasoline.The technique separates hydrogenation products without purpose, all
For freshening to the second riser, heavier part fails effective trans-utilization in hydrogenation products, not only adds the second riser and adds
The load of work, while add coke, dry gas yied.
US5152883 discloses a kind of LCO, recycle oil and clarified oil, and by hydrogenation, freshening produces height to FCC apparatus again
The method of octane rating gasoline.This method for heavy oil after FCC apparatus, by LCO, recycle oil and clarified oil in fcc product into
Row separation, after the processing of hydrogenated device, then will be greater than more than 221 DEG C of fraction seperation and comes out, then freshening to FCC devices
Produce high-knock rating gasoline.This method increases the side reaction such as full freshening, FCC apparatus carbon distribution after recycle oil and clarified oil hydrogenation,
And hydrogenation plant hydrogenation depth is not provided and illustrated.
CN101760239 discloses a kind of Application way of catalytic cracking diesel oil.This method is first by catalytic cracking diesel oil point
From into the component of the component less than 230 DEG C, boiling point between 230-310 DEG C and the component more than 310 DEG C, then exist to boiling point
Component between 230-310 DEG C and the component more than 310 DEG C are hydrogenated with different hydrogenation depths respectively, then two kinds are added
Hydrogen product isolates the diesel oil rich in mononuclear aromatics into fractionating column, then mixes and is sent to catalysis with the component before less than 230 DEG C
Cracking unit, so as to produce aromatic hydrocarbons or high-knock rating gasoline.Each fraction section of catalytic cracking diesel oil is fully converted into richness by the technique
Catalysis charging containing mononuclear aromatics, but it is related to two-stage hydrogenation, and group technology is complicated, and investment and operating cost are higher, warp
It is not up to optimal in Ji.
CN103805247 discloses a kind of combined technical method for processing poor ignition quality fuel.This method by poor ignition quality fuel first
Carry out hydro-upgrading reaction；The separating obtained liquid of reaction effluent carries out Aromatics Extractive Project；Aromatic component send to catalytic cracking and produces
High-knock rating gasoline, alkane and saturated hydrocarbons are blended into diesel oil distillate.This method fails aromatic component Selective Separation, more
The presence of cycloaromatics can increase slurry oil, coke and dry gas yied.
CN87107146A discloses a kind of combining technique of catalytic cracking and extraction of heavy oil aroma method.This method will urge
Change process to be combined with double aromatic solvent extraction process, catalytic cracking unit recycle oil is subjected to Aromatics Extractive Project, rich in virtue
The tapped oil of hydrocarbon does chemical products, and the charging raffinated oil as catalytic cracking unit, the method increase catalytic cracking unit
Disposal ability, reduce coke and dry gas yied, improve gasoline yield, and high-purity heavy crude aromatic hydrocarbons can be obtained.This method
Fail to combine hydrogenation technique, therefore gasoline yield increase rate is limited.
CN106753551A discloses a kind of method of catalytic cracking diesel oil producing high-octane gasoline.This method will be catalyzed
After diesel oil hydrofining, the cut less than 280 DEG C and the cut more than 280 DEG C are cut into, the cut more than 280 DEG C is taken out through aromatic hydrocarbons
What is raised raffinates oil, and together high-knock rating gasoline is produced into catalytic cracking unit with the cut less than 280 DEG C, and is rich in aromatic hydrocarbons
Tapped oil carry out aromatic hydrocarbons utilization.But contain a large amount of two rings in this method embodiment in the LCO of catalytic cracking unit pair fractionating column
And thrcylic aromatic hydrocarbon does not add utilization, directly goes out device；This method does not encyclopaedize hydrofinishing and arene extracting process at the same time.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of method that catalytic cracking diesel oil utilizes, the conjunction of this method craft science
Reason, gasoline yield is high, and slurry oil, coke and dry gas yied are low, and technique is simple, cost is low.
The second object of the present invention is to provide a kind of high-knock rating gasoline or high-knock rating gasoline blend component have vapour
The advantages of oil quality is high and of low cost.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
In a first aspect, the present invention provides a kind of method that catalytic cracking diesel oil utilizes, comprise the following steps：
(a) catalytic cracking diesel oil is formed and property analysis, determines cut point；
(b) fractionation cutting, isolated light fraction and heavy distillat are carried out to catalytic cracking diesel oil；
(c) heavy distillat is subjected to solvent pairs liquid-liquid extraction, obtains the extraction oil rich in aromatic hydrocarbons and the raffinate rich in saturated hydrocarbons
Oil；
(d) catalytic cracking production high-knock rating gasoline or high-octane rating are carried out to the raffinate oil rich in saturated hydrocarbons and light fraction
Gasoline blend component.
As further preferred technical solution, the content of the mononuclear aromatics with side chain is in more than 65wt.% in light fraction；
Preferably, in heavy distillat the total content of di pah and thrcylic aromatic hydrocarbon in more than 80wt.%.
As further preferred technical solution, solvent during extraction is the first extractant and the second extractant；
First extractant includes furfural or dimethyl sulfoxide (DMSO), and second extractant includes petroleum ether or solvent
Oil；
Preferably, the petroleum ether includes 60-90 DEG C of petroleum ether；
Preferably, the solvent naphtha includes 6# solvent naphthas.
As further preferred technical solution, the condition of catalytic cracking includes in step (d)：Reaction temperature is 490-
560 DEG C, oil ratio is 3~12, and the reaction time is 2-4 seconds, and atomization water vapour accounts for the 4-8wt.% of inlet amount, and reaction pressure is
100-300 kPas；
Preferably, the device of catalytic cracking reaction is Double-lifted pipe catalytic cracking device.
As further preferred technical solution, the extraction oil feeding slag that will be enriched in aromatic hydrocarbons is further included after step (c)
The step of oily hydrocracking unit.
As further preferred technical solution, the hydrogen-consuming volume being hydrocracked is 2%~3%；
Preferably, hydrocracking catalyst is included the use of in hydrocracking process, the hydrocracking catalyst includes
The active component of carrier and load on the carrier, the carrier includes solid acid and inorganic refractory oxides, with the load
On the basis of the gross weight of body, the content of the solid acid is 2-96wt.%, more preferably 3-85wt.%；
Preferably, on the basis of the gross weight of the carrier, the content of the inorganic refractory oxides is 15-95wt.%,
More preferably 25-90wt.%；
Preferably, the solid acid is included in amorphous silica-alumina, big-hole zeolite molecular sieve and mesopore zeolite molecular sieve extremely
It is two kinds few；
Preferably, the amorphous silica-alumina is the amorphous silica-alumina with structure of similar to thin diaspore.
As further preferred technical solution, further included before step (a) and hydrofinishing is carried out to light cycle oil to obtain
The step of to catalytic cracking diesel oil.
As further preferred technical solution, the method for the hydrofinishing is included in the presence of Hydrobon catalyst
Under, light cycle oil is contacted with hydrogen, the condition of contact includes：Reaction temperature is 260-400 DEG C, hydrogen dividing potential drop 2-10MPa, liquid
When air speed be 0.5-8.0h-1, hydrogen to oil volume ratio 150-1000Nm3/m3；
Preferably, Hydrobon catalyst includes hydrogenation activity component and carrier, and carrier includes aluminium oxide, silica, oxygen
Change at least one of titanium, zirconium oxide or molecular sieve；
Preferably, carrier is amorphous silica-alumina；
Preferably, hydrogenation activity component includes the mixture of nickel oxide, molybdenum oxide, tungsten oxide, fluorine and phosphorous oxide.
As further preferred technical solution, Hydrobon catalyst further includes organic additive, the organic additive bag
Include oxygen-containing organic compound and/or organic compounds containing nitrogen；
Preferably, oxygen-containing organic compound includes Organic Alcohol and/or organic acid；
Preferably, organic compounds containing nitrogen includes organic amine and/or organic amine salt.
Second aspect, the present invention provides the high-octane rating that a kind of method utilized using above-mentioned catalytic cracking diesel oil is obtained
Gasoline or high-knock rating gasoline blend component.
Compared with prior art, beneficial effects of the present invention are：
The method craft science that catalytic cracking diesel oil provided by the invention utilizes is reasonable, first by catalytic cracking diesel oil
Carry out composition and property analysis determine optimal cut point, to ensure in light fraction containing the largely monocyclic virtue with side chain
Hydrocarbon, contains substantial amounts of di pah and thrcylic aromatic hydrocarbon in heavy distillat；Then carry out fractionation cutting and obtain light fraction and heavy distillat, it is right
Heavy distillat carries out solvent pairs liquid-liquid extraction, obtains the extraction oil rich in aromatic hydrocarbons and the raffinate oil rich in saturated hydrocarbons, realizes to double distilled
Oily efficiently separated for two kinds in being divided to；Then catalytic cracking production high-octane rating is carried out to the raffinate oil rich in saturated hydrocarbons and light fraction
Gasoline or high-knock rating gasoline blend component, so as to fulfill in heavy distillat be rich in saturated hydrocarbons raffinate oil and light fraction it is effective
Utilize.By carrying out solvent pairs liquid-liquid extraction to heavy distillat, the extraction oil Selective Separation that can will be enriched in aromatic hydrocarbons comes out this method,
Reduce slurry oil, coke and dry gas yied, and the raffinate oil rich in saturated hydrocarbons can be efficiently used and convert it together with light fraction
For high-knock rating gasoline or high-knock rating gasoline blend component, gasoline yield greatly improved, and technique is simple, cost is low.
High-knock rating gasoline or high-knock rating gasoline blend component provided by the invention is using above-mentioned catalytic cracking diesel oil profit
Method produces to obtain, and has the advantages that gasoline quality is high and of low cost.
Brief description of the drawings
Fig. 1 is the process flow chart of embodiment 1.
Icon：1- hydrofining reactors；2- reaction effluents；3- high-pressure separators；4- circulating hydrogens；5- liquid phases are produced
Thing；The first strippers of 6-；The first gasoline of 7-；8- refined diesel oils one；9- refined diesel oils two；10- fractionating columns；11- light fractions；12-
Heavy distillat；13- liquid-liquid extraction towers；Raffinate oil of the 14- rich in saturated hydrocarbons；15- is rich in the extraction oil of aromatic hydrocarbons；16- second is stripped
Tower；The extractant that 17- first is recycled；18- richness aromatic naphtha；The first steam of 19-；The 3rd strippers of 20-；21- second is recycled
Extractant；22- enriched saturated hydrocarbons oil；The second steam of 23-；24- solvent tanks；The first extractants of 25-；It is molten that 26- contains extraction
The water of agent；27- dehydrating towers；28- solvents；29- sewage；The 3rd steam of 30-；The second riser reactors of 31-；32- second is settled
Device；The first reaction products of 33-；The first settlers of 34-；35- external warmers；36- Conventional catalytic raw materials；The main lifting tube reactions of 37-
Device；38- reaction products；39- main fractionating towers；40- first gas；The second gasoline of 41-；42- light cycle oils LCO；43- heavy-cycle oil
HCO；The first slurry oils of 44-；45- pair fractionating columns；46- second gas；The 3rd gasoline of 47-；48-LCO；The second slurry oils of 49-；50-
Second extractant.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.
In a first aspect, the present invention provides a kind of method that catalytic cracking diesel oil utilizes, comprise the following steps：
(a) catalytic cracking diesel oil is formed and property analysis, determines cut point；
(b) fractionation cutting, isolated light fraction and heavy distillat are carried out to catalytic cracking diesel oil；
(c) heavy distillat is subjected to solvent pairs liquid-liquid extraction, obtains the extraction oil rich in aromatic hydrocarbons and the raffinate rich in saturated hydrocarbons
Oil；
(d) catalytic cracking production high-knock rating gasoline or high-octane rating are carried out to the raffinate oil rich in saturated hydrocarbons and light fraction
Gasoline blend component.
In LCO, substantial amounts of aromatic hydrocarbons mainly based on mononuclear aromatics, double ring arene, also has the aromatic hydrocarbons of part tricyclic, in addition
Also there are a certain proportion of alkane, cycloalkane or alkene in LCO.LCO is unstable after hydrofinishing desulfurization, denitrogenation
Alkadienes obtains saturation, and part is bicyclic and saturation occurs for the aromatic ring of thrcylic aromatic hydrocarbon, and saturated hydrocarbons and mononuclear aromatics contain in hydrogenation products
Amount will greatly improve, and the mononuclear aromatics content especially with side chain can reach more than 50wt.%.Mononuclear aromatics with side chain is high
The precursor of octane components, these mononuclear aromatics side chains with side chain are easily broken, and chain can enter gasoline group on rear side of cracking
Point, and the mononuclear aromatics of remaining shorter side chain also just enters gasoline fraction, this part is high octane gasoline component.
The method craft science that above-mentioned catalytic cracking diesel oil utilizes is reasonable, first by being formed to catalytic cracking diesel oil
Optimal cut point is determined with property analysis, to ensure in light fraction containing the largely mononuclear aromatics with side chain, heavy distillat
In contain substantial amounts of di pah and thrcylic aromatic hydrocarbon；Then carry out fractionation cutting obtain light fraction and heavy distillat, to heavy distillat into
Row solvent pairs liquid-liquid extraction, obtains the extraction oil rich in aromatic hydrocarbons and the raffinate oil rich in saturated hydrocarbons, realizes to two kinds in heavy distillat
Oil efficiently separates；Then catalytic cracking production high-knock rating gasoline or height are carried out to the raffinate oil rich in saturated hydrocarbons and light fraction
Octane rating gasoline blend component, so as to fulfill to being rich in the raffinate oil of saturated hydrocarbons and efficiently using for light fraction in heavy distillat.Should
By carrying out solvent pairs liquid-liquid extraction to heavy distillat, the extraction oil Selective Separation that can will be enriched in aromatic hydrocarbons comes out, reduces method
Slurry oil, coke and dry gas yied, and the raffinate oil rich in saturated hydrocarbons can be efficiently used it is converted into Gaoxin together with light fraction
Alkane value gasoline or high-knock rating gasoline blend component, greatly improved gasoline yield, and technique is simple, cost is low.
Find by research, using single solvent extraction HLCO heavy distillat, while high extraction oil yield is obtained, also lose
A certain proportion of enriched saturated hydrocarbon oil, and enriched saturated hydrocarbon oil is excellent catalytic cracking feeds, can improve gasoline yield.For solution
Certainly this problem, liquid-liquid extraction bottom of towe introduce the second extractant, tower top introduce the first extractant, the first extractant,
HLCO heavy distillat, the density of the second extractant are sequentially reduced, and have certain density contrast.In this way, the first extractant with
HLCO heavy distillat counter current contacting, which absorbs, continues downward, and the second lighter extractant counter current contacting after aromatic hydrocarbons, due to the second extraction
Back-extraction of the solvent to aromatic hydrocarbons is taken, saturated hydrocarbons is extracted from extract, into raffinate, while the virtue of extract
Hydrocarbon content is improved.
Compared to single solvent extraction, had the characteristics that using double solvent extraction following：
1st, whole alkanes, cycloalkane are extracted from single extract in aromatic hydrocarbons, back in raffinate oil；
2nd, at the same time, also single major part one extracted in aromatic hydrocarbons, di pah are extracted, back in raffinate oil；
3rd, Dan Cui is higher than using the quantity of raffinate oil obtained by double solvent extraction, therefore gasoline production compares Dan Cuigao.
In step (a), conventional analysis method, such as element composition, boiling range, detailed hydrocarbon system composition etc. can be used.Root
Cut point is determined according to analysis data, farthest to separate mononuclear aromatics and di pah and thrcylic aromatic hydrocarbon to add respectively
To utilize.
In step (b), conventional separation method can be used, for example, the separation can carry out in fractionating column, fractionation
The operating condition of tower can include：Feeding temperature is 240-320 DEG C, column bottom temperature is 280-350 DEG C, tower top temperature 120-
280 DEG C, tower top pressure is 0.05-1.05MPa (gauge pressure).The diesel oil rich in mononuclear aromatics is separated at the top of from fractionating column (gently to evaporate
Point), the diesel oil (heavy distillat) containing polycyclic aromatic hydrocarbon is separated from bottom of towe.
In step (c), conventional liquid-liquid extraction method can be used, for example, the separation can be in liquid liquid extraction plant
Middle progress, operating pressure is 0.5~1MPa in extraction tower, and temperature is 35~110 DEG C, solvent ratio (heavy distillat:First extraction is molten
Agent:The mass ratio of second extractant) it is 1:(0.4-1.3):(0.2-0.8).
In a preferred embodiment, in light fraction the content of the mononuclear aromatics with side chain in more than 65wt.%.
Preferably, in heavy distillat the total content of di pah and thrcylic aromatic hydrocarbon in more than 80wt.%.Di pah refers to only
Hydrocarbon containing two phenyl ring, thrcylic aromatic hydrocarbon refer to the hydrocarbon only containing three phenyl ring.
Research finds, at a certain temperature by the catalytic diesel oil (HLCO, also known as catalytic cracking diesel oil) after hydrofinishing into
Row distillation cutting, the content of mononuclear aromatics reaches more than 65wt.% in the cut below cut point, in cut more than cut point
The total content of di pah and thrcylic aromatic hydrocarbon reaches more than 80wt.%, at this time, to the utilization rate higher of catalytic cracking diesel oil.
In a preferred embodiment, solvent during extraction is the first extractant and the second extractant；
First extractant includes furfural or dimethyl sulfoxide (DMSO), and second extractant includes petroleum ether or solvent
Oil.
Preferably, the petroleum ether includes 60-90 DEG C of petroleum ether.
Preferably, the solvent naphtha includes 6# solvent naphthas.
In step (d), catalytic cracking can use the catalyst cracking method of this area routine.The condition of catalytic cracking can be with
Including：Reaction temperature is 450-600 DEG C, oil ratio 1-20, and the reaction time is 0.2-8 seconds, and atomization water vapour accounts for inlet amount
1-20wt.%, reaction pressure are normal pressure~400 kPa.Above-mentioned 400 kPas refer to gauge pressure.
In a preferred embodiment, the condition of catalytic cracking includes in step (d)：Reaction temperature is 490-560
DEG C, oil ratio is 3~12, and the reaction time is 2-4 seconds, and atomization water vapour accounts for the 4-8wt.%, reaction pressure 100- of inlet amount
300 kPas.It is 490 DEG C that above-mentioned reaction temperature is typical but non-limiting, 500 DEG C, 510 DEG C, 520 DEG C, 530 DEG C, 540 DEG C,
550 DEG C or 560 DEG C；It is 3 that oil ratio (i.e. the volume ratio of catalyst and inlet amount) is typical but non-limiting, 4,5,6,7,8,9,
10th, 11 or 12；The typical but non-limiting reaction time is 2 seconds, 2.5 seconds, 3 seconds, 3.5 seconds or 4 seconds；Atomization water vapour accounts for charging
The percetage by weight of amount it is typical but non-limiting for 4wt.%, 4.5wt.%, 5wt.%, 5.5 wt.%, 6wt.%,
6.5wt.%, 7wt.%, 7.5wt.% or 8wt.%；It is 100 kPas that reaction pressure is typical but non-limiting, 150 kPas,
200 kPas, 250 kPas or 300 kPas.Above-mentioned reaction pressure refers to gauge pressure.
The device of the catalytic cracking reaction can be well known in the art, generally riser reactor or riser and
The combination of bed reactor.Such as can be fluid catalytic cracking of heavy oil device (RFCC) or adaptable multieffect catalysis split
Makeup put one kind in devices such as (reactors described in FDFCC-III, i.e. Chinese patent CN200510017861.1) or
It is several.
Preferably, the device of catalytic cracking reaction is Double-lifted pipe catalytic cracking device.Main riser processes catalytic cracking
Raw material, the processing light distillate of the second riser and the raffinate oil rich in saturated hydrocarbons.
Catalyst used in catalytic cracking can be any one or the combination of several of them provided by the prior art.These are urged
Fluidized cracking catalysts usually contain zeolite, inorganic oxide and optional clay, and the content of each component is respectively：Zeolite 2.5-
50wt.%, inorganic oxide 2.5-95 wt.%, clay 0-70wt.%.
In a preferred embodiment, the extraction oil feeding residual oil that will be enriched in aromatic hydrocarbons is further included after step (c)
The step of hydrocracking unit.Charging of the extraction oil rich in aromatic hydrocarbons as residual hydrocracking device, can be greatly lowered
Feedstock viscosity, extends the operation cycle, improves product yield.The residual oil handled by residual hydrocracking technique device, it is contained
The important indicators such as sulphur, nitrogen, metal and residual nitrogen, be greatly lowered, can be all as the process of the downstream processes such as catalysis, cracking
Qualification charging, can be relatively low utility value, be easy to cause the residual oil of environmental pollution, is completely converted into added value height, has good quality
Light-end products, improve light oil conversion ratio to greatest extent, in a sense, which makes crude oil obtain closely
100% conversion, realizes the hope eaten up crude oil in petroleum refining process and bled.
Conventional method for hydrogen cracking can be used during residual hydrocracking, hydrocracking condition can include：One section adds
340-400 DEG C of hydrogen refining reaction temperature, 380-450 DEG C of secondary hydrogenation cracking reaction temperature；Reaction pressure 14-20MPa；Consume hydrogen
Measure as inlet amount 1%~4%.
In a preferred embodiment, the hydrogen-consuming volume being hydrocracked is 2%~3%.Above-mentioned hydrogen-consuming volume is hydrogen-consuming volume
Account for the percent by volume of inlet amount.Typical but non-limiting above-mentioned hydrogen-consuming volume is 2%, 2.2%, 2.4%, 2.6%, 2.8%
Or 3%.
Preferably, hydrocracking catalyst is included the use of in hydrocracking process, the hydrocracking catalyst includes
The active component of carrier and load on the carrier, the carrier includes solid acid and inorganic refractory oxides, with the load
On the basis of the gross weight of body, the content of the solid acid is 2-96wt.%, more preferably 3-85wt.%.Solid acid is urged
Change function from the acid sites present on the surface of solids with catalytic activity, claim acid site, their majorities are non-transition
The oxide or mixed oxide of element.The content of above-mentioned solid acid it is typical but non-limiting for 2wt.%, 3wt.%,
5wt.%, 10wt.%, 15wt.%, 20wt.%, 25wt.%, 30wt.%, 35wt.%, 40wt.%, 45wt.%,
50wt.%, 55wt.%, 60wt.%, 65wt.%, 70wt.%, 75wt.%, 80wt.%, 85wt.%, 90wt.%,
95wt.% or 96wt.%.
Preferably, on the basis of the gross weight of the carrier, the content of the inorganic refractory oxides is 15-95wt.%,
More preferably 25-90wt.%.The contents of above-mentioned inorganic refractory oxides it is typical but non-limiting for 15wt.%,
20wt.%, 25wt.%, 30wt.%, 35 wt.%, 40wt.%, 45wt.%, 50wt.%, 55wt.%, 60wt.%,
65wt.%, 70wt.%, 75wt.%, 80wt.%, 85wt.%, 90wt.% or 95wt.%.The master of inorganic refractory oxides
Act on the effective carrier for being to provide cementation and hydrogenation active component being provided.The species of the inorganic refractory oxides also may be used
The conventional selection of this area is thought, for example, can be aluminium oxide, zirconium oxide, magnesia, thorium oxide, beryllium oxide, boron oxide, oxygen
One or more in cadmium, particularly preferably aluminium oxide.
Preferably, the solid acid is included in amorphous silica-alumina, big-hole zeolite molecular sieve and mesopore zeolite molecular sieve extremely
It is two kinds few.Big-hole zeolite molecular sieve refers to that aperture is more than the zeolite molecular sieve of 50nm, and mesopore zeolite molecular sieve refers to aperture in 2-
The zeolite molecular sieve of 50nm.
The amorphous silica-alumina can be the table of the existing various solid acid components that can act as hydrocracking catalyst
Face has acid silica-alumina.Preferably, the amorphous silica-alumina is the amorphous silicon with structure of similar to thin diaspore
Aluminium.
The active component is made of three kinds of molybdenum, cobalt and nickel components, in terms of oxide and with the hydrocracking catalyst
Gross weight on the basis of, the content of molybdenum is 5-23wt.%, and the content of cobalt is 0.8-6wt.%, and the content of nickel is 0.2-2wt.%.
In a preferred embodiment, further included before step (a) and hydrofinishing is carried out to light cycle oil to obtain
The step of catalytic cracking diesel oil.
The method of hydrogenation is included in the presence of Hydrobon catalyst, and LCO is contacted with hydrogen.The condition of contact can be with
Including：Reaction temperature is 250-450 DEG C, hydrogen dividing potential drop 1-12MPa, liquid hourly space velocity (LHSV) 0.3-10h-1, hydrogen to oil volume ratio 100-
1500Nm3/m3。
In a preferred embodiment, the method for the hydrofinishing is included in the presence of Hydrobon catalyst
Under, light cycle oil is contacted with hydrogen, the condition of contact includes：Reaction temperature is 260-400 DEG C, hydrogen dividing potential drop 2-10MPa, liquid
When air speed be 0.5-8.0h-1, hydrogen to oil volume ratio 150-1000Nm3/m3.Above-mentioned hydrogen to oil volume ratio refers to that hydrogen is gently followed with charging
The volume ratio of ring oil.Light cycle oil carries out hydrodesulfurization, hydrodenitrogeneration, the de- gold of hydrogenation under the action of Hydrobon catalyst
Category, alkene saturation and part aromatic hydrocarbons saturated reaction.It is 260 DEG C that above-mentioned reaction temperature is typical but non-limiting, 280 DEG C, 300
DEG C, 320 DEG C, 340 DEG C, 360 DEG C, 380 DEG C or 400 DEG C；Above-mentioned hydrogen dividing potential drop is typical but non-limiting for 2MPa, 3MPa, 4
MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa or 10MPa；Typical but non-limiting above-mentioned liquid hourly space velocity (LHSV) is 0.5h-1、1h-1、
2h-1、3h-1、4h-1、5h-1、6h-1、 7h-1Or 8h-1；Typical but non-limiting above-mentioned hydrogen to oil volume ratio is 150Nm3/m3、200
Nm3/m3、300Nm3/m3、400Nm3/m3、500Nm3/m3、600Nm3/m3、700 Nm3/m3、800Nm3/m3、900Nm3/m3Or
1000Nm3/m3。
Hydrobon catalyst can be conventional various Hydrobon catalysts.Hydrobon catalyst contains hydrogenation and lives
Property component and carrier.The hydrogenation activity component is group vi and/or group VIII metal, and carrier is inorganic resistance to thermal oxide
Thing.
Preferably, Hydrobon catalyst includes hydrogenation activity component and carrier, and carrier includes aluminium oxide, silica, oxygen
Change at least one of titanium, zirconium oxide or molecular sieve.
Preferably, carrier is amorphous silica-alumina.
Preferably, hydrogenation activity component includes the mixture of nickel oxide, molybdenum oxide, tungsten oxide, fluorine and phosphorous oxide.
In a preferred embodiment, Hydrobon catalyst further includes organic additive, and the organic additive includes
Oxygen-containing organic compound and/or organic compounds containing nitrogen.
Preferably, oxygen-containing organic compound includes Organic Alcohol and/or organic acid.
Preferably, organic compounds containing nitrogen includes organic amine and/or organic amine salt.
After hydrofinishing, hydrotreated product can be cooled down, then carry out gas-liquid separation, to liquid phase stream into
Row cutting.Gas-liquid separation can utilize conventional method, such as use high-pressure separator and low pressure separator successively.
Second aspect, the present invention provides the high-octane rating that a kind of method utilized using above-mentioned catalytic cracking diesel oil is obtained
Gasoline or high-knock rating gasoline blend component.
Embodiment 1
As shown in Figure 1, the present embodiment processing poor ignition quality fuel group technology flow is as follows：
The light cycle oil LCO42 and LCO48 from secondary fractionating column 45 from main fractionating tower 39 enters hydrofining reaction
Device 1, with hydrogenation catalyst haptoreaction；Reaction effluent 2 enters high-pressure separator 3, and it is anti-that circulating hydrogen 4 returns to hydrofinishing
Device 1 is answered, liquid product 5 is separated into the first gasoline 7, refined diesel oil 1 and refined diesel oil 29 through the first stripper 6；Refined bavin
Oil 1 can be used as diesel oil blending component；Refined diesel oil 29 enters fractionating column 10, and tower top obtains gently under the cut point of optimization
Cut 11, bottom of towe obtain heavy distillat 12；Light fraction 11 is into the second riser reactor of catalytic cracking unit 31；Heavy distillat 12 from
Middle part enters liquid-liquid extraction tower 13, and the first extractant 25 enters liquid-liquid extraction tower 13 from top, and the second extractant 50 is under
Portion enters liquid-liquid extraction tower 13,12 and first counter current contacting in tower of extractant 25 of heavy distillat, solvent mutually absorb aromatic hydrocarbons with
Continue downwards afterwards, with 50 counter current contacting of the second extractant, the second extractant 50 extracts the saturated hydrocarbons in solvent phase
Come, into raffinate；Bottom of towe obtains the extraction oil 15 rich in aromatic hydrocarbons, and tower top obtains the raffinate oil 14 rich in saturated hydrocarbons；It is rich in
The extraction oil 15 of aromatic hydrocarbons enters the second stripper 16, and the first steam 19 enters from bottom of towe；Second stripper, 16 bottom of towe obtains aromatic hydrocarbons
The rich aromatic naphtha 18 of purity >=95%, rich aromatic naphtha 18 are mixed into residual hydrocracking reactor with resid feed；Second stripping
16 tower top of tower obtains the extractant 17 of the first recycling；Raffinate oil 14 rich in saturated hydrocarbons enters the 3rd stripper 20, and second steams
Vapour 23 enters from bottom of towe；3rd stripper, 20 bottom of towe obtains enriched saturated hydrocarbon oil 22, and enriched saturated hydrocarbon oil 22 is into catalytic cracking unit
Two riser reactors 31；3rd stripper, 20 tower top obtains the extractant 21 of the second recycling；The extractant of first recycling
17 and second recycling extractant 21 enter solvent tank 24；First extractant 25 and 50 rework solution liquid of the second extractant extract
Take tower 13；Water 26 containing extractant enters dehydrating tower 27；3rd steam 30 enters from bottom of towe；27 tower top of dehydrating tower returns molten
Agent 28 is to solvent tank 24；Sewage 29 is discharged from 27 bottom of towe of dehydrating tower.
Light fraction 11 enters the second riser reactor of catalytic cracking unit 31 with enriched saturated hydrocarbon oil 22, is connect with catalyst
Touch reaction；By 32 separating catalyst of the second settler and the first reaction product 33；First reaction product 33 enters secondary fractionating column
45 are separated into second gas 46, the 3rd gasoline 47, LCO48 and the second slurry oil 49；It is anti-that Conventional catalytic raw material 36 enters main riser
Device 37 is answered, with catalyst haptoreaction；By 34 separating catalyst of the first settler and the second reaction product 38；Second reaction production
Thing 38 into main fractionating tower 39 be separated into first gas 40, the second gasoline 41, light cycle oil LCO42, heavy-cycle oil HCO43 and
First slurry oil 44；Light cycle oil LCO42 and LCO48 are back to hydrofining reactor 1；Second slurry oil 49 returns to main fractionating tower
39；Take heat superfluous in catalytic cracked regenerated burning process away by external warmer 35.
LCO is with the catalytic reaction condition of hydrogen：Reaction temperature is 320 DEG C, hydrogen dividing potential drop 6MPa, and liquid hourly space velocity (LHSV) is
5.0h-1, hydrogen to oil volume ratio 650Nm3/m3。
Hydrofining catalyst carrier used is by aluminium hydrate powder and Ludox with Al (OH)3/SiO2Butt ratio is 6:1 is mixed
Closing uniformly, be extruded into three leaf bar shapeds, 1.4 millimeters of outside diameter, wet bar is when 120 DEG C of dryings 4 are small, when roasting 3 is small under the conditions of 600 DEG C, system
Obtain the carrier that silica content is 18wt.%；200 grams of carrier is weighed, with containing 11.5 grams of ammonium paramolybdate, 20.6 grams of phosphoric acid, nitric acid
19 grams of nickel, 36.8 grams of ammonium metatungstate, 183 milliliters of the aqueous solution of 2.5 grams of phosphatase 11 impregnate the carrier 3 it is small when, 120 DEG C of dryings 4 are small
When, when 480 DEG C of roastings 4 are small, obtain Hydrobon catalyst.
The first extractant used in liquid-liquid extraction is furfural, and the second extractant is 60-90 DEG C of petroleum ether.
Boehmite that carrier of hydrocracking catalyst used is 70% by 46.3 grams of butts, 191.7 grams of butt are
MCM-22 (the silica alumina ratios 30 that 75% HY zeolites (lattice constant is 24.59 angstroms) and 29.8 grams of butts are 80%:1) mix
Close uniform, extrusion shaping, a diameter of 2 millimeters, then when 120 DEG C of drying 3 are small, then at 580 DEG C of roastings 3 it is small when obtain；Weigh
100 grams of carrier, (corresponding oxide is converted into 85 milliliters of ammonia spirits respectively containing ammonium molybdate, cobalt nitrate and nickel nitrate
Contain 169.1 g/l of MoO respectively3, 50.7 g/l of CoO, 12.7 g/l of NiO) dipping 1 it is small when, then by the load through dipping
Body in 120 DEG C drying 2 it is small when, then at 450 DEG C roasting 3 it is small when, obtain hydrocracking catalyst.
Catalyst used in embodiment 1 is commercial catalyst, the trade mark be respectively DFC-1 catalytic cracking catalysts and
RS-1000 Hydrobon catalysts and FC-20 hydrocracking catalysts, its property are shown in Table 1, table 2, table 3；Conventional catalytic used
Cracked stock property is shown in Table 4.
1 catalytic cracking catalyst property of table
2 Hydrobon catalyst property of table
3 hydrocracking catalyst property of table
4 Conventional catalytic feedstock property of table
Comparative example 1
Main riser is separated into Conventional catalytic cracking feedstock oil, crackate through main fractionating tower, what main fractionating tower was isolated
Raw gasoline lifts tube reaction into second.Two risers of control react under optimal conditions, the catalyst used in comparative example 1
The trade mark is DFC-1 catalytic cracking catalysts.
The operating condition of embodiment 1 and comparative example 1 is shown in Table 5, and embodiment 1 and the product distribution of comparative example 1 are shown in Table 6.
5 operating condition of table contrasts
" first " refers to the first extractant in the solvent ratio of table 5, and " second " refers to the second extractant.
6 product profiles versus of table
| Product is distributed, % | Embodiment 1 | Comparative example 1 |
| Dry gas | 3.6 | 4.2 |
| Liquefied gas | 17.7 | 16.9 |
| Gasoline | 63.0 | 42.5 |
| Diesel oil | 3.4 | 23.9 |
| Mink cell focus | 5.2 | 4.5 |
| Coke | 7.0 | 7.9 |
As can be seen from Table 6, when the second riser charging after raw gasoline is changed into hydrofining diesel oil, yield of gasoline
48.2% is improved, diesel yield significantly reduces, and dry gas and coke yield are declined slightly.
Although being illustrated and the invention has been described with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of method that catalytic cracking diesel oil utilizes, it is characterised in that comprise the following steps：
(a) catalytic cracking diesel oil is formed and property analysis, determines cut point；
(b) fractionation cutting, isolated light fraction and heavy distillat are carried out to catalytic cracking diesel oil；
(c) heavy distillat is subjected to solvent pairs liquid-liquid extraction, obtains the extraction oil rich in aromatic hydrocarbons and the raffinate oil rich in saturated hydrocarbons；
(d) catalytic cracking production high-knock rating gasoline or high-knock rating gasoline are carried out to the raffinate oil rich in saturated hydrocarbons and light fraction
Blend component.
2. the method that catalytic cracking diesel oil according to claim 1 utilizes, it is characterised in that the list with side chain in light fraction
The content of cycloaromatics is in more than 65wt.%；
Preferably, in heavy distillat the total content of di pah and thrcylic aromatic hydrocarbon in more than 80wt.%.
3. the method that catalytic cracking diesel oil according to claim 1 utilizes, it is characterised in that solvent during extraction is first
Extractant and the second extractant；
First extractant includes furfural or dimethyl sulfoxide (DMSO), and second extractant includes petroleum ether or solvent naphtha；
Preferably, the petroleum ether includes 60-90 DEG C of petroleum ether；
Preferably, the solvent naphtha includes 6# solvent naphthas.
4. the method that catalytic cracking diesel oil according to claim 1 utilizes, it is characterised in that catalytic cracking in step (d)
Condition include：Reaction temperature is 490-560 DEG C, and oil ratio is 3~12, and the reaction time is 2-4 seconds, and atomization water vapour accounts for charging
The 4-8wt.% of amount, reaction pressure are 100-300 kPas；
Preferably, the device of catalytic cracking reaction is Double-lifted pipe catalytic cracking device.
5. the method that catalytic cracking diesel oil according to claim 1 utilizes, it is characterised in that also wrapped after step (c)
The step of including the extraction oil feeding residual hydrocracking device that will be enriched in aromatic hydrocarbons.
6. the method that catalytic cracking diesel oil according to claim 5 utilizes, it is characterised in that the hydrogen-consuming volume being hydrocracked is
2%~3%；
Preferably, hydrocracking catalyst is included the use of in hydrocracking process, the hydrocracking catalyst includes carrier
With the active component of load on the carrier, the carrier includes solid acid and inorganic refractory oxides, with the carrier
On the basis of gross weight, the content of the solid acid is 2-96wt.%, more preferably 3-85wt.%；
Preferably, on the basis of the gross weight of the carrier, the content of the inorganic refractory oxides is 15-95wt.%, into one
Step is preferably 25-90wt.%；
Preferably, the solid acid includes at least two in amorphous silica-alumina, big-hole zeolite molecular sieve and mesopore zeolite molecular sieve
Kind；
Preferably, the amorphous silica-alumina is the amorphous silica-alumina with structure of similar to thin diaspore.
7. the method utilized according to claim 1-6 any one of them catalytic cracking diesel oils, it is characterised in that step (a) it
Before further include to light cycle oil carry out hydrofinishing to obtain catalytic cracking diesel oil the step of.
8. the method that catalytic cracking diesel oil according to claim 7 utilizes, it is characterised in that the method for the hydrofinishing
It is included in the presence of Hydrobon catalyst, light cycle oil is contacted with hydrogen, the condition of contact includes：Reaction temperature is
260-400 DEG C, hydrogen dividing potential drop 2-10MPa, liquid hourly space velocity (LHSV) 0.5-8.0h-1, hydrogen to oil volume ratio 150-1000Nm3/m3；
Preferably, Hydrobon catalyst includes hydrogenation activity component and carrier, carrier include aluminium oxide, silica, titanium oxide,
At least one of zirconium oxide or molecular sieve；
Preferably, carrier is amorphous silica-alumina；
Preferably, hydrogenation activity component includes the mixture of nickel oxide, molybdenum oxide, tungsten oxide, fluorine and phosphorous oxide.
9. the method that catalytic cracking diesel oil according to claim 8 utilizes, it is characterised in that Hydrobon catalyst also wraps
Organic additive is included, the organic additive includes oxygen-containing organic compound and/or organic compounds containing nitrogen；
Preferably, oxygen-containing organic compound includes Organic Alcohol and/or organic acid；
Preferably, organic compounds containing nitrogen includes organic amine and/or organic amine salt.
10. high-knock rating gasoline that the method utilized using claim 1-9 any one of them catalytic cracking diesel oils is obtained or
High-knock rating gasoline blend component.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707475A (en) * | 2018-05-28 | 2018-10-26 | 中石化（洛阳）科技有限公司 | A kind of method of catalytic cracking diesel oil and the method for processing poor ignition quality fuel |
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| CN106753551A (en) * | 2017-01-22 | 2017-05-31 | 中石化炼化工程（集团）股份有限公司 | A kind of method that utilization catalytic cracking diesel oil produces high-knock rating gasoline |
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| JPH10102070A (en) * | 1996-09-24 | 1998-04-21 | Inst Fr Petrole | Production of catalytic cracking gasoline of low sulfur content and system therefor |
| CN101144029A (en) * | 2007-09-21 | 2008-03-19 | 袁培林 | Catalytic cracking processing technique for inferior oil material |
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