CN108102703A - A kind of processing and treating method of catalytic diesel oil - Google Patents
A kind of processing and treating method of catalytic diesel oil Download PDFInfo
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- CN108102703A CN108102703A CN201611045477.7A CN201611045477A CN108102703A CN 108102703 A CN108102703 A CN 108102703A CN 201611045477 A CN201611045477 A CN 201611045477A CN 108102703 A CN108102703 A CN 108102703A
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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
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/16—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention discloses a kind of processing and treating methods of catalytic diesel oil.Catalytic diesel oil raw material is cut into light component and heavy constituent；Light component carries out hydrofinishing and hydro-upgrading reaction, obtains gasoline and diesel component；Gained heavy constituent is separated, and obtains thrcylic aromatic hydrocarbon component and non-thrcylic aromatic hydrocarbon component, and gained thrcylic aromatic hydrocarbon component carries out hydrofinishing and hydro-conversion, obtains gasoline component and diesel component；Gasoline products are obtained after the mixing of two parts gasoline, diesel product is obtained after the mixing of two parts diesel component.The present invention can be directed to the independent processing of making choice property of different type raw material by reasonably separating and process, so as to reasonably produce qualified gasoline and diesel product using poor quality catalytic cracking diesel.
Description
Technical field
The present invention relates to a kind of processing and treating method of catalytic diesel oil, specifically a kind of processing catalytic cracking diesel oil life
The method for producing premium-type gasoline and production fine-quality diesel oil.
Background technology
Catalytic cracking is most important secondary processing process and the core of heavy oil lighting in current petroleum refining industry
Technique.With Global Oil increasingly heaviness, the processing capacity of FCC apparatus is also continuously improved, and using various mink cell focuses as raw material, leads to
It crosses catalytic cracking reaction and obtains major product high-knock rating gasoline, while generate substantial amounts of sulphur, nitrogen, arene content height, 16
Alkane value or Cetane lndex are low, and the catalytic diesel oil that stability is very poor.And the requirement of environmental regulation is also increasingly harsh, while bavin
The index of oil product is also stepping up, and has strict requirements to sulfur content therein, arene content, Cetane lndex etc..
So while the yield of this part poor ignition quality fuel is reduced, it is also desirable to find a kind of suitable method and it is processed
To meet the requirement that enterprise product dispatches from the factory.
Catalytic Hydrogenation Techniques, rationally using petroleum resources, improve product quality for improving the level of crude oil processing, improve light
Matter oil yield and reduction atmosphere pollution all have great importance, the condition being especially deteriorated again in current this petroleum resources change
Under, the importance of catalytic hydrogenation just more highlights, and by being suitably hydrogenated with, can improve the hydrogen-carbon ratio in fuel oil,
Optimize product quality and improve discharge standard, become the indispensable component of petrochemical industry at present, it is main
Process can be divided into hydrotreating and be hydrocracked.
It is very severe due to catalytic diesel oil property, so the means that can be currently handled are relatively simple, with regard to China
For, catalytic diesel oil and hydrogen addition technology are predominantly combined processing by the means that can be relied on, such as by catalytic diesel oil and straight run bavin
Oil mixing after carry out hydrofinishing, catalytic diesel oil is mixed with straight-run gas oil after be hydrocracked and occur in recent years general
Catalytic diesel oil individually carries out the transformation technology of cracking production gasoline.
CN1955257A describes a kind of method of high-output qulified industrial chemicals, and poor quality mainly is catalyzed catalytic cracking bavin
Oil mixes in proportion with hydrogenating materials, and then by controlling, reaction condition produces catalytic reforming raw material and quality steam cracks second processed
Alkene raw material.Although catalytic cracking poor ignition quality fuel can be processed, add the processing approach of inferior raw material and be converted into quality product,
But the ratio for mixing refining catalytic diesel oil is still subject to certain restrictions, accessible catalytic diesel oil amount very little, while in condition of high voltage
The consumption of lower processing catalytic diesel oil hydrogen is very big.
CN103773455A is the invention discloses a kind of vegetable and animals oils, catalytic diesel oil Unionfining technological process, substantially
Or catalytic diesel oil is handled by way of hydrofinishing, although catalytic diesel oil can be processed by suitable raw material proportioning,
It is the catalytic diesel oil amount very little that refining can be mixed due to the limitation of diesel product index, can not thoroughly solves big catalysed refinery enterprise
The process problem of a large amount of catalytic diesel oils.
CN104611029A discloses a kind of catalytic cracking diesel oil hydrogenating conversion process, and catalytic diesel oil is first after being mixed with hydrogen
Hydrofining reaction is carried out into hydrofining reactor, hydrocracking reactor is then entered back into and carries out hydrocracking reaction.
Although can process catalytic diesel oil component with effect by certain catalyst grade produces high-knock rating gasoline, chemical hydrogen consumption
It is relatively high, it is larger to the hydrogen resources requirement of enterprise.
The content of the invention
In view of the problems of the existing technology, the technical problem to be solved in the present invention is to provide a kind of processing catalytic diesel oil is former
The hydrocracking method of material.Carry out cutting separation after the catalytic diesel oil analysis that this method will be conventional, by tricyclic therein and
Above aromatic hydrocarbons heavy constituent（Aromatic hydrocarbons simultaneously containing a small amount of monocyclic and bicyclic belt length side chain）And aromatic hydrocarbons light component separates, restructuring
Dividing by obtaining thrcylic aromatic hydrocarbon and non-thrcylic aromatic hydrocarbon after aromatics seperation device, non-thrcylic aromatic hydrocarbon is mixed with above-mentioned aromatic hydrocarbons light component,
Thrcylic aromatic hydrocarbon directly generates high-knock rating gasoline after being reacted, raw after blending ingredients carry out the modification reaction of open loop not chain rupture
Into high cetane number diesel oil.While handling catalytic diesel oil raw material, each component is individually processed, with strong points, especially
For conversion reaction, base feed has turned into optimum thrcylic aromatic hydrocarbon, can produce good fuel oil products, simultaneously
Compared to other techniques, there is the characteristics of chemical hydrogen consumption is low, and product restructuring is flexible.
The present invention provides a kind of combined technical methods for processing catalytic diesel oil, include the following steps：
a）Catalytic diesel oil raw material obtains light component and heavy constituent after cutting separates；
b）Step a）Gained light component as feedstock oil into the reactor containing hydrofinishing and catalyst for hydro-upgrading into
Row modification reaction, obtained reaction effluent carry out gas-liquid separation, fractional distillation process, obtain reformulated gasoline and modification diesel oil；
c）Step a）The heavy constituent of gained enters aromatics seperation device, and thrcylic aromatic hydrocarbon therein and non-thrcylic aromatic hydrocarbon component are carried out
Separation；
d）Step c）The non-thrcylic aromatic hydrocarbon component of gained and step b）In light component mixing, carry out modification reaction together；
e）Step c）The thrcylic aromatic hydrocarbon of gained enters the reactor containing hydrofinishing and hydrogenation conversion catalyst as feedstock oil
Middle carry out conversion reaction, obtained reaction effluent carry out the processes such as gas-liquid separation, fractionation, obtain conversion gasoline and convert diesel oil
Deng；
f）Step b）Middle gained reformulated gasoline and step e）Gasoline products are obtained after middle gained conversion gasoline mixing；Step b）It is described
Modification diesel oil directly as diesel product；Step e）It is acquired conversion diesel oil after cycling with step a）In light component mixing
Carry out jointly modification reaction or with step b）In the mixing of modification diesel oil as diesel product.
Step a）The initial boiling point of the catalytic diesel oil component is generally 160~240 DEG C, preferably 180~220 DEG C, evaporates eventually
Generally 320~420 DEG C of point, preferably 350~390 DEG C, arene content is preferably generally 60~90 wt% in more than 50wt%,
Middle thrcylic aromatic hydrocarbon is preferably generally more than 10wt% in more than 5wt%；The density of the diesel raw material is generally in 0.91gcm-3With
On, preferably 0.93gcm-3More than.
The catalytic diesel oil raw material can be that any base of processing belongs to oily kind of obtained catalytic cracking production, such as can select
The catalytic diesel oil obtained from processing middle-eastern crude can be specifically to process the catalytic diesel oil that Iran crude, Saudi Arabia's crude oil etc. obtain
Component.
Step a）The cutting is separated into conventional gas-liquid separation process, and well known flash distillation point in the industry may be employed
From or the separated mode of column plate, the purpose is to which catalytic diesel oil is divided into two parts of weight, according to the description in this method,
Cut-point is generally 290~350 DEG C, preferably 300~340 DEG C.The light component is the liquid fraction less than cut-point, described
Restructuring be divided into liquid fraction higher than cut-point.
Step b）With step e）Described in Hydrobon catalyst include carrier and the hydrogenation metal that is loaded.With catalysis
On the basis of the weight of agent, metal component of group VIB in the periodic table of elements is generally included, as tungsten and/or molybdenum are calculated as 10% with oxide
~ 35%, it is preferably 15% ~ 30%；Group VIII metal such as nickel and/or cobalt are calculated as 1% ~ 7% with oxide, are preferably 1.5% ~ 6%.Carrier
For inorganic refractory oxide, aluminium oxide, amorphous silicon aluminium, silica, titanium oxide etc. are selected generally from.It is wherein conventional hydrocracking
Pretreatment catalyst can select existing various commercial catalysts, such as Fushun Petrochemical Research Institute（FRIPP）Development is opened
Hair 3936,3996, the Hydrobon catalysts such as FF-16, FF-26, FF-36, UDS-6；This field can also be pressed as needed
Common sense prepared.
Step b）With step e）Described in gas-liquid separation, fractional distillation process be content well-known to those having ordinary skill in the art.
Gas-liquid separation is the separation process of hydro-upgrading process product, generally mainly contains high-low pressure separator, Xun Huan hydrogen system etc.；
The process that fractional distillation process further refines for the liquid-phase product of gas-liquid separation, generally mainly contains stripper, fractionating column, side line tower
Deng.
Step b）The catalyst for hydro-upgrading is the catalyst for hydro-upgrading containing molecular sieve, refers to that general hydrogenation is split
Change catalyst or be exclusively used in the catalyst for hydro-upgrading of the present invention.The catalyst for hydro-upgrading include hydrogenation active metals,
Molecular sieve component and alumina support.General catalyst for hydro-upgrading is divided by hydrogenation active metal components such as Wo, Mo, Co, Ni
The compositions such as sub- screen banks point and alumina support, on the basis of the weight of catalyst, the content of hydrogenation component is 5%~40%.It is special
It is to include WO by weight in the catalyst for hydro-upgrading of the present invention3(or MoO3) 10~30wt%, NiO (or CoO) 3~
25~60wt% of 15wt%, 10~40wt% of molecular sieve and aluminium oxide, wherein molecular sieve can be Y type molecular sieves.Its main effect
It is that can be directed to the hydro-upgrading process that double ring arene carries out saturation open loop but not chain rupture, conventional hydro modifying catalyst can select
Select existing various commercial catalysts, for example, FRIPP develop 3963, the catalyst such as FC-18.It can also press as needed
The common sense of this field prepares specific catalyst for hydro-upgrading.
Step c）The aromatics seperation device is the technical process of physical extraction, and principle is for not jljl using solvent
The difference of matter solubility is extracted, then separated process again, and solvent can be sulfolane, furfural, NMP or phenol etc., this
Process can be realized using industrial widely used Aromatics Extractive Project or furfural extraction unit, preferably furfural treatment unit,
Extracting part operating condition be：0.01~0.8MPa of tower pressure interior force, 50~150 DEG C of temperature, solvent quality cycle matter than 1~8
Measure ratio 0~0.6；Preferred operating condition is 0.02~0.1MPa of tower pressure interior force, and temperature is 60~110 DEG C, solvent quality than 2~
7, cycle mass ratio 0.2~0.5.
Step c）The aromatics seperation device or the technical process of adsorbing separation, utilize different type molecule
The difference of size selects or prepares suitable molecular sieve and carries out effective adsorption process to it, then using desorption separation etc.
Step, so as to which ideal composition and undesirable components be separated.
Step e）The hydrogenation conversion catalyst is the hydrogenation conversion catalyst containing molecular sieve, is special according to this method
The catalyst of preparation.The hydrogenation conversion catalyst includes hydrogenation active metals, molecular sieve component and alumina support.Generally
Hydrogenation conversion catalyst by the hydrogenation active metal components such as Wo, Mo, Co, Ni, the compositions such as molecular sieve component and alumina support.
The hydrogenation conversion catalyst for being exclusively used in the present invention is to include WO by weight3(or MoO3) 8~28 wt%, NiO (or CoO) 3~
15~50 wt% of 13 wt%, 20~50 wt% of molecular sieve and aluminium oxide.
Step e）Hydrogenation conversion catalyst in, the molecular sieve be small crystal grain Y-shaped molecular sieve.Small-grain Y-type molecule
The grain size of sieve is 400~600nm, and infrared 0.2~0.5mmol/g of total acid, middle strong acid ratio is more than 75%（mmol·g-1/mmol·
g-1）, 2.430~2.436nm of cell parameter；0.5~0.7 cm of pore volume3The secondary pore pore volume of/g, wherein 2-8nm account for total pore volume
Ratio is more than 55%.The Y little crystal grain types molecular sieve has acid centre that is more accessible and exposing, is conducive to hydrocarbon point
The diffusion of son can improve the preferential conversion ability of cyclic hydrocarbon particularly thrcylic aromatic hydrocarbon, orient by the aromatic ring among thrcylic aromatic hydrocarbon into
It row saturation and is broken, the maximum amount of high-octane gasoline component of production.Hydro-conversion containing the small crystal grain Y-shaped molecular sieve
Catalyst, main function are the reactions for the making choice property of thrcylic aromatic hydrocarbon that can be directed in raw material, and to two rings of non-tricyclic
And the selectivity of mononuclear aromatics is poor.There are certain difference, conventional Y type molecular sieves with conventional Y type molecular sieve for the Y type molecular sieve
Grain size be generally 800~1200nm, pore volume is 0.35~0.50 cm3/ g, 2-8nm secondary pore pore volume account for the ratio of total pore volume
Example general 30~50%, middle strong acid ratio 50~70%.The hydrogenation conversion catalyst can be as described above according to ability
The common sense in domain prepares satisfactory catalyst.
In the present invention, the term " middle strong acid " is the conventional conception of field of catalyst preparation.It uses NH3- TPD is carried out
Analysis, 150-250 DEG C of desorption are defined as weak acid, and 250-400 DEG C of desorption is defined as middle strong acid, the boundary of 400-500 DEG C of desorption
It is set to strong acid,
Step e）In, the hydrogenation conversion catalyst preferably matches somebody with somebody filling scheme using catalyst grade.Hydrogenation conversion catalyst bag
At least two catalyst beds are included, according to the engagement sequence with reaction mass, the crystalline substance of Y type molecular sieve in the catalyst of upstream bed
Born of the same parents' parameter is generally 2.430~2.433nm, infrared 0.2~0.35 mmol/g of total acid；Y types molecule in catalyst in down stream
The cell parameter of sieve is generally 2.433~2.436nm, infrared 0.35~0.5 mmol/g of total acid.With the catalysis in the bed of upstream
Agent is compared, in down stream in catalyst secondary pore account for total pore volume ratio it is low 5~20 percentage points, and Y type molecular sieve contains
Amount is higher by 5~20 percentage points.The routine of this field may be employed in the modification process of the Y type molecular sieve wherein met the requirements
Technology carries out, and the method as described in being referred to CN104588073A is modified Y type molecular sieve processing.
It, can be by catalyst according to the difference of activity according to the difference of the cell parameter of Y type molecular sieve and infrared total acid content
It is matched.So the Hydrogenation of catalyst and cracking performance can more be closed along the flow direction of reaction mass
Reason it is excessive, tricyclic complexity aromatic hydrocarbons therein is particularly to reactant, is more targetedly hydrogenated with and cracking process, by it
Intermediate ring carries out saturation cracking, directs it to further maximum and is converted into high-octane gasoline component so that product
The content of middle polycyclic aromatic hydrocarbon can be reduced significantly, and the selectivity of hydro-conversion further improves.
The catalyst loaded using grading technology, the catalyst of upstream is first with containing a large amount of thrcylic aromatic hydrocarbons and appropriate two
The catalytic diesel oil heavy constituent of cycloaromatics, which is in contact, is reacted.Since the polarity of thrcylic aromatic hydrocarbon is stronger, adsorption capacity is strong, and cracks
Difficulty is little, therefore the catalyst of upstream has suitable molecular sieve content and secondary pore ratio, acid moderate, can be effective
Thrcylic aromatic hydrocarbon is converted into the high octane gasoline component containing mononuclear aromatics, and the molecular sieve in the catalyst in downstream and
Secondary pore ratio is slightly higher.It is acid stronger, can two cycloaromatics be further converted into the high-knock rating gasoline containing mononuclear aromatics
Component, therefore above-mentioned catalyst grading distribution scheme is used, the complexity that can be reacted according to different component in raw material is big by it
Part is converted into target product, selectively further improves.
Step b）The reaction condition of described modification reaction is：Volume space velocity is 0.5~4.0h-1, preferably 0.8~2.5h-1；Hydrogen partial pressure is 4~13MPa, preferably 6~10MPa；Entrance hydrogen to oil volume ratio is 300:1~800:1, preferably 400:1~700:
1；Reaction temperature is 340~410 DEG C, preferably 360~400 DEG C.
Step c）The reaction condition of the conversion reaction is：Volume space velocity is 0.5~4.0h-1, preferably 0.8~2.5h-1；Hydrogen partial pressure is 4~13MPa, preferably 6~10MPa；Entrance hydrogen to oil volume ratio is 300:1~800:1, preferably 400:1~700:
1；Reaction temperature is 360~430 DEG C, preferably 380~420 DEG C.According to the difference that cut point and aromatic hydrocarbons are distributed, conversion reaction root
It is more than the conversion ratio of cut point fraction according to the content control of thrcylic aromatic hydrocarbon in raw material, general control mass transitions rate is not higher than 70%,
Preferably no greater than 50%.
Step f）The gasoline products and diesel product are that can enter the high-quality reconciliation that reconciliation pond carries out product oil reconciliation
Component.
Compared with prior art, catalytic diesel oil processing and treating method of the invention has the following advantages：
1st, the higher catalytic diesel oil of arene content is processed, it, will after the separated cutting process of weight and aromatics seperation device
Component containing thrcylic aromatic hydrocarbon and non-thrcylic aromatic hydrocarbon carry out respectively it is separately machined, can will be most suitable as hydro-conversion raw material
Thrcylic aromatic hydrocarbon carries out conversion reaction.The technology of preparing of combined catalyst and technologic state modulator, can be to greatest extent
Producing high-octane gasoline component, and can non-thrcylic aromatic hydrocarbon mixture be subjected to saturation open loop and hydrogenation process, to greatest extent
Production high cetane number diesel component.The method of the present invention is separated by rational raw material and process, can be by difference
The raw material of type is targetedly individually processed, and complicated petroleum refining process is simplified, and is urged in processing poor quality
When changing diesel oil, while considering difficulty of processing, the processing suitability and specific aim of each component are referred into maximum, had very big
Advantage.
2nd, separation, hydro-upgrading and hydro-conversion are carried out depth coupling by the method for the present invention in technological process, are being had
On the basis of specific aim handles raw material and improves product quality, preferable comprehensive process effect is obtained.Although in the course of the description
Each unit independence is stronger, but different units organically can be combined and shared in practical application, has and saves equipment, behaviour
Make the advantages such as expense is low, simultaneously because the improvement for the heat-exchange system that assemblage zone comes, decrease the energy of device to a certain extent
It consumes, reduce investment, be with a wide range of applications.
3rd, according to the method for the present invention, had developed again on the basis of original catalytic diesel oil hydrogenation conversion catalyst new
The stronger reforming catalyst of specific aim and a gross appearance of technological progress can provide more catalysis selecting partys for enterprise
To bringing more intuitive economic benefit.The specific surface of small crystal grain molecular sieve used in hydrogenation conversion catalyst of the present invention is big, especially
It is that external surface area substantially increases, the ratio between surface atom number and volume atomicity increased dramatically, and duct is shortened, and exposed aperture is increased,
So that small crystal grain molecular sieve has higher reactivity and surface energy, apparent bulk effect and skin effect are shown.
Specifically, there are following several respects：The increase of molecular sieve outer surface product so that more activated centres are exposed, and are effectively disappeared
Except diffusion effect, catalyst efficiency is made to be not fully exerted, the reactivity worth so as to make macromolecular is improved；Surface energy
Increase so that the increase of the adsorbance of molecular sieve, adsorption rate are accelerated, so that effective adsorption capacity of molecular sieve is changed
It is kind；The duct of small crystal grain molecular sieve is short, and crystal inside diffusional resistance is small, and huge external surface area has small crystal grain molecular sieve in addition
Exposed to outside, this not only improves the quick disengaging of reactant or product molecule, and can prevent or reduce because of production in more apertures
Accumulation of the object in duct and form knot carbon, improve the turnover rate of reaction and the service life of molecular sieve；With uniform skeleton
Component radial distribution, so as to improve activity and selectivity；It is more advantageous to the realization of Zeolite synthesis post-modification technology；For dividing
For the catalyst of son sieve carrying metal, be conducive to improve payload amount and the improvement of metal component using small crystal grain molecular sieve
The dispersion performance of metal component.It additionally can further increase the ratio of secondary pore in molecular sieve by subsequent modification
Example.Unimpeded molecular sieve pore passage structure is more conducive to macromolecules adsorption reaction and desorption, enhances determining for macromolecular heavy aromatics significantly
To hydro-conversion ability, intermediate ring filling and cracking can so that high octane gasoline component is more in product.
Description of the drawings
Fig. 1 is the flow diagram of present invention process method.
Specific embodiment
The combined technical method of the present invention is described in detail below in conjunction with the accompanying drawings.Technological process is only listed in Fig. 1
It is main to illustrate, it is omitted some necessary equipment and container in schematic diagram.
As shown in Figure 1, present invention processing catalytic diesel oil group technology flow is as follows：Catalytic diesel oil raw material 1 enters separator 2
Afterwards, top obtains light component 3, and lower part obtains heavy constituent 12, after light component 3 is mixed with hydrogen 4, into hydro-upgrading reactor 5,
With catalyst haptoreaction, reaction effluent 6 is into separation, fractionating system 7, and top discharge gas phase 8, middle part obtains reformulated gasoline
9, bottom obtains modification diesel oil 10；For heavy constituent 12 into aromatics seperation device 13, top obtains non-tricyclic component 14 and light component 3
Together into reforming reactor 5, bottom is obtained after tricyclic component 15 mixes with hydrogen 16, into hydroconversion reactions device 17, with
The reforming catalyst of grading（A and B）Haptoreaction, reaction effluent 18 discharge gas phase into separation, fractionating system 19, top
20, middle part obtains conversion gasoline 21, and bottom obtains conversion diesel oil 22 and is recycled back to before reactor 5 and light component 3 and non-tricyclic group
Divide the common reaction of 14 mixing or be mixed to get qualified diesel oil 11 with modification diesel oil 10；Reformulated gasoline 9 is mixed with conversion gasoline 21
To specification gasoline 23.
The combined technical method of the present invention is further described followed by specific embodiment.
Aromatics seperation device involved in following embodiment and/or comparative example, operating condition are as follows：Furfural is selected as pumping
Extraction solvent, tower 0.04~0.13MPa of voltage-controlled system, temperature are 50~90 DEG C, and solvent is than 3, recycle ratio 0.3, can will be different types of
Aromatic hydrocarbons is compared preferable separation.
Embodiment 1
Using group technology flow shown in FIG. 1, catalytic diesel oil is selected to carry out hydrogenation production as raw material, weight component is selected to cut
Cutpoint is 290 DEG C, and heavy aromatics separation selection furfural extraction unit, purpose product is premium-type gasoline and diesel oil.Make in embodiment
Catalyst be commercial catalyst FF-36 hydrotreating catalysts, 3963 catalyst for hydro-upgrading and this technology it is special plus
Hydrogen reforming catalyst A and B（In catalyst composition in addition to metal oxide and Y type molecular sieve, surplus is aluminium oxide）.
The combined technical method of the present invention is further described followed by specific embodiment.
Embodiment 1
Using technological process shown in FIG. 1, catalytic diesel oil is selected to carry out hydrogenation production as raw material, select weight component cut point
For 300 DEG C, purpose product is premium-type gasoline and diesel oil.The catalyst used in embodiment is hydrogenated with for commercial catalyst FF-36
Handle catalyst, 3963 catalyst for hydro-upgrading and hydrogenation conversion catalyst A.
Embodiment 2
Using group technology flow shown in FIG. 1, catalytic diesel oil is selected to carry out hydrogenation production as raw material, weight component is selected to cut
Cutpoint is 300 DEG C, and purpose product is premium-type gasoline and diesel oil.The catalyst used in embodiment is commercial catalyst FF-36
Hydrotreating catalyst, 3963 catalyst for hydro-upgrading and the special hydrogenation conversion catalyst A and B of this technology.
Embodiment 3
Using technological process shown in FIG. 1, catalytic diesel oil is selected to carry out hydrogenation production as raw material, select weight component cut point
For 310 DEG C, purpose product is premium-type gasoline and diesel oil.The catalyst used in embodiment is hydrogenated with for commercial catalyst FF-36
Handle catalyst, 3963 catalyst for hydro-upgrading and hydrogenation conversion catalyst A and B.
Comparative example 1
Using technological process shown in FIG. 1, catalytic diesel oil is selected to carry out hydrogenation production as raw material, select the cutting of weight component
Point is 300 DEG C, and purpose product is premium-type gasoline and diesel oil.The catalyst used in comparative example adds for commercial catalyst FF-36
Hydrogen handles the hydrogenation conversion catalyst C of catalyst, 3963 catalyst for hydro-upgrading and routine.
Comparative example 2
Comparative example 2 is Conventional catalytic diesel oil hydrogenation conversion process process, and catalytic diesel oil is selected to carry out hydrogenation production, mesh as raw material
Product be premium-type gasoline and ordinary diesel oil.The catalyst used in comparative example is urged for commercial catalyst FF-36 hydrotreatings
The hydrogenation conversion catalyst C of agent and routine.
Special and conventional hydrogenation conversion catalyst property is shown in Table 1, and the property of feedstock oil is shown in Table 2, and operating condition is shown in Table
3, major product property is shown in Table 4.
The main physico-chemical property of the special catalyst of 1 this technology of table
2 feedstock oil property list of table
3 reaction condition of table
3 reaction condition of continued
It can be seen from table 2 and 3 embodiment of table and comparative example for a large amount of catalytic diesel oil production gasoline are processed, this technology
There is very big advantage in hydrogen consumption.
4 product main character of table
Using present invention processing catalytic diesel oil raw material it can be seen from examples detailed above, compared with comparative example, in a large amount of processing catalysis
On the basis of diesel oil and low hydrogen consumption, the naphtha and diesel product property produced are respectively provided with certain advantage.
It can be seen that from above example and comparative example after catalytic diesel oil raw material is cut and separated by this method respectively
Processing, can the maximum amount of processing diesel component inferior, can according to the actual conditions of enterprise, from the balances of hydrogen resources or
It is flexible to adjust diesel and gasoline ratio example in the angle of saving, it is produced according to the changes in demand in market.
Separation, hydro-upgrading and hydro-conversion are combined in technological process, in targetedly processing raw material simultaneously
On the basis of improving product quality, preferable comprehensive process effect is obtained.Although each unit independence is stronger in the course of the description,
But different units can be combined in practical application and organically combine and share, have that save equipment, operating cost low etc. excellent
Point, simultaneously because the improvement for the heat-exchange system that assemblage zone comes, decreases the energy consumption of device, reduces throwing to a certain extent
Money, is with a wide range of applications.
Claims (18)
1. a kind of combined technical method for processing catalytic diesel oil, includes the following steps：
a）Catalytic diesel oil raw material obtains light component and heavy constituent after cutting separates；The light component and heavy constituent are cut
Temperature is cut as 290~350 DEG C；
b）Step a）Gained light component as feedstock oil into the reactor containing hydrofinishing and catalyst for hydro-upgrading into
Row modification reaction, obtained reaction effluent carry out gas-liquid separation, fractional distillation process, obtain reformulated gasoline and modification diesel oil；
c）Step a）The heavy constituent of gained enters aromatics seperation device, and thrcylic aromatic hydrocarbon therein and non-thrcylic aromatic hydrocarbon component are carried out
Separation；
d）Step c）The non-thrcylic aromatic hydrocarbon component of gained and step b）In light component mixing, carry out modification reaction together；
e）Step c）The thrcylic aromatic hydrocarbon of gained enters the reactor containing hydrofinishing and hydrogenation conversion catalyst as feedstock oil
Middle carry out conversion reaction, obtained reaction effluent carry out the processes such as gas-liquid separation, fractionation, obtain conversion gasoline and convert diesel oil
Deng；
f）Step b）Middle gained reformulated gasoline and step e）Gasoline products are obtained after middle gained conversion gasoline mixing；Step b）It is described
Modification diesel oil directly as diesel product；Step e）It is acquired conversion diesel oil after cycling with step a）In light component mixing
Carry out jointly modification reaction or with step b）In the mixing of modification diesel oil as diesel product.
2. combined technical method described in accordance with the claim 1, which is characterized in that step a）At the beginning of the catalytic diesel oil component
It evaporates a little for 160~240 DEG C, the end point of distillation is 320~420 DEG C, and arene content is in more than 50wt%.
3. combined technical method described in accordance with the claim 2, which is characterized in that step a）At the beginning of the catalytic diesel oil component
It evaporates a little for 180~220 DEG C, the end point of distillation is 350~390 DEG C, and arene content is 60~90 wt%.
4. according to the combined technical method described in Claims 2 or 3, which is characterized in that the density of the diesel raw material is
0.91g·cm-3More than.
5. combined technical method described in accordance with the claim 1, which is characterized in that the cutting temperature of light component and the heavy constituent
It spends for 300~340 DEG C.
6. combined technical method described in accordance with the claim 1, which is characterized in that the Hydrobon catalyst includes carrier
With the hydrogenation metal loaded；On the basis of the weight of catalyst, including metal component of group VIB in the periodic table of elements to aoxidize
Object is calculated as 10% ~ 35%, and group VIII metal such as nickel and/or cobalt are calculated as 1% ~ 7% with oxide；Carrier is inorganic refractory oxide.
7. combined technical method described in accordance with the claim 1, which is characterized in that step b）The catalyst for hydro-upgrading bag
Include hydrogenation active metals, molecular sieve component and alumina support；On the basis of the weight of catalyst, catalyst for hydro-upgrading includes
WO3Or MoO325~60 wt% of 10~30 3~15wt% of wt%, NiO or CoO, 10~40 wt% of molecular sieve and aluminium oxide.
8. combined technical method described in accordance with the claim 1, which is characterized in that step c）The aromatics seperation uses furfural
Refined, the operating condition of extracting part is：0.01~0.8MPa of tower pressure interior force, 50~150 DEG C of temperature, solvent is followed than 1~8
Ring is than 0~0.6.
9. according to the combined technical method described in claim 8, which is characterized in that the operating condition is：Tower pressure interior force
0.02~0.1MPa, temperature are 60~110 DEG C, and solvent is than 2~7, recycle ratio 0.2~0.5.
10. combined technical method described in accordance with the claim 1, which is characterized in that step e）The hydrogenation conversion catalyst
Include WO by weight3Or MoO38~28 3~13 wt% of wt%, NiO or CoO, 20~50 wt% of Y type molecular sieve and aluminium oxide
15~50 wt%.
11. according to the combined technical method described in claim 10, which is characterized in that the grain size of the Y type molecular sieve is 400
~600nm, infrared 0.2~0.5mmol/g of total acid, middle strong acid ratio are more than 75%, 2.430~2.436nm of cell parameter；Pore volume
0.5~0.7 cm3The secondary pore pore volume of/g, wherein 2-8nm account for the ratio of total pore volume more than 55%.
12. according to the combined technical method described in claim 11, which is characterized in that the hydrogenation conversion catalyst is included extremely
Few two catalyst beds, compared with the catalyst in the bed of upstream, the secondary pore of 2-8nm accounts for always in catalyst in down stream
The ratio of pore volume is 5~20 percentage points low, and the content of Y type molecular sieve is higher by 5~20 percentage points.
13. according to the combined technical method described in claim 12, which is characterized in that according to the engagement sequence with reaction mass,
The cell parameter of Y type molecular sieve is 2.430~2.433nm, infrared 0.2~0.35 mmol/ of total acid in the catalyst of upstream bed
g；The cell parameter of Y type molecular sieve is 2.433~2.436nm in catalyst in down stream, infrared total acid 0.35~0.5
mmol/g。
14. combined technical method described in accordance with the claim 1, which is characterized in that step b）The reaction of the modification reaction
Condition is：Volume space velocity is 0.5~4.0h-1, hydrogen partial pressure is 4~13MPa, and entrance hydrogen to oil volume ratio is 300:1~800:1, instead
It is 340~410 DEG C to answer temperature.
15. combined technical method according to claim 14, which is characterized in that step b）The reaction of the modification reaction
Condition is：Volume space velocity is 0.8~2.5h-1, hydrogen partial pressure is 6~10MPa, and entrance hydrogen to oil volume ratio is 400:1~700:1, instead
It is 360~400 DEG C to answer temperature.
16. combined technical method described in accordance with the claim 1, which is characterized in that step e）The reaction of the conversion reaction
Condition is：Volume space velocity is 0.5~4.0h-1, hydrogen partial pressure is 4~13MPa, and entrance hydrogen to oil volume ratio is 300:1~800:1, instead
It is 360~430 DEG C to answer temperature.
17. according to the combined technical method described in claim 16, which is characterized in that step e）The reaction of the conversion reaction
Condition is：Volume space velocity is 0.8~2.5h-1, hydrogen partial pressure is 6~10MPa, and entrance hydrogen to oil volume ratio is 400:1~700:1, instead
It is 380~420 DEG C to answer temperature.
18. combined technical method described in accordance with the claim 1, which is characterized in that step e）The hydroconversion reactions control
System is more than step a）The mass transitions rate of cut point temperature fractions is not higher than 60%.
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