CN106520193B - A method of the high aromatic hydrocarbons inferior raw material of processing - Google Patents
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Abstract
The present invention relates to refining arts, disclose a kind of method of the high aromatic hydrocarbons inferior raw material of processing, and this method includes：High aromatic hydrocarbons inferior raw material, gas-liquid mixed logistics and tail oil from hydrocracking reaction area are introduced into hydrotreating reaction area and are reacted；Then the reaction effluent in the hydrotreating reaction area is detached and is fractionated successively, obtain light petrol, middle gasoline, heavy petrol, intermediate oil, diesel oil and tail oil；The tail oil and the optional diesel oil are introduced into hydrotreating reaction area and are recycled, and is introduced into hydrocracking reaction area and reacts after the intermediate oil is mixed with hydrogeneous logistics, obtains the gas-liquid mixed logistics.The bicyclic above aromatic component of low value in high aromatic hydrocarbons inferior raw material can be efficiently converted into high octane gasoline component by the above method using the present invention, while take into account the small molecules aromatic hydrocarbons such as production benzene,toluene,xylene.
Description
Technical field
The present invention relates to refining arts, and in particular, to a method of the high aromatic hydrocarbons inferior raw material of processing, more specifically,
It is related to a kind of method that high-knock rating gasoline and/or aromatic hydrocarbons are produced by high aromatic hydrocarbons inferior raw material.
Background technology
Crude resources is increasingly in short supply, and each oil plant is numerous and confused to consider further processing oil refining process in order to increase economic efficiency
In low-value product, to improve the yield of high-value product.
As the catalytic cracking technology of one of the main heavy oil lighting technology in China, although catalytic cracking vapour can be produced
The high-value products such as oil, but also have a large amount of catalytic cracking diesel oil (i.e. LCO) and catalytic cracking recycle oil (i.e. HCO) etc. low simultaneously
Value product generates.Moreover, in order to improve light oil yield, oil plant further increases catalyzed cracking processing depth and processing energy
Power, the yield for resulting in the low-value products such as LCO and HCO further increase.
For the LCO in above-mentioned low-value product, general oil plant processes LCO using conventional hydro process for refining, takes off
Except the impurity such as sulphur, nitrogen in diesel oil, saturation part aromatic hydrocarbons, production low-sulfur diesel-oil blending manufacture.But the technical process Cetane number
Increase rate is limited, and diesel oil density variation is also little.For HCO, general oil plant uses catalytic cracking unit self-loopa
To further increase yield of gasoline, but make the utilization ratio of HCO not high using the mode of operation of self-loopa.
Domestic and international each oil refining enterprise develops the relevant technologies one after another, to improve the economy of LCO and HCO processing and utilization processes.
CN103865577A discloses a kind of method that catalytic cracking diesel oil produces light aromatics and clean fuel oil product.It should
Method includes：(1) catalytic cracking diesel oil is mixed with hydrogen, and hydrofining reaction is carried out at the same time after being mixed with crackate, with de-
Sulphur removal nitrogen impurity, and carry out alkene saturation and aromatic hydrogenation saturation；(2) catalytic cracking diesel oil after refining is cut, wherein
>355 DEG C of distillate comes back for being hydrocracked after mixing with hydrogen；(3) cutting tails oil is stripped, obtains richness
Tapped oil containing polycyclic aromatic hydrocarbon and raffinating oil rich in alkane；(4) it raffinates oil as cleaning diesel oil blending component rich in alkane；
(5) aromatic hydrocarbons tapped oil hydrocracking reaction production light aromatics and clean gasoline blending component are rich in；(6) tapped oil is hydrocracked
Component detaches after cutting,>195 DEG C of fraction is used as cleaning diesel oil blending component,<195 DEG C of distillate obtains light aromatics production
Product and clean gasoline blending component.But this method is not particularly suited for the Gao Fang that processing polycyclic aromatic hydrocarbon content is higher than 30 weight %
Hydrocarbon inferior raw material can not obtain high-octane gasoline when processing high aromatic hydrocarbons inferior raw material using the method for the prior art
And the diesel oil of high cetane number.
CN103214332A discloses a kind of method producing light aromatics and high-quality oil product by catalytic cracking.This method
Include the following steps：(1) catalytic cracking diesel oil is stripped with extraction solvent, obtains the tapped oil and richness rich in polycyclic aromatic hydrocarbon
Raffinating oil containing alkane；(2) tapped oil is carried out under hydrogenation conditions hydrofinishing and be hydrocracked production light aromatics,
High-knock rating gasoline fraction.This method, can by-product Cetane number high diesel oil and high-octane rating while obtaining light aromatics
Gasoline.However this method is not suitable for processing the high aromatic hydrocarbons inferior raw material that polycyclic aromatic hydrocarbon content is higher than 30 weight % yet, using this
When the method for the prior art processes high aromatic hydrocarbons inferior raw material, the bavin of high-octane gasoline and high cetane number can not be obtained
Oil.
CN103773489A discloses a kind of method of hydrotreating handling high nitrogen, high aromatic hydrocarbons poor ignition quality fuel raw material, and this method is adopted
With the integrated two-stage method technological process of the first reaction zone-centre separation-second reaction zone, high nitrogen, high arene content bavin inferior
Oil carries out hydrodenitrogeneration, the bicyclic above aromatic hydrogenation saturated reaction in the first reaction zone, after centre detaches, obtains organic nitrogen and contains
Amount is less than 200ppm, and total arene content adds hydrogen logistics more than 60 weight %, raw material is provided for second reaction zone；It is anti-second
Answer area after mitigating refined and hydro-upgrading, fractionation obtains high octane gasoline component.However, processing high aromatic hydrocarbons using this method
When inferior raw material, obtained high octane gasoline component yield is low, and product is single.
Invention content
The purpose of the present invention is the economic values of the high aromatic hydrocarbons inferior feedstock oil of maximization, and obtain high-knock rating gasoline
And/or aromatic hydrocarbons.
To achieve the goals above, the method that the present invention provides a kind of high aromatic hydrocarbons inferior raw material of processing, this method including
Implement in the system in hydrotreating reaction area, hydrocracking reaction area and fractionating column, this method includes：High aromatic hydrocarbons is inferior former
Material, the gas-liquid mixed logistics from hydrocracking reaction area and the tail oil from fractionating column introduce containing Hydrobon catalyst and
Hydrodesulfurization nitrogen is carried out in the hydrotreating reaction area of hydrocracking catalyst I, arenes selectivity adds hydrogen saturation, arenes selectivity
Open loop and accordance side chain cracking reaction；Then by the reaction effluent in the hydrotreating reaction area successively carry out separation and
Fractionation, obtains light petrol, middle gasoline, heavy petrol, intermediate oil, diesel oil and tail oil；By the tail oil and the optional bavin
Oil, which is introduced into hydrotreating reaction area, to be recycled, and is introduced to contain after the intermediate oil is mixed with hydrogeneous logistics and be added
It is reacted in the hydrocracking reaction area of hydrogen Cracking catalyst, obtains the gas-liquid mixed logistics, wherein the high aromatic hydrocarbons is bad
Matter raw material is light cycle oil and/or heavy-cycle oil from catalytic cracking unit.
The above method using the present invention can be by the bicyclic above aromatic component of the low value in high aromatic hydrocarbons inferior raw material
It is efficiently converted into high octane gasoline component, while taking into account the small molecules aromatic hydrocarbons such as production benzene,toluene,xylene.Moreover, of the invention
The above method also have the advantages that high income, easy to operate and lower-cost.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.Many equipment are omitted in figure, such as
Pump, heat exchanger etc., but this is well known to those of ordinary skill in the art.In the accompanying drawings：
Fig. 1 is the flow diagram of method provided by the invention.
Reference sign
1, high aromatic hydrocarbons inferior raw material 2, hydrotreating reaction area
3, cold high pressure separator 4, cold low separator
5, fractionating column 6, digester
7, circulating hydrogen compressor 8, hydrocracking reaction area
9, the hydrogeneous logistics after new hydrogen 10, pressurization
11, the gas-liquid mixed logistics of hydrocracking reaction area raw material 12, hydrocracking reaction area
13, the reaction effluent in hydrotreating reaction area
14, cold high pressure separator gaseous stream
15, hydrogen-rich gas 16, cold high pressure separator acid water
17, cold high pressure separator liquid phase stream 18, dry gas
19, cold low separator acid water 20, cold low separator liquid phase stream
21, tower overhead gas 22, light petrol
23, middle gasoline and heavy petrol 24, intermediate oil
25, diesel oil 26, tail oil
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In method of the present invention, " I ", " II " do not represent successively secondary in case of no particular description
Sequence, merely to distinguishing, those skilled in the art should not be construed as limiting the scope of the present invention.
The present invention provides a kind of method of the high aromatic hydrocarbons inferior raw material of processing, this method including hydrotreating reaction area,
Implement in the system of hydrocracking reaction area and fractionating column, this method includes：By high aromatic hydrocarbons inferior raw material, anti-from being hydrocracked
The gas-liquid mixed logistics in area and tail oil from fractionating column is answered to introduce containing Hydrobon catalyst and hydrocracking catalyst I
Hydrodesulfurization nitrogen is carried out in hydrotreating reaction area, arenes selectivity adds hydrogen saturation, arenes selectivity open loop and accordance side
Chain cracking reaction；Then the reaction effluent in the hydrotreating reaction area is detached and is fractionated successively, obtain light petrol,
Middle gasoline, heavy petrol, intermediate oil, diesel oil and tail oil；It is anti-that the tail oil and the optional diesel oil are introduced into hydrotreating
It answers in area and is recycled, and introduce adding containing hydrocracking catalyst after the intermediate oil is mixed with hydrogeneous logistics
Hydrogen cracking reaction is reacted in area, obtains the gas-liquid mixed logistics, wherein the high aromatic hydrocarbons inferior raw material is to carry out self-catalysis
The light cycle oil and/or heavy-cycle oil of cracking unit.
In the present invention, the hydrogeneous logistics refers to being capable of providing the logistics of hydrogen, including new hydrogen, recycle hydrogen, hydrogen rich gas
Body and other gaseous streams for being capable of providing hydrogen and other any one being capable of providing in the liquid phase stream of hydrogen or more
Kind.Heretofore described hydrogeneous logistics can be the same or different, and those skilled in the art are in the skill for having understood the present invention
It can be clearly understood that heretofore described hydrogeneous logistics after art scheme.
In method of the present invention, the method for the separation preferably includes to flow out the reaction in hydrotreating reaction area
Object introduces cold high pressure separator and cold low separator successively.
The method of the present invention further include by hydrogen-rich gas isolated in cold high pressure separator after desulfurization as hydrogeneous
Logistics recycles.H in hydrogeneous logistics after the preferably described desulfurization of the present invention2S a concentration of 300-1000 μ L/L, preferably 500-
800μL/L。
In method of the present invention, the diesel oil obtained after fractionation can go out device as low-sulfur diesel-oil blending component.
It is different according to production purpose in method of the present invention, it can be by production gasoline scheme and production aromatic hydrocarbons scheme
To carry out.According to production decision difference, light petrol, middle gasoline, the cut coverage of heavy petrol are different.Specifically, as follows：
Implement by production gasoline scheme, the light petrol is done less than 100 DEG C；The middle gasoline and heavy petrol press mixed steam
Oil goes out device, ranging from 85-205 DEG C of boiling range；Ranging from 190-300 DEG C of the boiling range of the midbarrel, the intermediate oil
In total arene content be higher than 70 weight %；Ranging from 280-355 DEG C of the diesel oil boiling range；The tail oil boiling range initial boiling point is more than
345℃；
Under preferable case, implement by production gasoline scheme, the light petrol is done less than 65 DEG C；The boiling range of the middle gasoline
Ranging from 60-155 DEG C, benzene,toluene,xylene content is more than 40 weight % in the middle gasoline fraction；The heavy petrol evaporates
Ranging from 150 DEG C to 205 DEG C of journey, sulfur content are less than 10 μ g/g；Ranging from 190-300 DEG C of the boiling range of the intermediate oil, institute
It states arene content in intermediate oil and is higher than 70 weight %；Ranging from 280-355 DEG C of the boiling range of the diesel oil；The tail oil evaporates
Journey initial boiling point is more than 345 DEG C.
When implementing by production aromatic hydrocarbons scheme, the middle gasoline is introduced into Aromatics Extractive Project unit, extraction benzene, toluene and two
After toluene, raffinates oil and can be used as high octane value gasoline blending component with light petrol and heavy petrol.
Method according to the present invention, wherein light cycle oil and heavy-cycle oil in the preferred high aromatic hydrocarbons inferior raw material
Weight ratio be 1-10：1.
Under preferable case, in the present invention, the boiling point of the high aromatic hydrocarbons inferior raw material is 165-450 DEG C, total arene content
Higher than 60 weight %, wherein the bicyclic above arene content is higher than 40 weight %.In the case of more preferably, Gao Fang of the present invention
Total arene content is higher than 70 weight % in hydrocarbon inferior raw material, wherein the bicyclic above arene content is higher than 50 weight %.
In method of the present invention, in hydrotreating reaction area, high aromatic hydrocarbons inferior raw material successively with hydrofinishing
Catalyst, hydrocracking catalyst I haptoreactions.High aromatic hydrocarbons inferior raw material carried out on Hydrobon catalyst hydrodesulfurization,
Hydrodenitrogeneration and arenes selectivity add hydrogen saturated reaction, effectively remove sulfide and nitride, and carry out to the bicyclic above aromatic hydrocarbons
Add hydrogen to be saturated, generates alkylbenzene and the mononuclear aromatics with naphthenic base.Hydrofining reaction product without any intermediate separation and
Directly with hydrocracking catalyst I haptoreactions, selective opening is carried out to the mononuclear aromatics with naphthenic base, then to alkyl
Benzene class mononuclear aromatics carries out alkyl side chain cracking reaction, converts the aromatic hydrocarbons in diesel oil distillate to the gasoline such as benzene,toluene,xylene
The aromatic hydrocarbons of fraction small molecular.
In method of the present invention, the reaction condition for preferably controlling the hydrotreating reaction area makes described plus hydrogen
The selectivity for handling mononuclear aromatics in the reaction effluent of reaction zone is not less than 80%.In the present invention, hydrotreating reaction area
Reaction effluent in the computational methods of selectivity of mononuclear aromatics be：
The selectivity of mononuclear aromatics=(reaction stream in hydrotreating reaction area in the reaction effluent in hydrotreating reaction area
Go out the content of mononuclear aromatics in the high aromatic hydrocarbons inferior raw material of content-of mononuclear aromatics in object)/(in high aromatic hydrocarbons inferior raw material it is bicyclic with
The content of the bicyclic above aromatic hydrocarbons in the reaction effluent in the content of upper aromatic hydrocarbons-hydrotreating reaction area) × 100%.
A kind of preferred embodiment according to the present invention, it is fragrant in the diesel oil in method of the present invention
Hydrocarbon content is less than 60 weight %, and the diesel oil goes out device as cleaning diesel product.
Another kind preferred embodiment according to the present invention, in method of the present invention, the diesel oil
Middle arene content is 60 weight % or more, and the diesel oil is introduced into hydrotreating reaction area and is recycled.
Method according to the present invention, containing including hydrocracking catalyst I in the preferably described hydrocracking reaction area
With at least two hydrocracking catalysts of hydrocracking catalyst II.
In method of the present invention, the total volume with the hydrocracking catalyst in the hydrocracking reaction area is
Benchmark, nitrogen content is higher than 50 μ g/g in intermediate oil, and the admission space of the preferably described hydrocracking catalyst I, which accounts for, to be hydrocracked
The 20-40% of hydrocracking catalyst total volume in reaction zone.
In method of the present invention, the total volume with the hydrocracking catalyst in the hydrocracking reaction area is
Benchmark, nitrogen content is no more than 50 μ g/g in intermediate oil, and the admission space of the preferably described hydrocracking catalyst I accounts for plus hydrogen is split
Change the 5-18% of hydrocracking catalyst total volume in reaction zone.
In method of the present invention, the nitrogen removal performance of the preferably described Hydrobon catalyst is good, to the bicyclic above virtue
Hydrocarbon adds hydrogen saturation performance excellent.It can be containing silica support, at least one selected from VIII group in the Hydrobon catalyst
Metallic element and at least one metallic element selected from group vib.
Under preferable case, in the present invention, on the basis of the total weight of the Hydrobon catalyst, group VIII metal member
Content of the element in terms of oxide is 1.5-7 weight %, and content of the group vib metallic element in terms of oxide is 7-35 weight %.
In the case of more preferably, in the Hydrobon catalyst, the group VIII metal element is Co and/or Ni,
The group vib metallic element is Mo and/or W.
Method according to the present invention also contains selected from P elements, fluorine element in the preferably described Hydrobon catalyst
With the auxiliary element of at least one of boron element, on the basis of the total weight of the Hydrobon catalyst, the auxiliary agent member
The total content of element based on the element is not higher than 10 weight %.
Method according to the present invention also contains organic additive in the preferably described Hydrobon catalyst, with described
On the basis of the total weight of Hydrobon catalyst, total content of the organic additive in terms of carbon is not higher than 10 weight %.
In method of the present invention, the organic additive in the Hydrobon catalyst can be selected from oxygen-containing chemical combination
At least one of object and nitrogenous compound.The oxygenatedchemicals is selected from least one of Organic Alcohol and organic acid, described
Nitrogenous compound is selected from least one of organic amine and organic ammonium salt.Specifically, the oxygenatedchemicals is preferably selected from second two
Alcohol, glycerine, polyethylene glycol (molecular weight 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, amino three
At least one of acetic acid, 1,2- cyclohexanediamine tetraacetic acids, citric acid, tartaric acid and malic acid；Be more preferably selected from ethylene glycol,
At least one of glycerine, polyethylene glycol and citric acid；The nitrogenous compound is preferably selected from ethylenediamine, diethylidene three
At least one in amine, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, nitrilotriacetic acid, ethylenediamine tetra-acetic acid (EDTA) and its ammonium salt
Kind, it is more preferably selected from EDTA and/or nitrilotriacetic acid.Organic additive of the present invention can also include Organic Alcohol simultaneously
And organic acid.
In method of the present invention, it is also filled with hydrogenation protecting catalyst in the preferably described hydrotreating reaction area,
There is no particular limitation for type of the method for the present invention to hydrogenation protecting catalyst, and those skilled in the art can make according to conventional
Various hydrogenation protecting catalysts are selected, and illustratively the hydrogenation protecting of RG series are used to urge in the embodiment of the present invention
Agent.
In method of the present invention, the hydrogenation protecting catalyst in the preferably described hydrotreating reaction area plus hydrogen essence
The admission space ratio of catalyst and hydrocracking catalyst I processed is 1：1-10：1-10.
In method of the present invention, the preferably described hydrocracking catalyst I has preferable anti-nitrogen performance, and has
Excellent selective opening cracking function and alkyl side chain cracking function, has good selectivity out cycloalkyl-monocyclic aromatic hydrocarbons
Ring cracking performance, and there is good alkyl side chain cracking performance, it can be effectively by the double ring arene in diesel oil or light wax oil fraction
And thrcylic aromatic hydrocarbon is converted into the small molecule aromatic hydrocarbons in the gasoline fractions such as alkyl benzene mononuclear aromatics and benzene,toluene,xylene.
Under preferable case, in method of the present invention, carrier, extremely can be contained in the hydrocracking catalyst I
Lack a kind of metallic element selected from VIII group and at least one metallic element selected from group vib, contains Y type molecules in the carrier
Sieve and aluminium oxide, on the basis of the carrier, the content of Y type molecular sieve is 3-80 weight %, and the content of aluminium oxide is 20-97 weights
Measure %.Under preferable case, in the hydrocracking catalyst I, the carrier mixes by Y type molecular sieve with boehmite,
Molding, drying simultaneously roast to obtain, and the boehmite includes PB1, is characterized with X-ray diffraction, the κ of the PB11And κ2Respectively
More than 1 to less than equal to 3, wherein κ1=h2/h1、κ2=h3/h2, h1、h2And h3Respectively in 2 θ in the x-ray diffraction spectra of PB1
The peak height for three diffraction maximums that angle is 24-30 °, 35-41 ° and 46-52 °.In the present invention, the hydrocracking catalyst is being prepared
In the step of agent I, the preferably described drying condition includes：Temperature is 50-350 DEG C, time 1-24h；The roasting condition packet
It includes：Temperature is 400-700 DEG C, time 0.5-6h.
Under preferable case, in method of the present invention, in the hydrocracking catalyst I, it is with the carrier
The content of benchmark, Y type molecular sieve is 5-70 weight %, and the content of aluminium oxide is 30-95 weight %；It is characterized with X-ray diffraction, it is described
The κ of PB11And κ2It is each independently 1.02-2.4；The more preferable κ1For 1.2-2.3, κ2For 1.02-1.4.
Under preferable case, in method of the present invention, in the hydrocracking catalyst I, the ratio table of the PB1
Area is 100-350m2/ g, Kong Rongwei 0.7-1.2mL/g.
In the case of more preferably, in method of the present invention, in the hydrocracking catalyst I, the PB1's
Specific surface area is 150-280m2/ g, Kong Rongwei 0.85-1.12mL/g.
In method of the present invention, in the hydrocracking catalyst I, the preferably described Y type molecular sieve is super steady Y
Type molecular sieve.
Under preferable case, in the present invention, the lattice constant of the Y type molecular sieve is 2.460-2.430, and specific surface area is
550-700m2/ g, Kong Rongwei 0.30-0.45mL/g.
Method according to the present invention also contains P elements in the Y type molecular sieve, using the Y type molecular sieve as base
The content of standard, P elements is 0.1-2.5 weight %；It is preferred that the content of the P elements is 0.4-2.0 weight %.
A kind of preferred embodiment according to the present invention, the boehmite is PB1 and PB2, in terms of butt
And on the basis of carrier, the content of PB1 is that the content of 10-90 weight %, PB2 are 5-60 weight %, with infrared spectrum characterization,
The δ values of PB2 are 1.5-4.5, wherein δ=I1/(I2+I3), I1For 3665- in the infrared hydroxyl spectrum of the boehmite
3680cm-1Locate the peak height of absorption peak, I2For 3720-3730cm-1Locate the peak height of absorption peak, I3For 3760-3780cm-1Locate absorption peak
Peak height.It is preferred that being counted by butt and on the basis of carrier, the content of PB1 is that the content of 20-80 weight %, PB2 are 10-50 weights
% is measured, the δ values of the PB2 are 1.8-3.8.In the present invention, the PB2 is PB1 in the modification of 70-400 DEG C of dry 0.5-14h
Object, the particularly preferred PB2 are PB1 in 220-330 DEG C of dry 1-6 hours modifier.
In the present invention, the boehmite PB1 and the boehmite PB2 can be by using the prior arts
Method be prepared and can also be commercially available.It is illustratively listed in the embodiment of the present invention and prepares boehmite
The method of PB1, those skilled in the art should not be construed as the limitation to technical scheme of the present invention.
Method according to the present invention, in the hydrocracking catalyst I, the group VIII metal element is selected from nickel
And/or cobalt, the group vib metallic element is selected from molybdenum/or tungsten, described on the basis of the total weight of the hydrocracking catalyst I
The total content of nickel and/or cobalt in terms of oxide is 1-15 weight %, and the total content of the molybdenum/or tungsten in terms of oxide is 5-40 weights
Measure %.
In the method for the invention, in hydrocracking catalyst I, for each parameter in the preparation method of the carrier
Not requiring particularly, those skilled in the art can select according to routine operation in the art, for example, the present invention
There is no particular limitation to the mixing, molding temperature and other operating conditions for method, and the present invention no longer goes to live in the household of one's in-laws on getting married one by one herein
It states.
Method according to the present invention, in the hydrocracking reaction area, the preferably described hydrocracking catalyst II
In contain complex carrier and the VIII group non-noble metal j element that is supported on the complex carrier and/or group vib base metal member
Element.
Under preferable case, method according to the present invention is hydrocracked in the hydrocracking reaction area with described
On the basis of the total weight of catalyst II, the complex carrier containing 50-90 weight %, 1-10 weights in the hydrocracking catalyst II
Measure the group vib metallic element in terms of oxide of the group VIII metal element and 5-40 weight % in terms of oxide of %.
In the case of more preferably, method according to the present invention, in the hydrocracking reaction area, described plus hydrogen is split
Change the group VIII metal member in terms of oxide of the complex carrier containing 60-85 weight % in catalyst II, 1.5-6.0 weight %
The group vib metallic element in terms of oxide of element and 10-35 weight %.
In method of the present invention, the preferably described hydrocracking catalyst II has excellent alkyl side chain cracking anti-
It answers, and has the function of partial selective open loop cracking.In the hydrocracking catalyst II, with the gross weight of the complex carrier
On the basis of amount, the solid acid group of aluminium oxide and 0.5-95 weight % containing 5-99.5 weight % in the preferably described complex carrier
Point；The solid acid component of aluminium oxide containing 20-99 weight % and 1-80 weight % in the more preferred complex carrier.
In method of the present invention, the preferably described solid acid component is selected from silica, silica-alumina and molecule
At least one of sieve.
Method according to the present invention, the preferably described molecular sieve are selected from zeolite with macroporous structure, with mesoporous knot
At least one of the zeolite of structure and zeolite with small structure.The more preferable molecular sieve be y-type zeolite, Beta zeolites and
At least one of ZSM-5 zeolite.
The reaction condition of method according to the present invention, the hydrotreating reaction area includes：Hydrogen partial pressure is 5.0-
12.0MPa, preferably 5.5-10.0MPa.
The reaction condition of method according to the present invention, the hydrotreating reaction area includes：Reaction temperature is 300-
450 DEG C, preferably 350-450 DEG C.
In method of the present invention, in hydrotreating reaction area, the reaction of the preferably described Hydrobon catalyst
Temperature is 10-50 DEG C lower than the reaction temperature of the hydrocracking catalyst I；More preferably low 20-45 DEG C.
The reaction condition of method according to the present invention, the hydrotreating reaction area includes：Hydrogen to oil volume ratio is
400-2500, preferably 700-2300.
Method according to the present invention, with the stereometer of the high aromatic hydrocarbons inferior raw material, the hydrotreating reaction area
Reaction condition include：Volume space velocity is 0.2-6.0h when liquid-1, preferably 0.5-3.0h-1。
In method of the present invention, the reaction condition in the hydrocracking reaction area includes：Hydrogen partial pressure is 5.0-
12.0MPa, preferably 5.5-10.0MPa.
In method of the present invention, the reaction condition in the hydrocracking reaction area includes：Reaction temperature is 300-
450 DEG C, preferably 350-430 DEG C.
In method of the present invention, the reaction condition in the hydrocracking reaction area includes：Hydrogen to oil volume ratio is
400-2500, preferably 500-1600.
In method of the present invention, with the stereometer of the intermediate oil, the hydrocracking reaction area it is anti-
The condition is answered to include：Volume space velocity is 0.2-20.0h when liquid-1, preferably 1.0-10.0h-1。
In the present invention, the gas-liquid mixed logistics that hydrocracking reaction area obtains without it is any it is intermediate detach, directly with height
Aromatic hydrocarbons inferior raw material mixes, and into hydrotreating reaction area, is contacted successively with Hydrobon catalyst, hydrocracking catalyst I
Reaction.Wherein, the hydrogenated desulfurization of high aromatic hydrocarbons inferior raw material, hydrodenitrogeneration, arenes selectivity add hydrogen saturation, the list with naphthenic ring
The cracking of cycloaromatics selective opening, alkyl benzene mononuclear aromatics alkyl side chain cracking reaction, are converted into rich in benzene, toluene, diformazan
Antiknock component in the gasoline fraction of benzene.
A kind of preferred embodiment according to the present invention, method of the invention are illustrated using flow shown in FIG. 1
Technological process in figure carries out, specifically as follows：
High aromatic hydrocarbons inferior raw material 1 is after raw oil pump pressurizes, with the hydrocracking reaction area from hydrocracking reaction area 8
Gas-liquid mixed logistics 12 together enter hydrotreating reaction area 2.The reaction effluent 13 in hydrotreating reaction area is introduced cold
High-pressure separator 3 carries out gas-liquid separation, and the cold high pressure separator gaseous stream 14 that cold high pressure separator 3 obtains enters recycle hydrogen de
Sulphur tank 6 carries out H2S is removed, hydrogen-rich gas 15 after desulfurization pressurizeed after the pressurization of circulating hydrogen compressor 7 after hydrogeneous logistics
10, the hydrogeneous logistics 10 after the pressurization is recycled to hydrocracking reaction area entrance and the cold hydrogen of each bed.By cold high pressure separator 3
Obtained cold high pressure separator acid water 16 is extracted out.The isolated cold high pressure separator liquid phase stream 17 of cold high pressure separator 3
Gas-liquid separation is further carried out into cold low separator 4.By the isolated dry gas 18 of cold low separator 4 and cold low point
It is extracted out from device acid water 19, the introducing fractionating column 5 of cold low separator liquid phase stream 20 is fractionated.Fractionating column 5 is detached
It is extracted out to tower overhead gas 21, light petrol 22, middle gasoline and heavy petrol 23.Intermediate oil 24 rich in aromatic hydrocarbons and new hydrogen 9 and pressurization
Hydrogeneous logistics 10 afterwards forms hydrocracking reaction area raw material 11 and enters hydrocracking reaction area after mixing.Fractionating column 5 is obtained
Diesel oil 25 extract out, or recycled in return hydrotreating reaction area after the diesel oil is mixed with tail oil 26.
Specifically, the method described in the present invention also has the following advantages that：
(1) present invention is using the integrated technological process in hydrotreating reaction area and hydrocracking reaction area, wherein adding at hydrogen
Reason reaction zone includes Hydrobon catalyst and hydrocracking catalyst I, and hydrocracking reaction area includes that at least two plus hydrogen are split
Change catalyst.On the one hand the bicyclic above aromatic hydrocarbons in high aroamtic hydrocarbon raw material is carried out plus hydrogen is saturated and alkyl side chain cracking, generation benzene,
The high octane gasoline components such as toluene and dimethylbenzene；On the other hand the intermediate oil that will be enriched in mononuclear aromatics is individually adding hydrogen to split
Change and carry out selective opening and alkyl side chain cracking reaction in reaction zone, continues to generate the production of the high values such as benzene, toluene and dimethylbenzene
Product；
(2) in the present invention, Hydrobon catalyst has excellent nitrogen removal performance, and is saturated to the bicyclic above aromatic hydrogenation
Performance is excellent；
(3) hydrocracking catalyst I has certain anti-nitrogen poisoning capability in the present invention, has good selectivity open loop
Cracking capability and certain alkyl side chain cracking performance effectively can convert the bicyclic above aromatic hydrocarbons to alkyl benzene mononuclear aromatics,
And it is partially converted into the aromatic hydrocarbons of gasoline fraction small molecular；
(4) the hydrocracking catalyst II in the present invention has the function of excellent alkyl side chain cracking, and has centainly
Selective opening cracking capability effectively can convert alkyl benzene mononuclear aromatics in intermediate oil to gasoline fraction small molecular
Aromatic hydrocarbons；
(5) technological process recycled using diesel oil and/or tail oil in the present invention can will be unconverted in diesel oil and/or tail oil
The bicyclic above aromatic hydrocarbons further carries out plus hydrogen saturation, selective opening and alkyl side chain cracking；
(6) high aromatic hydrocarbons inferior raw material can be efficiently converted into the Gaoxin such as benzene,toluene,xylene by method using the present invention
Alkane value gasoline, while production section low-sulfur diesel-oil blending component can be taken into account, on the basis of high aroamtic hydrocarbon raw material, light petrol can be produced
For RON up to 90 or so, sulfur content is less than 10 μ g/g, can be used as high octane value gasoline blending component；Middle gasoline, the RON of heavy petrol are equal
Up to 90-98, sulfur content is less than 10 μ g/g；Production sulfur content can be taken into account simultaneously and is less than 10 μ g/g, and Cetane number improves 10 compared with raw material
Low-sulfur more than a unit cleans diesel oil blending component.
The present invention will be described in detail by way of examples below.In following embodiment, in the feelings being not particularly illustrated
Under condition, used a variety of materials are all from commercially available.
In the examples below, the trade names of the hydrogenation protecting catalyst A are RG series hydrogenation protecting catalysts, tool
It is body RG-30 catalyst, RG-30A catalyst and RG-30B catalyst.Hydrogenation protecting catalyst A is by Sinopec share
Co., Ltd's catalyst Chang Ling branch company produces.
The composition of Hydrobon catalyst B：It is counted by oxide and on the basis of the total weight of Hydrobon catalyst B, Ni
Content is that 5.5 weight %, Mo contents are 26.5 weight %, and P content is 1.5 weight %, with the glycerine of the content meter of carbon
Content be 3 weight %, surplus is silica support.
The preparation method of hydrocracking catalyst C is：
(1) boehmite PB1 is prepared
The sodium metaaluminate of the aluminum sulfate of a concentration of 93g/L of the 500mL of clear and a concentration of 195g/L is slow simultaneously
It is added in reaction kettles of the 2L with stirring, controlling reaction temperature is 40 DEG C, pH value 7.3.After the reaction was complete, stirring is added a concentration of
The sodium carbonate of 0.5mol/L to solution ph is 9.7.After 50 DEG C of reaction 1h of constant temperature, filtering, deionized water is washed three times, in baking oven
120 DEG C of temperature of ventilation dry 3h, obtain boehmite PB1.The k of PB11It is 1.85, k2It is 1.0mL/ for 1.21 and its hole appearance
g；
(2) carrier is prepared
By 300g boehmite powder PB1 with 16 grams of 366.7 grams of super stable molecular sieve LAY, sesbania powder mixing, it is extruded into circumscribed circle
A diameter of 1.6 millimeters of trilobal item, 120 DEG C dry 3 hours, and 600 DEG C of roasting temperatures 3 hours obtain carrier, vehicle group becomes
PB1 contents are 45 weight %, and the content of molecular sieve is 55 weight %；
(3) catalyst is prepared
After above-mentioned carrier is cooled to room temperature, 100 grams of carriers (Zigong, Sichuan cemented carbide works, oxygen containing ammonium metatungstate is taken
Change W content is 82 weight %) 51 grams, (Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content are 51 weights to basic nickel carbonate
Measure %) 8.7 grams, 10.5g citric acids, 77ml aqueous solutions dipping, 180 DEG C are dried 10 hours, and the holes catalyst C, 300-500nm are obtained
Pore volume account for total pore volume ratio be 2.3%.On the basis of catalyst C total amounts, wherein the content of nickel oxide is 2.85 weights
% is measured, the content of tungstic acid is 28 weight %.
The group of hydrocracking catalyst D becomes：With the total weight of hydrocracking catalyst D, ZSM-5 (solid acid component)
Content be contents of 60 the weight %, Co in terms of oxide be contents of 3.5 the weight %, Mo in terms of oxide be 10.0 weights
% is measured, surplus is aluminium oxide.
In the following Examples and Comparative Examples, in case of no particular description, in hydrotreating reaction area, catalyst
A, the admission space of catalyst B and catalyst C ratio are 1：10：8.
Feedstock oil E, F and G used in following embodiment and comparative example are all from catalytic cracking unit, nature and characteristic
It is listed in table 1.
From table 1 it follows that the total arene contents of feedstock oil E are up to 88.0 weight %, wherein the bicyclic above arene content
Reach 69.0 weight %, nitrogen content is 523 μ g/g, and the boiling range end point of distillation is 347 DEG C；The total arene contents of feedstock oil F are up to 83.9 weights
% is measured, wherein the bicyclic above arene content, up to 74.0 weight %, nitrogen content is 1130 μ g/g, the boiling range end point of distillation is 412 DEG C；Raw material
The oily total arene contents of G are 82.1 weight %, wherein the bicyclic above arene content, up to 52.4 weight %, nitrogen content is 1500 μ g/g,
The boiling range end point of distillation is 350 DEG C.As seen from the data in Table 1, feedstock oil E and feedstock oil G is typical poor quality catalytic cracking diesel, i.e.,
LCO, feedstock oil F are typical heavy catalytic cycle oil, i.e. HCO, three kinds of inferior raw materials are generally with arene content height, density
Feature high, Cetane number is low.
Table 1
| Feedstock oil | E | F | G |
| Density (20 DEG C), g/cm3 | 0.9632 | 1.0384 | 0.9446 |
| Sulphur, μ g/g | 7200 | 10000 | 3100 |
| Nitrogen, μ g/g | 523 | 1130 | 1500 |
| Cetane lndex | 19.3 | 15.7 | 22.8 |
| Survey Cetane number | 15.4 | - | <19.3 |
| Total arene content, weight % | 88.0 | 83.9 | 82.1 |
| The bicyclic above arene content, weight % | 69.0 | 74.0 | 52.4 |
| Boiling range (ASTM D-86), DEG C | |||
| Initial boiling point | 199 | 262 | 199 |
| 10% | 233 | 354 | 232 |
| 30% | 254 | 368 | 253 |
| 50% | 274 | 370 | 269 |
| 70% | 301 | 374 | 295 |
| 90% | 328 | 400 | 326 |
| The end point of distillation | 347 | 412 | 350 |
Embodiment 1
The present embodiment carries out with the following method：
Feedstock oil E and feedstock oil F is 7 by weight：3 carry out being mixed to get high aromatic hydrocarbons inferior raw material, and high aromatic hydrocarbons is inferior former
Material introduces hydrotreating reaction area after being mixed with the gas-liquid mixed logistics from hydrocracking reaction area, with hydrogenation protecting catalyst
A, Hydrobon catalyst B, hydrocracking catalyst C haptoreactions.Hydrotreating reaction area product enters cold high pressure separator
Gas-liquid separation is carried out, obtained gaseous stream removes H through desulphurization of recycle hydrogen tank2S retains H in recycle hydrogen2500 μ L/L of S concentration, obtain
To hydrogen-rich gas, the hydrogen-rich gas is recycled；The liquid phase stream that cold high pressure separator obtains sequentially enters cold low point
Dry gas, liquefied gas, light petrol, high-knock rating gasoline, intermediate oil, diesel oil and tail oil are obtained from device and fractionating column.Wherein, in
Between distillate enter hydrocracking reaction area successively with hydrocracking catalyst C and hydrocracking catalyst D haptoreactions, tail oil
It is introduced into hydrotreating reaction area and is recycled.
Reaction process condition is as shown in table 2, and the yield and property of product are as shown in table 3.
As can be seen from Table 3, it is 5.7 μ g/g, RON up to 90 that light petrol yield, which is 17.82 weight %, S contents,；High-octane rating
Yield of gasoline is that 49.17 weight %, S contents are 6.3 μ g/g, RON 94；Diesel yield is that 26.20 weight %, S contents are 8.5
μ g/g, Cetane number 45.
Embodiment 2
The present embodiment carries out with the following method：
Feedstock oil E and feedstock oil F is 9 by weight：1 carries out being mixed to get high aromatic hydrocarbons inferior raw material, and high aromatic hydrocarbons is inferior former
Material introduces hydrotreating reaction area after being mixed with the gas-liquid mixed logistics from hydrocracking reaction area, with hydrogenation protecting catalyst
A, Hydrobon catalyst B, hydrocracking catalyst C haptoreactions.Hydrotreating reaction area product enters cold high pressure separator
Gas-liquid separation is carried out, obtained gaseous stream removes H through desulphurization of recycle hydrogen tank2S retains H in recycle hydrogen2500 μ L/L of S concentration, obtain
To hydrogen-rich gas, the hydrogen-rich gas is recycled；The liquid phase stream that cold high pressure separator obtains sequentially enters cold low point
Dry gas, liquefied gas, light petrol, high-knock rating gasoline, intermediate oil, diesel oil and tail oil are obtained from device and fractionating column.Wherein, in
Between distillate enter hydrocracking reaction area successively with hydrocracking catalyst C and hydrocracking catalyst D haptoreactions, tail oil
It is introduced into hydrotreating reaction area and is recycled.
Reaction process condition is as shown in table 2, and product yield and property are as shown in table 3.
As can be seen from Table 3, it is 4.5 μ g/g, RON up to 89 that light petrol yield, which is 18.88 weight %, S contents,；High-octane rating
Yield of gasoline is that 58.62 weight %, S contents are 5.0 μ g/g, RON 95；Diesel yield is that 13.98 weight %, S contents are 7.5
μ g/g, Cetane number 40.
Embodiment 3
The present embodiment carries out with the following method：
For feedstock oil G as high aromatic hydrocarbons inferior raw material, high aromatic hydrocarbons inferior raw material is mixed with the gas-liquid from hydrocracking reaction area
Hydrotreating reaction area is introduced after closing logistics mixing, with hydrogenation protecting catalyst A, Hydrobon catalyst B, hydrocracking catalyst
Agent C haptoreactions.Hydrotreating reaction area product enters cold high pressure separator and carries out gas-liquid separation, and obtained gaseous stream is through following
Ring hydrogen digester removes H2S retains H in recycle hydrogen2800 μ L/L of S concentration obtain hydrogen-rich gas, and the hydrogen-rich gas is by cycle profit
With；The liquid phase stream that cold high pressure separator obtains sequentially enters cold low separator and fractionating column obtains dry gas, liquefied gas, light vapour
Oil, high-knock rating gasoline, intermediate oil, diesel oil and tail oil.Wherein, intermediate oil enter hydrocracking reaction area successively with
Hydrocracking catalyst C and hydrocracking catalyst D haptoreactions.
Reaction process condition is as shown in table 2, and product yield and property are as shown in table 3.
As can be seen from Table 3, it is 2.8 μ g/g, RON up to 91 that light petrol yield, which is 21.51 weight %, S contents,；High-octane rating
Yield of gasoline is that 55.21 weight %, S contents are 3.5 μ g/g, RON 98；Diesel yield is that 14.22 weight %, S contents are 6.0
μ g/g, Cetane number 37.
Embodiment 4
The present embodiment is carried out using method similar to Example 1, except that：
In the present embodiment, the reaction condition in control hydrotreating reaction area so that the reaction in the hydrotreating reaction area
The selectivity of mononuclear aromatics is less than 80% in product, specifically as shown in table 4.Remaining is in the same manner as in Example 1.
The reaction condition of the present embodiment is as shown in table 4, and product yield and property are as shown in table 6.
It is 3.0 μ g/g, RON that the yield of light petrol component, which is 18.15 weight %, S contents, it can be seen from the result of table 6
It is 80.0；High-knock rating gasoline yield is that 50.23 weight %, S contents are 4.0 μ g/g, RON 84.5；Diesel yield is 21.69
Weight %, S content is 6.3 μ g/g, Cetane number 44.3.
Embodiment 5
The present embodiment is carried out using method similar to Example 2, except that：
The type of Hydrobon catalyst is different, and the Hydrobon catalyst in the present embodiment is B-5, and group becomes：With oxygen
Compound meter and on the basis of the total weight of Hydrobon catalyst B-5, Ni contents are that 7.5 weight %, Mo contents are 37.2 weights
% is measured, P content is 1.5 weight %, and with the content of the glycerine of the content meter of carbon for 3 weight %, surplus carries for silica
Body.Remaining is in the same manner as in Example 2.
The reaction condition of the present embodiment is as shown in table 4, and product yield and property are as shown in table 6.
It is 12.30 μ g/g that the yield of light petrol component, which is 16.56 weight %, S contents, it can be seen from the result of table 6,
RON is up to 86.0；High-knock rating gasoline yield is that 50.38 weight %, S contents are 18.60 μ g/g, RON 90.1；Diesel yield is
23.02 weight %, S contents are 25.3 μ g/g, Cetane number 40.0.
Embodiment 6
The present embodiment is carried out using method similar to Example 3, except that：
The type of hydrocracking catalyst I is different, and the hydrocracking catalyst in the present embodiment is C-6, and group becomes：With oxygen
Compound meter and on the basis of the total weight of Hydrobon catalyst C-6,0.5 weight % of group VIII metal oxide content, group vib
Metal oxide content is 18 weight %, compound MoBeta molecular sieve contents 40%, wherein 6.5 weight of Mo contents in molecular sieve
Measure %.Remaining is in the same manner as in Example 3.
The reaction condition of the present embodiment is as shown in table 4, and product yield and property are as shown in table 6.
It is 9.35 μ g/g, RON that the yield of light petrol component, which is 18.3 weight %, S contents, it can be seen from the result of table 6
Up to 89.0；High-knock rating gasoline yield is that 40.3 weight %, S contents are 6.4 μ g/g, RON 93.0；Diesel yield is 30.45
Weight %, S content is 8.3 μ g/g, Cetane number 35.5.
Embodiment 7
The present embodiment is carried out using method similar to Example 1, except that：
The type of hydrocracking catalyst II is different, and the hydrocracking catalyst II in the present embodiment is D-7, and group becomes：
It is counted by oxide and on the basis of the total weight of Hydrobon catalyst D-7, contents of the Co in terms of oxide is 3.5 weight %,
Contents of the Mo in terms of oxide is 10.0 weight %, and surplus is aluminium oxide.Remaining is in the same manner as in Example 1.
The reaction condition of the present embodiment is as shown in table 5, and product yield and property are as shown in table 6.
It is 6.8 μ g/g that the yield of light petrol component, which is 10.1 weight %, S contents, it can be seen from the result of table 6, and RON reaches
88.0；High-knock rating gasoline yield is that 25.5 weight %, S contents are 8.80 μ g/g, RON 88.0；Diesel yield is 59.62 weights
% is measured, S contents are 8.9 μ g/g, Cetane number 41.0.
Embodiment 8
The present embodiment is carried out using method similar to Example 2, except that：
In the present embodiment, in the hydrocracking reaction area, hydrocracking catalyst C and hydrocracking catalyst D's
Admission space ratio is 1：1.Remaining is in the same manner as in Example 2.
The reaction condition of the present embodiment is as shown in table 5, and product yield and property are as shown in table 6.
It is 5.5 μ g/g that the yield of light petrol component, which is 17.0 weight %, S contents, it can be seen from the result of table 6, and RON reaches
88.0；High-knock rating gasoline yield is that 51.80 weight %, S contents are 6.8 μ g/g, RON 93.0；Diesel yield is 20.05 weights
% is measured, S contents are 8.8 μ g/g, Cetane number 43.0.
Embodiment 9
The present embodiment is carried out using method similar to Example 3, except that：
In the present embodiment, in the hydrotreating reaction area, the reaction temperature ratio of Hydrobon catalyst B is hydrocracked
The reaction temperature of catalyst C is 10 DEG C low.Remaining is in the same manner as in Example 3.
The reaction condition of the present embodiment is as shown in table 5, and product yield and property are as shown in table 6.
It is 3.2 μ g/g that the yield of light petrol component, which is 18.3 weight %, S contents, it can be seen from the result of table 6, and RON reaches
88.5；High-knock rating gasoline yield is that 51.3 weight %, S contents are 4.5 μ g/g, RON 92.0；Diesel yield is 19.4 weights
% is measured, S contents are 7.6 μ g/g, Cetane number 33.0.
Table 2
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Each fraction yield of product and property | |||
| Dry gas, weight % | 1.45 | 1.70 | 1.85 |
| Liquefied gas, weight % | 8.32 | 9.55 | 10.20 |
| Light petrol | |||
| Boiling range range, DEG C | <85 | <85 | <85 |
| Yield, weight % | 17.82 | 18.88 | 21.51 |
| S contents, μ g/g | 5.7 | 4.5 | 2.8 |
| RON | 90 | 89 | 91 |
| High-knock rating gasoline | |||
| Boiling range range, DEG C | 85-205 | 85-205 | 85-205 |
| Yield, weight % | 49.17 | 58.62 | 55.21 |
| S contents, μ g/g | 6.3 | 5.0 | 3.5 |
| RON | 94 | 95 | 98 |
| Diesel oil | |||
| Boiling range range, DEG C | 280-345 | 280-345 | 280-345 |
| Yield, weight % | 26.20 | 13.98 | 14.22 |
| S contents, μ g/g | 8.5 | 7.5 | 6.0 |
| Cetane number | 40 | 45 | 37 |
Table 4
Table 5
Table 6
It, can be most by comparison as can be seen that when processing high aromatic hydrocarbons inferior raw material using process provided by the invention
Change the economic value of high aromatic hydrocarbons inferior feedstock oil greatly, and obtains high-knock rating gasoline and/or aromatic hydrocarbons.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (26)
1. a kind of method of the high aromatic hydrocarbons inferior raw material of processing, this method is including hydrotreating reaction area, hydrocracking reaction area
Implement in the system of fractionating column, which is characterized in that this method includes：By high aromatic hydrocarbons inferior raw material, come from hydrocracking reaction
The gas-liquid mixed logistics in area and tail oil from fractionating column introduce containing Hydrobon catalyst and hydrocracking catalyst I's plus
Hydrodesulfurization nitrogen is carried out in hydrogen processing reaction zone, arenes selectivity adds hydrogen saturation, arenes selectivity open loop and accordance side chain
Cracking reaction；Then the reaction effluent in the hydrotreating reaction area is detached and is fractionated successively, obtain light petrol, in
Gasoline, heavy petrol, intermediate oil, diesel oil and tail oil；The tail oil and the optional diesel oil are introduced into hydrotreating reaction
It is recycled in area, and containing hydrocracking catalyst plus hydrogen is introduced after the intermediate oil is mixed with hydrogeneous logistics
Cracking reaction is reacted in area, obtains the gas-liquid mixed logistics, wherein the high aromatic hydrocarbons inferior raw material is to carry out self-catalysis to split
Disguise the light cycle oil and/or heavy-cycle oil set.
2. according to the method described in claim 1, wherein, the weight of light cycle oil and heavy-cycle oil in the high aromatic hydrocarbons inferior raw material
Amount is than being 1-10：1.
3. according to the method described in claim 1, wherein, the boiling point of the high aromatic hydrocarbons inferior raw material is 165-450 DEG C, total aromatic hydrocarbons
Content is higher than 60 weight %, wherein the bicyclic above arene content is higher than 40 weight %.
4. according to the method described in claim 1, wherein, the reaction condition for controlling the hydrotreating reaction area makes described add
The selectivity of mononuclear aromatics is not less than 80% in the reaction effluent of hydrogen processing reaction zone.
5. according to the method described in claim 1, wherein, it includes hydrocracking catalyst to contain in the hydrocracking reaction area
At least two hydrocracking catalysts of I and hydrocracking catalyst II；With being hydrocracked in the hydrocracking reaction area
On the basis of the total volume of catalyst,
Nitrogen content is higher than 50 μ g/g in intermediate oil, and the admission space of the hydrocracking catalyst I accounts for hydrocracking reaction
The 20-40% of hydrocracking catalyst total volume in area；Or
Nitrogen content is no more than 50 μ g/g in intermediate oil, and the admission space of the hydrocracking catalyst I, which accounts for, to be hydrocracked instead
Answer the 5-18% of hydrocracking catalyst total volume in area.
6. according to the method described in any one of claim 1-4, wherein contain silica in the Hydrobon catalyst
Carrier and load at least one metallic element selected from VIII group on the carrier and at least one metal selected from group vib
Element.
7. according to the method described in claim 6, wherein, in the Hydrobon catalyst, being catalyzed with the hydrofinishing
On the basis of the total weight of agent, content of the group VIII metal element in terms of oxide be 1.5-7 weight %, group vib metallic element with
The content of oxide meter is 7-35 weight %.
8. according to the method described in claim 7, wherein, in the Hydrobon catalyst, the group VIII metal element
For Co and/or Ni, the group vib metallic element is Mo and/or W.
9. described to help according to the method described in claim 6, wherein, auxiliary element is also contained in the Hydrobon catalyst
Agent element is selected from least one of P elements, fluorine element and boron element, using the total weight of the Hydrobon catalyst as base
Standard, the total content of the auxiliary element based on the element are not higher than 10 weight %.
10. according to the method described in claim 9, wherein, also containing organic additive in the Hydrobon catalyst, with institute
On the basis of the total weight for stating Hydrobon catalyst, total content of the organic additive in terms of carbon is not higher than 10 weights
Measure %.
11. according to the method described in any one of claim 1-4, wherein contain load in the hydrocracking catalyst I
Body, at least one metallic element selected from VIII group and at least one metallic element selected from group vib contain Y in the carrier
Type molecular sieve and aluminium oxide, on the basis of the carrier, the content of Y type molecular sieve is 3-80 weight %, and the content of aluminium oxide is
20-97 weight %.
12. according to the method for claim 11, wherein in the hydrocracking catalyst I, the carrier is by Y types point
Son sieve is mixed with boehmite, is molded, drying and roast to obtain, and the boehmite includes PB1, is characterized with X-ray diffraction,
The κ of the PB11And κ2Respectively it is more than 1 to less than equal to 3, wherein κ1=h2/h1、κ2=h3/h2, h1、h2And h3Respectively PB1
X-ray diffraction spectra in 2 angles θ be 24-30 °, 35-41 ° and 46-52 ° three diffraction maximums peak height.
13. according to the method for claim 12, wherein in the hydrocracking catalyst I, using the carrier as base
The content of standard, Y type molecular sieve is 5-70 weight %, and the content of aluminium oxide is 30-95 weight %；It is characterized with X-ray diffraction, it is described
The κ of PB11And κ2It is each independently 1.02-2.4.
14. according to the method for claim 13, wherein the κ1For 1.2-2.3, κ2For 1.02-1.4.
15. according to the method described in claim 5, wherein, complex carrier and load are contained in the hydrocracking catalyst II
VIII group non-noble metal j element on the complex carrier and/or group vib non-noble metal j element.
16. according to the method for claim 15, wherein in the hydrocracking catalyst II, be hydrocracked with described
On the basis of the total weight of catalyst II, the complex carrier containing 50-90 weight %, 1-10 weights in the hydrocracking catalyst II
Measure the group vib metallic element in terms of oxide of the group VIII metal element and 5-40 weight % in terms of oxide of %.
17. according to the method for claim 16, wherein contain 60-85 weight %'s in the hydrocracking catalyst II
Complex carrier, the group VIII metal element in terms of oxide of 1.5-6.0 weight % and 10-35 weight % in terms of oxide
Group vib metallic element.
18. according to the method for claim 15, wherein in the hydrocracking catalyst II, with the complex carrier
Total weight on the basis of, the solid acid group of aluminium oxide and 0.5-95 weight % containing 5-99.5 weight % in the complex carrier
Point.
19. according to the method for claim 18, wherein in the hydrocracking catalyst II, in the complex carrier
The solid acid component of aluminium oxide containing 20-99 weight % and 1-80 weight %.
20. according to the method for claim 18, wherein the solid acid component be selected from silica, silica-alumina and
At least one of molecular sieve, the molecular sieve are selected from the zeolite with macroporous structure, the zeolite with central hole structure and have
At least one of the zeolite of small structure.
21. according to the method described in any one of claim 1-4, wherein with the stereometer of the high aromatic hydrocarbons inferior raw material,
The reaction condition in the hydrotreating reaction area includes：Hydrogen partial pressure is 5.0-12.0MPa；Reaction temperature is 300-450 DEG C；Hydrogen oil
Volume ratio is 400-2500；Volume space velocity is 0.2-6.0h when liquid-1。
22. according to the method for claim 21, wherein with the stereometer of the high aromatic hydrocarbons inferior raw material, at described plus hydrogen
Reason reaction zone reaction condition include：Hydrogen partial pressure is 5.5-10.0MPa；Reaction temperature is 350-450 DEG C；Hydrogen to oil volume ratio is
700-2300；Volume space velocity is 0.5-3.0h when liquid-1。
23. according to the method for claim 21, wherein in hydrotreating reaction area, the Hydrobon catalyst
Reaction temperature is 10-50 DEG C lower than the reaction temperature of the hydrocracking catalyst I.
24. according to the method for claim 23, wherein the reaction temperature of the Hydrobon catalyst is split than described plus hydrogen
The reaction temperature for changing catalyst I is 20-45 DEG C low.
25. according to the method described in any one of claim 1-4, wherein described with the stereometer of the intermediate oil
The reaction condition in hydrocracking reaction area includes：Hydrogen partial pressure is 5.0-12.0MPa；Reaction temperature is 300-450 DEG C；Hydrogen oil volume
Than for 400-2500；Volume space velocity is 0.2-20.0h when liquid-1。
26. according to the method for claim 25, wherein described to be hydrocracked instead with the stereometer of the intermediate oil
The reaction condition in area is answered to include：Hydrogen partial pressure is 5.5-10.0MPa；Reaction temperature is 350-430 DEG C；Hydrogen to oil volume ratio is 500-
1600；Volume space velocity is 1.0-10.0h when liquid-1。
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| CN1955261A (en) * | 2005-10-24 | 2007-05-02 | 中国石油化工股份有限公司 | Hydrocracking method of midbarrel oil circulation |
| CN101747936A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Hydrogenation method for producing high-quality low-sulfur diesel fraction |
| CN101760233A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Method for hydrocracking of coked wax oil |
| CN103773487A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrocracking method for catalytic cracking diesel |
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| TWI630269B (en) * | 2014-02-20 | 2018-07-21 | 中國石油化工科技開發有限公司 | Hydrocracking catalyst and use thereof |
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| CN1955261A (en) * | 2005-10-24 | 2007-05-02 | 中国石油化工股份有限公司 | Hydrocracking method of midbarrel oil circulation |
| CN101747936A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Hydrogenation method for producing high-quality low-sulfur diesel fraction |
| CN101760233A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Method for hydrocracking of coked wax oil |
| CN103773487A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrocracking method for catalytic cracking diesel |
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