A kind of hydrofinishing and hydrocracking combined process
Technical field
The invention belongs to petroleum refining fields, and in particular to a kind of generation fine quality catalytic cracking raw material and high-quality be hydrocracked
The hydrofinishing of product and hydrocracking combined process.
Background technique
Hydrogen addition technology is the important manufacturing process of light materialization of heavy oil and light-end products quality upgrading.Hydrocracking technology because
Feedstock oil is adaptable, product flexibility is good, liquid product yield is high, high quality has obtained faster development.
Existing hydrocracking technology can be divided into three kinds according to processing flow: one-stage serial hydrocracking process flow, single hop add hydrogen
Process process and two-stage reforming process flow.One-stage serial hydrocracking technology uses two kinds of catalyst,
That is pretreating catalyst by hydrocracking and hydrocracking catalyst, both catalyst are seated in weighted BMO spaces reactor respectively
In hydrocracking reactor, the catalyst in each reactor is layering filling under normal conditions.Catalytic cracking is heavy
One of the important means of oily lighting, but with the in poor quality and heaviness of catalyzed cracking processing raw material, operating condition is got over
Come harsher, light-end products yield and product property are deteriorated, and hydrotreating of FCC feedstock technology not only can remove sulphur,
The content of nitrogen, metal impurities can also improve the cracking performance of charging, reduce FCC operating severity, improve product distribution, mention
High purpose product selectivity reduces dry gas and coke yield, improves the economy of FCC apparatus, reduces purpose product sulfur content, subtracts
SOx and NOx content etc. in few regenerated flue gas.There are the sulphur and nitrogen of certain content in catalytic cracking light cycle oil (LCO), with organic
The form of compound exists, and arene content is high, and the content of the above aromatic hydrocarbons of especially two rings is high, and usual LCO is recycled directly back to
Continue to convert in catalytic cracking unit, catalytic cracking unit is entered back into after perhaps adding hydrogen into hydrotreater or enters
Other devices are processed or directly as products.
CN101003746A, CN001955260A, CN001955257A, CN103059960A and CN001955263A are public
The hydrocracking process or group technology of a kind of wax oil and catalytic cracking diesel oil Combined machining opened.Such technology can be with wax
Oil and LCO are feedstock oil, are yielded products of quality by method for hydrogen cracking or combined method, and especially high-quality heavy naphtha is made
For the raw material of catalytic reforming, rather than catalytically cracked material is generated, re-starts conversion without Returning catalyticing cracking device.
CN106701175A, CN102465035A and CN001896192A, which are disclosed in a kind of hydroprocessing technique, mixes refining
The technology of LCO, main purpose is production fine quality catalytic cracking raw material, or LCO is allowed to split in hydrotreater and catalysis
The coupling technique that makeup recycles between setting, realizes the clean manufacturing of catalytic cracking unit, but due to wax oil or residual oil etc. and LCO
The hydrogenation depth of direct hydrogenation after mixing, LCO not can be effectively controlled, and cannot produce high-quality hydrocracked product.
It is usually all that LCO directly mixes refining to urging in conclusion compare existing LCO hydrogen addition technology and hydrocracking technology
Change and carried out plus hydrogen in cracked stock pretreatment unit, then returns again to catalytic cracking unit or LCO mixes refining to being hydrocracked original
In material oil, enter in hydrocracking unit after weighted BMO spaces and produce hydrocracked naphtha product, in same covering device with
Wax oil and LCO are that feedstock oil produces high-quality hydrocracked product simultaneously and the Combined machining technology of catalytically cracked material is less, and
And without the Combined machining technology of reaction mass coupling.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of hydrofinishing and hydrocracking combined process, i.e., by from
Gaseous stream is reacted using extraction section in the middle part of the weighted BMO spaces reactor of hydrocracking unit, by the wax oil feedstock oil
It is hydrocracked with LCO feedstock oil by weighted BMO spaces-and produces high-quality hydrocracked product and excellent with hydrofinishing group technology
Matter catalytically cracked material.
A kind of hydrofinishing of the invention and hydrocracking combined process, include the following steps:
A, wax oil feedstock oil is urged under the conditions of weighted BMO spaces by the first weighted BMO spaces of weighted BMO spaces reactor first
Agent bed obtains the first weighted BMO spaces logistics, this part reaction stream is divided into two parts, and a portion passes through gas-liquid point
It is separated from device, gained gaseous stream extracts weighted BMO spaces reactor out;
B, gained remainder the first weighted BMO spaces logistics and the hydrogen being supplemented into mixing continue that hydrogen is being added to locate in advance in step a
Pass through the second hydrogenation pretreatment catalyst bed of weighted BMO spaces reactor under the conditions of reason, weighted BMO spaces logistics continuation is adding
The hydrocracking catalyst bed for passing through hydrocracking reactor under hydrogen cracking conditions, is hydrocracked logistics and is separated, is fractionated
To be hydrocracked high pressure hydrogen-rich gas, be hydrocracked gas product, hydrocracked naphtha product, be hydrocracked boat product of coal,
It is hydrocracked diesel product and hydrocracking tail oil product;
C, after the first weighted BMO spaces gaseous stream of the resulting extraction device of step a is mixed with LCO, in hydroprocessing condition
Pass through the Hydrobon catalyst bed of hydrofining reactor down, hydrotreated refinery stream is separated, is fractionated to obtain hydrotreating
High pressure hydrogen-rich gas, hydrofinishing gas, hydrofinishing naphtha, hydrofining diesel oil.
Hydrofinishing according to the present invention and hydrocracking combined process, wherein can also include step d: step b be obtained
Be hydrocracked the hydrofinishing high pressure hydrogen-rich gas mixing that high pressure hydrogen-rich gas and step c obtain after be recycled.
The impurity such as S, N, O in wax oil feedstock oil by obtaining partial removal when the first hydrogenation pretreatment catalyst bed,
Aromatic hydrocarbons obtains to a certain extent plus hydrogen saturation, extraction section weighted BMO spaces gaseous phase materials and supplement the logistics after new hydrogen after
Continuous to obtain good hydrocracked product by hydrogenation pretreatment catalyst bed and hydrocracking catalyst bed, such as plus hydrogen is split
Change light naphthar, be hydrocracked heavy naphtha, be hydrocracked boat coal, be hydrocracked diesel oil and hydrocracking tail oil etc., because of extraction
The ammonia of partial hydrogenation denitrogenation production, that is, reduce inhibition of the ammonia to hydrocracking catalyst cracking activity center, quite
In improving the activity of hydrocracking catalyst, or reduce hydrocracking operation can scale;Research shows that: the virtue of LCO
Hydrocarbon adds hydrogen saturation depth to be affected fcc gasoline product quality, and especially mononuclear aromatics is high-octane rating in gasoline
Component increases the octane number for adding the content of mononuclear aromatics in hydrogen LCO to can be increased catalytically cracked gasoline, and that extracts out adds hydrogen to locate in advance
It manages and contains certain density hydrogen sulfide and ammonia in gaseous stream, inhibiting effect is equivalent to the activity for reducing hydrogenation catalyst,
And pass through the adjusting of volume space velocity and reaction temperature, it just can control the hydrogenation depth of LCO, i.e., in the premise for meeting sulfur content
Lower two cycloaromatics and polycyclic aromatic hydrocarbon by LCO add hydrogen to mononuclear aromatics, rather than hydrogenation depth excessively generates cycloalkane, or
Hydrogenation depth deficiency generates two cycloaromatics, and the product after such hydrotreating can be improved when being re-introduced into catalytic cracking unit
The content of Aromatics in Fcc Naphtha, to improve the octane number of catalytically cracked gasoline.
Compared with prior art, hydrofinishing of the present invention is with the advantages of hydrocracking combined process:
It 1, include at least two hydrogenation pretreatment catalyst beds in weighted BMO spaces reactor in the present invention.Existed by setting
Gas-liquid separator among weighted BMO spaces reactor bed is by a portion weighted BMO spaces gaseous phase materials extraction step, i.e.,
Effective distribution to weighted BMO spaces material stock can be achieved, then obtained material is made to pass through hydrogenation combination technique, so as to
Produce the purpose product of different size.And in the prior art, Hydrofining Technology and hydrocracking technology are typically only capable to basis
This technology produces the purpose product of hydrogenation technique a kind of.
2, the present invention is by being arranged gas-liquid separator among the catalyst bed of weighted BMO spaces reactor, by wax oil original
Material extracts weighted BMO spaces reactor by the first weighted BMO spaces gaseous stream of weighted BMO spaces, and it is mixed with LCO
Close and be sent into the hydrofining reactor that is separately provided and carry out hydrogenation reaction, due to contain in the gaseous stream of extraction hydrogen sulfide and
Ammonia is unfavorable for the hydrodesulfurization reaction of LCO, but controls LCO by adjusting the reaction conditions such as volume space velocity and reaction temperature
Hydrogenation depth, i.e. the depth that two cycloaromatics and polycyclic aromatic hydrocarbon add hydrogen to be saturated in control LCO, control as far as possible by two cycloaromatics it is good
Polycyclic aromatic hydrocarbon adds hydrogen to mononuclear aromatics, and LCO after hydrogen will be added to carry out reducing reaction difficulty or raising when catalytic cracking again in this way
Arene content in catalytically cracked gasoline improves the octane number of gasoline;And for being hydrocracked for part, because having extracted gas out
Mutually ammonia of the part containing the first hydrogenation pretreatment catalyst bed catalyst hydrodenitrogeneration reaction production, that is, accordingly reduce
Ammonia divides the inhibition to follow-up hydrogenation Cracking catalyst cracking activity center, is equivalent to the work for improving hydrocracking catalyst
Property, or reduce the severity of hydrocracking operation.
3, in the present invention, the extraction gaseous stream that is obtained among weighted BMO spaces reactor hydrogenation pretreatment catalyst bed
Itself has very high temperature and pressure, and it is anti-that newly-installed hydrofinishing can be directly entered after mixing with the LCO after heat exchange
It answers in device and is reacted, to make full use of heat entrained by this thigh point pretreatment gaseous phase materials, realize weighted BMO spaces
The coupling operation of reactor and hydrofining reactor.
4, in the present invention, hydrocracking reaction system is identical with the operating pressure of hydrofining reaction system, therefore two
A set of hydrogen desulphurization system and a set of hydrogen gas circulating system can be used in high pressure hydrogen-rich gas in system, and utilizes and add hydrogen pre-
The heat of gas phase and the LCO mixing after heat exchange are extracted in processing can meet the requirement of hydrofining reaction, only use a heating
Furnace can meet the heat source requirement of group technology, to save equipment investment and operating cost.
Detailed description of the invention
Fig. 1 is principle process schematic diagram of the invention.
Wherein: 1- wax oil feedstock oil, 2- weighted BMO spaces reactor, 3- weighted BMO spaces extract logistics, 4-LCO raw material out
Oil, 5- hydrocracking reactor, 6- are hydrocracked logistics, 7- hydrofining reactor, and 8- is hydrocracked high-pressure separator, and 9- adds
Hydrogen refines high-pressure separator, and 10- is hydrocracked fractionating column, 11- hydrotreating fractionating column, and 12- is hydrocracked light naphtha product,
13- is hydrocracked heavy naphtha product, and 14- is hydrocracked boat product of coal, and 15- is hydrocracked diesel product, and 16- is hydrocracked tail
Oil product, 17- hydrofinishing gas products, 18- hydrofinishing naphtha, 19- hydrofining diesel oil, 20- are hydrocracked high pressure
Separator hydrogen-rich gas, 21- hydrofinishing high-pressure separator hydrogen-rich gas, 22- supplement hydrogen, 23- gas-liquid separator.
Specific embodiment
The initial boiling point of wax oil raw material described in step a is 100~400 DEG C, and the end point of distillation is 405~650 DEG C.The wax oil is former
Material oil can be one of straight-run gas oil, wax tailings, deasphalted oil that PETROLEUM PROCESSING obtains etc., the coal tar obtained from coal
It is wherein several mixed to be also possible to them for one of oil, coal direct liquefaction oil, ICL for Indirect Coal Liquefaction oil, synthetic oil, shale oil etc.
Close oil.
Hydrogenation pretreatment catalyst described in step a and step b is conventional wax oil hydrogenation pretreatment catalyst.Generally
Using VI B race and/or group VIII metal as active component, using aluminium oxide or silicon-containing alumina as carrier, group VIB metal is generally
Mo and/or W, group VIII metal are generally Co and/or Ni.With the poidometer of catalyst, group VIB tenor is in terms of oxide
For 10wt%~35wt%, group VIII metal content is calculated as 3wt%~15wt% with oxide;Its property is as follows: specific surface be 100~
650m20.15~0.6mL/g of/g, Kong Rongwei.Main catalyst have Fushun Petrochemical Research Institute develop 3936,
3996, FF-16, the hydrogenation pretreatment catalysts such as FF-26, FF-36, FF-46, FF-56 series are also possible to domestic and international catalyst
The function of company's exploitation is similar to catalyst, and such as HC-K, HC-P of Uop Inc., TK-555, TK-565 of Topsoe company are catalyzed
Agent and KF-847, KF-848 of Akzo company etc..The operating condition of this field routine can be used in weighted BMO spaces condition, generally
For reaction pressure 3.0MPa~19.0MPa, reaction temperature is 300 DEG C~450 DEG C, volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen
Oil volume ratio is 100:1~2000:1.
The fraction of stream of extraction described in step a accounts for the volume of weighted BMO spaces reactor inlet hydrogen total amount in terms of gas phase
Ratio is 5~95 v%, preferably 10~80 v%.
Hydrocracking catalyst described in step b is conventional wax oil hydrogenation Cracking catalyst.Generally with group VIB and/
Or group VIII metal is active component, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.It should
The carrier of catalyst contains one of aluminium oxide, silicon-containing alumina and molecular sieve or a variety of, preferably contains molecular sieve, described
Molecular sieve can be Y type molecular sieve, beta molecular sieve, Sapo type molecular sieve etc..With the poidometer of catalyst, group VIB metal contains
Amount is calculated as 10wt%~35wt% with oxide, and group VIII metal content is calculated as 3wt%~15wt% with oxide, and molecular sieve content is
5wt%~80wt%.Main commercial catalyst has the 3824 of Fushun Petrochemical Research Institute's development, 3825,3976, FC-
12, FC-14, FC-20, FC-24, FC-26, FC-32, FC-50 catalyst etc., the HC-12, HC-14 of Uop Inc., HC-24,
HC-39 etc..For hydrocracking catalyst, it is desirable that have certain hydrogenation activity and certain lytic activity, should guarantee to add
Hydrogen processing generates generate alkene and aromatic hydrocarbons in fraction in oil and hydrocracking process plus hydrogen saturation, also requires the aromatic hydrocarbons after saturation
The reaction of open loop occurs.Conventional operating condition can be used in the operating condition being hydrocracked, generally are as follows: and reaction pressure 3.0MPa~
19.0MPa, reaction temperature are 300 DEG C~450 DEG C, volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen to oil volume ratio be 100:1~
2000:1。
Separation described in step b generally includes to be hydrocracked high-pressure separator and low pressure separator separates two parts.Its
High-pressure separator is isolated to be hydrocracked high pressure hydrogen-rich gas and liquid, and the isolated liquid of high-pressure separator enters low
Press separator.Low pressure separator is by the isolated hydrocarbon-rich gas of highly pressurised liquid product and low pressure liquid product.Hydrocarbon-rich gas is through dividing
Gas product is hydrocracked from what is needed.
Fractionation described in step b carries out in being hydrocracked fractionating column system.Low pressure liquid product divides in fractionating column
It evaporates to obtain and is hydrocracked light naphtha product, is hydrocracked heavy naphtha product, is hydrocracked boat product of coal, is hydrocracked diesel oil
Product and hydrocracking tail oil product.
LCO raw material described in step c is the light cycle oil of catalytic cracking unit, and initial boiling point is 100~200 DEG C, the end point of distillation
It is 320~400 DEG C.The virtues such as some coker gas oils, ethylene cracking tar, coal tar can also be blended in the LCO feedstock oil
High one or more of the diesel oil distillate of hydrocarbon content.
Hydrobon catalyst described in step c is conventional diesel oil hydrofining catalyst.Generally with VI B race and/
Or group VIII metal is active component, using aluminium oxide or silicon-containing alumina as carrier, group VIB metal is generally Mo and/or W,
Group VIII metal is generally Co and/or Ni.With the poidometer of catalyst, group VIB tenor with oxide be calculated as 10wt%~
35wt%, group VIII metal content are calculated as 3wt%~15wt% with oxide, and property is as follows: specific surface is 100~650m2/ g,
0.15~0.6mL/g of Kong Rongwei.Main catalyst has the 3936 of Fushun Petrochemical Research Institute's development, FF-14, FF-
16, the Hydrobon catalysts such as FF-24, FF-26, FF-36, FF-56, FHUDS-5, FHUDS-7 are also possible to be catalyzed both at home and abroad
The function of agent company exploitation is similar to catalyst, and such as HC-K, HC-P of Uop Inc., TK-555, TK-565 of Topsoe company are catalyzed
Agent and KF-847, KF-848 of Akzo company etc..Conventional operating condition, generally reaction pressure can be used in operating condition
3.0MPa~19.0MPa, reaction temperature are 260 DEG C~450 DEG C, preferably 280 DEG C~410 DEG C, volume space velocity 0.2h when liquid-1~
6.0h-1, hydrogen to oil volume ratio is 100:1~2000:1.
Separation described in step c carries out in hydrotreating high-pressure separator and low pressure separator.Wherein hydrotreating
The isolated hydrotreating high pressure hydrogen-rich gas of high-pressure separator and liquid, the isolated liquid of high-pressure separator enter low pressure
Separator.Low pressure separator is by the isolated hydrocarbon-rich gas of highly pressurised liquid product and low pressure liquid product.Hydrocarbon-rich gas is through separating
The hydrofinishing gaseous product needed.
Fractionation described in step c carries out in hydrogenation refining fractionation Tower System.Low pressure liquid product divides in fractionating column
It evaporates to obtain hydrofinishing naphtha product and hydrofining diesel oil.
It is hydrocracked gas product described in step b and step c and hydrofinishing gas products can be separately as production
Product can also be mixed into mixed gas product.
Light naphtha product and hydrofinishing naphtha are hydrocracked described in step b and step c can be separately as
Product can also be mixed into mixing naphtha product.
Heavy naphtha product is hydrocracked described in step b can be separately as product.
Boat product of coal is hydrocracked described in step b can be separately as product.
Diesel product is hydrocracked described in step b can be separately as product.
Hydrocracking tail oil described in step b is separately as product.
Feedstock oil of the hydrofining diesel oil described in step c as catalytic cracking unit.
It can be used directly as recycle hydrogen after the mixing of high pressure hydrogen-rich gas described in step d, also can choose and pass through
It is recycled after desulphurization of recycle hydrogen system removing hydrogen sulfide.
In the present invention, two Hydrobon catalyst beds are preferably comprised in the hydrofining reactor, i.e., first adds
Hydrogen catalyst for refining bed and the second Hydrobon catalyst bed (being divided according to reaction mass engagement sequence).Increase simultaneously
The process that LCO raw material is carried out to distillation cutting, is preferably divided into two parts according to light fraction and heavy distillat for LCO feedstock oil, described
The temperature spot of cutting is 245 ~ 300 DEG C, i.e., the fraction range of light fraction is initial boiling point to cut-point temperature, the fraction model of heavy distillat
It encloses for cut-point temperature to the end point of distillation.Gaseous stream of the acquired heavy distillat first with the extraction of weighted BMO spaces reactor is mixed into
Enter the first Hydrobon catalyst bed in hydrofining reactor, then hydrofining reaction material continues mixed with light fraction
The gaseous stream extracted out into the second Hydrobon catalyst bed or weighted BMO spaces reactor is closed to mix with heavy distillat first
It closes and enters First hydrofining reactor, hydrofining reaction logistics continuation and light fraction are mixed into subsequent hydrofinishing
Reactor.Due to based on polycyclic aromatic hydrocarbon, being reacted by more Hydrobon catalysts in heavy distillat, can achieve control
The purpose of aromatic hydrogenation depth, and the Hydrobon catalyst reaction that double ring arene is recorded a demerit less in light fraction, can be with double distilled
Point achieve the purpose that control aromatic hydrogenation depth simultaneously, i.e., double ring arene while meeting sulfur content after hydrofinishing and polycyclic
Aromatic hydrocarbons moderately plus hydrogen is to mononuclear aromatics, can satisfy the catalytically cracked gasoline of sulfur content requirement after further catalytic cracking,
And the octane number of gasoline can be improved.
In the present invention, the first hydrogenation pretreatment catalyst bed and the setting of the second hydrogenation pretreatment catalyst bed
In a weighted BMO spaces reactor, or it is separately positioned in more than two weighted BMO spaces reactors.In the present invention
It is preferred that using first way.
Equally, the first Hydrobon catalyst bed and the setting of the second Hydrobon catalyst bed add at one
In hydrogen finishing reactor, or it is separately positioned in more than two hydrofining reactors.First is preferably used in the present invention
Kind mode.
In conjunction with Fig. 1, method of the invention is specific as follows: wax oil feedstock oil 1 is mixed into recycle hydrogen first plus hydrogen is located in advance
Reactor 2 is managed, enters gas-liquid separator 23, extraction by a part in the reaction stream of the first hydrogenation pretreatment catalyst bed
Weighted BMO spaces gaseous stream 3, the logistics after extracting weighted BMO spaces gaseous stream 3 out go successively to add after mixing with hydrogen make-up
Hydrogen cracker 5 is hydrocracked generation logistics 6 into high-pressure separator 8 is hydrocracked and carries out gas-liquid separation, isolated
Liquid enters fractionation in fractionating column 10 and obtains being hydrocracked light naphtha product 12, is hydrocracked heavy naphtha product 13 plus hydrogen
Cracking boat product of coal 14 is hydrocracked diesel product 15 and hydrocracking tail oil product 16, and the weighted BMO spaces of extraction extract gas out
Phase logistics 3 enters hydrofining reactor 7 after mixing with LCO feedstock oil, passes through the generation logistics of Hydrobon catalyst bed
Into gas-liquid separation is carried out in hydrofinishing high-pressure separator 9, isolated liquid enters fractionation in fractionating column 11 and is added
Hydrogen processed gas product 17, hydrofinishing naphtha 18, hydrofining diesel oil 19, to be hydrocracked high-pressure separator 8 isolated
Gas 20 and the isolated gas 21 of hydrofinishing high-pressure separator 9 mix after after circulating hydrogen compressor is pressurized with supplement
The mixing of hydrogen 22 is used as recycle hydrogen.
Illustrate the present invention program and effect below by embodiment.
Embodiment 1-4
Protective agent FZC-100, FZC-105 and FZC106 are China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute
The hydrogenation protecting agent of development and production;Catalyst FF-56 is China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute
The hydrotreating catalyst of development and production;Catalyst FC-32 is that Sinopec Group Fushun petrochemical industry is ground
The hydrocracking catalyst for studying carefully institute's development and production, contains Y type molecular sieve;Catalyst FHUDS-5 is that Sinopec's share has
The Hydrobon catalyst of Fushun Petrochemical Research Institute, limit company development and production.
The main character of 1 wax oil feedstock oil of table
2 process conditions of table
2 process conditions of continued
Wherein, in embodiment 4, LCO light fraction and heavy distillat cutting temperature are 280 DEG C.
3 test result of table
Using hydrofinishing of the invention and hydrocracking combined process it can be seen from embodiment, by from weighted BMO spaces
A part of gas phase reaction logistics of extraction in reactor, extraction gaseous stream and LCO mixed hydrogenation purification production fine quality catalytic cracking
Raw material, remaining weighted BMO spaces logistics continues weighted BMO spaces and hydrocracking catalyst produces the mesh of high-quality hydrocracked product
, production method is flexible.