CN109988625A - A kind of hydrofinishing and hydrocracking combined process - Google Patents

A kind of hydrofinishing and hydrocracking combined process Download PDF

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Publication number
CN109988625A
CN109988625A CN201711470870.5A CN201711470870A CN109988625A CN 109988625 A CN109988625 A CN 109988625A CN 201711470870 A CN201711470870 A CN 201711470870A CN 109988625 A CN109988625 A CN 109988625A
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oil
hydrogen
weighted bmo
bmo spaces
reactor
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CN109988625B (en
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刘涛
李宝忠
曾榕辉
张学辉
吴锐
关明华
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of hydrofinishing and hydrocracking combined process.Wax oil raw material enters weighted BMO spaces reactor, is divided into two strands by the material after the hydrogenation pretreatment catalyst bed of top;One material enters the gas-liquid separator being arranged among bed, and gaseous phase materials extract weighted BMO spaces reactor out, carry out hydrofining reaction after mixing with LCO;Another strand of material fills into the mixture flow of hydrogen for logistics remaining after liquid phase, extraction in reactor and newly, continues the hydrogenation pretreatment catalyst bed for flowing downwardly through lower part, weighted BMO spaces logistics enters hydrocracking reactor;Gained hydrocracking reaction material carries out gas-liquid separation and fractionation, obtains the hydrocracked products such as naphtha, boat coal, diesel oil and tail oil;Hydrofining reaction logistics carries out gas-liquid separation and fractionation, obtains naphtha and plus hydrogen LCO.The present invention provide for the first time it is a kind of on a set of hydrogenation technique device and meanwhile production be hydrocracked light-end products and plus hydrogen LCO hydrogenation combination technique.

Description

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.

Claims (18)

1. a kind of hydrofinishing 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.
2. group technology described in accordance with the claim 1, which is characterized in that further include step d: what step b was obtained is hydrocracked It is recycled after the hydrotreating high pressure hydrogen-rich gas mixing that high pressure hydrogen-rich gas and step c are obtained.
3. group technology described in accordance with the claim 1, which is characterized in that the initial boiling point of the wax oil raw material is 100~400 DEG C, the end point of distillation is 405~650 DEG C.
4. group technology described in accordance with the claim 3, which is characterized in that the wax oil feedstock oil is selected from straight-run gas oil, coke Change at least one of wax oil, deasphalted oil, coal tar, coal direct liquefaction oil, ICL for Indirect Coal Liquefaction oil, synthetic oil and shale oil.
5. group technology described in accordance with the claim 1, which is characterized in that the initial boiling point of the LCO is 100~200 DEG C, eventually Evaporate a little is 320~400 DEG C.
6. group technology described in accordance with the claim 1, which is characterized in that also blend coker gas oil in the LCO, ethylene is split Solve at least one of tar and coal tar.
7. group technology described in accordance with the claim 1, which is characterized in that the hydrogenation pretreatment catalyst with VI B race and/ Or group VIII metal is active component, using aluminium oxide or silicon-containing alumina as carrier;With the poidometer of catalyst, group VIB gold Belong to content and 10wt%~35wt% is calculated as with oxide, group VIII metal content is calculated as 3wt%~15wt% with oxide;Its property is such as Under: specific surface is 100~650m20.15~0.6mL/g of/g, Kong Rongwei.
8. group technology described in accordance with the claim 1, which is characterized in that the condition of the weighted BMO spaces are as follows: 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 is 100:1~2000:1.
9. group technology described in accordance with the claim 1, which is characterized in that the gaseous stream extracted out in step a accounts for plus hydrogen is located in advance The percent by volume for managing reactor inlet hydrogen total amount is 5%~95%, preferably 10%~80%.
10. group technology described in accordance with the claim 1, which is characterized in that the hydrocracking catalyst is with group VIB And/or group VIII metal is active component, catalyst carrier contains one of aluminium oxide, silicon-containing alumina and molecular sieve or more Kind, the molecular sieve is Y type molecular sieve, beta molecular sieve or Sapo type molecular sieve.
11. group technology according to claim 10, which is characterized in that 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%.
12. group technology described in accordance with the claim 1, which is characterized in that the hydrocracking condition are as follows: 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 is 100:1~2000:1.
13. group technology described in accordance with the claim 1, which is characterized in that the Hydrobon catalyst with VI B race and/ Or group VIII metal is active component, using aluminium oxide or silicon-containing alumina as carrier;With the poidometer of catalyst, group VIB gold Belong to content and 10wt%~35wt% is calculated as with oxide, group VIII metal content is calculated as 3wt%~15wt% with oxide;Its property is such as Under: specific surface is 100~650m20.15~0.6mL/g of/g, Kong Rongwei.
14. group technology described in accordance with the claim 1, which is characterized in that hydroprocessing condition described in step c are as follows: reaction Pressure 3.0MPa~19.0MPa, reaction temperature are 300 DEG C~450 DEG C, preferably 320 DEG C~410 DEG C, volume space velocity when liquid 0.2h-1~6.0h-1, hydrogen to oil volume ratio is 100:1~2000:1.
15. group technology described in accordance with the claim 1, which is characterized in that the hydrofining reactor include there are two plus Hydrogen catalyst for refining bed, i.e. the first Hydrobon catalyst bed and the second Hydrobon catalyst bed.
16. group technology according to claim 15, which is characterized in that the method also includes: LCO raw material is cut into Light fraction and heavy distillat, the temperature of the cutting are 245 ~ 300 DEG C;The of the heavy distillat and the extraction of weighted BMO spaces reactor Added after the mixing of one weighted BMO spaces gaseous stream by the first Hydrobon catalyst bed in hydrofining reactor, first Hydrogen refining reaction material is mixed with light fraction through the second Hydrobon catalyst bed.
17. group technology described in accordance with the claim 1, which is characterized in that the first hydrogenation pretreatment catalyst bed It is arranged in a weighted BMO spaces reactor with the second hydrogenation pretreatment catalyst bed, or is separately positioned on two or more Weighted BMO spaces reactor in.
18. according to group technology described in claim 15 or 16, which is characterized in that the first Hydrobon catalyst bed Layer and the second Hydrobon catalyst bed are arranged in a hydrofining reactor, or are separately positioned on more than two In hydrofining reactor.
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CN103059944A (en) * 2011-10-21 2013-04-24 中国石油化工股份有限公司 Hydrocracking technological method for processing inferior raw material
CN105586084A (en) * 2014-10-23 2016-05-18 中国石油化工股份有限公司 Catalytic hydrogenation method for inferior wax oil

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CN103059944A (en) * 2011-10-21 2013-04-24 中国石油化工股份有限公司 Hydrocracking technological method for processing inferior raw material
CN105586084A (en) * 2014-10-23 2016-05-18 中国石油化工股份有限公司 Catalytic hydrogenation method for inferior wax oil

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