CN109988640A - A kind of flexible hydrocracking process - Google Patents
A kind of flexible hydrocracking process Download PDFInfo
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- CN109988640A CN109988640A CN201711468998.8A CN201711468998A CN109988640A CN 109988640 A CN109988640 A CN 109988640A CN 201711468998 A CN201711468998 A CN 201711468998A CN 109988640 A CN109988640 A CN 109988640A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/302—Viscosity
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/304—Pour point, cloud point, cold flow properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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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 flexible hydrocracking process.Wax oil raw material is after weighted BMO spaces, into hydrocracking reactor, is divided into two strands by the material after the hydrocracking catalyst bed of top；One material is extracted out hydrocracking reactor among bed, and is entered hydroisomerizing cracker and carried out isocraking reaction；Another strand of material continues to flow downwardly through the hydrocracking catalyst bed of lower part；Gained hydrocracking reaction material and hydroisomerizing cracking reaction material carry out gas-liquid separation and fractionation respectively, obtain different size, naphtha, boat coal, diesel oil and tail oil product.The present invention provide for the first time it is a kind of on a set of hydrogenation technique device and meanwhile produce two or more different size light naphthars, heavy naphtha, boat coal, diesel oil, tail oil product hydrocracking process, heat entrained by partial cracking material can be made full use of, realizes the coupling operation of hydrocracking reactor and hydroisomerizing cracker.
Description
Technical field
The invention belongs to petroleum refining fields, and in particular to a kind of flexibly to produce the high-quality light naphthar of heterogeneity, scheelite
The hydrocracking process of cerebrol, navigate coal, diesel oil, tail oil product.
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.According to tail oil, whether circulate operation can be divided into three kinds: one way is primary
Pass through process flow, part circulation technology process and complete alternation process flow.Hydrocracking technology uses two kinds of catalysis
Agent, pretreating catalyst by hydrocracking and hydrocracking catalyst, wherein hydrocracking catalyst is according to using Cracking Component
It is different can be divided into different types of catalyst again, main Cracking Component includes amorphous silica-alumina, Y type molecular sieve, β type point
Son sieve, SAPO Series Molecules sieve and ZSM-5 molecular sieve etc..A group timesharing, obtained light oil are hydrocracked using different type
Product composition and property also have biggish difference, and the composition and property of tail oil also have biggish difference.
CN103055922B discloses a kind of preparation method of body phase hydrocracking catalyst, CN105018139B, CN
The all disclosed a kind of high-output qulified industrial chemicals of low energy consumption of 001293228A, CN001508225A and CN104611020B adds hydrogen
The method that gradation uses two kinds of different Y type molecular sieves in cracking method.Such technology can using wax oil as feedstock oil, by using
Method for hydrogen cracking containing Y type molecular sieve hydrocracking catalyst yields products of quality, wherein in tail oil Determination of Alkane Content it is high,
BMCI value is low, is the raw material of quality steam cracking ethylene preparation, but the product for being hydrocracked each obtained fraction only has
A kind of specification.
CN105582992A discloses a kind of hydroisomerisation catalysts and its preparation method and application and a kind of plus hydrogen
Cracking tail oil hydroisomerization process, such technology can using wax oil as feedstock oil, by using contain heterogeneous types molecular sieve
The method for hydrogen cracking of hydrocracking catalyst yields products of quality, and wherein isomery content height, condensation point are low in tail oil, viscosity index (VI)
Height, the product for being the raw material of High Quality Lube Base Oils, but being hydrocracked each obtained fraction only have a kind of specification.
CN103394368B discloses a kind of light oil type hydrogen cracking catalyst and preparation method thereof containing composite molecular screen
And application, CN103551186B disclose a kind of middle oil type hydrocracking catalyst containing composite molecular screen and preparation method thereof and
Using US4837396A discloses a kind of preparation of complex type molecular sieve catalysis.Such technology can using wax oil as feedstock oil,
By using the method for hydrogen cracking containing Y type molecular sieve and heterogeneous types molecular sieve complex type molecular sieve hydrocracking catalyst
Various high-quality hydrocracked products are produced, but the product of each fraction only has a kind of specification.
CN001169919C is disclosed a kind of to be raised productivity and improved the quality the method for diesel oil by fraction oil.Such technology can be with wax oil
Feedstock oil, while being catalyzed using containing Y zeolite catalyst and containing two kinds of heterogeneous types molecular sieve hydrocracking catalyst
The method for hydrogen cracking of agent produces various high-quality hydrocracked products, but the product of each fraction only has a kind of specification.
In conclusion the existing hydrocracking technology using two kinds of different type molecular sieve catalysts of comparison, uses Y type
The hydrocracking technology of molecular sieve hydrocracking catalyst, obtained heavy naphtha product sulfur content is low, virtue dive it is relatively high,
Navigating, product of coal smoke point is relatively high, and diesel product sulfur content is low, and Cetane number is high, but condensation point is relatively high, tail oil product virtue
Hydrocarbon content is low, and density is relatively small, and BMCI value is relatively low, but condensation point is very high, and typically larger than 30 DEG C；Use heterogeneous types
The hydrocracking technology of molecular sieve hydrocracking catalyst, obtained heavy naphtha product sulfur content is low, and virtue is latent relatively slightly lower,
Diesel product sulfur content is low, and condensation point is low, but Cetane number is relatively slightly lower, and tail oil density is relatively large, but isomery hydrocarbon content
Height, condensation point is very low, and usually less than 0 DEG C；Use the hydrocracking technology of the complex type molecular sieve catalysis of isomery containing Y-, Huo Zheji
Skill is hydrocracked with use hydrocracking catalyst containing Y type molecular sieve and the molecular sieve hydrocracking catalyst containing heterogeneous types
Art, obtained tail oil property is between using Y type molecular sieve hydrocracking catalyst and heterogeneous types molecular sieve is used to split
Change between catalyst.Above-mentioned hydrocracking process technology, the hydrocracking tail oil differentiation of product produced in identical conversion ratio
It is larger, wherein being the quality raw materials of preparing ethylene by steam cracking using the tail oil of Y zeolite catalyst, use heterogeneous types molecule
The tail oil of sieve catalyst is can directly to produce High Quality Lube Base Oils or the raw material as High Quality Lube Base Oils, is made
Using hydrocracking catalyst containing Y type molecular sieve and contain heterogeneous types with the complex type molecular sieve catalysis of isomery containing Y- or gradation
The tail oil that molecular sieve hydrocracking catalyst obtains can be used as the raw material of preparing ethylene by steam cracking or as high-quality lubricating oil
The raw material of base oil.When above-mentioned several hydrocracking process therefore are used alone, different types of add can only be selected as needed
Hydrogen Cracking catalyst is perhaps made using two kinds of hydrocracking catalyst gradations of two kinds of molecular sieve composite catalysts or selection
With, but these techniques can only produce a kind of tail oil product of property, i.e. operating flexibility compares poor.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of flexible hydrocracking process, i.e., by from using Y type to add hydrogen
Extraction section reaction stream in the middle part of the hydrocracking reactor of Cracking catalyst, adds hydrogen by Y type for the wax oil feedstock oil
Cracking catalysis catalyst hydrocracking and heterogeneous types hydrocracking catalyst hydroisomerizing cracking combined method flexibly produce high quality
Preparing ethylene by steam cracking raw material, High Quality Lube Base Oils raw material and plurality of specifications naphtha product and high-quality automotive fuel
Product.
A kind of flexible hydrocracking process of the invention, includes the following steps:
A, wax oil feedstock oil obtains weighted BMO spaces first under the conditions of weighted BMO spaces through hydrogenation pretreatment catalyst bed
Logistics；
B, the weighted BMO spaces logistics that step a is obtained is urged under hydrocracking condition by being hydrocracked containing Y type molecular sieve
Agent bed obtains first and is hydrocracked logistics, this part reaction stream is divided into two parts, and a portion extraction is hydrocracked
Reactor；
C, in step b the first of remainder be hydrocracked logistics continue under hydrocracking condition by containing Y type molecular sieve
Hydrocracking catalyst bed, be hydrocracked logistics and separated, be fractionated to obtain and be hydrocracked high pressure hydrogen-rich gas, be hydrocracked
Gas products, hydrocracked naphtha product are hydrocracked boat product of coal, are hydrocracked diesel product and hydrocracking tail oil production
Product；
D, first of extraction device obtained by step b is hydrocracked logistics under hydroisomerizing cracking conditions by containing isomeric types
The hydroisomerizing Cracking catalyst bed of type molecular sieve, hydroisomerizing cracked-stream are separated, are fractionated to obtain hydroisomerizing cracking
High pressure hydrogen-rich gas, hydroisomerizing cracked gas product, hydroisomerizing cracked naphtha product, hydroisomerizing cracking boat coal produce
Product, hydroisomerizing cracked diesel oil product and hydroisomerizing cracking tail oil product.
Flexible hydrocracking process according to the present invention, wherein can also include step e: what step c was obtained be hydrocracked
It is recycled after the hydroisomerizing cracking high pressure hydrogen-rich gas mixing that high pressure hydrogen-rich gas and step d are obtained.
The impurity such as S, N, O in wax oil feedstock oil are effectively removed when passing through hydrogenation pretreatment catalyst, and aromatic hydrocarbons is certain
It is obtained in degree plus hydrogen saturation, weighted BMO spaces logistics continues through the hydrocracking catalyst containing Y zeolite catalyst
Cyclic hydrocarbon generating unit divides ring-opening reaction when bed, and aromatic hydrocarbons further adds hydrogen to be saturated, and macromolecular is cracked into small molecule, a part plus hydrogen
Cracked-stream continues to be hydrocracked, available high just because Y type molecular sieve has the characteristics of preferential cracking macromolecular cyclic hydrocarbon
The low boat product of coal of structure hydrocarbon content, arene content, diesel product and tail oil product；The first of extraction section is hydrocracked logistics warp
It crosses after the hydroisomerizing Cracking catalyst containing heterogeneous types molecular sieve catalyst and continues isomery and be hydrocracked, because of isomeric types
Type molecular sieve has the characteristics that isomery and cracking, the isocraking product of available high isomery hydrocarbon content, especially diesel oil produce
The condensation point of product is low, the condensation point of tail oil product is low, and viscosity index (VI) is high.
Compared with prior art, the advantages of present invention flexible hydrocracking process, is:
It 1, include at least two hydrocracking catalyst beds in hydrocracking reactor in the present invention.Adding hydrogen by setting
Cracking material extraction step among cracker bed is not necessarily to special operation, can be realized to being hydrocracked material stock
Effectively distribution, then make obtained material by different hydrocracking process, so as to flexibly produce the mesh of different size
Product, especially tail oil product.Meanwhile abstraction reaction logistics is technically also to be easily achieved among reactor bed
's.And in the prior art, although by adjusting conversion ratio and the adjustment available a variety of light-end products of product boiling range, by
It is exported in only one hydrocracking reactor, therefore the same fraction range of a set of hydrocracking unit is typically only capable to obtain one kind
Light naphtha product, heavy naphtha product, boat product of coal and the diesel product of type, especially can only obtain a kind of tail oil product；
If it is intended to obtaining the hydrocracked product of different size, then two sets or more of hydrocracking unit is needed.Therefore, the present invention is first
It is secondary to provide one kind on a set of hydrocracking process device while producing two or more same fraction ranges, but different size tail
Oil product, two or more different sizes boat product of coal, two or more different size diesel products and a variety of different size naphthas
The hydrocracking process of product.
2, the present invention is hydrocracked logistics extraction by the way that first is arranged among the catalyst bed of hydrocracking reactor
Device extracts wax oil raw material instead by the logistics of weighted BMO spaces and the first hydrocracking catalyst bed being hydrocracked
Device is answered, and is respectively fed to the hydroisomerizing cracker being separately provided and carries out hydroisomerizing cracking reaction, is further dropped
Low this is hydrocracked the condensation point of rear material, so that method of the invention can flexibly produce different arene contents, different different
Naphtha product, boat product of coal, diesel product and the tail oil product of structure hydrocarbon content.
3, in the present invention, in the product that two reactor streams are fractionated, by adding hydrogen containing Y zeolite catalyst
The heavy naphtha virtue obtained after cracking is dived, and relatively high, boat product of coal smoke point is relatively high, and diesel product Cetane number is relatively
Height, tail oil product paraffinicity is high, BMCI value is relatively low；It is hydrocracked, contains containing Y zeolite catalyst by part
There are the naphtha isomery hydrocarbon content height obtained after heterogeneous types molecular sieve catalyst hydroisomerizing cracking, boat product of coal freezing point low,
Diesel product condensation point is low, and tail oil product hydrocarbon isomer content is high, viscosity index (VI) is big, condensation point is low；The different rule of production can be met respectively
The needs of the naphtha of lattice, navigate product of coal, diesel product and tail oil product.
4, in the present invention, the liquid itself obtained among hydrocracking reactor hydrocracking catalyst bed has very high
Temperature and pressure, can be directly entered in newly-installed hydroisomerizing cracker and be reacted, to make full use of
Heat entrained by this strand of partly upgraded material realizes that the coupling of hydroisomerizing cracker and hydrocracking reactor is grasped
Make.
Detailed description of the invention
Fig. 1 is principle process schematic diagram of the invention.
Wherein: 1- feedstock oil, 2- weighted BMO spaces reactor, 3- weighted BMO spaces logistics, 4- hydrocracking reactor, 5-
Hydroisomerizing cracked stock logistics, 6- are hydrocracked logistics, 7- hydroisomerizing cracker, and 8- is hydrocracked high pressure separation
Device, 9- hydroisomerizing cracking high-pressure separator, 10- are hydrocracked fractionating column, 11- hydroisomerizing cracking fractionating column, and 12- adds hydrogen to split
Change light naphtha product, 13- is hydrocracked heavy naphtha product, and 14- is hydrocracked boat product of coal, and 15- is hydrocracked diesel oil production
Product, 16- hydrocracking tail oil product, 17- hydroisomerizing cracking light naphtha product, 18- hydroisomerizing cracking heavy naphtha produce
Product, 19- hydroisomerizing cracking boat product of coal, 20- hydroisomerizing cracked diesel oil product, 21- hydroisomerizing cracking tail oil product,
22- is hydrocracked high-pressure separator hydrogen-rich gas, 23- hydroisomerizing cracking high-pressure separator hydrogen-rich gas, and 24- supplements hydrogen.
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, catalytic cycle oil that PETROLEUM PROCESSING obtains etc., from coal
One of obtained coal tar, coal direct liquefaction oil, ICL for Indirect Coal Liquefaction oil, synthetic oil, shale oil etc., be also possible to them its
In several miscella.
Hydrogenation pretreatment catalyst described in step a is conventional wax oil hydrogenation pretreatment catalyst.Generally with VI B race
And/or group VIII metal be active component, using aluminium oxide or silicon-containing alumina as carrier, group VIB metal be generally Mo and/or
W, group VIII metal are generally Co and/or Ni.With the poidometer of catalyst, group VIB tenor is calculated as 10wt% with oxide
~35wt%, group VIII metal content are calculated as 3wt%~15wt% with oxide；Its property is as follows: specific surface area be 100~
650m20.15~0.6mL/g of/g, Kong Rongwei.Available commercial catalysts have Fushun Petrochemical Research Institute to develop
3936,3996, the hydrogenation pretreatment catalysts such as FF-16, FF-26, FF-36, FF-46, FF-56 series are also possible to both at home and abroad
The function of catalyst Co. exploitation is similar to catalyst, such as HC-K, HC-P of Uop Inc., TK-555, TK-565 of Topsoe company
Catalyst and KF-847, KF-848 of Akzo company etc..Conventional operating condition, generally reaction pressure can be used in operating condition
Power 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
For 100:1~2000:1.
Hydrocracking catalyst described in step b and step c is conventional wax oil hydrogenation Cracking catalyst.Generally with the VIth
B race and/or group VIII metal are active component, and group VIB metal is generally Mo and/or W, group VIII metal be generally Co and/
Or Ni.The carrier of the catalyst contains one of aluminium oxide, silicon-containing alumina and molecular sieve or a variety of, preferably contains molecule
Sieve；The molecular sieve is preferably Y type molecular sieve.With the poidometer of catalyst, group VIB tenor is calculated as with oxide
10wt%~35wt%, group VIII metal content are calculated as 3wt%~15wt% with oxide, and molecular sieve content is 5wt%~80wt%.It is main
The catalyst wanted has the 3824 of Fushun Petrochemical Research Institute's development, 3825,3976, FC-12, FC-24, FC-26, FC-
32, FC-50 catalyst etc., HC-12, HC-14, HC-24, HC-39 etc. of Uop Inc..For hydrocracking catalyst,
It is required that having certain hydrogenation activity and certain lytic activity, it should guarantee that hydrotreating generates and be generated in oil and hydrocracking process
In fraction alkene and aromatic hydrocarbons plus hydrogen saturation, the aromatic hydrocarbons after also requiring saturation the reaction of open loop occurs.The operation item being hydrocracked
Conventional operating condition can be used in part, 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 is 100:1~2000:1.
The mass ratio that the fraction of stream of extraction described in step b accounts for feedstock oil in terms of liquid phase is 5~95wt%, preferably
10~80wt%.
Separation described in step c generally comprises 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 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 warp
Isolated needs are hydrocracked gas product.
Fractionation described in step c 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.
Hydroisomerizing Cracking catalyst described in step d is conventional wax oil hydrogenation isocraking catalyst.Generally with
VI B race and/or group VIII metal are active component, and group VIB metal is generally Mo and/or W, and group VIII metal is generally Co
And/or Ni.The carrier of the catalyst contains one of aluminium oxide, silicon-containing alumina and molecular sieve or a variety of, preferably contains and divides
Son sieve, the molecular sieve can be beta molecular sieve, Sapo type molecular sieve etc..With the poidometer of catalyst, group VIB metal
Content is calculated as 10wt%~35wt% with oxide, and group VIII metal content is calculated as 3wt%~15wt%, molecular sieve content with oxide
For 5wt%~80wt%.FC-14, FC-20 etc. that main commercial catalyst has Fushun Petrochemical Research Institute to develop.It is right
For hydrocracking catalyst, it is desirable that have certain hydrogenation activity and certain lytic activity, should guarantee alkene in reaction mass
Hydrocarbon and aromatic hydrocarbons plus hydrogen saturation, also require linear paraffin that isomerization reaction occurs.The operating condition of hydroisomerizing cracking can be used often
The operating condition of rule, generally are as follows: reaction pressure 3.0MPa~19.0MPa, reaction temperature are 300 DEG C~450 DEG C, and volume is empty when liquid
Fast 0.2h-1~6.0h-1, hydrogen to oil volume ratio is 100:1~2000:1.
Separation described in step d carries out in hydroisomerizing cracking high-pressure separator and low pressure separator.Wherein plus hydrogen
The isolated hydroisomerizing cracking high pressure hydrogen-rich gas of isocraking high-pressure separator and liquid, high-pressure separator are isolated
Liquid enters low pressure separator.Low pressure separator is by the isolated hydrocarbon-rich gas of highly pressurised liquid product and low pressure liquid product.It is rich
Appropriate hydrocarbon gas is isolated to the hydroisomerizing cracked gas product of needs.
Fractionation described in step d carries out in hydroisomerizing cracking fractionating column system.Low pressure liquid product is in fractionating column
Middle fractionation obtains hydroisomerizing cracking light naphtha product, hydroisomerizing cracking heavy naphtha product, hydroisomerizing cracking boat coal
Product, hydroisomerizing cracked diesel oil product and hydroisomerizing cracking tail oil product.
Gas product and hydroisomerizing cracked gas product are hydrocracked described in step c and step d individually to be made
For product, mixed gas product can also be mixed into.
It is hydrocracked light naphtha product described in step c and step d and hydroisomerizing cracking light naphtha product can
Mixing light naphtha product can also be mixed into separately as product.
It is hydrocracked heavy naphtha product described in step c and step d and hydroisomerizing cracking heavy naphtha product can
Mixing heavy naphtha product can also be mixed into separately as product.
Boat product of coal and hydroisomerizing cracking boat product of coal are hydrocracked described in step c and step d individually to be made
For product, mixing boat product of coal can also be mixed into.
Diesel product and hydroisomerizing cracked diesel oil product are hydrocracked described in step c and step d individually to be made
For product, mixed diesel product can also be mixed into.
Hydrocracking tail oil described in step c is separately as product.
Hydroisomerizing cracking tail oil described in step d is separately as product.
It can be used directly as recycle hydrogen after the mixing of high pressure hydrogen-rich gas described in step e, also can choose and pass through
It is recycled after desulphurization of recycle hydrogen system removing hydrogen sulfide.
In the present invention, the hydrogenation pretreatment catalyst bed, the first hydrocracking catalyst bed, second are hydrocracked
Catalyst bed is arranged in a reactor；Alternatively, hydrogenation pretreatment catalyst bed is arranged in individual weighted BMO spaces
In reactor, the first hydrocracking catalyst bed and the second hydrocracking catalyst bed are arranged in a hydrogenator
It is interior；Or hydrogenation pretreatment catalyst bed, hydrocracking catalyst and hydrogenator catalyst bed are separately positioned on
In three hydrogenators.
In conjunction with Fig. 1, method of the invention is specific as follows: it is anti-that feedstock oil 1 is mixed into weighted BMO spaces with recycle hydrogen first
Device 2 is answered, weighted BMO spaces logistics 3 enters hydrocracking reactor 4, by the reaction stream of the first hydrocracking catalyst bed
Middle extraction hydroisomerizing cracked stock logistics 5, the logistics after extracting hydroisomerizing cracked stock logistics 5 out go successively to follow-up hydrogenation
Cracking catalyst bed is hydrocracked generation logistics 6 into high-pressure separator 8 is hydrocracked and carries out gas-liquid separation, isolated
Liquid enter in fractionating column 10 fractionation obtain being hydrocracked light naphtha product 12, be hydrocracked heavy naphtha product 14 plus
Hydrogen cracking boat product of coal 14 is hydrocracked diesel product 15 and hydrocracking tail oil product 16, hydroisomerizing cracked stock logistics 5
Into hydroisomerizing cracker 7, hydroisomerizing cracking is entered by the product stream of hydroisomerizing Cracking catalyst bed
Carry out gas-liquid separation in high-pressure separator 9, isolated liquid enters fractionation in fractionating column 11, and to obtain hydroisomerizing cracking light
Naphtha product 17, hydroisomerizing cracking heavy naphtha product 18, hydroisomerizing cracking boat product of coal 19, hydroisomerizing cracking bavin
Oil product 20 and hydroisomerizing cracking tail oil product 21, are hydrocracked light naphtha product 12 and hydroisomerizing cracking light naphthar
Product 17 can obtain mixing light naphtha product, be hydrocracked heavy naphtha product separately as product after can also mixing
13 and hydroisomerizing cracking heavy naphtha product 18 can separately as product, be obtained after can also mixing mixing heavy naphtha produce
Product, being hydrocracked boat product of coal 14 and hydroisomerizing cracking boat product of coal 19 can obtain after can also mixing separately as product
Navigate product of coal to mixing, be hydrocracked diesel product 15 and hydroisomerizing cracked diesel oil product 20 can separately as product,
Mixed diesel product is obtained after can mixing, and is hydrocracked the isolated gas 22 of high-pressure separator 8 and hydroisomerizing cracking
The isolated gas 23 of high-pressure separator 9 is mixed with supplement hydrogen 24 as circulation after circulating hydrogen compressor is pressurized after mixing
Hydrogen.
Illustrate the present invention program and effect below by embodiment.
Embodiment 1-3
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 catalyst for hydro-upgrading for studying carefully institute's development and production, contains Y type molecular sieve；Catalyst FC-20 is that Sinopec's share is limited
The hydroisomerizing Cracking catalyst of Fushun Petrochemical Research Institute, company development and production, contains beta molecular sieve.
The main character of 1 wax oil feedstock oil of table
2 process conditions of table
2 process conditions of continued
3 test result of table
Using hydrocracking process of the invention it can be seen from embodiment, by extracting one out out of hydrocracking reactor
Divide reaction stream, and realizes that production heterogeneity is hydrocracked using hydrocracking catalyst and hydroisomerizing Cracking catalyst
The purpose of product, production method are flexible.
Claims (12)
1. a kind of flexible hydrocracking process, includes the following steps:
A, wax oil feedstock oil obtains weighted BMO spaces first under the conditions of weighted BMO spaces through hydrogenation pretreatment catalyst bed
Logistics；
B, the weighted BMO spaces logistics that step a is obtained is urged under hydrocracking condition by being hydrocracked containing Y type molecular sieve
Agent bed obtains first and is hydrocracked logistics, this part reaction stream is divided into two parts, and a portion extraction is hydrocracked
Reactor；
C, in step b the first of remainder be hydrocracked logistics continue under hydrocracking condition by containing Y type molecular sieve
Hydrocracking catalyst bed, be hydrocracked logistics and separated, be fractionated to obtain and be hydrocracked high pressure hydrogen-rich gas, be hydrocracked
Gas products, hydrocracked naphtha product are hydrocracked boat product of coal, are hydrocracked diesel product and hydrocracking tail oil production
Product；
D, first of extraction device obtained by step b is hydrocracked logistics under hydroisomerizing cracking conditions by containing isomeric types
The hydroisomerizing Cracking catalyst bed of type molecular sieve, hydroisomerizing cracked-stream are separated, are fractionated to obtain hydroisomerizing cracking
High pressure hydrogen-rich gas, hydroisomerizing cracked gas product, hydroisomerizing cracked naphtha product, hydroisomerizing cracking boat coal produce
Product, hydroisomerizing cracked diesel oil product and hydroisomerizing cracking tail oil product.
2. flexible hydrocracking process described in accordance with the claim 1, which is characterized in that further include step e: step c is obtained
It is recycled after being hydrocracked the hydroisomerizing cracking high pressure hydrogen-rich gas mixing that high pressure hydrogen-rich gas and step d are obtained.
3. flexible hydrocracking process 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. flexible hydrocracking process described in accordance with the claim 3, which is characterized in that the wax oil feedstock oil is selected from straight run
Wax oil, wax tailings, deasphalted oil, catalytic cycle oil, coal tar, coal direct liquefaction oil, ICL for Indirect Coal Liquefaction oil, synthetic oil and page
At least one of shale oil.
5. flexible hydrocracking process described in accordance with the claim 1, which is characterized in that weighted BMO spaces described in step a are urged
Agent is using VI B race and/or group VIII metal as active component, using aluminium oxide or silicon-containing alumina as carrier；With the weight of catalyst
Meter, group VIB tenor are calculated as 10wt%~35wt% with oxide, group VIII metal content with oxide be calculated as 3wt%~
15wt%；Its property is as follows: specific surface area is 100~650m20.15~0.6mL/g of/g, Kong Rongwei.
6. flexible hydrocracking process described in accordance with the claim 1, which is characterized in that the weighted BMO spaces 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 oil
Volume ratio is 100:1~2000:1.
7. flexible hydrocracking process described in accordance with the claim 1, which is characterized in that add hydrogen described in step b and step c
For Cracking catalyst using group VIB and/or group VIII metal as active component, catalyst carrier contains Y type molecular sieve；With catalyst
Poidometer, group VIB tenor is calculated as 10wt%~35wt% with oxide, and group VIII metal content is calculated as with oxide
3wt%~15wt%, Y type molecular sieve content are 5wt%~80wt%.
8. flexible hydrocracking process described in accordance with the claim 1, which is characterized in that the condition being hydrocracked are as follows: anti-
Answer 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 body
Product is than being 100:1~2000:1.
9. flexible hydrocracking process described in accordance with the claim 1, which is characterized in that the hydroisomerizing Cracking catalyst
Using group VIB and/or group VIII metal as active component, catalyst carrier contains molecular sieve, and the molecular sieve is beta molecular sieve
Or Sapo type molecular sieve；With the poidometer of catalyst, group VIB tenor is calculated as 10wt%~35wt% with oxide, and the VIIIth
Race's tenor is calculated as 3wt%~15wt% with oxide, and molecular sieve content is 5wt%~80wt%.
10. flexible hydrocracking process described in accordance with the claim 1, which is characterized in that the hydroisomerizing cracking conditions
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.
11. flexible hydrocracking process described in accordance with the claim 1, which is characterized in that the logistics extracted out in step b is with liquid phase
The mass ratio that meter accounts for feedstock oil is 5~95wt%, preferably 10~80wt%.
12. flexible hydrocracking process described in accordance with the claim 1, which is characterized in that the hydrogenation pretreatment catalyst bed
Layer, the first hydrocracking catalyst bed, the second hydrocracking catalyst bed are arranged in a reactor；Alternatively, plus hydrogen
Pretreatment catalyst bed is arranged in individual weighted BMO spaces reactor, and the first hydrocracking catalyst bed and second adds
Hydrogen Cracking catalyst bed is arranged in a hydrogenator；Or it hydrogenation pretreatment catalyst bed, is hydrocracked and urges
Agent and hydrogenator catalyst bed are separately positioned in three hydrogenators.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684415A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical materials to maximum with low cost |
| CN104560156A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocracking method |
| CN104560169A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocracking method for producing heavy naphtha from high-nitrogen stock |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684415A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical materials to maximum with low cost |
| CN104560156A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocracking method |
| CN104560169A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocracking method for producing heavy naphtha from high-nitrogen stock |
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