CN109988623A - Flexible inverted sequence hydrocracking process - Google Patents
Flexible inverted sequence hydrocracking process Download PDFInfo
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- CN109988623A CN109988623A CN201711469564.XA CN201711469564A CN109988623A CN 109988623 A CN109988623 A CN 109988623A CN 201711469564 A CN201711469564 A CN 201711469564A CN 109988623 A CN109988623 A CN 109988623A
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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
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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
- 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
- C10G2300/307—Cetane number, cetane index
-
- 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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- 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 inverted sequence hydrocracking process.Wax oil feedstock oil be hydrocracked generate material mix after carry out weighted BMO spaces, weighted BMO spaces product stream carries out separation fractionation and obtains gas, distillate and tail oil, gained tail oil carries out being hydrocracked pretreatment, and by the first hydrocracking catalyst bed in hydrocracking reactor, obtains material and be divided into two strands；One material enters separator and is separated, and gained liquid phase stream extracts hydrocracking reactor out, and enters hydroisomerizing cracker and carry out isocraking reaction；Another strand of material continues to flow downwardly through the second hydrocracking catalyst bed；Hydroisomerizing cracking reaction material carries out gas-liquid separation and fractionation, obtains hydroisomerizing pressure naphtha, boat coal, diesel oil and tail oil product.The present invention provides a kind of on a set of hydrogenation technique device while producing the hydrocracking process of two or more different size light naphthars, heavy naphtha, boat coal, diesel oil, tail oil product.
Description
Technical field
The invention belongs to petroleum refining fields, and in particular to one kind flexibly produces high-quality light naphthar of different nature, again
The inverted sequence hydrocracking process of naphtha, 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.Inverted sequence hydrocracking technology is a kind of for raw material
Middle light fraction is more or the hydrocracking technology of the mostly equal exploitations of impurity (such as oxygen, metal) content.Hydrocracking technology uses two
The catalyst of seed type, pretreating catalyst by hydrocracking and hydrocracking catalyst, wherein hydrocracking catalyst is according to making
Different with Cracking Component can be divided into different types of catalyst again, and main Cracking Component includes amorphous silica-alumina, Y type
Molecular sieve, beta molecular sieve, SAPO Series Molecules sieve and ZSM-5 molecular sieve etc..A group timesharing, institute are hydrocracked using different type
Obtained light-end products composition and property also has biggish difference, and the composition and property of tail oil also have biggish difference.
CN101333459A discloses a kind of hydrogenating conversion process using inverted sequence hydrocracking process process, this method
It is suitble to the processing of long distillate feedstock oil；CN105733674A discloses a kind of inverted sequence method for hydrogen cracking, will mainly hydrogen be added to split
A part of gas phase extraction device of change process production, reduces the further cracking of small molecule material；CN103055922B is public
A kind of preparation method of body phase hydrocracking catalyst, CN105018139B, CN 001293228A, CN001508225A are opened
Two kinds are used with gradation in a kind of all disclosed method for hydrogen cracking of the high-output qulified industrial chemicals of low energy consumption of CN104611020B
The method of different Y type molecular sieves.Such technology can be hydrocracked using wax oil as feedstock oil by using containing Y type molecular sieve
The method for hydrogen cracking of catalyst yields products of quality, and wherein Determination of Alkane Content height, BMCI value are low in tail oil, is quality steam cracking
The raw material of ethylene processed, 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 distillate.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, or inverted sequence hydrocracking process technology is used, but the product of the same fraction range of these techniques is typically only capable to production one
The product of kind specification, 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 inverted sequence hydrocracking process, i.e., by from using Y type
The gas-liquid separator extraction section liquid phase reactor logistics being arranged in the middle part of the hydrocracking reactor of hydrocracking catalyst, by wax oil
Feedstock oil is hydrocracked by Y type hydrocracking catalyst and is combined instead with heterogeneous types hydrocracking catalyst hydroisomerizing cracking
Sequence method for hydrogen cracking flexibly produces naphtha product and the combustion of high-quality motor of High Quality Lube Base Oils raw material and plurality of specifications
Expect product.
Flexible inverted sequence hydrocracking process of the invention, includes the following steps:
A, it wax oil feedstock oil and is hydrocracked to generate logistics and enter under the conditions of weighted BMO spaces and weighted BMO spaces reactor and leads to
Hydrogenation pretreatment catalyst bed is crossed, weighted BMO spaces logistics is obtained；
B, the weighted BMO spaces logistics that step a is obtained is separated, is fractionated to obtain and is hydrocracked high pressure hydrogen-rich gas, hydrocracking gas
Body product, hydrocracked naphtha product are hydrocracked boat product of coal, are hydrocracked diesel product and hydrocracking tail oil (follows
Ring oil)；
C, the hydrocracking tail oil (recycle oil) that step b is obtained is blended in recycle hydrogen to be entered in the case where being hydrocracked pretreatment condition
It is hydrocracked preatreating reactors and passes through hydrogenation pretreatment catalyst bed, obtain being hydrocracked pretreatment stream, hydrogen is added to split
Change processing logistics to split under hydrocracking condition by first plus hydrogen in hydrocracking reactor containing Y zeolite catalyst
Change catalyst bed, obtain first and be hydrocracked logistics, this part reaction stream is divided into two parts, and a portion is to pass through gas
The isolated liquid stream of liquid/gas separator, and extract hydrocracking reactor out；
D, in step c the first of remainder be hydrocracked logistics continuation pass through hydrocracking reactor under hydrocracking condition
In the second hydrocracking catalyst bed containing Y zeolite catalyst, obtain being hydrocracked logistics, be hydrocracked logistics with
Feedstock oil is mixed into weighted BMO spaces reactor；
E, first of extraction device obtained by step c is hydrocracked after liquid stream mixes with recycle hydrogen, in hydroisomerizing cracking
Under the conditions of pass through the hydroisomerizing Cracking catalyst bed containing heterogeneous types molecular sieve catalyst of hydroisomerizing cracker
Layer, hydroisomerizing cracked-stream are separated, are fractionated to obtain hydroisomerizing cracking high pressure hydrogen-rich gas, the production of hydroisomerizing cracked gas
Product, hydroisomerizing cracked naphtha product, hydroisomerizing cracking boat product of coal, hydroisomerizing cracked diesel oil product and hydroisomerizing
Cracking tail oil product.
Hydrocracking process according to the present invention, wherein can also include step f: what step b was obtained be hydrocracked high pressure
It is recycled after the hydroisomerizing cracking high pressure hydrogen-rich gas mixing that hydrogen-rich gas and step e are obtained.
The impurity such as S, N, O in wax oil feedstock oil are obtained when passing through hydrogenation pretreatment catalyst and are removed to a certain extent, aromatic hydrocarbons
It obtains to a certain extent plus hydrogen saturation, the hydrocracking tail oil that weighted BMO spaces product stream obtains after separation fractionation (follows
Ring oil) it is actually that hydrocracking tail oil again passes by the mixing of weighted BMO spaces and wax oil feedstock oil after weighted BMO spaces
Oil, the logistics obtain being hydrocracked pretreatment stream, continue through and urge containing Y type molecular sieve after being hydrocracked pretreatment
Cyclic hydrocarbon generating unit divides ring-opening reaction when the hydrocracking catalyst bed of agent, and aromatic hydrocarbons further adds hydrogen to be saturated, and macromolecular is split
It is melted into small molecule, a part is hydrocracked logistics and continues to be hydrocracked, because Y type molecular sieve has preferential cracking macromolecular cyclic annular
The characteristics of hydrocarbon, available high normal hydrocarbon content, arene content low boat product of coal, diesel product and tail oil；One of extraction
Divide first to be hydrocracked logistics to continue after the hydroisomerizing Cracking catalyst containing heterogeneous types molecular sieve catalyst
Isomery is hydrocracked, because heterogeneous types molecular sieve has the characteristics that isomery and cracking, the isomery of available high isomery hydrocarbon content
Cracked product, the condensation point of especially gained diesel 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 inverted sequence hydrocracking process, is:
It 1, include at least two hydrocracking catalyst beds in hydrocracking reactor in the present invention.Adding hydrogen by setting
A portion cracked liquid material extraction step can be realized to adding hydrogen gas-liquid separator among cracker bed
Effective distribution of cracking material stock, then make obtained material by different hydrocracking process, so as to flexibly produce
The purpose product of different size especially increases low condensation point tail oil product.Meanwhile the abstraction reaction logistics among reactor bed
Technically and it is easily achieved.And in the prior art, although the boiling range by adjusting conversion ratio and adjustment product can be with
A variety of light-end products are obtained, but since only one hydrocracking reactor exports, a set of hydrocracking unit is same
Fraction range is typically only capable to a type of light naphtha product, heavy naphtha product, boat product of coal and diesel product, especially only
It can obtain a kind of tail oil product；If it is intended to obtain the hydrocracked product of different size, two sets or more are needed to be hydrocracked
Device.Therefore, the present invention provides one kind on a set of hydrocracking process device for the first time while producing two or more same fractions
Range, but different size tail oil product, two or more different sizes boat product of coal, two or more different size diesel products and
The hydrocracking process of a variety of different size naphtha products.
2, the present invention among the catalyst bed of hydrocracking reactor by being arranged gas-liquid separator, by wax oil raw material
By weighted BMO spaces and what is be hydrocracked first be hydrocracked liquid stream and extract reactor, and is sent to and is separately provided
Hydroisomerizing cracker carry out hydroisomerizing cracking reaction, further decrease the condensation point for being hydrocracked rear material, from
And enables method of the invention flexibly to produce different arene contents, the naphtha product of different isomerization hydrocarbon content, boat coal and produce
Product, diesel product and tail oil product.
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
It is high；It is hydrocracked by part containing Y zeolite catalyst, containing after the hydroisomerizing cracking of heterogeneous types molecular sieve catalyst
Obtained naphtha isomery hydrocarbon content is high, boat product of coal freezing point is low, and diesel product condensation point is low, tail oil product hydrocarbon isomer content height,
Viscosity index (VI) is big, condensation point is low；Naphtha, boat product of coal, diesel product and the tail oil that production different size can be met respectively produce
The needs of product.
4, in the present invention, wax oil feedstock oil has gas-liquid separation process after weighted BMO spaces, what hydrogenation process generated
H2S and NH3System will be moved out of, although unreacted sulphur and nitrogen will in hydroprocessing processes the reaction was continued production H2S and
NH3, but the H in system2S partial pressure and NH3Partial pressure is all effectively reduced, therefore reduces hydrocracking reaction and plus hydrogen
The severity of isocraking reaction, be conducive to the operating condition for optimizing hydrocracking reactor and hydroisomerizing cracker and
Product quality is improved, or extends the cycle of operation.
5, 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
This thigh divides heat entrained by compound 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- are hydrocracked preatreating reactors, and 4- is hydrocracked instead
Device, 5- hydroisomerizing cracked stock logistics are answered, 6- is hydrocracked logistics, 7- hydroisomerizing cracker, and 8- is hydrocracked height
Separator, 9- hydroisomerizing cracking high-pressure separator are pressed, 10- is hydrocracked fractionating column, 11- hydroisomerizing cracking fractionating column, 12-
It 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, 16- hydrocracking tail oil (recycle oil), 17- hydroisomerizing cracking light naphtha product, 18- hydroisomerizing cracking
Heavy naphtha product, 19- hydroisomerizing cracking boat product of coal, 20- hydroisomerizing cracked diesel oil product, 21- hydroisomerizing cracking
Tail oil product, 22- are hydrocracked high-pressure separator hydrogen-rich gas, 23- hydroisomerizing cracking high-pressure separator hydrogen-rich gas, 24-
Supplement hydrogen, 25- gas-liquid separator, 26- hydroisomerizing cracking recycle 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.
Pretreating catalyst by hydrocracking described in hydrogenation pretreatment catalyst described in step a and step c is routine
Wax oil hydrogenation pretreatment catalyst.Generally using VI B race and/or group VIII metal as active component, with aluminium oxide or siliceous oxygen
Change aluminium is carrier, and group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.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%, property are as follows: specific surface is 100~650m20.15~0.6mL/g of/g, Kong Rongwei.Main catalyst has Fushun
3936, the 3996 of Petroleum Chemical Engineering Institute's development, FF-16, FF-26, FF-36, FF-46, FF-56 series etc. adds hydrogen to locate in advance
Catalyst is managed, is also possible to the function of domestic and international catalyst Co. exploitation similar to catalyst, such as HC-K, HC-P of Uop Inc.,
TK-555, TK-565 catalyst and KF-847, KF-848 of Akzo company of Topsoe company etc..Described in step a plus hydrogen is pre-
Handling pretreating catalyst by hydrocracking described in catalyst and step c may be the same or different.The behaviour of weighted BMO spaces
Conventional operating condition, generally reaction pressure 3.0MPa~19.0MPa can be used as condition, reaction temperature is 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.
Separation described in step b 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 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 (recycle oil).
Pretreated operating condition is hydrocracked described in step c can be used conventional operating condition, generally reaction pressure
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 c 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 urges
Agent carrier contains aluminium oxide and/or silicon-containing alumina and Y type molecular sieve.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 catalyst have Fushun Petrochemical Research Institute develop 3824,3825,3976, 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 adding hydrogen
For Cracking catalyst, it is desirable that have certain hydrogenation activity and certain lytic activity, should guarantee that hydrotreating generates oil and adds
Generated in hydrogen cracking process alkene and aromatic hydrocarbons in fraction plus hydrogen saturation, the aromatic hydrocarbons after also requiring saturation the reaction of open loop occurs.
Conventional operating condition can be used in the operating condition being hydrocracked, generally are as follows: reaction pressure 3.0MPa~19.0MPa, reaction temperature
Degree is 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.
Gas-liquid separator described in step c is between hydrocracking reactor bed or what catalyst bed entrance was arranged sets
It is standby.Gas-liquid separator includes at least reaction stream entrance, and several parts such as liquid phase conduit and gas phase conduit, wherein liquid phase conduit will divide
Hydrocracking reactor is pulled out from obtained liquid phase, isolated gas phase is introduced lower part hydrocracking catalyst by gas phase conduit
Agent bed.
A part of hydrocracking reaction logistics enters gas-liquid separator by gas-liquid separator entrance in step c, extraction
The weight percent that Partial Liquid Phase logistics accounts for feedstock oil is 5~95 wt%, preferably 10~80 wt%.
Conventional operating condition can be used in the operating condition being hydrocracked described in step d, generally 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.
Hydroisomerizing Cracking catalyst described in step e 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 be aluminium oxide, silicon-containing alumina and molecular sieve in it is one or more, preferably contain molecular sieve,
The molecular sieve can be beta molecular sieve, Sapo type molecular sieve etc..With the poidometer of catalyst, group VIB tenor with
Oxide is calculated as 10wt%~35wt%, and group VIII metal content is calculated as 3wt%~15wt%, molecular sieve content 5wt% with oxide
~80wt%.FC-14, FC-20 etc. that main catalyst has Fushun Petrochemical Research Institute to develop.For being hydrocracked
For catalyst, it is desirable that have certain hydrogenation activity and certain lytic activity, should guarantee alkene and aromatic hydrocarbons in reaction mass
Add hydrogen to be saturated, also requires linear paraffin that isomerization reaction occurs.Conventional operation item can be used in the operating condition of hydroisomerizing cracking
Part, generally 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.
Separation described in step e 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 e 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 b and step e individually to be made
For product, mixed gas product can also be mixed into.
It is hydrocracked light naphtha product described in step b and step e 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 b and step e 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 b and step e 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 b and step e individually to be made
For product, mixed diesel product can also be mixed into.
Hydrocracking tail oil described in step b (recycle oil) can also be separately as product.
Hydroisomerizing cracking tail oil described in step e 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 conjunction with Fig. 1, method of the invention is specific as follows: feedstock oil 1 first be hydrocracked generate logistics 6 be mixed into plus
Hydrogen pretreatment reactor 2 enters by the weighted BMO spaces product stream of hydrogenation pretreatment catalyst bed and is hydrocracked high pressure
Separator 8 carries out gas-liquid separation, and isolated liquid enters fractionation in fractionating column 10 and obtains being hydrocracked light naphtha product
12, it is hydrocracked heavy naphtha product 14, boat product of coal 14 is hydrocracked, is hydrocracked diesel product 15 and hydrocracking tail oil
(recycle oil) 16, is hydrocracked recycle oil 16 and hydrogen is mixed into and is hydrocracked preatreating reactors 3, pre-processes by cracking
The product stream of catalyst bed enters hydrocracking reactor 4, by the reaction stream of the first hydrocracking catalyst bed
Middle a part, which enters in gas-liquid separator 25, carries out gas-liquid separation, regard liquid phase therein extraction as hydroisomerizing cracked stock object
Stream 5, the logistics after extracting hydroisomerizing cracked stock logistics 5 out go successively to follow-up hydrogenation Cracking catalyst bed, and what is obtained adds
Hydrogen cracking generates logistics 6 and enters weighted BMO spaces reactor 2, and hydroisomerizing cracked stock logistics 5 mixes laggard with recycle hydrogen 26
Enter hydroisomerizing cracker 7, it is high to enter hydroisomerizing cracking by the product stream of hydroisomerizing Cracking catalyst bed
Gas-liquid separation is carried out in pressure separator 9, isolated liquid enters fractionation in fractionating column 11 and obtains hydroisomerizing cracking pumice
Naphtha product 17, hydroisomerizing cracking heavy naphtha product 18, hydroisomerizing cracking boat product of coal 19, hydroisomerizing cracked diesel oil
Product 20 and hydroisomerizing cracking tail oil product 21, are hydrocracked light naphtha product 12 and hydroisomerizing cracking light naphthar produces
Product 17 can obtain mixing light naphtha product, be hydrocracked heavy naphtha product 13 separately as product after can also mixing
With hydroisomerizing cracking heavy naphtha product 18 mixing heavy naphtha can be obtained after can also mixing and is produced separately as product
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 flexible inverted sequence hydrocracking process of the invention it can be seen from embodiment, by out of hydrocracking reactor
It extracts a part of reaction stream out, and realizes production heterogeneity using hydrocracking catalyst and hydroisomerizing Cracking catalyst
The purpose of hydrocracked product, production method are flexible.
Claims (15)
1. a kind of flexible inverted sequence hydrocracking process, includes the following steps:
A, it wax oil feedstock oil and is hydrocracked to generate logistics and enter under the conditions of weighted BMO spaces and weighted BMO spaces reactor and leads to
Hydrogenation pretreatment catalyst bed is crossed, weighted BMO spaces logistics is obtained；
B, the weighted BMO spaces logistics that step a is obtained is separated, is fractionated to obtain and is hydrocracked high pressure hydrogen-rich gas, hydrocracking gas
Body product, hydrocracked naphtha product are hydrocracked boat product of coal, are hydrocracked diesel product and hydrocracking tail oil；
C, the hydrocracking tail oil that step b is obtained is blended in enter in the case where being hydrocracked pretreatment condition with recycle hydrogen and be hydrocracked
Preatreating reactors simultaneously passes through hydrogenation pretreatment catalyst bed, obtains being hydrocracked pretreatment stream, hydrocracked, treated object
Stream passes through the first hydrocracking catalyst containing Y zeolite catalyst in hydrocracking reactor under hydrocracking condition
Bed obtains first and is hydrocracked logistics, this part reaction stream is divided into two parts, and a portion is to pass through gas-liquid separator
It is separated, acquired liquid stream extracts hydrocracking reactor out；
D, in step c the first of remainder be hydrocracked logistics continuation pass through hydrocracking reactor under hydrocracking condition
In the second hydrocracking catalyst bed containing Y zeolite catalyst, obtain being hydrocracked logistics, be hydrocracked logistics with
Wax oil feedstock oil is mixed into weighted BMO spaces reactor；
E, first of extraction device obtained by step c is hydrocracked after liquid stream mixes with recycle hydrogen, in hydroisomerizing cracking
Under the conditions of pass through the hydroisomerizing Cracking catalyst bed containing heterogeneous types molecular sieve catalyst of hydroisomerizing cracker
Layer, hydroisomerizing cracked-stream are separated, are fractionated to obtain hydroisomerizing cracking high pressure hydrogen-rich gas, the production of hydroisomerizing cracked gas
Product, hydroisomerizing cracked naphtha product, hydroisomerizing cracking boat product of coal, hydroisomerizing cracked diesel oil product and hydroisomerizing
Cracking tail oil product.
2. hydrocracking process described in accordance with the claim 1, which is characterized in that further include step f: step b is obtained plus hydrogen
It is recycled after the hydroisomerizing cracking high pressure hydrogen-rich gas mixing that cracking high pressure hydrogen-rich gas and step e are obtained.
3. hydrocracking process described in accordance with the claim 1, which is characterized in that the initial boiling point of wax oil raw material described in step a is
100~400 DEG C, the end point of distillation is 405~650 DEG C.
4. 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 shale
At least one of oil.
5. hydrocracking process described in accordance with the claim 1, which is characterized in that hydrogenation pretreatment catalyst described in step a
With pretreating catalyst by hydrocracking described in step c using VI B race and/or group VIII metal as active component, with aluminium oxide or
Silicon-containing alumina is carrier；With the poidometer of catalyst, group VIB tenor is calculated as 10wt%~35wt% with oxide, the
VIII race's tenor is calculated as 3wt%~15wt% with oxide；Its property is as follows: specific surface area is 100~650m2/ g, Kong Rongwei
0.15~0.6mL/g.
6. hydrocracking process described in accordance with the claim 1, which is characterized in that weighted BMO spaces condition described in step a 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. hydrocracking process described in accordance with the claim 1, which is characterized in that be hydrocracked pretreatment item described in step c
Part 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.
8. hydrocracking process described in accordance with the claim 1, which is characterized in that hydrocracking catalyst described in step c with
Group VIB and/or group VIII metal are active component, and catalyst carrier contains aluminium oxide and/or silicon-containing alumina and Y type point
Son sieve.
9. hydrocracking process according to claim 8, which is characterized in that 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%, Y type molecular sieve with oxide
Content is 5wt%~80wt%.
10. hydrocracking process described in accordance with the claim 1, which is characterized in that the hydrocracking condition are as follows: reaction pressure
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.
11. hydrocracking process described in accordance with the claim 1, which is characterized in that the liquid phase stream extracted out in step c accounts for raw material
The weight percent of oil is 5~95 wt%, preferably 10~80 wt%.
12. hydrocracking process described in accordance with the claim 1, which is characterized in that hydrocracking condition described in step d 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.
13. hydrocracking process described in accordance with the claim 1, which is characterized in that hydroisomerizing cracking catalysis described in step e
Using group VIB and/or group VIII metal as active component, catalyst carrier contains aluminium oxide and/or silicon-containing alumina, and divides for agent
In son sieve, the molecular sieve is beta molecular sieve or Sapo type molecular sieve.
14. hydrocracking process according to claim 13, which is characterized in that 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, and molecular sieve contains
Amount is 5wt%~80wt%.
15. hydrocracking process described in accordance with the claim 1, which is characterized in that the hydroisomerizing cracking conditions 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.
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| CN114437788A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Fischer-Tropsch synthetic oil processing technology |
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| CN103059960A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Flexible hydrocracking method |
| CN103666555A (en) * | 2012-08-31 | 2014-03-26 | 中国石油化工股份有限公司 | Hydrogen cracking method for increasing production of middle distillate oil |
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| CN103059960A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Flexible hydrocracking method |
| CN103666555A (en) * | 2012-08-31 | 2014-03-26 | 中国石油化工股份有限公司 | Hydrogen cracking method for increasing production of middle distillate oil |
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| CN112552958A (en) * | 2019-09-25 | 2021-03-26 | 中国石油化工股份有限公司 | Wax oil raw material processing technology |
| CN112552958B (en) * | 2019-09-25 | 2023-03-31 | 中国石油化工股份有限公司 | Wax oil raw material processing technology |
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