CN109988618A - A kind of flexible single-section two-catalyst hydrocracking technique - Google Patents
A kind of flexible single-section two-catalyst hydrocracking technique Download PDFInfo
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- CN109988618A CN109988618A CN201711469372.9A CN201711469372A CN109988618A CN 109988618 A CN109988618 A CN 109988618A CN 201711469372 A CN201711469372 A CN 201711469372A CN 109988618 A CN109988618 A CN 109988618A
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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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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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
- C10G2300/70—Catalyst aspects
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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
- 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 single-section two-catalyst hydrocracking techniques.Wax oil raw material enters single-section two-catalyst hydrocracking reactor after mixing with hydrogen, is divided into two strands by the material after top hydrogenation pretreatment catalyst and Catalyst For Single-stage Hydrocracking bed；One material carries out isocraking reaction through extracting single hop reactor among bed out, into hydroisomerizing cracker；Another strand of material continues to flow downwardly through the Catalyst For Single-stage Hydrocracking bed of lower part；Single-stage hydrocracking reaction mass and hydroisomerizing cracking reaction material are separated and are fractionated respectively, and different size distillate and tail oil product are obtained.The present invention provides a kind of on a set of hydrogenation technique device while producing the single-section two-catalyst hydrocracking technique of two or more different size light naphthars, heavy naphtha, boat coal, diesel oil, tail oil product, heat entrained by partial cracking material can be made full use of, realizes the coupling operation of single-section two-catalyst hydrocracking reactor and hydroisomerizing cracker.
Description
Technical field
The invention belongs to petroleum refining fields, and in particular to one kind flexibly produce high-quality naphtha of different nature, boat coal,
The single-section two-catalyst hydrocracking technique of 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.The wherein catalysis that single-stage hydrocracking technology uses
Agent is mainly a type of Catalyst For Single-stage Hydrocracking, and usage quantity usually accounts for 80% or more of total catalyst volume, and
The volume of hydrogenation pretreatment catalyst accounts for total catalyst volume and has reached 20% or more in single-section two-catalyst hydrocracking technology, makes
The Cracking Component of hydrocracking catalyst is mainly amorphous silica-alumina, can also contain a small amount of Y type molecular sieve, β type molecule
Sieve, SAPO Series Molecules sieve and ZSM-5 molecular sieve etc..A group timesharing, obtained light-end products are hydrocracked using different type
Composition and property have biggish difference, and the composition and property of tail oil also have biggish difference.
CN001952062A discloses a kind of single-section two-catalyst hydrocracking method, is related to gradation and is urged using weighted BMO spaces
The hydrocracking process of agent and hydrocracking catalyst fecund intermediate oil；CN100569921C discloses a kind of single hop and adds
Hydrogen cracking method, this method are the single-stage hydrocracking technique of the hydrogenation pretreatment catalyst prepared using body phase method；
CN001075550C discloses a kind of single-stage hydrocracking process, and this method is to use to contain Y type molecular sieve single-stage hydrocracking
The single-stage hydrocracking technique of catalyst；CN001415707A disclose it is a kind of raised productivity and improved the quality the method for diesel oil by distillate, should
Method is hydrocracked in the filling of original hydrocracking catalyst rear portion containing isomery performance hydrocracking catalyst with reaching reduction
The purpose of product condensation point, but there was only a kind of rule by the product of above-mentioned each obtained fraction of these hydrocracking process
Lattice.
CN001566283A, CN001766051A and CN101402048A etc. disclose a kind of middle oil type hydrocracking and urge
Agent and preparation method thereof is prepared for urging in the single-stage hydrocracking that amorphous silicon aluminium and a small amount of Y type molecular sieve are acid centre
Agent；CN001712498A discloses a kind of hydrogenation catalyst and preparation method thereof of maximum diesel oil yield, the catalyst with
Amorphous silicon aluminium and modified beta molecular sieve are main cracking center, but are hydrocracked skill using these hydrocracking catalysts
The product of each obtained fraction of art only has 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 US6670295 and US4837396A disclose a kind of preparation of complex type molecular sieve catalysis.By using such catalysis
The hydrocracking technology of agent can be using wax oil as feedstock oil, by using compound containing Y type molecular sieve and heterogeneous types molecular sieve
The various high-quality hydrocracked products of method for hydrogen cracking production of type molecular sieve hydrocracking catalyst, but each fraction
Product only has a kind of specification, and is substantially all in one-stage serial hydrocracking or hydrogenation modifying process.
In conclusion the existing hydrocracking technology using several different type cracking center catalyst of comparison, uses
Amorphous silicon aluminium single-section two-catalyst hydrocracking catalyst or amorphous silicon aluminium-Y type molecular sieve Catalyst For Single-stage Hydrocracking
Single-stage hydrocracking technology, obtained boat product of coal freezing point is relatively high, smoke point is relatively low, diesel product Cetane number
Height, but condensation point is relatively high, tail oil product condensation point is very high, and typically larger than 30 DEG C；It is split using heterogeneous types molecular sieve
Change the single-section two-catalyst hydrocracking technology of catalyst, obtained boat coal smoke point is relatively high, and diesel product sulfur content is low, condensation point
Low, tail oil density is relatively large, but isomery hydrocarbon content is high, and condensation point is very low, and usually less than 0 DEG C.Two doses of above-mentioned single hop plus hydrogen
Process technology, the hydrocracking tail oil differentiation of product produced in identical conversion ratio is larger, wherein using Y type molecular sieve
The tail oil of catalyst is the raw material of fine quality catalytic cracking raw material, preparing ethylene by steam cracking, uses heterogeneous types molecular sieve catalyst
Tail oil be that can directly produce High Quality Lube Base Oils or the raw material as High Quality Lube Base Oils.Therefore individually make
When with above-mentioned several hydrocracking process, different types of single-section two-catalyst hydrocracking catalyst can only be selected as needed, or
Person uses two kinds of molecular sieve composite catalysts, or two kinds of hydrocracking catalyst gradations is selected to use, but these techniques
A kind of tail oil product of property can only be produced, 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 single-section two-catalyst hydrocracking technique, i.e., by from making
It is anti-with extraction section in the middle part of the single-section two-catalyst hydrocracking reactor of hydrogenation pretreatment catalyst and Catalyst For Single-stage Hydrocracking
Logistics is answered, the wax oil feedstock oil is hydrocracked and heterogeneous types hydrocracking catalyst by Catalyst For Single-stage Hydrocracking
Agent hydroisomerizing cracking combined method flexibly produces the hydrocracking tail oil product of a variety of high quality, the naphtha of plurality of specifications produces
Product and the high-quality automotive fuel product of plurality of specifications.
A kind of method of flexible single-section two-catalyst hydrocracking technique of the invention, includes the following steps:
A, wax oil feedstock oil is added under the conditions of single-section two-catalyst hydrocracking by single-section two-catalyst hydrocracking reactor top first
Hydrogen pretreatment catalyst bed and Catalyst For Single-stage Hydrocracking bed, obtain the first single-stage hydrocracking logistics, this part is anti-
Logistics is answered to be divided into two parts, a portion extracts single-section two-catalyst hydrocracking reactor out；
B, the first single-stage hydrocracking logistics of remainder continues to add under hydrocracking condition by two doses of single hop in step a
The lower part Catalyst For Single-stage Hydrocracking bed of hydrogen cracker, single-section two-catalyst hydrocracking logistics are separated, are fractionated to obtain
Single-section two-catalyst hydrocracking high pressure hydrogen-rich gas, single-section two-catalyst hydrocracking gas products, single-section two-catalyst hydrocracking naphtha
Product, single-section two-catalyst hydrocracking boat product of coal, single-section two-catalyst hydrocracking diesel product and single-section two-catalyst hydrocracking tail oil
Product；
C, the first single-stage hydrocracking logistics of extraction device obtained by step a passes through list under single hop hydroisomerizing cracking conditions
The single hop hydroisomerizing Cracking catalyst bed containing heterogeneous types molecular sieve catalyst of section hydroisomerizing cracker, it is single
Section hydroisomerizing cracked-stream is separated, is fractionated to obtain single hop hydroisomerizing cracking high pressure hydrogen-rich gas, single hop hydroisomerizing is split
Change gas products, single hop hydroisomerizing cracked naphtha product, single hop hydroisomerizing cracking boat product of coal, single hop hydroisomerizing to split
Change diesel product and single hop hydroisomerizing cracking tail oil product.
Hydrocracking process according to the present invention, wherein can also include two doses of step d: step b obtained single hop plus hydrogen
It is recycled after the single hop hydroisomerizing cracking high pressure hydrogen-rich gas mixing that cracking high pressure hydrogen-rich gas and step c are obtained.
The impurity such as S, N, O in wax oil feedstock oil pass through hydrogenation pretreatment catalyst and single-section two-catalyst hydrocracking catalyst
When effectively removed, aromatic hydrocarbons obtains to a certain extent plus hydrogen saturation, and cyclic hydrocarbon generating unit divides ring-opening reaction, and macromolecular is cracked into
Small molecule, a portion single-stage hydrocracking logistics continue single-stage hydrocracking, available normal hydrocarbon content is higher,
The lower boat product of coal of arene content, diesel product and tail oil product；A part the first single-stage hydrocracking logistics of extraction passes through
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
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 single-section two-catalyst hydrocracking technique, is:
It 1, include at least two Catalyst For Single-stage Hydrocracking beds in single-section two-catalyst hydrocracking reactor in the present invention.It is logical
The cracking material extraction step being arranged among single-stage hydrocracking reactor bed is crossed, special operation is not necessarily to, can be realized pair
Effective distribution of single-section two-catalyst hydrocracking material stock, then make obtained material by different hydrocracking process, thus
The purpose product of different size, especially tail oil product can flexibly be produced.Meanwhile the abstraction reaction object among reactor bed
Stream is technically also to be easily achieved.And in the prior art, although the boiling range by adjusting conversion ratio and adjustment product can
To obtain a variety of light-end products, but due to only one single-section two-catalyst hydrocracking reactor outlet, a set of single hop adds
The same fraction range of hydrogen cracking unit is typically only capable to a type of light naphtha product, heavy naphtha product, boat product of coal, bavin
Oil product and tail oil product；If it is intended to obtaining the hydrocracked product of different size, two doses of single hop of two sets or more is needed to add
Hydrogen cracking unit.Therefore, the present invention provides one kind on a set of single-section two-catalyst hydrocracking process unit for the first time while producing
Two or more same fraction ranges, product of coal, two or more differences but different size tail oil product, two or more different sizes navigate
The single-section two-catalyst hydrocracking technique of specification diesel product and a variety of different size naphtha products.
2, the present invention is hydrocracked by the way that first is arranged among the catalyst bed of single-section two-catalyst hydrocracking reactor
Wax oil raw material is extracted reaction by the first single-stage hydrocracking logistics of single-section two-catalyst hydrocracking by logistics withdrawing device
Device, and be sent to the hydroisomerizing cracker being separately provided and carry out hydroisomerizing cracking reaction, it further decreases this and adds
The condensation point of material after hydrogen cracking, so that method of the invention can flexibly produce different arene contents, different isomerization hydrocarbon contains
Naphtha product, boat product of coal, diesel product and the tail oil product of amount.
3, in the present invention, in the product that two reactor streams are fractionated, by containing Catalyst For Single-stage Hydrocracking
Or the heavy naphtha virtue obtained after being hydrocracked containing a small amount of Y type molecular sieve hydrocracking catalyst dive it is relatively high, boat coal produce
Product smoke point is relatively high, and diesel product Cetane number is relatively high, and tail oil product paraffinicity is high, BMCI value is relatively low；
It is hydrocracked by part containing Catalyst For Single-stage Hydrocracking, 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, the liquid that is obtained among single-section two-catalyst hydrocracking reactor Catalyst For Single-stage Hydrocracking bed
Itself 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 thigh division compound material, hydroisomerizing cracker and single-stage hydrocracking are realized
The coupling operation of reactor.
Detailed description of the invention
Fig. 1 is principle process schematic diagram of the invention.
Wherein: 1- feedstock oil, 2- hydrocracking reactor, 3- are hydrocracked logistics, 4- hydroisomerizing cracked stock logistics,
5- hydroisomerizing cracker, 6- are hydrocracked high-pressure separator hydrogen-rich gas, and 7- hydroisomerizing cracking high-pressure separator is rich
Hydrogen, 8- are hydrocracked high-pressure separator, 9- hydroisomerizing cracking high-pressure separator, and 10- is hydrocracked fractionating column, and 11- adds
Hydrogen isocraking fractionating column, 12- are hydrocracked light naphtha product, and 13- is hydrocracked heavy naphtha product, and 14- is hydrocracked
Navigate product of coal, and 15- is hydrocracked diesel product, 16- hydrocracking tail oil product, 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- supplement hydrogen, 23- 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 405~620 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 is 100~650m2/
0.15~0.6mL/g of g, Kong Rongwei.Main catalyst has 3936,3996, FF- that Fushun Petrochemical Research Institute develops
16, the hydrogenation pretreatment catalysts such as FF-26, FF-36, FF-46, FF-56 series are also possible to domestic and international catalyst Co. exploitation
Function similar to catalyst, such as HC-K, HC-P of Uop Inc., TK-555, TK-565 catalyst and Akzo of Topsoe company
KF-847, KF-848 etc. of company.Operating condition can be used conventional operating condition, and generally 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。
Catalyst For Single-stage Hydrocracking described in step a is conventional wax oil Catalyst For Single-stage Hydrocracking.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, the molecule
Sieve can be Y type molecular sieve.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, and molecular sieve content is 0wt%~40wt%.Main catalyst is comforted
ZHC-01, ZHC-02, ZHC-03, ZHC-04, FC-28, FC-34 catalyst etc. that suitable Petroleum Chemical Engineering Institute develops,
TK-925, TK-925, TK-951 etc. that Haldor Topsoe company develops, the KF- that Albemarle company develops
1023 and KF-1023 etc..For hydrocracking catalyst, it is desirable that have certain hydrogenation activity and certain lytic activity, both
Guarantee that hydrotreating generates generate alkene and aromatic hydrocarbons in fraction in oil and hydrocracking process plus hydrogen saturation, also requires saturation
The reaction of open loop occurs for aromatic hydrocarbons afterwards.Conventional operating condition can be used in the operating condition being hydrocracked, 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.
In the present invention, the volume of the hydrogenation pretreatment catalyst accounts for single-stage hydrocracking catalyst in reactor total volume
Volume fraction be 20% ~ 70%, preferably 30% ~ 65%.
The mass ratio that the fraction of stream of extraction described in step a accounts for feedstock oil in terms of liquid phase is 5~95 wt%, preferably
10~80 wt%.
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 product.
Single hop hydroisomerizing Cracking catalyst described in step c is conventional wax oil hydrogenation isocraking catalyst.Generally
Using group VIB and/or group VIII metal as active component, 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
There is molecular sieve, the molecular sieve can be beta molecular sieve, Sapo type molecular sieve etc..With the poidometer of catalyst, group VIB
Tenor is calculated as 10wt%~35wt% with oxide, and group VIII metal content is calculated as 3wt%~15wt%, molecular sieve with oxide
Content is 2wt%~40wt%.The FC-14 catalyst etc. that main 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 c 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 c 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 c 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 c 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 c and hydroisomerizing cracking heavy naphtha product can
Mixing heavy naphtha product can also be mixed into separately as product.
Described in step b and step c being hydrocracked boat product of coal and hydroisomerizing cracking boat product of coal can be independent
As 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 c individually to be made
For product, mixed diesel product can also be mixed into.
Hydrocracking tail oil described in step b is separately as product.
Hydroisomerizing cracking tail oil described in step c is separately as product.
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 conjunction with Fig. 1, method of the invention is specific as follows: feedstock oil 1 is mixed into two doses of single hop plus hydrogen with recycle hydrogen first
Cracker 2, by extracting hydroisomerizing cracked stock logistics 4 in the reaction stream of the first hydrocracking catalyst bed out,
Logistics after extraction hydroisomerizing cracked stock logistics 4 goes successively to subsequent Catalyst For Single-stage Hydrocracking bed, and two doses of single hop
It is hydrocracked generation logistics 3 and carries out gas-liquid separation into high-pressure separator 8 is hydrocracked, isolated liquid enters fractionating column
In 10 fractionation obtain being hydrocracked light naphtha product 12, be hydrocracked heavy naphtha product 13, be hydrocracked boat product of coal 14,
It is hydrocracked diesel product 15 and hydrocracking tail oil product 16, hydroisomerizing cracked stock logistics 4 enters hydroisomerizing cracking
Reactor 5 is entered in hydroisomerizing cracking high-pressure separator 9 by the product stream of hydroisomerizing Cracking catalyst bed and is carried out
Gas-liquid separation, isolated liquid enter fractionation in fractionating column 11 and obtain hydroisomerizing cracking light naphtha product 17 plus hydrogen
Isocraking heavy naphtha product 18, hydroisomerizing cracking boat product of coal 19, hydroisomerizing cracked diesel oil product 20 and add hydrogen it is different
Structure cracking tail oil product 21, being hydrocracked light naphtha product 12 and hydroisomerizing cracking light naphtha product 17 can individually make
For product, mixing light naphtha product is obtained after can also mixing, is hydrocracked heavy naphtha product 13 and hydroisomerizing cracking
Heavy naphtha product 18 can obtain mixing heavy naphtha product, be hydrocracked boat coal separately as product after can also mixing
Product 14 and hydroisomerizing cracking boat product of coal 19 can obtain mixing boat product of coal separately as product after can also mixing,
Being hydrocracked diesel product 15 and hydroisomerizing cracked diesel oil product 20 can be mixed after can also mixing separately as product
Diesel product is closed, the isolated gas 6 of high-pressure separator 8 is hydrocracked and hydroisomerizing cracking high-pressure separator 9 separates
To gas 7 mix after after circulating hydrogen compressor is pressurized with supplement hydrogen 22 mix be used as recycle hydrogen 23.
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-28 is that Sinopec Group Fushun petrochemical industry is ground
The Catalyst For Single-stage Hydrocracking for studying carefully institute's development and production, contains Y type molecular sieve；Catalyst Z HC-02 is Sinopec's share
The Catalyst For Single-stage Hydrocracking of Fushun Petrochemical Research Institute, Co., Ltd development and production is free of molecular sieve；Catalyst FC-14
For the single hop hydroisomerizing Cracking catalyst of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development and production,
Contain beta molecular sieve.
The main character of 1 wax oil feedstock oil of table
| Wax oil 1 | Wax oil 2 | |
| Density, g/cm3 | 0.905 | 0.918 |
| Fraction range, DEG C | 320~546 | 345~560 |
| Sulfur content, wt% | 1.1 | 2.0 |
| Nitrogen content, wt% | 0.132 | 0.075 |
| Condensation point, DEG C | 32 | 34 |
2 embodiment process conditions of table
3 embodiment test result of table
Using single-section two-catalyst hydrocracking technique of the invention it can be seen from embodiment, by from single-section two-catalyst hydrocracking
A part of reaction stream of extraction in reactor, and come using Catalyst For Single-stage Hydrocracking and single hop hydroisomerizing Cracking catalyst
Realize that the purpose of production heterogeneity hydrocracked product, production method are flexible.
Claims (12)
1. a kind of method of flexible single-section two-catalyst hydrocracking technique, includes the following steps:
A, wax oil feedstock oil is added under the conditions of single-section two-catalyst hydrocracking by single-section two-catalyst hydrocracking reactor top first
Hydrogen pretreatment catalyst bed and Catalyst For Single-stage Hydrocracking bed, obtain the first single-stage hydrocracking logistics, this part is anti-
Logistics is answered to be divided into two parts, a portion extracts single-section two-catalyst hydrocracking reactor out；
B, the first single-stage hydrocracking logistics of remainder continues to pass through single hop two under the conditions of single-stage hydrocracking in step a
The lower part Catalyst For Single-stage Hydrocracking bed of catalyst hydrocracking reactor, single-section two-catalyst hydrocracking logistics are separated, are fractionated
Obtain single-section two-catalyst hydrocracking high pressure hydrogen-rich gas, single-section two-catalyst hydrocracking gas products, single-section two-catalyst hydrocracking stone
Naphtha product, single-section two-catalyst hydrocracking boat product of coal, single-section two-catalyst hydrocracking diesel product and single-section two-catalyst hydrocracking
Tail oil product；
C, the first single-stage hydrocracking logistics of extraction device obtained by step a is added under hydroisomerizing cracking conditions by single hop
The single hop hydroisomerizing Cracking catalyst bed containing heterogeneous types molecular sieve catalyst of hydrogen isocraking reactor, single hop add
Hydrogen isocrackate flows through separation, fractionation, obtains single hop hydroisomerizing cracking high pressure hydrogen-rich gas, single hop hydroisomerizing cracked gas
Body product, single hop hydroisomerizing cracked naphtha product, single hop hydroisomerizing cracking boat product of coal, single hop hydroisomerizing cracking bavin
Oil product and single hop hydroisomerizing cracking tail oil product.
2. hydrocracking process described in accordance with the claim 1, which is characterized in that further include step d: the single hop that step b is obtained
Recycling after the single hop hydroisomerizing cracking high pressure hydrogen-rich gas mixing that two-catalyst hydrocracking high pressure hydrogen-rich gas and step c are obtained makes
With.
3. hydrocracking process described in accordance with the claim 1, which is characterized in that the initial boiling point of the wax oil raw material be 100~
400 DEG C, the end point of distillation is 405~620 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 the volume of the hydrogenation pretreatment catalyst accounts for
The volume fraction of single-stage hydrocracking catalyst in reactor total volume is 20% ~ 70%, preferably 30% ~ 65%.
6. hydrocracking process described in accordance with the claim 1, which is characterized in that the hydrogenation pretreatment catalyst is with VI B
Race and/or group VIII metal are active component, using aluminium oxide or silicon-containing alumina as carrier；With the poidometer of catalyst, the VIth B
Race's tenor is calculated as 10wt%~35wt% with oxide, and group VIII metal content is calculated as 3wt%~15wt% with oxide；Its property
Matter is as follows: specific surface is 100~650m20.15~0.6mL/g of/g, Kong Rongwei.
7. hydrocracking process described in accordance with the claim 1, which is characterized in that the Catalyst For Single-stage Hydrocracking is with
VI B race and/or group VIII metal are active component, and catalyst carrier contains one in aluminium oxide, silicon-containing alumina and molecular sieve
Kind is a variety of, and the molecular sieve is Y type molecular sieve.
8. hydrocracking process according to claim 7, 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%, molecular sieve content with oxide
For 0wt%~40wt%.
9. hydrocracking process described in accordance with the claim 1, which is characterized in that the single-stage hydrocracking condition 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.
10. hydrocracking process described in accordance with the claim 1, which is characterized in that the fraction of stream extracted out in step a is with liquid phase
The mass ratio that meter accounts for feedstock oil is 5~95 wt%, preferably 10~80 wt%.
11. hydrocracking process described in accordance with the claim 1, which is characterized in that the single hop hydroisomerizing cracking catalysis
Using group VIB and/or group VIII metal as active component, catalyst carrier contains molecular sieve for agent, and the molecular sieve is β type point
Son sieve, Sapo type molecular sieve；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, and molecular sieve content is 2wt%~40wt%.
12. 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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| CN1952062A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Single-section two-catalyst hydrocracking method |
| CN101089138A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Single-stage hydrocracking process |
| 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 |
| CN105778995A (en) * | 2016-04-18 | 2016-07-20 | 武汉凯迪工程技术研究总院有限公司 | Method and device for producing good-quality diesel oil through combined hydrogenation of low-temperature Fischer-Tropsch synthesis oil and inferior crude oil |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1952062A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Single-section two-catalyst hydrocracking method |
| CN101089138A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Single-stage hydrocracking process |
| 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 |
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