CN109988599A - A kind of flexible hydrogenation modifying process of poor ignition quality fuel - Google Patents
A kind of flexible hydrogenation modifying process of poor ignition quality fuel Download PDFInfo
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- CN109988599A CN109988599A CN201811289680.8A CN201811289680A CN109988599A CN 109988599 A CN109988599 A CN 109988599A CN 201811289680 A CN201811289680 A CN 201811289680A CN 109988599 A CN109988599 A CN 109988599A
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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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 hydrogenation modifying process of poor ignition quality fuel.Diesel raw material enters hydrofining reactor, is divided into two strands by the material after the Hydrobon catalyst bed of top；One material is extracted out finishing reactor among bed, and is entered supplement hydrofining reactor and carried out supplement hydrogenation reaction；Another strand of material continues to flow downwardly through the Hydrobon catalyst bed of lower part, hydrotreated refinery stream goes successively to hydro-upgrading reactor, gained hydro-upgrading reaction mass and supplement hydrofining reaction material carry out gas-liquid separation and fractionation respectively, obtain fine-quality diesel oil product and high-quality FCC charging.The present invention provides for the first time a kind of on a set of hydrogenation technique device while producing the hydrogenation combination techniques of two or more different purpose diesel oil distillates, heat entrained by part purification material can be made full use of, realize hydrofining reactor and supplements the coupling operation of hydrofining reactor.
Description
Technical field
The invention belongs to petroleum refining fields, and in particular to one kind flexibly produces fine-quality diesel oil by feedstock oil of poor ignition quality fuel
The flexible diesel oil hydrogenation modification technique of product and high-quality FCC feedstock.
Background technique
Environmental regulation it is increasingly strict, it is desirable that the quality of diesel product is higher and higher, mainly sulfur content, Cetane number,
The limitation of density and condensed-nuclei aromatics content is increasing.Diesel product can be greatly lowered in hydro-upgrading of inferior diesel technology
Sulfur content and arene content, and reduce density and improve Cetane number.Fluid catalytic cracking (FCC) is the weight of light materialization of heavy oil
One of means are wanted, but with the in poor quality and heaviness of catalyzed cracking processing raw material, operating condition is more and more harsher, lightweight
Product yield and product property are deteriorated, and hydrotreating of FCC feedstock technology not only can remove sulphur, nitrogen, metal impurities
Content, can also improve the cracking performance of charging, reduce FCC operating severity, improve product distribution, improve the selection of purpose product
Property, dry gas and coke yield are reduced, the economy of FCC apparatus is improved, reduces purpose product sulfur content, is reduced in regenerated flue gas
SOx and NOx content etc..There are the sulphur and nitrogen of certain content in catalytic cracking light cycle oil (LCO), in the form of organic compound
In the presence of, and arene content is high, and the content of the above aromatic hydrocarbons of especially two rings is high, and usual LCO is recycled directly back to catalytic cracking unit
Inside continue to convert, catalytic cracking unit is entered back into after perhaps adding hydrogen into hydrotreater or enters other devices and is processed
Or directly as product.
Diesel oil fraction hydrogenating modification technology, such as CN1156752A and CN1289832A, are catalyzed using hydrofinishing
The hydrogenation technique technology of agent and Y type molecular sieve catalyst for hydro-upgrading.Diesel oil fraction hydrogenating isomerization-visbreaking technology, such as
CN1718683A and CN1712499A etc. using Hydrobon catalyst and contains β zeolite hydroisomerizing pour point depression catalyst, uses
One-stage serial process produces diesel product, but under the conditions of identical hydro-upgrading, phase low compared with hydro-upgrading diesel cetane-number
It is harsh compared with hydrodewaxing process conditions with process conditions when low freezing point diesel fuel product.CN101875856A, CN102465035A and
CN106701189A, CN106701190A, which are disclosed, mixes refining LCO in a kind of processing of wax oil hydrogenation or residual hydrocracking technique
Technology, main purpose is production fine quality catalytic cracking raw material, or LCO is allowed to split in wax oil hydrotreating unit and catalysis
The coupling technique that makeup recycles between setting, realizes the clean manufacturing of catalytic cracking unit, but after being mixed due to wax oil with LCO directly
Add hydrogen, the hydrogenation depth of LCO not can be effectively controlled, can only be with the sulfur content or nitrogen of mixed hydrogenation product (catalytically cracked material)
Content is unfavorable for producing effective control of premium with LCO as control target.
It is received in conclusion existing diesel oil hydrogenation modification technology can obtain higher diesel product with poor-quality diesel-oil by cut fraction
Rate, product quality are greatly improved, such as Cetane number, sulfur content, arene content, density or condensation point significantly drop
The condensation point of low diesel product meets the index request of low-coagulation diesel oil, the diesel oil that hydro-upgrading obtains directly as product, without
Produce FCC feedstock.Existing LCO hydrogen addition technology, be usually all LCO directly mix refining to diesel refining, wax oil hydrogenation processing or
It carries out adding hydrogen in residual hydrocracking device, the hydrogenated diesel oil obtained after mixed hydrogenation adds hydrogen wax oil directly as diesel product
With hydrogenated residue and add hydrogen LCO collectively as the raw material of catalytic cracking unit, i.e. LCO returns again to catalytic cracking unit after adding hydrogen,
Due to not controlling the hydrogenation depth of LCO deliberately, the total sulfur and total nitrogen content of hydrotreated blends material are only controlled, causes to be catalyzed
The quality of cracking gasoline does not reach best.And the diesel product of above-mentioned technology production is usually only a kind of, product
Flexibility is poor.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of flexible hydrogenation modifying process of poor ignition quality fuel, i.e., by from adding
The poor ignition quality fuel feedstock oil is passed through hydro-upgrading and supplement plus hydrogen by extraction section reaction stream in the middle part of hydrogen finishing reactor
Purification combined method flexibly produces the hydro-upgrading diesel product and high-quality FCC feedstock of high quality.
The flexible hydrogenation modifying process of a kind of poor ignition quality fuel of the invention, includes the following steps:
A, poor ignition quality fuel feedstock oil is catalyzed first under Hydrofinishing conditions by the first hydrofinishing of hydrofining reactor
Agent bed obtains the first hydrotreated refinery stream, this part reaction stream is divided into two parts, and it is anti-that a portion extracts hydrofinishing out
Answer device；
B, the first hydrotreated refinery stream continuation of remainder passes through hydrofining reactor under Hydrofinishing conditions in step a
The second Hydrobon catalyst bed, obtain hydrotreated refinery stream；
C, the hydrotreated refinery stream that step b is obtained enters hydro-upgrading reactor, and by adding hydrogen to change under the conditions of hydro-upgrading
Matter catalyst bed, hydro-upgrading logistics are separated, are fractionated to obtain hydro-upgrading high pressure hydrogen-rich gas, the production of hydro-upgrading gas
Product, hydro-upgrading naphtha product and hydro-upgrading diesel product；
D, the first hydrotreated refinery stream of extraction device obtained by step a individually or after mixing with other inferior feedstock oils is adding hydrogen
By the supplement Hydrobon catalyst bed of supplement hydrofining reactor under purification condition, supplement hydrotreated refinery stream is through dividing
Supplement hydrofinishing high pressure hydrogen-rich gas, supplement hydrofinishing gas, supplement hydrofinishing naphtha and supplement are obtained from, fractionation
Hydrofining diesel oil.
The flexible hydrogenation modifying process of poor ignition quality fuel according to the present invention, wherein can also include step e: step c be obtained
It is recycled after the supplement hydrofinishing high pressure hydrogen-rich gas mixing that hydro-upgrading high pressure hydrogen-rich gas and step d are obtained.
Diesel oil hydrogenation modification technique use two kinds of catalyst, Hydrobon catalyst can will diesel raw material oil in
The impurity such as S, N, O effectively removed, aromatic hydrocarbons obtains to a certain extent plus hydrogen saturation, and hydrotreated refinery stream continues through plus hydrogen
Cyclic hydrocarbon generating unit divides ring-opening reaction or macromolecular cleavage at small molecule when modifying catalyst bed, that is, effectively improves diesel oil
The Cetane number of product reduces density, or reduces condensation point, the whole quality for improving diesel product.Product quality, environmental protection are wanted
Ask, the requirement of technological operation etc. all limits the raw material oil nature of catalytic cracking unit, the especially limitation of sulfur content,
And due to the difference of feedstock oil composition, the distribution of catalytic cracking product and property also have biggish difference；Research shows that: LCO
Aromatic hydrogenation saturation depth be affected to fcc gasoline product quality, especially mononuclear aromatics is Gaoxin in gasoline
Alkane value component increases the octane number for adding the content of mononuclear aromatics in hydrogen LCO to can be increased catalytically cracked gasoline, and that extracts out adds hydrogen
A part of polycyclic aromatic hydrocarbon has obtained partial hydrogenation saturation in purification stream, after further passing through supplement Hydrobon catalyst
Further hydrogen can be added to be saturated remaining polycyclic aromatic hydrocarbon, that is, pass through the adjusting of volume space velocity and reaction temperature, can just control
The hydrogenation depth of LCO processed, i.e., under the premise of meeting sulfur content by LCO two cycloaromatics and polycyclic aromatic hydrocarbon add hydrogen to monocycle virtue
Hydrocarbon, rather than hydrogenation depth excessively generates cycloalkane or hydrogenation depth deficiency generates two cycloaromatics, after such hydrofinishing
The content of Aromatics in Fcc Naphtha can be improved in product when being re-introduced into catalytic cracking unit, to improve catalytic cracking
The octane number of gasoline.For above two technique, common part is to require poor ignition quality fuel carrying out hydrofinishing, only
The depth of hydrofinishing is different, and hydro-upgrading not only needs completely to remove the impurity such as sulphur nitrogen oxygen, but also needs to control deeper
Aromatic hydrogenation depth, and when LCO adds hydrogen as FCC feedstock, mainly controls aromatic hydrogenation to mononuclear aromatics.
Compared with prior art, the advantages of poor ignition quality fuel of the present invention flexible hydrogenation modifying process, is:
It 1, include at least two Hydrobon catalyst beds in hydrofining reactor in the present invention.Adding hydrogen by setting
Purification material extraction step among finishing reactor bed is not necessarily to special operation, can be realized to hydrofinishing material stock
Effectively distribution, then make obtained material by different hydrogenation techniques, so as to flexibly produce fine-quality diesel oil product and excellent
Matter catalytically cracked material.Meanwhile abstraction reaction logistics is technically also to be easily achieved among reactor bed.And existing
Have in technology, a set of hydrogenation plant is typically only capable to obtain a kind of diesel product of specification；If it is intended to obtaining the bavin of different size
Oil product needs two sets or more of hydrogenation plant.Therefore, it is same on a set of hydrogenation technique device to provide one kind for the first time by the present invention
When produce the hydroconversion process of two or more different specifications diesel oil distillate products.
2, the present invention among the catalyst bed of hydrofining reactor by being arranged the extraction of the first hydrotreated refinery stream
Device, the first hydrotreated refinery stream by diesel raw material by partial hydrogenation purification extracts reactor, and is sent to individually
The supplement hydrofining reactor of setting carries out supplement hydrogenation reaction, the degree of control supplement hydrogenation reaction, and control aromatic hydrocarbons and adds
The depth of hydrogen, so that method of the invention is able to produce fine quality catalytic cracking raw material.
3, in the present invention, it is higher, close that diesel raw material oil obtains Cetane number after deep hydrofinishing and hydro-upgrading
Spend that lower or condensation point is lower, the good diesel product of the impurity such as no sulphur nitrogen.
4, in the present invention, the material itself obtained among hydrofining reactor Hydrobon catalyst bed has very high
Temperature and pressure, can be directly entered in newly-installed supplement hydrofining reactor and be reacted, to make full use of
Heat entrained by this thigh point purification material realizes that hydrofining reactor and the coupling of supplement hydrofining reactor are grasped
Make.
Detailed description of the invention
Fig. 1 is principle process schematic diagram of the invention.
Wherein: 1- feedstock oil 1,2- hydrofining reactor, 3- hydrotreated refinery stream, 4- hydro-upgrading reactor, 5- take out
Effluent stream, 6- hydro-upgrading logistics, 7- supplement hydrofining reactor, 8- hydro-upgrading high-pressure separator, 9- supplement plus hydrogen essence
High-pressure separator processed, 10- hydro-upgrading fractionating column, 11- supplement hydrogenation refining fractionation tower, 12- hydro-upgrading gas products, 13-
Hydro-upgrading naphtha product, 14- hydro-upgrading diesel product, 15- supplement hydrofinishing gas products, 16- supplement plus hydrogen essence
Naphtha product processed, 17- supplement hydrofining diesel oil product, 18- hydro-upgrading high-pressure separator gaseous product, and 19- supplement adds
Hydrogen refines high-pressure separator gaseous product, and 20- supplements hydrogen, 21- feedstock oil 2.
Specific embodiment
The initial boiling point of poor ignition quality fuel raw material described in step a is 100~260 DEG C, and the end point of distillation is 300~450 DEG C, main to show
It is larger for density, the features such as arene content is more.The poor ignition quality fuel feedstock oil can be the naphthenic base that PETROLEUM PROCESSING obtains
One of straight-run diesel oil, coker gas oil, catalytic diesel oil, hydroprocessed diesel etc., the coal tar obtained from coal, DCL/Direct coal liquefaction
One of oil, ICL for Indirect Coal Liquefaction oil, shale oil etc. are also possible to their wherein several miscellas.
Step a, Hydrobon catalyst described in step b and step d is conventional diesel oil hydrofining catalyst.One
As using VI B race and/or group VIII metal as active component, using aluminium oxide or silicon-containing alumina as carrier, group VIB metal is general
For Mo and/or W, group VIII metal is generally Co and/or Ni.With the poidometer of catalyst, group VIB tenor is with oxide
It is calculated as 10wt%~35wt%, group VIII metal content is calculated as 3wt%~15wt% with oxide, and property is as follows: specific surface 100
~650m20.15~0.6mL/g of/g, Kong Rongwei.Main catalyst have Fushun Petrochemical Research Institute develop FH-5,
The Hydrobon catalysts such as FH-98,3936,3996, FHUDS series are also possible to the function class of World Catalyst company exploitation
Like catalyst, such as HC-K, HC-P of Uop Inc., TK-555, TK-565 catalyst of Topsoe company and the KF- of Akzo company
847, KF-848 etc..Step a, Hydrobon catalyst described in step b and step d may be the same or different.Step a
Conventional operating condition can be used in the operating condition, and generally reaction pressure 3.0MPa~15.0MPa, reaction temperature is
300 DEG C~430 DEG C, volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen to oil volume ratio is 100:1~2000:1.
The weight percent 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
For 10~80wt%.
Operating condition described in step b can be used conventional operating condition, and generally reaction pressure 3.0MPa~
15.0MPa, reaction temperature are 300 DEG C~430 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 hydro-upgrading described in step c is conventional diesel oil hydrogenation modification catalyst, generally with group VIB and/
Or group VIII metal is active component, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.It should
The carrier of catalyst is one or more in aluminium oxide, silicon-containing alumina and molecular sieve, preferably containing molecular sieve, the molecule
Sieve can be Y type molecular sieve, 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
~40wt%, alumina content are 10wt%~80wt%, specific surface 100m2/ g~650m2/ g, Kong Rongwei 0.15mL/g~
0.50mL/g.Main catalyst has the 3963 of Fushun Petrochemical Research Institute's development, FC-18, FC-32, FC-14, FC-
20 catalyst etc..For catalyst for hydro-upgrading, it is desirable that have certain hydrogenation activity and certain lytic activity, should guarantee
In diesel oil distillate alkene and aromatic hydrocarbons plus hydrogen saturation, the aromatic hydrocarbons after also requiring saturation the reaction of open loop occurs.The behaviour of hydro-upgrading
Conventional operating condition can be used as condition, generally are as follows: reaction pressure 3.0MPa~15.0MPa, reaction temperature be 300 DEG C~
430 DEG C, volume space velocity 0.3h when liquid-1~15.0h-1, hydrogen to oil volume ratio is 100:1~2000:1.
Separation described in step c generally comprises hydro-upgrading high-pressure separator and low pressure separator separates two parts.
The isolated hydro-upgrading high pressure hydrogen-rich gas of its high-pressure separator and liquid, the isolated liquid of high-pressure separator enter
Low pressure separator.Low pressure separator is by the isolated hydrocarbon-rich gas of highly pressurised liquid product and low pressure liquid product.Hydrocarbon-rich gas warp
The hydro-upgrading gaseous product of isolated needs.
Fractionation described in step c carries out in hydro-upgrading fractionating column system.Low pressure liquid product divides in fractionating column
It evaporates to obtain hydro-upgrading naphtha product and hydro-upgrading diesel product.
Other poor ignition quality fuel feedstock oils described in step d can be identical as poor ignition quality fuel described in step a, can also not
Together, preferably fraction does low, the low diesel raw material of polycyclic aromatic hydrocarbon content compared with poor ignition quality fuel described in step a.
Conventional operating condition, generally stagnation pressure 3.0MPa~15.0MPa can be used in operating condition described in step d, instead
Answering temperature is 300 DEG C~430 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 d carries out in supplement hydrofinishing high-pressure separator and low pressure separator.Wherein supplement
The isolated supplement hydrofinishing high pressure hydrogen-rich gas of hydrofinishing 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 supplement hydrofinishing gaseous product of needs.
Fractionation described in step d is stripper or fractionating column system, low pressure liquid product stripper or in fractionating column
Fractionation obtains supplement hydrofinishing naphtha product and supplements hydrofining diesel oil product.
Hydro-upgrading gas products described in step c and step d and supplement hydrofinishing gas products can individually be made
For product, mixed gas product can also be mixed into.
Hydro-upgrading naphtha product described in step c and step d and supplement hydrofinishing naphtha product can be single
It is solely used as product, mixing naphtha product can also be mixed into.
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, inferior feedstock oil further can be divided into gently and again two parts according to fraction, the segmentation
Temperature spot is 245 ~ 300 DEG C, i.e., the fraction range of light fraction is initial boiling point to cut-point temperature, and the fraction range of heavy distillat is point
Cutpoint temperature is to the end point of distillation.Therefore, another technical solution of the invention includes:
A kind of flexible hydrogenation modification method of poor ignition quality fuel, including the following contents:
A, poor ignition quality fuel feedstock oil is cut into light fraction and heavy distillat；Heavy distillat is first under Hydrofinishing conditions by adding hydrogen smart
First Hydrobon catalyst bed of reactor processed, obtains the first hydrotreated refinery stream, this part reaction stream is divided into two
Point, a portion extracts hydrofining reactor out；
B, in step a remainder the first hydrotreated refinery stream, individually or with part light fraction under Hydrofinishing conditions lead to
The the second Hydrobon catalyst bed for crossing hydrofining reactor, obtains hydrotreated refinery stream；
C, the hydrotreated refinery stream that step b is obtained enters hydro-upgrading reactor, and by adding hydrogen to change under the conditions of hydro-upgrading
Matter catalyst bed, hydro-upgrading logistics are separated, are fractionated to obtain hydro-upgrading high pressure hydrogen-rich gas, the production of hydro-upgrading gas
Product, hydro-upgrading naphtha product and hydro-upgrading diesel product；
D, added under Hydrofinishing conditions by supplement after the first hydrotreated refinery stream extracted out obtained by step a is mixed with light fraction
The supplement Hydrobon catalyst bed of hydrogen finishing reactor, supplement hydrotreated refinery stream are separated, are fractionated to obtain supplement plus hydrogen
Refine high pressure hydrogen-rich gas, supplement hydrofinishing gas, supplement hydrofinishing naphtha and supplement hydrofining diesel oil.
In the technical scheme, Hydrobon catalyst and Hydrofinishing conditions are the same as above-mentioned content.
Wherein, the weight percent of the whole light fractions of gained in step a is accounted for into the light fraction of supplement hydrofining reactor
Than being 10% ~ 100%.Light fraction into the second Hydrobon catalyst bed of hydrofining reactor accounts for whole light fractions
Weight percent be 0 ~ 90%.
In the present invention, " first " and " second " is determined according to the engagement sequence with reaction raw materials.Add hydrogen
In finishing reactor, first to contact with reaction raw materials be " first " catalyst bed, contacted with reaction raw materials thereafter and be " the
Two " catalyst beds.
Due to based on polycyclic aromatic hydrocarbon, being reacted by more Hydrobon catalysts in heavy distillat, can achieve control
The purpose of aromatic hydrogenation depth processed, and double ring arene is reacted by less Hydrobon catalyst in light fraction, can with again
Fraction achievees the purpose that control aromatic hydrogenation depth simultaneously, i.e. diesel oil after supplement hydrofinishing can meet sulfur content requirement
While its double ring arene and polycyclic aromatic hydrocarbon moderately plus hydrogen to mononuclear aromatics, can satisfy sulphur after further catalytic cracking and contain
Desired catalytically cracked gasoline is measured, and the octane number of gasoline can be improved.At the same time, heavy distillat adds hydrogen essence by more
Less Hydrobon catalyst is passed through in catalyst processed, light fraction, can further strengthen the hydrogenation depth of aromatic hydrocarbons, meets and adds hydrogen
The requirement of modification as far as possible, can produce the lower high-quality hydro-upgrading diesel product of polycyclic aromatic hydrocarbon content.
In conjunction with Fig. 1, method of the invention is specific as follows: feedstock oil 1 is mixed into hydrofining reaction with recycle hydrogen first
Device 2, by extracting supplement hydrofinishing feed stream 5, extraction supplement in the reaction stream of the first Hydrobon catalyst bed out
The first hydrotreated refinery stream after hydrofinishing feed stream enters follow-up hydrogenation catalyst for refining bed, hydrofinishing product
Stream 3 enters hydro-upgrading reactor 4, and the hydro-upgrading of catalyst for hydro-upgrading bed generates logistics 6 and enters hydro-upgrading high pressure
Separator 8 carries out gas-liquid separation, and isolated liquid enters fractionation in fractionating column 10 and obtains hydro-upgrading gas products 12, adds
Hydrogen modifies naphtha product 13 and hydro-upgrading diesel product 14, extraction supplement hydrofinishing feed stream 5 and supplement plus hydrogen essence
Feed stream 21 processed mixes laggard supplement hydrofining reactor 7, by the generation logistics for supplementing Hydrobon catalyst bed
Into gas-liquid separation is carried out in supplement hydrofinishing high-pressure separator 9, isolated liquid, which enters in stripper 11, to be mended
Fill hydrofinishing gas products 15, supplement hydrofinishing naphtha product 16 and supplement hydrofining diesel oil 17, hydro-upgrading gas
Body product 12 and supplement hydrofinishing gas products 15 can obtain mixed gas production separately as product after can also mixing
Product, hydro-upgrading naphtha product 13 and supplement hydrofinishing naphtha product 16 can also be mixed separately as product
After obtain mixing naphtha product, the isolated gas 18 of hydro-upgrading high-pressure separator 8 and supplement hydrofinishing high pressure point
The gas 19 isolated from device 9 is mixed with supplement hydrogen 20 as recycle hydrogen after circulating hydrogen compressor after mixing.
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 FHUDS-5 is the petrochemical industry research of Sinopec Group Fushun
The Hydrobon catalyst of institute's development and production；Catalyst FHUDS-6 is Sinopec Group Fushun petroleum
The Hydrobon catalyst of work research institute development and production；Catalyst 3963 is Sinopec Group Fushun petroleum
The catalyst for hydro-upgrading of chemical research institute's development and production, contains Y type molecular sieve.
The main character of table 1 diesel raw material oil
2 process conditions of table
2 process conditions of continued
3 test result of table
Wherein, catalytic diesel oil heavy distillat and light fraction cutting temperature are 260 DEG C.
Using flexible hydrogenation modifying process of the invention it can be seen from embodiment, by out of hydrofining reactor
It extracts a part of reaction stream out, and realizes using catalyst for hydro-upgrading and supplement catalyst production fine-quality diesel oil product and excellent
The purpose of matter catalytically cracked material, production method are flexible.
Claims (14)
1. a kind of flexible hydrogenation modifying process of poor ignition quality fuel, includes the following steps:
A, poor ignition quality fuel feedstock oil is catalyzed first under Hydrofinishing conditions by the first hydrofinishing of hydrofining reactor
Agent bed obtains the first hydrotreated refinery stream, this part reaction stream is divided into two parts, and it is anti-that a portion extracts hydrofinishing out
Answer device；
B, the first hydrotreated refinery stream continuation of remainder passes through hydrofining reactor under Hydrofinishing conditions in step a
The second Hydrobon catalyst bed, obtain hydrotreated refinery stream；
C, the hydrotreated refinery stream that step b is obtained enters hydro-upgrading reactor, and by adding hydrogen to change under the conditions of hydro-upgrading
Matter catalyst bed, hydro-upgrading logistics are separated, are fractionated to obtain hydro-upgrading high pressure hydrogen-rich gas, the production of hydro-upgrading gas
Product, hydro-upgrading naphtha product and hydro-upgrading diesel product；
D, the first hydrotreated refinery stream of extraction device obtained by step a individually or after mixing with other inferior feedstock oils is adding hydrogen
By the supplement Hydrobon catalyst bed of supplement hydrofining reactor under purification condition, supplement hydrotreated refinery stream is through dividing
Supplement hydrofinishing high pressure hydrogen-rich gas, supplement hydrofinishing gas, supplement hydrofinishing naphtha and supplement are obtained from, fractionation
Hydrofining diesel oil.
2. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that further include step e: step c is obtained plus hydrogen
It is recycled after the supplement hydrofinishing high-pressure hydrogen-rich gas mixing that modification high pressure hydrogen-rich gas and step d are obtained.
3. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that the fore-running of poor ignition quality fuel raw material described in step a
Point is 100~260 DEG C, and the end point of distillation is 300~450 DEG C.
4. hydrogenation modifying process described in accordance with the claim 3, which is characterized in that the poor ignition quality fuel raw material is selected from naphthenic base
Straight-run diesel oil, coker gas oil, catalytic diesel oil, hydroprocessed diesel, coal tar, coal direct liquefaction oil, ICL for Indirect Coal Liquefaction oil, shale
At least one of oil.
5. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that step a, add hydrogen described in step b and step d
Purification 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. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that Hydrofinishing conditions described in step a are as follows: anti-
Answer pressure 3.0MPa~15.0MPa, reaction temperature is 300 DEG C~430 DEG C, volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen oil
Volume ratio is 100:1~2000:1.
7. hydrogenation modifying 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 weight percent that meter accounts for feedstock oil is 5~95 wt%, preferably 10~80 wt%.
8. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that Hydrofinishing conditions described in step b are as follows: anti-
Answer pressure 3.0MPa~15.0MPa, reaction temperature is 300 DEG C~430 DEG C, volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen oil
Volume ratio is 100:1~2000:1.
9. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that catalyst for hydro-upgrading described in step c with
Group VIB and/or group VIII metal are active component, and the carrier of catalyst contains aluminium oxide and molecular sieve, the molecular sieve
For Y type molecular sieve, beta molecular sieve or Sapo type molecular sieve.
10. hydrogenation modifying process according to claim 9, 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%~40wt%, and alumina content is 10wt%~80wt%；Its specific surface area is 100m2/ g~650m2/ g, Kong Rongwei
0.15mL/g~0.50mL/g.
11. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that the condition of hydro-upgrading described in step c are as follows:
Reaction pressure 3.0MPa~15.0MPa, reaction temperature are 300 DEG C~430 DEG C, volume space velocity 0.3h when liquid-1~15.0h-1, hydrogen
Oil volume ratio is 100:1~2000:1.
12. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that Hydrofinishing conditions described in step d are as follows:
Reaction pressure 3.0MPa~15.0MPa, reaction temperature are 300 DEG C~430 DEG C, volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen oil
Volume ratio is 100:1~2000:1.
13. a kind of hydro-upgrading of inferior diesel method, including the following contents:
A, poor ignition quality fuel feedstock oil is cut into light fraction and heavy distillat；Heavy distillat is first under Hydrofinishing conditions by adding hydrogen smart
First Hydrobon catalyst bed of reactor processed, obtains the first hydrotreated refinery stream, this part reaction stream is divided into two
Point, a portion extracts hydrofining reactor out；
B, in step a remainder the first hydrotreated refinery stream, individually or with part light fraction under Hydrofinishing conditions lead to
The the second Hydrobon catalyst bed for crossing hydrofining reactor, obtains hydrotreated refinery stream；
C, the hydrotreated refinery stream that step b is obtained enters hydro-upgrading reactor, and by adding hydrogen to change under the conditions of hydro-upgrading
Matter catalyst bed, hydro-upgrading logistics are separated, are fractionated to obtain hydro-upgrading high pressure hydrogen-rich gas, the production of hydro-upgrading gas
Product, hydro-upgrading naphtha product and hydro-upgrading diesel product；
D, added under Hydrofinishing conditions by supplement after the first hydrotreated refinery stream extracted out obtained by step a is mixed with light fraction
The supplement Hydrobon catalyst bed of hydrogen finishing reactor, supplement hydrotreated refinery stream are separated, are fractionated to obtain supplement plus hydrogen
Refine high pressure hydrogen-rich gas, supplement hydrofinishing gas, supplement hydrofinishing naphtha and supplement hydrofining diesel oil.
14. hydrogenation modification method according to claim 13, which is characterized in that enter the light of supplement hydrofining reactor
The weight percent that fraction accounts for light fraction obtained by step a is 10% ~ 100%, is urged into the second hydrofinishing of hydrofining reactor
The weight percent that the light fraction of agent bed accounts for light fraction obtained by step a is 0 ~ 90%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1727448A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Method for rectifying qualities of fractions of diesel oil |
| CN101089143A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Inferior fraction oil upgrading process |
| CN101724457A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation combined method for diesel oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727448A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Method for rectifying qualities of fractions of diesel oil |
| CN101089143A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Inferior fraction oil upgrading process |
| CN101724457A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation combined method for diesel oil |
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