CN109988601A - A kind of hydrogenation technique of flexible production low freezing point diesel fuel - Google Patents
A kind of hydrogenation technique of flexible production low freezing point diesel fuel Download PDFInfo
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- CN109988601A CN109988601A CN201711468920.6A CN201711468920A CN109988601A CN 109988601 A CN109988601 A CN 109988601A CN 201711468920 A CN201711468920 A CN 201711468920A CN 109988601 A CN109988601 A CN 109988601A
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- catalyst
- pour point
- point depression
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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
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
-
- 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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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of hydrogenation techniques for producing low freezing point diesel fuel.Diesel raw material is after hydrofinishing, into hydro-upgrading reactor, is divided into two strands by the material after catalyst for hydro-upgrading bed；One material is extracted out reforming reactor among bed, and is entered hydroisomerizing pour point depression catalyst bed and carried out pour point depression reaction；Another strand of material continues to flow downwardly through the hydroisomerizing pour point depression catalyst bed of lower part；Gained hydroisomerizing pour point depression reaction mass and hydrodewaxing reaction mass carry out gas-liquid separation and fractionation respectively, obtain the diesel product of different size.The present invention provides for the first time a kind of on a set of hydrogenation technique device while producing the hydrogenation coupling process of two or more different size diesel products, heat entrained by partial hydrogenation modification material can be made full use of, realizes the coupling operation of hydro-upgrading pour point depression reactor and hydrodewaxing reactor.
Description
Technical field
The invention belongs to petroleum refining fields, and in particular to a kind of hydrogenation technique of flexibly production low freezing point diesel fuel product.
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.In addition, the diesel product of cold district is to solidifying when winter
Point has different limitation and requirement, and the diesel product in China can be divided into 5#, 0#, -10#, -20#, -35# and -50# according to condensation point
Equal different sizes.The condensation point of diesel oil can be effectively reduced in hydrodewaxing technology.
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.Such technology can increase diesel product Cetane number
More than 10 units, but the variation of the condensation point of diesel oil is little.
Diesel oil fraction hydrogenating isomerization-visbreaking technology, such as CN1718683A and CN1712499A, are catalyzed using hydrofinishing
Agent and contain β zeolite hydroisomerizing pour point depression catalyst, produces diesel product using one-stage serial process, but identical plus hydrogen changes
Low compared with hydro-upgrading diesel cetane-number under the conditions of matter, process conditions are compared with hydrodewaxing technique when identical low freezing point diesel fuel product
Condition is harsh.
Diesel oil fraction hydrogenating pour point depression technology, such as CN102051232A and CN1257107A, use Hydrobon catalyst
With hydrodewaxing catalyst, low freezing point diesel fuel product is produced using one-stage serial process, but diesel product yield is lower.
Hydrobon catalyst is used alternatingly by CN102453531A, CN103805258A and CN103805254A etc. and hydrodewaxing is urged
Agent, obtained diesel product condensation point is low, but diesel yield is relatively low, can only produce a kind of diesel product.
Using hydrogen addition technology CN105087063A, diesel oil distillate is directly passed through after hydroisomerizing pour point depression, using reaction heat
Hydrodewaxing is crossed to produce low freezing point diesel fuel product, but the technique can only produce a kind of diesel product of condensation point specification.
In conclusion existing diesel oil hydrogenation modification technology can obtain higher diesel product yield, product quality is obtained
To increasing substantially, such as Cetane number, sulfur content, arene content, density, but condensation point reduces amplitude less or does not drop
It is low, it is not able to satisfy the requirement of low freezing point diesel fuel.The solidifying of diesel product can be greatly lowered in existing hydroisomerizing pour point depression technology
Point can satisfy the index request of low-coagulation diesel oil, but yield is lower when production low freezing point diesel fuel product.Existing hydrodewaxing
The condensation point of diesel product can be greatly lowered in technology, can satisfy the index request of low-coagulation diesel oil, but diesel yield is lower,
Usually less than 90m%, and diesel product Quality advance amplitude is little, especially the n-alkane cracking into gas of high cetane number
The Cetane number that will lead to diesel product when body or naphtha cut reduces.It is single using product when coupling hydro technology.On
The diesel product for stating technology production only has one kind, and product flexibility is poor.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of hydrogenation technique of flexibly production low freezing point diesel fuel, that is, passes through
It is from extraction section reaction stream in the middle part of hydro-upgrading pour point depression reactor that the diesel raw material oil is different by hydro-upgrading plus hydrogen
Structure pour point depression and hydrodewaxing coupling process flexibly produce the hydroisomerizing pour point depression diesel product and hydrodewaxing diesel oil of different condensation points
Product.
One kind of the invention flexibly produces the hydrogenation technique of low freezing point diesel fuel, includes the following steps:
A, diesel raw material oil obtains hydrotreated refinery stream by Hydrobon catalyst bed first under Hydrofinishing conditions；
B, the hydrotreated refinery stream that step a is obtained obtains adding hydrogen by catalyst for hydro-upgrading bed under the conditions of hydro-upgrading
Logistics is modified, this part reaction stream is divided into two parts, and a portion extracts hydro-upgrading reactor out；
C, remaining hydro-upgrading logistics passes through hydroisomerizing pour point depression catalyst bed under the conditions of hydroisomerizing pour point depression in step b
Layer, the logistics of hydroisomerizing pour point depression are separated, are fractionated to obtain hydroisomerizing pour point depression high pressure hydrogen-rich gas, the production of hydroisomerizing pour point depression gas
Product, hydroisomerizing pour point depression naphtha product and hydroisomerizing pour point depression diesel product；
D, the hydro-upgrading logistics extracted out obtained by step b passes through the hydrodewaxing of hydrodewaxing reactor under the conditions of hydrodewaxing
Catalyst bed, hydrodewaxing logistics are separated, are fractionated to obtain hydrodewaxing high pressure hydrogen-rich gas, hydrodewaxing gas plus hydrogen
Pour point depression naphtha and hydrodewaxing diesel product.
Hydrogenation technique according to the present invention, wherein can also include step e: step c obtained hydroisomerizing pour point depression high pressure
It is recycled after the hydrodewaxing high pressure hydrogen-rich gas mixing that hydrogen-rich gas and step d are obtained.
In the present invention, the Hydrobon catalyst bed, catalyst for hydro-upgrading bed, hydroisomerizing pour point depression catalyst
Bed can be set in a reactor, and three catalyst beds can such as be respectively set in a hydrogenator；Or
Person, Hydrobon catalyst bed are arranged in individual hydrofining reactor, and catalyst for hydro-upgrading bed and plus hydrogen
Isomerization-visbreaking catalyst bed is arranged in a hydrogenator；Or Hydrobon catalyst bed, hydro-upgrading are urged
Agent and hydroisomerizing pour point depression catalyst bed are separately positioned in three hydrogenators.The hydrodewaxing catalyst bed
Layer is usually provided separately in a hydrodewaxing reactor.
The impurity such as S, N, O in diesel raw material oil are effectively removed when passing through Hydrobon catalyst, the certain journey of aromatic hydrocarbons
It is obtained on degree plus hydrogen is saturated, it is anti-to separate ring for cyclic hydrocarbon generating unit when hydrotreated refinery stream continues through catalyst for hydro-upgrading bed
It answers, low cetane value constituents become high cetane number component, and a part of hydro-upgrading logistics continues hydroisomerizing pour point depression, most
Big degree improves the Cetane number of diesel oil, obtains that condensation point is relatively high, but the diesel product of high cetane number；One of extraction
It is relatively slightly lower to obtain Cetane number, but coagulates for the condensation point for dividing hydro-upgrading logistics to reduce diesel oil after hydrodewaxing catalyst
The low-down diesel product of point.
Compared with prior art, the advantages of hydrogenation technique of flexible production low freezing point diesel fuel of the invention, is:
It 1, include that at least one catalyst for hydro-upgrading bed adds at least one in the present invention, in hydro-upgrading pour point depression reactor
Hydrogen isomerization-visbreaking catalyst bed.Step is extracted by the way that the hydro-upgrading material among hydroisomerizing pour point depression reactor bed is arranged in
Suddenly, it is not necessarily to special operation, effective distribution to hydro-upgrading material stock can be realized, then makes obtained material by different
Hydrogenation technique, so as to flexibly produce the purpose diesel product of different condensation points.Meanwhile the abstraction reaction among reactor bed
Logistics is technically also to be easily achieved.And in the prior art, a set of hydrogenation plant is typically only capable to obtain a kind of specification
Diesel product；If it is intended to obtaining the diesel product of different size, two sets or more of hydrogenation plant is needed.Therefore, the present invention is first
Secondary provide a kind of on a set of hydrogenation technique device while producing the hydro-conversion works of two or more different size diesel products
Skill.
2, the present invention passes through the catalyst for hydro-upgrading and hydroisomerizing pour point depression catalyst in hydro-upgrading pour point depression reactor
Hydro-upgrading logistics withdrawing device is set among bed, diesel raw material is extracted by the material stream of hydrofinishing and hydro-upgrading
Reactor out, and be respectively fed to the hydrodewaxing catalyst bed (reactor) being separately provided and carry out hydrodewaxing reaction,
The condensation point of material after the hydro-upgrading is further decreased, so that method of the invention can flexibly produce different condensation points, no
With the diesel product of Cetane number.
3, in the present invention, the diesel product Cetane number obtained after hydro-upgrading, hydroisomerizing pour point depression is high, condensation point phase
To slightly higher；The diesel product condensation point obtained after partial hydrogenation modification, hydrodewaxing is low, and Cetane number is relatively slightly lower；It can be with
Meet the needs of the high-quality diesel product of production different size respectively.
4, in the present invention, among hydro-upgrading pour point depression reactor modifying catalyst bed and isomerization-visbreaking catalyst bed
To liquid itself there is very high temperature and pressure, can be directly entered in newly-installed hydrodewaxing reactor carry out it is anti-
It answers, to make full use of heat entrained by this strand of partly upgraded material, realizes hydrodewaxing reactor and hydroisomerizing pour point depression
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- hydrofining reactor, 3- hydrotreated refinery stream, 4- hydro-upgrading pour point depression reactor, 5-
Hydrodewaxing feed stream, 6- hydroisomerizing pour point depression logistics, 7- hydrodewaxing reactor, the separation of 8- hydroisomerizing pour point depression high pressure
Device, 9- hydrodewaxing high-pressure separator, 10- hydroisomerizing pour point depression fractionating column, 11- hydrodewaxing fractionating column, 12- hydroisomerizing drop
Solidifying gas products, 13- hydroisomerizing pour point depression naphtha product, 14- hydroisomerizing pour point depression diesel product, 15- hydrodewaxing gas
Product, 16- hydrodewaxing naphtha product, 7- hydrodewaxing diesel product, 18- hydroisomerizing pour point depression high-pressure separator gas produce
Object, 19- hydrodewaxing high-pressure separator gaseous product, 20- supplement hydrogen.
Specific embodiment
The initial boiling point of diesel raw material described in step a is 100~260 DEG C, and the end point of distillation is 300~450 DEG C.The diesel oil is former
Material oil can be one of straight-run diesel oil, coker gas oil, catalytic diesel oil, hydroprocessed diesel that PETROLEUM PROCESSING obtains etc., from
One of coal tar, coal direct liquefaction oil, ICL for Indirect Coal Liquefaction oil, shale oil that coal obtains etc., it is wherein several to be also possible to them
The miscella of kind.
Hydrobon catalyst described in step a is conventional diesel oil hydrofining catalyst.Generally with VI B race and/
Or group VIII metal is active component, using aluminium oxide or silicon-containing alumina as carrier；Group VIB metal is generally Mo and/or W,
Group VIII metal is generally Co and/or Ni.With the poidometer of catalyst, group VIB tenor with oxide be calculated as 10wt%~
35wt%, group VIII metal content are calculated as 3wt%~15wt% with oxide, and property is as follows: specific surface area is 100~650m2/
0.15~0.6mL/g of g, Kong Rongwei.FH-5, FH- that available commercial catalyst has Fushun Petrochemical Research Institute to develop
98, the 3936, Hydrobon catalysts such as 3996, FHUDS series, the function of being also possible to the exploitation of World Catalyst company similar are urged
Agent, such as HC-K, HC-P of Uop Inc., the KF-847 of TK-555, TK-565 catalyst of Topsoe company and Akzo company,
KF-848 etc..Conventional operating condition, generally reaction pressure 3.0MPa~15.0MPa, reaction temperature can be used in operating condition
It 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.
Catalyst for hydro-upgrading described in step b 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 contains one of aluminium oxide, silicon-containing alumina and molecular sieve or a variety of, preferably contains molecular sieve；Described
Molecular sieve can be Y type molecular sieve.With the poidometer of catalyst, group VIB tenor with oxide be calculated as 10wt%~
35wt%, group VIII metal content are calculated as 3wt%~15wt% with oxide, and molecular sieve content is 5wt%~40wt%, and aluminium oxide contains
Amount is 10wt%~80wt%；Its specific surface is 100m2/ g~650m2/ g, Kong Rongwei 0.15mL/g~0.50mL/g.It is main to urge
Agent has the 3963 of Fushun Petrochemical Research Institute's development, FC-18, FC-32 catalyst etc..For catalyst for hydro-upgrading
For, it is desirable that have certain hydrogenation activity and certain lytic activity, should guarantee alkene and aromatic hydrocarbons in diesel oil distillate plus hydrogen it is full
With the reaction of the aromatic hydrocarbons generation open loop after also requiring saturation.The operating condition of hydro-upgrading can be used conventional operating condition, and one
As 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 to oil volume ratio is 100:1~2000:1.
Hydroisomerizing pour point depression catalyst described in step c is conventional diesel oil hydrogenation isomerization-visbreaking catalyst, generally with the
VI B race and/or group VIII metal are active component, and group VIB metal is generally Mo and/or W, and group VIII metal is generally Co
And/or Ni.The carrier of the catalyst contains one of aluminium oxide, silicon-containing alumina and molecular sieve or a variety of, preferably contains and divides
Son sieve, the molecular sieve can be beta molecular sieve, Sapo type molecular sieve etc..With the poidometer of catalyst, group VIB metal
Content is calculated as 10wt%~35wt% with oxide, and group VIII metal content is calculated as 3wt%~15wt%, molecular sieve content with oxide
For 5wt%~40wt%, alumina content is 10wt%~80wt%；Its specific surface area is 100m2/ g~650m2/ g, Kong Rongwei
0.15mL/g~0.50mL/g.FC-14, FC-20 etc. that main catalyst has Fushun Petrochemical Research Institute to develop.It is right
For catalyst for hydro-upgrading, it is desirable that have certain hydrogenation activity and certain lytic activity, should guarantee alkene in diesel oil distillate
Hydrocarbon and aromatic hydrocarbons plus hydrogen saturation, also require linear paraffin that isomerization reaction occurs.The operating condition of hydroisomerizing pour point depression can be used often
The operating condition of rule, generally are as follows: reaction pressure is 3.0MPa~15.0MPa, and reaction temperature is 300 DEG C~430 DEG C, volume when liquid
Air speed is 0.3h-1~15.0h-1, hydrogen to oil volume ratio is 100:1~2000:1.
The mass ratio that the fraction of stream of extraction described in step b accounts for feedstock oil in terms of liquid phase is 5~95wt%, preferably
10~80wt%.
Separation described in step c generally comprises hydroisomerizing pour point depression high-pressure separator and low pressure separator separates two
Point.The isolated hydroisomerizing pour point depression high pressure hydrogen-rich gas of its 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 pour point depression gaseous product of needs.
Fractionation described in step c carries out in hydroisomerizing pour point depression fractionating column system.Low pressure liquid product is in fractionating column
Middle fractionation obtains hydroisomerizing pour point depression naphtha product and hydroisomerizing pour point depression diesel product.
Hydrodewaxing catalyst described in step d is conventional hydrodewaxing catalyst, generally with group VIB and/or the
VIII race's metal is active component, and group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.The catalysis
The carrier of agent contains one of aluminium oxide, silicon-containing alumina and molecular sieve or a variety of, preferably contains molecular sieve, the molecule
Sieve can be ZSM-5, ZSM-11, ZSM-22, ZSM-35 type molecular sieve, preferably ZSM-5 molecular sieve.With the poidometer of catalyst,
Total metal contents in soil is calculated as 1wt%~20wt% with oxide, and molecular sieve content is 40wt%~85wt%, binder content 10wt%
~40wt%.Main catalyst has the 3881 of Fushun Petrochemical Research Institute's development, FDW-1 catalyst etc..Hydrodewaxing
Operating condition conventional operating condition can be used, generally are as follows: reaction pressure be 3.0MPa~15.0MPa, reaction temperature 300
DEG C~440 DEG C, volume space velocity is 0.3h when liquid-1~12.0h-1, hydrogen to oil volume ratio is 100:1~1500:1.
Separation described in step d carries out in hydrodewaxing high-pressure separator and low pressure separator.Wherein hydrodewaxing
The isolated hydrodewaxing high pressure hydrogen-rich gas of high-pressure separator and liquid, the isolated liquid of high-pressure separator enter low pressure
Separator.Low pressure separator is by the isolated hydrocarbon-rich gas of highly pressurised liquid product and low pressure liquid product.Hydrocarbon-rich gas is through separating
The hydrodewaxing gaseous product needed.
Fractionation described in step d is carried out in fractionating column system.Low pressure liquid product is fractionated in fractionating column to be obtained adding hydrogen
Pour point depression naphtha product and hydrodewaxing diesel product.
Hydroisomerizing pour point depression gas products described in step c and step d and hydrodewaxing gas products can individually be made
For product, mixed gas product can also be mixed into.
Hydroisomerizing pour point depression naphtha product described in step c and step d and hydrodewaxing 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 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, hydrotreated refinery stream 3 enter hydro-upgrading pour point depression reactor 4, take out in the reaction stream by catalyst for hydro-upgrading bed
Hydrodewaxing feed stream 5 out, the logistics after extracting hydrodewaxing feed stream 5 out go successively to the catalysis of follow-up hydrogenation isomerization-visbreaking
Agent bed, hydroisomerizing pour point depression generates logistics 6 and enters the progress gas-liquid separation of hydroisomerizing pour point depression high-pressure separator 8, isolated
Liquid enter in fractionating column 10 fractionation and obtain hydroisomerizing pour point depression gas products 12,13 and of hydroisomerizing pour point depression naphtha product
Hydroisomerizing pour point depression diesel product 14, hydrodewaxing feed stream 5 enter hydrodewaxing reactor 7, are catalyzed by hydrodewaxing
The product stream of agent bed, which enters, carries out gas-liquid separation in hydrodewaxing high-pressure separator 9, isolated liquid enters fractionation
Fractionation obtains hydrodewaxing gas products 15, hydrodewaxing naphtha product 16 and hydrodewaxing diesel product 17 in tower 11, adds
Hydrogen isomerization-visbreaking gas products 12 and hydrodewaxing gas products 15 can be mixed after can also mixing separately as product
Gas products, hydroisomerizing pour point depression naphtha product 13 and hydrodewaxing naphtha product 16 can be separately as products, can also
To obtain mixing naphtha product, hydroisomerizing pour point depression high-pressure separator 8 isolated gas 18 and hydrodewaxing after mixing
The isolated gas 19 of high-pressure separator 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 3963 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 hydrodewaxing catalyst of Fushun Petrochemical Research Institute, company development and production, contains beta molecular sieve；Catalyst 3881 is China
The hydrodewaxing catalyst of Fushun Petrochemical Research Institute, petrochemical industry limited liability company development and production contains ZSM-5 type point
Son sieve.
The main character of table 1 diesel raw material oil
2 embodiment process conditions of table and test result
2 embodiment process conditions of continued and test result
Using hydrogenation technique of the invention it can be seen from embodiment, by being extracted out out of hydro-upgrading isomerization-visbreaking reactor
A part of reaction stream, and production heterogeneity diesel oil is realized using hydroisomerizing pour point depression catalyst and hydrodewaxing catalyst
Purpose, production method is flexible.
Claims (15)
1. a kind of hydrogenation technique of flexibly production low freezing point diesel fuel, includes the following steps:
A, diesel raw material oil obtains hydrotreated refinery stream by Hydrobon catalyst bed first under Hydrofinishing conditions；
B, the hydrotreated refinery stream that step a is obtained obtains adding hydrogen by catalyst for hydro-upgrading bed under the conditions of hydro-upgrading
Logistics is modified, this part reaction stream is divided into two parts, and a portion extracts hydrogenator out；
C, the hydro-upgrading logistics of remainder passes through hydroisomerizing pour point depression catalyst under the conditions of hydroisomerizing pour point depression in step b
Bed, the logistics of hydroisomerizing pour point depression are separated, are fractionated to obtain hydroisomerizing pour point depression high pressure hydrogen-rich gas, hydroisomerizing pour point depression gas
Product, hydroisomerizing pour point depression naphtha product and hydroisomerizing pour point depression diesel product；
D, the hydro-upgrading logistics extracted out obtained by step b passes through the hydrodewaxing of hydrodewaxing reactor under the conditions of hydrodewaxing
Catalyst bed, hydrodewaxing logistics are separated, are fractionated to obtain hydrodewaxing high pressure hydrogen-rich gas, hydrodewaxing gas plus hydrogen
Pour point depression naphtha and hydrodewaxing diesel product.
2. hydrogenation technique described in accordance with the claim 1, which is characterized in that further include step e: the hydroisomerizing that step c is obtained
It is recycled after the hydrodewaxing high pressure hydrogen-rich gas mixing that pour point depression high pressure hydrogen-rich gas and step d are obtained.
3. hydrogenation technique described in accordance with the claim 1, which is characterized in that the initial boiling point of the diesel raw material is 100~260
DEG C, the end point of distillation is 300~450 DEG C.
4. hydrogenation technique described in accordance with the claim 3, which is characterized in that the diesel raw material oil is selected from straight-run diesel oil, coke
Change one of diesel oil, catalytic diesel oil, hydroprocessed diesel, coal tar, coal direct liquefaction oil, ICL for Indirect Coal Liquefaction oil and shale oil
Or it is several.
5. hydrogenation technique described in accordance with the claim 1, which is characterized in that Hydrobon catalyst described in step a 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.
6. hydrogenation technique described in accordance with the claim 1, which is characterized in that the operating condition of step a 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 to oil volume ratio 100:1
~2000:1.
7. hydrogenation technique described in accordance with the claim 1, which is characterized in that the catalyst for hydro-upgrading with group VIB and/
Or group VIII metal is active component, the carrier of catalyst contains aluminium oxide and molecular sieve；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%, molecule with oxide
Sieve content is 5wt%~40wt%, and alumina content is 10wt%~80wt%；Specific surface area is 100m2/ g~650m2/ g, Kong Rongwei
0.15mL/g~0.50mL/g.
8. hydrogenation technique described in accordance with the claim 1, which is characterized in that the condition of the hydro-upgrading 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 to oil volume ratio
For 100:1~2000:1.
9. hydrogenation technique described in accordance with the claim 1, which is characterized in that hydroisomerizing pour point depression catalyst described in step c with
Group VIB and/or group VIII metal are active component, and catalyst carrier contains aluminium oxide and molecular sieve；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%, molecular sieve content are 5wt%~40wt%, and alumina content is 10wt%~80wt%；Specific surface area is 100m2/ g~
650m2/ g, Kong Rongwei 0.15mL/g~0.50mL/g.
10. hydrogenation technique described in accordance with the claim 1, which is characterized in that the operating condition of hydroisomerizing pour point depression are as follows: reaction pressure
Power is 3.0MPa~15.0MPa, and reaction temperature is 300 DEG C~430 DEG C, and volume space velocity is 0.3h when liquid-1~15.0h-1, hydrogen oil
Volume ratio is 100:1~2000:1.
11. hydrogenation technique described in accordance with the claim 1, which is characterized in that the hydrodewaxing catalyst is with group VIB
And/or group VIII metal is active component, the carrier of catalyst contains aluminium oxide and molecular sieve, the molecular sieve be ZSM-5,
ZSM-11, ZSM-22 or ZSM-35 type molecular sieve, with the poidometer of catalyst, total metal contents in soil with oxide be calculated as 1wt%~
20wt%, molecular sieve content are 40wt%~85wt%, and alumina content is 10wt%~40wt%.
12. hydrogenation technique described in accordance with the claim 1, which is characterized in that the operating condition of hydrodewaxing are as follows: reaction pressure is
3.0MPa~15.0MPa, reaction temperature are 300 DEG C~440 DEG C, and volume space velocity is 0.3h when liquid-1~12.0h-1, hydrogen oil volume
Than for 100:1~1500:1.
13. hydrogenation technique described in accordance with the claim 1, which is characterized in that the fraction of stream extracted out in step b is accounted in terms of liquid phase
The mass ratio of feedstock oil is 5~95wt%.
14. hydrogenation technique described in accordance with the claim 1, which is characterized in that the fraction of stream extracted out in step b is accounted in terms of liquid phase
The mass ratio of feedstock oil is 10~80wt%.
15. hydrogenation technique described in accordance with the claim 1, which is characterized in that the Hydrobon catalyst bed, hydro-upgrading
Catalyst bed, hydroisomerizing pour point depression catalyst bed are arranged in a reactor；Alternatively, Hydrobon catalyst bed is set
It sets in individual hydrofining reactor, catalyst for hydro-upgrading bed and hydroisomerizing pour point depression catalyst bed are arranged one
In a hydrogenator；Or Hydrobon catalyst bed, catalyst for hydro-upgrading and hydroisomerizing pour point depression catalyst bed
Layer is separately positioned in three hydrogenators.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289831A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing high-quality low-coagulation diesel oil with high hexadecane value |
| CN1712499A (en) * | 2004-06-21 | 2005-12-28 | 中国石油化工股份有限公司 | Diesel production from hydrogenation upgrading isomerizing pour-point reduction |
| 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 |
| CN103805270A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of low-condensation point diesel oil |
-
2017
- 2017-12-29 CN CN201711468920.6A patent/CN109988601B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289831A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing high-quality low-coagulation diesel oil with high hexadecane value |
| CN1712499A (en) * | 2004-06-21 | 2005-12-28 | 中国石油化工股份有限公司 | Diesel production from hydrogenation upgrading isomerizing pour-point reduction |
| 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 |
| CN103805270A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of low-condensation point diesel oil |
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Effective date of registration: 20230921 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |