CN109988598A - A kind of flexible diesel oil hydrogenation modification technique - Google Patents
A kind of flexible diesel oil hydrogenation modification technique Download PDFInfo
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- CN109988598A CN109988598A CN201711468928.2A CN201711468928A CN109988598A CN 109988598 A CN109988598 A CN 109988598A CN 201711468928 A CN201711468928 A CN 201711468928A CN 109988598 A CN109988598 A CN 109988598A
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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
- C10G2300/20—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
- C10G2300/304—Pour point, cloud point, cold flow properties
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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
- C10G2300/307—Cetane number, cetane index
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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 diesel oil hydrogenation modification techniques.Diesel raw material is after hydrofinishing, into hydro-upgrading reactor, is divided into two strands by the material after the catalyst for hydro-upgrading bed of top；One material is extracted out reforming reactor among bed, and is entered hydroisomerizing pour point depression reactor and carried out isomerization-visbreaking reaction；Another strand of material continues to flow downwardly through the catalyst for hydro-upgrading bed of lower part；Gained hydro-upgrading reaction mass and hydroisomerizing pour point depression reaction mass carry out gas-liquid separation and fractionation respectively, obtain the diesel product of different size.The present invention provides a kind of on a set of hydrogenation technique device while producing the hydrogenation modifying process of two or more different size diesel products, heat entrained by partly upgraded material can be made full use of, realizes the coupling operation of hydro-upgrading reactor and hydroisomerizing pour point depression reactor.
Description
Technical field
The invention belongs to petroleum refining fields, and in particular to a kind of diesel oil hydrogenation modification of flexibly production fine-quality diesel oil product
Technique.
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.
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.Above-mentioned technology is raw
The diesel product of 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 flexible diesel oil hydrogenation modification technique, i.e., by from adding hydrogen to change
Extraction section reaction stream in the middle part of qualitative response device, and the diesel raw material oil is passed through into hydro-upgrading and hydroisomerizing pour point depression group
Conjunction method flexibly produces the hydro-upgrading diesel product and hydroisomerizing pour point depression diesel product of high quality.
A kind of flexible diesel oil hydrogenation modification technique of the invention, includes the following steps:
A, diesel raw material oil obtains hydrotreated refinery stream by Hydrobon catalyst bed first under Hydrofinishing conditions；
B, under the conditions of hydro-upgrading, the hydrotreated refinery stream that step a is obtained is obtained by the first catalyst for hydro-upgrading bed
First hydro-upgrading logistics, this part reaction stream are divided into two parts, and a portion extracts hydrogenator out；
C, under the conditions of hydro-upgrading, the first hydro-upgrading logistics of remainder continues through the second hydro-upgrading in step b
Catalyst bed, the second hydro-upgrading logistics are separated, are fractionated to obtain hydro-upgrading high pressure hydrogen-rich gas, and hydro-upgrading gas produces
Product, hydro-upgrading naphtha product and hydro-upgrading diesel product；
D, under the conditions of hydroisomerizing pour point depression, the first hydro-upgrading logistics of the resulting extraction of step b passes through hydroisomerizing pour point depression
The hydroisomerizing pour point depression catalyst bed of reactor, the logistics of hydroisomerizing pour point depression are separated, are fractionated to obtain hydroisomerizing pour point depression height
Press hydrogen-rich gas, hydroisomerizing pour point depression gas, hydroisomerizing pour point depression naphtha and hydroisomerizing pour point depression diesel product.
Flexible diesel oil hydrogenation modification technique according to the present invention, wherein can also include step e: step c obtain plus hydrogen
It is recycled after the hydroisomerizing pour point depression high pressure hydrogen-rich gas mixing that modification high pressure hydrogen-rich gas and step d are obtained.
In the present invention, the Hydrobon catalyst bed, the first catalyst for hydro-upgrading bed and the second hydro-upgrading
Catalyst bed can be set in a reactor, and three catalyst beds can such as be respectively set；Alternatively, hydrofinishing is urged
Agent bed is arranged in individual hydrofining reactor, and the first catalyst for hydro-upgrading bed and the second hydro-upgrading are urged
Agent bed is arranged in a hydro-upgrading reactor；Or Hydrobon catalyst bed is urged with the first hydro-upgrading
Agent bed is arranged in a hydrogenator, and the second catalyst for hydro-upgrading bed is arranged in a hydrogenator
It is interior.
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 hydro-upgrading, maximum journey
Degree improves the Cetane number of diesel oil, obtains that condensation point is relatively high, but the diesel product of high cetane number；A part of extraction
One hydro-upgrading logistics reduces the condensation point of diesel oil after hydroisomerizing pour point depression catalyst, and it is higher to obtain Cetane number, but coagulates
The relatively low diesel product of point.
Compared with prior art, the advantages of flexible diesel oil hydrogenation modification technique of the invention, is:
It 1, include at least two catalyst for hydro-upgrading beds in hydro-upgrading reaction member in the present invention.Added by setting
Modification material extraction step among hydrogen modifying catalyst bed is not necessarily to special operation, can be realized to hydro-upgrading material stock
Effective distribution, then make obtained material by different hydrogenation techniques, so as to flexibly produce the purpose of different size
Diesel product.Meanwhile abstraction reaction logistics is technically also to be easily achieved among catalyst bed.And in the prior art
In, a set of hydrogenation plant is typically only capable to obtain a kind of diesel product of specification；If it is intended to the diesel product of different size is obtained,
Need two sets or more of hydrogenation plant.Therefore, the present invention provides one kind on a set of hydrogenation technique device for the first time while producing
The hydroconversion process of two or more different size diesel products.
2, the present invention is taken out by the way that the first hydro-upgrading logistics is arranged among the modifying catalyst bed of hydro-upgrading unit
Diesel raw material is extracted reactor by hydrofinishing and the first hydro-upgrading logistics of hydro-upgrading by device out, and by its
It is respectively fed to the hydroisomerizing pour point depression reactor being separately provided and carries out hydrodewaxing reaction, further decrease object after the hydro-upgrading
The condensation point of material, so that method of the invention can flexibly produce the diesel product of different condensation points, different Cetane number.
3, in the present invention, the diesel product Cetane number obtained after hydro-upgrading is high；By partial hydrogenation modification, add
The diesel product condensation point obtained after hydrogen isomerization-visbreaking reduces, and Cetane number is relatively high；Production different size can be met respectively
High-quality diesel product needs.
4, in the present invention, the liquid itself obtained among hydro-upgrading unit modifying catalyst bed has very high temperature
And pressure, it can be directly entered in newly-installed hydroisomerizing pour point depression reactor and be reacted, to make full use of this thigh
Divide heat entrained by modification material, realizes the coupling operation of hydrodewaxing reactor and hydro-upgrading reactor.
Detailed description of the invention
Fig. 1 is principle process schematic diagram of the invention.Fig. 1 is to be arranged a hydrofining reactor, a hydro-upgrading
It is illustrated for reactor and a hydrodewaxing reactor.
Wherein: 1- feedstock oil, 2- hydrofining reactor, 3- hydrotreated refinery stream, 4- hydro-upgrading reactor, 5- add hydrogen
Isomerization-visbreaking feed stream, 6- hydro-upgrading logistics, 7- hydroisomerizing pour point depression reactor, 8- hydro-upgrading high-pressure separator, 9-
Hydroisomerizing pour point depression high-pressure separator, 10- hydro-upgrading fractionating column, 11- hydroisomerizing pour point depression fractionating column, 12- hydro-upgrading gas
Body product, 13- hydro-upgrading naphtha product, 14- hydro-upgrading diesel product, 15- hydroisomerizing pour point depression gas products, 16-
Hydroisomerizing pour point depression naphtha product, 7- hydroisomerizing pour point depression diesel product, 18- hydro-upgrading high-pressure separator gaseous product,
19- hydroisomerizing pour point depression 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 is 100~650m2/ g,
0.15~0.6mL/g of Kong Rongwei.Main catalyst have Fushun Petrochemical Research Institute develop FH-5, FH-98,
3936, the Hydrobon catalysts such as 3996, FHUDS series are also possible to the similar catalysis of function of World Catalyst company exploitation
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 and step c is conventional diesel oil hydrogenation modification catalyst, generally with the VIth
B race and/or group VIII metal are active component, and group VIB metal is generally Mo and/or W, group VIII metal be generally Co and/
Or Ni.The carrier of the catalyst includes one of aluminium oxide, silicon-containing alumina and molecular sieve or a variety of, preferably contains molecule
Sieve, the molecular sieve can be Y type molecular sieve.In a preferred embodiment, with the poidometer of catalyst, contain
VI B race metal 10wt%~35wt% in terms of oxide, group VIII metal 3wt%~15wt% in terms of oxide, molecular sieve 5wt%~
40wt%, aluminium oxide 10wt%~80wt%；The specific surface area of catalyst is 100m2/ g~650m2/ g, Kong Rongwei 0.15mL/g~
0.50mL/g.Main commercial catalyst has the 3963 of Fushun Petrochemical Research Institute's development, FC-18, FC-32 catalyst
Deng.For catalyst for hydro-upgrading, it is desirable that have certain hydrogenation activity and certain lytic activity, should guarantee diesel oil distillate
Middle alkene and aromatic hydrocarbons plus hydrogen saturation, the aromatic hydrocarbons after also requiring saturation the reaction of open loop occurs.The operating condition of hydro-upgrading can
Using conventional operating condition, generally are as follows: reaction pressure 3.0MPa~15.0MPa, reaction temperature are 300 DEG C~430 DEG C, when liquid
Volume space velocity 0.3h-1~15.0h-1, hydrogen to oil volume ratio is 100:1~2000:1.
A preferred embodiment of the invention, the catalyst that the first catalyst for hydro-upgrading bed uses are to add hydrogen
Catalyst A, the catalyst that the second catalyst for hydro-upgrading bed uses are hydrogenation catalyst B.Point in the hydrogenation catalyst A
The percentage composition x of son sieve1Lower than the percentage composition x of the molecular sieve in the hydrogenation catalyst B2, preferably x1Compare x2Low 1-
6 percentage points, more preferably x1Compare x2Low 2-5 percentage points.According to above-mentioned preferred embodiment, hydro-upgrading reaction can be obtained
Better open loop effect is obtained, to facilitate the Cetane number for further improving products obtained therefrom.This is because feedstock oil passes through
After first catalyst for hydro-upgrading bed, a part of hydrogenated purification of polycyclic aromatic hydrocarbon is saturated and modifies after reaction outermost one
Ring has carried out ring-opening reaction, and hydrocarbon molecule volume after such open loop increases, increase steric hindrance increased accordingly continue into
The difficulty of row modification reaction, therefore the content of molecular sieve suitably increases to mention in the second catalyst for hydro-upgrading (i.e. catalyst B)
The reactivity of high catalyst can preferably complete the ring-opening reaction of subsequent second ring, so as to increase gained diesel oil
Cetane number.
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 includes hydro-upgrading high-pressure separator and low pressure separator separates two parts.Its
The isolated hydro-upgrading high pressure hydrogen-rich gas of high-pressure separator and liquid, the isolated liquid of high-pressure separator enter low
Press 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 dividing
From the hydro-upgrading gaseous product needed.
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.
Hydroisomerizing pour point depression catalyst described in step d 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 be aluminium oxide, silicon-containing alumina and molecular sieve in it is one or more, preferably contain molecular sieve,
The molecular sieve can be beta molecular sieve, Sapo type molecular sieve etc..With the poidometer of catalyst, group VIB tenor with
Oxide is calculated as 10wt%~35wt%, and group VIII metal content is calculated as 3wt%~15wt%, molecular sieve content 5wt% with oxide
~40wt%, alumina content are 10wt%~80wt%, specific surface 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.For hydro-upgrading
For catalyst, it is desirable that have certain hydrogenation activity and certain lytic activity, should guarantee alkene and aromatic hydrocarbons in diesel oil distillate
Add hydrogen to be saturated, also requires linear paraffin that isomerization reaction occurs.The operating condition of hydroisomerizing pour point depression use usual operating conditions, 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.
Separation described in step d carries out in hydroisomerizing pour point depression high-pressure separator and low pressure separator.Wherein plus hydrogen
The isolated hydroisomerizing pour point depression high pressure hydrogen-rich gas of isomerization-visbreaking 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 d carries out in fractionating column system.Low pressure liquid product is fractionated in fractionating column to be added
Hydrogen isomerization-visbreaking naphtha product and hydroisomerizing pour point depression diesel product.
Hydro-upgrading gas products described in step c and step d and hydroisomerizing pour point depression 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 hydroisomerizing pour point depression 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 reactor 4, take out in the reaction stream by the first catalyst for hydro-upgrading bed
Hydroisomerizing pour point depression feed stream 5 out, the logistics after extracting hydrodewaxing feed stream 5 out go successively to follow-up hydrogenation modification catalysis
Agent bed, hydro-upgrading generate logistics 6 enter hydro-upgrading high-pressure separator 8 carry out gas-liquid separation, isolated liquid into
Enter fractionation in fractionating column 10 and obtains hydro-upgrading gas products 12, hydro-upgrading naphtha product 13 and hydro-upgrading diesel product
14, hydroisomerizing pour point depression feed stream 5 enters hydroisomerizing pour point depression reactor 7, passes through hydroisomerizing pour point depression catalyst bed
Product stream, which enters in hydroisomerizing pour point depression high-pressure separator 9, carries out gas-liquid separation, and isolated liquid enters fractionating column 11
Middle fractionation obtains hydroisomerizing pour point depression gas products 15, hydroisomerizing pour point depression naphtha product 16 and hydroisomerizing pour point depression diesel oil and produces
Product 17, hydro-upgrading gas products 12 and hydroisomerizing pour point depression gas products 15 can be separately as products, after can also mixing
Mixed gas product is obtained, hydro-upgrading naphtha product 13 and hydroisomerizing pour point depression naphtha product 16 can be separately as productions
Product, obtained after can also mixing mixing naphtha product, the isolated gas 18 of hydro-upgrading high-pressure separator 8 and plus hydrogen it is different
The isolated gas 19 of structure pour point depression high-pressure separator 9 is mixed with supplement hydrogen 20 as circulation after circulating hydrogen compressor after mixing
Hydrogen.
Illustrate the present invention program and effect below by embodiment.
Embodiment 1-4
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；The content of Y type molecular sieve is than 3963 in 3963B catalyst
The content of Y type molecular sieve is high 4 percentage points (numbers) in catalyst, other are constant；Catalyst FC-20 is Sinopec's share
The hydrodewaxing catalyst of Fushun Petrochemical Research Institute, Co., Ltd development and production, contains beta molecular sieve.
The main character of table 1 diesel raw material oil
2 embodiment process conditions of table and test result
3 embodiment process conditions of table and test result
Using flexible diesel oil hydrogenation modification technique of the invention it can be seen from embodiment, by out of hydro-upgrading reactor
It extracts a part of reaction stream out, and realizes production heterogeneity using catalyst for hydro-upgrading and hydroisomerizing pour point depression catalyst
The purpose of diesel oil, production method are flexible.
Claims (15)
1. a kind of flexible diesel oil hydrogenation modification technique, includes the following steps:
A, diesel raw material oil obtains hydrotreated refinery stream by Hydrobon catalyst bed first under Hydrofinishing conditions；
B, under the conditions of hydro-upgrading, the hydrotreated refinery stream that step a is obtained is obtained by the first catalyst for hydro-upgrading bed
First hydro-upgrading logistics, this part reaction stream are divided into two parts, and a portion extracts hydrogenator out；
C, under the conditions of hydro-upgrading, the first hydro-upgrading logistics of remainder continues through the second hydro-upgrading in step b
Catalyst bed, the second hydro-upgrading logistics are separated, are fractionated to obtain hydro-upgrading high pressure hydrogen-rich gas, and hydro-upgrading gas produces
Product, hydro-upgrading naphtha product and hydro-upgrading diesel product；
D, under the conditions of hydroisomerizing pour point depression, the first hydro-upgrading logistics of the resulting extraction of step b passes through hydroisomerizing pour point depression
The hydroisomerizing pour point depression catalyst bed of reactor, the logistics of hydroisomerizing pour point depression are separated, are fractionated to obtain hydroisomerizing pour point depression height
Press hydrogen-rich gas, hydroisomerizing pour point depression gas, hydroisomerizing pour point depression naphtha and hydroisomerizing pour point depression diesel product.
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 hydrodewaxing 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 initial boiling point of the diesel raw material be 100~
260 DEG C, 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 diesel raw material oil is selected from straight run bavin
The structures such as oil, coker gas oil, catalytic diesel oil, hydroprocessed diesel, coal tar, coal direct liquefaction oil, ICL for Indirect Coal Liquefaction oil, shale oil
At one or more of one group of substance.
5. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that Hydrobon catalyst described in step a is equal
Using VI B race and/or group VIII metal as active component, using aluminium oxide or silicon-containing alumina as carrier；With the poidometer of catalyst,
Group VIB tenor is calculated as 10wt%~35wt% with oxide, group VIII metal content with oxide be calculated as 3wt%~
15wt%；Its property is as follows: specific surface 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 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 is
100:1~2000:1.
7. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that the catalyst for hydro-upgrading is with the VIth B
Race and/or group VIII metal are active component, catalyst carrier include one of aluminium oxide, silicon-containing alumina and molecular sieve or
It is a variety of.
8. hydrogenation modifying process according to claim 7, which is characterized in that the catalyst carrier include aluminium oxide and
Molecular sieve；With the poidometer of catalyst, group VIB tenor is calculated as 10wt%~35wt% with oxide, and group VIII metal contains
Amount is calculated as 3wt%~15wt% with oxide, and molecular sieve content is 5wt%~40wt%, and alumina content is 10wt%~80wt%；Its
Specific surface is 100m2/ g~650m2/ g, Kong Rongwei 0.15mL/g~0.50mL/g.
9. hydrogenation modifying process according to claim 8, which is characterized in that the first catalyst for hydro-upgrading bed used
Catalyst is hydrogenation catalyst A, and the catalyst that the second catalyst for hydro-upgrading bed uses is hydrogenation catalyst B, described plus hydrogen
The percentage composition x of molecular sieve in catalyst A1Lower than the percentage composition x of the molecular sieve in the hydrogenation catalyst B2。
10. hydro-upgrading pour point depression technique according to claim 9, which is characterized in that x1Compare x2Low 1-6 percentage points, preferably
x1Compare x2Low 2-5 percentage points.
11. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that the condition of the hydro-upgrading are as follows: stagnation 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.
12. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that the fraction of stream extracted out in step b is with liquid phase
The mass ratio that meter accounts for feedstock oil is 5~95wt%.
13. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that the fraction of stream extracted out in step b is with liquid phase
The mass ratio that meter accounts for feedstock oil is 10~80wt%.
14. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that the operating condition of hydroisomerizing pour point depression are as follows: anti-
Answer pressure 3.0MPa~15.0MPa, reaction temperature is 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.
15. hydrogenation modifying process described in accordance with the claim 1, which is characterized in that the Hydrobon catalyst bed, first
Catalyst for hydro-upgrading bed and the second catalyst for hydro-upgrading bed are arranged in a reactor；Alternatively, hydrofinishing is urged
Agent bed is arranged in individual hydrofining reactor, the first catalyst for hydro-upgrading bed and the catalysis of the second hydro-upgrading
Agent bed is arranged in a hydro-upgrading reactor；Or Hydrobon catalyst bed and the first hydro-upgrading are catalyzed
Agent bed is arranged in a hydrogenator, and the second catalyst for hydro-upgrading bed is arranged in a hydrogenator.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059934A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrogenation, modification and pour point depression method by consideration of product quality of 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 |
| CN103805244A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of clean diesel oil with low condensation point |
| CN105087064A (en) * | 2014-05-06 | 2015-11-25 | 中国石油化工股份有限公司 | Method for producing clean low freezing point diesel oil by treating high nitrogen diesel oil |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059934A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrogenation, modification and pour point depression method by consideration of product quality of 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 |
| CN103805244A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of clean diesel oil with low condensation point |
| CN105087064A (en) * | 2014-05-06 | 2015-11-25 | 中国石油化工股份有限公司 | Method for producing clean low freezing point diesel oil by treating high nitrogen diesel oil |
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