CN109988622A - A kind of flexible diesel oil hydrogenation modification pour point depression technique - Google Patents
A kind of flexible diesel oil hydrogenation modification pour point depression technique Download PDFInfo
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- CN109988622A CN109988622A CN201711469562.0A CN201711469562A CN109988622A CN 109988622 A CN109988622 A CN 109988622A CN 201711469562 A CN201711469562 A CN 201711469562A CN 109988622 A CN109988622 A CN 109988622A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
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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
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
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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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- 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)
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Abstract
The invention discloses a kind of flexible diesel oil hydrogenation modification pour point depression 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 hydrodewaxing reactor and carried out pour point depression 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 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 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 hydrodewaxing reactor and hydro-upgrading 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
Pour point depression 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 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 and hydrodewaxing is used alternatingly in CN102453531A, CN103805258A and CN103805254A etc.
Catalyst, obtained diesel product condensation point is low, but diesel yield is relatively low, can only produce a kind of diesel product.
Using a kind of production method of fine-quality diesel oil of combined hydrogenation technology CN1415705A, feedstock oil is hydrogenated to be refined and adds
Gas-liquid separation is carried out after hydrogen pour point depression, product liquid reuses noble metal catalyst and carries out hydrogenation aromatics-removing, due to using two-stage method
Technique, process is complicated, and can only produce a kind of diesel product.
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 condensation point of diesel product can be greatly lowered in existing hydrodewaxing technology, can
To meet the index request of low-coagulation diesel oil, but diesel yield is lower, usually less than 90m%, and diesel product Quality advance width
Degree less, will lead to the ten of diesel product when the n-alkane of high cetane number being especially cracked into gas or naphtha cut
Six alkane values reduce.It is single using process complexity, product when combined hydrogenation technology.The diesel product of above-mentioned technology production only has
One kind, product flexibility are 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 pour point depression technique, i.e., by from adding
Extraction section reaction stream in the middle part of hydrogen reforming reactor combines the diesel raw material oil by hydro-upgrading and hydrodewaxing
Method flexibly produces the hydro-upgrading diesel product and hydrodewaxing diesel product of high quality.
A kind of method of flexible diesel oil hydrogenation modification pour point depression 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 changed by first plus hydrogen of hydro-upgrading reactor
Matter catalyst bed obtains the first hydro-upgrading logistics, this part reaction stream is divided into two parts, a portion extraction plus hydrogen
Reactor；
C, under the conditions of hydro-upgrading, the first hydro-upgrading logistics of remainder continues through hydro-upgrading reaction in step b
Second catalyst for hydro-upgrading bed of device, the second hydro-upgrading logistics are separated, are fractionated to obtain hydro-upgrading high pressure hydrogen rich gas
Body, hydro-upgrading gas products, hydro-upgrading naphtha product and hydro-upgrading diesel product；
D, under the conditions of hydrodewaxing, the first hydro-upgrading logistics extracted out obtained by step b passes through adding for hydrodewaxing reactor
Hydrogen pour point depression catalyst bed, hydrodewaxing logistics are separated, are fractionated to obtain hydrodewaxing high pressure hydrogen-rich gas, hydrodewaxing gas
Body, hydrodewaxing naphtha and hydrodewaxing diesel product.
Hydro-upgrading pour point depression technique according to the present invention, wherein can also include step e: the hydro-upgrading that step c is obtained
It is recycled after the hydrodewaxing high pressure hydrogen-rich gas mixing that 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 second plus hydrogen change
Matter catalyst bed can be set in a hydrogenator, such as can set gradually three in a hydro-upgrading reactor
A catalyst bed；Alternatively, Hydrobon catalyst bed is arranged in individual hydrogenator, and the first hydro-upgrading is urged
Agent bed and the second catalyst for hydro-upgrading bed are arranged in a hydro-upgrading reactor；Or hydrofinishing is urged
Agent bed and the first catalyst for hydro-upgrading bed are arranged in a hydro-upgrading reactor, and the second hydro-upgrading is catalyzed
Agent bed is arranged in another hydro-upgrading 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 hydro-upgrading reaction, 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；Extraction section
First hydro-upgrading logistics further reduced the condensation point of diesel oil after passing through hydrodewaxing catalyst, obtains Cetane number satisfaction and wants
It asks, but the diesel product of low condensation point.
Compared with prior art, the advantages of flexible diesel oil hydrogenation modification pour point depression technique of the invention, is:
1, in the present invention, hydro-upgrading reactive moieties include at least two catalyst for hydro-upgrading beds.Adding hydrogen by setting
Modification material extraction step among modifying catalyst bed is not necessarily to special operation, can be realized to hydro-upgrading material stock
Effectively distribution, then make obtained material by different hydrogenation techniques, so as to flexibly produce the purpose bavin of different size
Oil 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 among the modifying catalyst bed of hydro-upgrading reactor by being arranged the first hydro-upgrading logistics
Diesel raw material is extracted reactor by hydrofinishing and the first hydro-upgrading logistics of hydro-upgrading by withdrawing device, and will
It is respectively fed to the hydrodewaxing reactor being separately provided and carries out hydrodewaxing reaction, further decreases material after the hydro-upgrading
Condensation point 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 pour point depression is low, and Cetane number is relatively high；The high-quality of production different size can be met respectively
Measure the needs of diesel product.
4, in the present invention, the liquid itself obtained among catalyst for hydro-upgrading bed has very high temperature and pressure,
It, which can be directly entered in newly-installed hydrodewaxing reactor, is reacted, to make full use of this burst of partly upgraded material institute
The heat of carrying 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.It is provided with a hydrofining reactor, a hydro-upgrading is anti-
Answer device and a hydrodewaxing reactor；It include two catalyst for hydro-upgrading beds in hydro-upgrading reactor.
Wherein: 1- feedstock oil, 2- hydrofining reactor, 3- hydrotreated refinery stream, 4- hydro-upgrading reactor, 5- add hydrogen
Pour point depression feed stream, 6- hydro-upgrading logistics, 7- hydrodewaxing reactor, 8- hydro-upgrading high-pressure separator, 9- hydrodewaxing
High-pressure separator, 10- hydro-upgrading fractionating column, 11- hydrodewaxing fractionating column, 12- hydro-upgrading gas products, 13- add hydrogen to change
Matter naphtha product, 14- hydro-upgrading diesel product, 15- hydrodewaxing gas products, 16- hydrodewaxing naphtha product, 7-
Hydrodewaxing diesel product, 18- hydro-upgrading high-pressure separator gaseous product, 19- hydrodewaxing high-pressure separator gaseous product,
20- supplements 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.Hydrobon catalyst
Generally using VI B race and/or group VIII metal as active component, using aluminium oxide or silicon-containing alumina as carrier, group VIB metal one
As be Mo and/or W, group VIII metal is generally Co and/or Ni.With the poidometer of catalyst, group VIB tenor is to aoxidize
Object is calculated as 10wt%~35wt%, and group VIII metal content is calculated as 3wt%~15wt% with oxide, and property is as follows: specific surface is
100~650m20.15~0.6mL/g of/g, Kong Rongwei.Main catalyst has Fushun Petrochemical Research Institute to develop
The Hydrobon catalysts such as FH-5, FH-98,3936,3996, FHUDS series are also possible to the function of World Catalyst company exploitation
It can be similar to catalyst, such as HC-K, HC-P of Uop Inc., TK-555, TK-565 catalyst of Topsoe company and Akzo company
KF-847, KF-848 etc..Conventional operating condition, such as hydrogen partial pressure can be used in the operating condition of hydrofinishing in step a
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.
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 is one of aluminium oxide, silicon-containing alumina and molecular sieve or a variety of, preferably contains molecular sieve.
The molecular sieve can be Y type molecular sieve.With the poidometer of catalyst, group VIB tenor is calculated as 10wt% with oxide
~35wt%, group VIII metal content are calculated as 3wt%~15wt% with oxide, and molecular sieve content is 5wt%~40wt%, aluminium oxide
Content is 10wt%~80wt%, specific surface 100m2/ g~650m2/ g, Kong Rongwei 0.15mL/g~0.50mL/g.It is main
Catalyst has the 3963 of Fushun Petrochemical Research Institute's development, FC-18, FC-32 catalyst etc..Hydro-upgrading is catalyzed
For agent, it is desirable that there are certain hydrogenation activity and certain lytic activity, should guarantee alkene and aromatic hydrocarbons in diesel oil distillate plus hydrogen
The reaction of open loop occurs for saturation, the aromatic hydrocarbons after also requiring saturation.Conventional operating condition can be used in the operating condition of hydro-upgrading,
Generally 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.
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.
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 is one or more in aluminium oxide, silicon-containing alumina and molecular sieve, and preferably containing molecular sieve, the molecular sieve can
To select ZSM-5, ZSM-11, ZSM-22 or ZSM-35 type molecular sieve, preferably ZSM-5 molecular sieve.With the poidometer of catalyst, always
Tenor is calculated as 1wt%~20wt% with oxide, and molecular sieve content is 40wt%~85wt%, binder content be 10wt%~
40wt%.Main catalyst has the 3881 of Fushun Petrochemical Research Institute's development, FDW-1 catalyst etc..Hydrodewaxing
Conventional operating condition can be used in operating condition, generally are as follows: hydrogen partial pressure 3.0MPa~15.0MPa, reaction temperature be 300 DEG C~
440 DEG C, volume space velocity 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 carries out in fractionating column system, and low pressure liquid product is fractionated in fractionating column to be added
Hydrogen pour point depression naphtha product and hydrodewaxing diesel product.
Hydro-upgrading gas products described in step c and step d and hydrodewaxing gas products can be separately as productions
Product can also be mixed into mixed gas product.
Hydro-upgrading naphtha product described in step c and step d and hydrodewaxing naphtha product can individually be made
For 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
Hydrodewaxing feed stream 5 out, the logistics after extracting hydrodewaxing feed stream 5 out go successively to subsequent second hydro-upgrading and urge
Agent bed, hydro-upgrading generate logistics 6 and enter the progress gas-liquid separation of hydro-upgrading high-pressure separator 8, isolated liquid
Hydro-upgrading gas products 12, hydro-upgrading naphtha product 13 and hydro-upgrading diesel oil is obtained into fractionation in fractionating column 10 to produce
Product 14, hydrodewaxing feed stream 5 enter hydrodewaxing reactor 7, are flowed by the product of hydrodewaxing catalyst bed
Enter and carry out gas-liquid separation in hydrodewaxing high-pressure separator 9, isolated liquid enters fractionation in fractionating column 11 and obtains adding hydrogen
Pour point depression gas products 15, hydrodewaxing naphtha product 16 and hydrodewaxing diesel product 17,12 He of hydro-upgrading gas products
Hydrodewaxing gas products 15 can obtain mixed gas product, hydro-upgrading stone brain separately as product after can also mixing
Oil product 13 and hydrodewaxing naphtha product 16 can obtain mixing naphtha and produce separately as product after can also mixing
Product, the isolated gas 18 of hydro-upgrading high-pressure separator 8 and the isolated gas 19 of hydrodewaxing high-pressure separator 9 are mixed
It is mixed with supplement hydrogen 20 as recycle hydrogen after circulating hydrogen compressor after conjunction.
Illustrate technical solutions and effects of the present invention below by specific 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 3881 is Sinopec's share
The hydrodewaxing catalyst of Fushun Petrochemical Research Institute, Co., Ltd development and production, contains type ZSM 5 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 hydrogenation modifying process of the invention it can be seen from embodiment, by extracting one out out of hydro-upgrading reactor
Divide reaction stream, and realize the purpose of production heterogeneity diesel oil using catalyst for hydro-upgrading and hydrodewaxing catalyst,
Production method is flexible.And hydro-upgrading part carries out gradation by using the modifying catalyst of two kinds of different molecular sieve contents, it can
To increase the Cetane number of gained modification diesel oil, while increasing the production chains of this method.
Claims (16)
1. a kind of flexible diesel oil hydrogenation modification pour point depression 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 changed by first plus hydrogen of hydro-upgrading reactor
Matter catalyst bed obtains the first hydro-upgrading logistics, this part reaction stream is divided into two parts, a portion extraction plus hydrogen
Reactor；
C, under the conditions of hydro-upgrading, the first hydro-upgrading logistics of remainder continues through hydro-upgrading reaction in step b
Second catalyst for hydro-upgrading bed of device, the second hydro-upgrading logistics are separated, are fractionated to obtain hydro-upgrading high pressure hydrogen rich gas
Body, hydro-upgrading gas products, hydro-upgrading naphtha product and hydro-upgrading diesel product；
D, under the conditions of hydrodewaxing, the first hydro-upgrading logistics extracted out obtained by step b passes through adding for hydrodewaxing reactor
Hydrogen pour point depression catalyst bed, hydrodewaxing logistics are separated, are fractionated to obtain hydrodewaxing high pressure hydrogen-rich gas, hydrodewaxing gas
Body, hydrodewaxing naphtha and hydrodewaxing diesel product.
2. hydro-upgrading pour point depression technique described in accordance with the claim 1, which is characterized in that further include step e: step c is obtained
It is recycled after the hydrodewaxing high pressure hydrogen-rich gas mixing that hydro-upgrading high pressure hydrogen-rich gas and step d are obtained.
3. hydro-upgrading pour point depression 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. hydro-upgrading pour point depression 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, coker gas oil, catalytic diesel oil, hydroprocessed diesel, coal tar, coal direct liquefaction oil, ICL for Indirect Coal Liquefaction oil, shale oil etc.
One or more of the one group of substance constituted.
5. hydro-upgrading pour point depression technique described in accordance with the claim 1, which is characterized in that the catalysis of hydrofinishing described in step a
Agent 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 is 100~650m20.15~0.6mL/g of/g, Kong Rongwei.
6. hydro-upgrading pour point depression technique described in accordance with the claim 1, which is characterized in that the operating condition of step a are as follows: hydrogen partial pressure
For 3.0MPa~15.0MPa, reaction temperature is 300 DEG C~430 DEG C, and volume space velocity is 0.2h when liquid-1~6.0h-1, hydrogen oil volume
Than for 100:1~2000:1.
7. hydro-upgrading pour point depression technique described in accordance with the claim 1, which is characterized in that described in step b and step c plus hydrogen changes
Matter catalyst using group VIB and/or group VIII metal as active component, the carrier of catalyst be aluminium oxide, silicon-containing alumina and
It is one or more in molecular sieve.
8. hydro-upgrading pour point depression technique according to claim 7, which is characterized in that the carrier of catalyst for hydro-upgrading is oxygen
Change aluminium and molecular sieve；With the poidometer of catalyst, group VIB tenor is calculated as 10wt%~35wt%, the VIIIth race with oxide
Tenor is calculated as 3wt%~15wt% with oxide, and molecular sieve content is 5wt%~40wt%, alumina content be 10wt%~
80wt%, specific surface 100m2/ g~650m2/ g, Kong Rongwei 0.15mL/g~0.50mL/g.
9. hydro-upgrading pour point depression technique according to claim 8, which is characterized in that the first catalyst for hydro-upgrading bed makes
Catalyst is hydrogenation catalyst A, and the catalyst that the second catalyst for hydro-upgrading bed uses is hydrogenation catalyst B, described
The percentage composition x of molecular sieve in hydrogenation catalyst A1Lower than the percentage composition of the molecular sieve in the hydrogenation catalyst B
x2。
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. hydro-upgrading pour point depression technique described in accordance with the claim 1, which is characterized in that the condition of the hydro-upgrading are as follows: hydrogen
3.0MPa~15.0MPa is divided, reaction temperature is 300 DEG C~430 DEG C, volume space velocity 0.3h when liquid-1~15.0h-1, hydrogen oil body
Product is than being 100:1~2000:1.
12. hydro-upgrading pour point depression technique described in accordance with the claim 1, which is characterized in that the fraction of stream extracted out in step b with
The mass ratio that liquid phase meter accounts for feedstock oil is 5~95 wt%.
13. hydro-upgrading pour point depression technique described in accordance with the claim 1, which is characterized in that the fraction of stream extracted out in step b with
The mass ratio that liquid phase meter accounts for feedstock oil is 10~80 wt%.
14. hydro-upgrading pour point depression technique described in accordance with the claim 1, which is characterized in that the hydrodewaxing catalyst with
Group VIB and/or group VIII metal are active component, and the carrier of catalyst is aluminium oxide and/or silicon-containing alumina and molecular sieve,
The molecular sieve is ZSM-5, ZSM-11, ZSM-22 or ZSM-35 type molecular sieve.
15. hydro-upgrading pour point depression technique according to claim 14, which is characterized in that with the poidometer of catalyst, metal
Active component content is calculated as 1wt%~20wt% with oxide, and molecular sieve content is 40wt%~85wt%, and binder content is
10wt%~40wt%.
16. hydro-upgrading pour point depression technique described in accordance with the claim 1, which is characterized in that the Hydrobon catalyst bed
Layer, the first catalyst for hydro-upgrading bed and the second catalyst for hydro-upgrading bed are arranged in a hydrogenator；Alternatively,
Hydrobon catalyst bed is arranged in individual hydrogenator, and the first catalyst for hydro-upgrading bed and second plus hydrogen
Modifying catalyst bed is arranged in a hydro-upgrading reactor；Or Hydrobon catalyst bed and first adds hydrogen
Modifying catalyst bed is arranged in a hydro-upgrading reactor, and the second catalyst for hydro-upgrading bed is arranged at another
In hydro-upgrading reactor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103773488A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation method for reducing condensation point of diesel |
| 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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| 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 |
| CN103773488A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation method for reducing condensation point of diesel |
| 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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