CN108165309A - A kind of process of diesel oil high value added utilization - Google Patents
A kind of process of diesel oil high value added utilization Download PDFInfo
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- CN108165309A CN108165309A CN201711470143.9A CN201711470143A CN108165309A CN 108165309 A CN108165309 A CN 108165309A CN 201711470143 A CN201711470143 A CN 201711470143A CN 108165309 A CN108165309 A CN 108165309A
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- diesel oil
- oil
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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
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- 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
-
- 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
- C10G2400/18—Solvents
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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 present invention relates to a kind of processes of diesel oil high value added utilization.The method process includes：The cycloalkane dehydrogenation reactor equipped with dehydrogenation is initially entered after diesel oil and hydrogen mixing after hydrofinishing and carries out cycloalkane selective dehydrogenation reaction, dehydrogenation product obtains high cetane number diesel oil, heat conduction oil base oil, high fragrant solvent naphtha and high-purity hydrogen after Aromatics Extractive Project, rectifying.Present invention process method adaptability to raw material is strong, can handle the straight-run diesel oil after hydrofinishing, coker gas oil or catalytic cracking diesel oil one or more of mixed diesels therein.Dehydrogenation reaction occurs for the cycloalkane in the diesel oil after hydrofinishing, and the post-treated high-purity hydrogen for having obtained high value, high cetane number diesel oil, heat conduction oil base oil and Gao Fang solvent naphthas, the added value of raw material is improved while reducing diesel and gasoline ratio, realizes the high value added utilization of diesel oil.
Description
Technical field
The invention belongs to diesel oil processing and utilization fields, and in particular to a kind of process of diesel oil high value added utilization.
Background technology
Has there is the trend that heaviness and in poor quality are accelerated in international and national crude oil at present, and crude quality is caused to become
Difference, sulphur, nitrogen and arene content are higher in diesel oil, need to carry out hydrofinishing under relatively severe condition, which results in add hydrogen
Diesel oil naphthene content after refined is higher, Cetane number is low.And the diesel and gasoline ratio of China's consumption in recent years continues to decline, diesel oil is superfluous
Problem is further prominent, how to be transformed into the diesel oil of low value and is urgently solved as current Diesel Market with high value-added product
Certainly the problem of.
Most of utilization of diesel oil is concentrated on catalytic diesel oil at this stage, is mainly split by aromatic hydrogenation saturation plus hydrogen
The means Arene removals such as solution improve diesel quality, but there are limitations for both methods.Aromatic hydrogenation saturation is to improving diesel oil
Cetane number it is extremely limited, be generally only capable of 4~8 units of raising；Though hydrocracking can obtain high cetane number diesel oil, raw
Into small-molecule substance reduce production of diesel oil.The means product added value of above processing catalytic diesel oil is low, and cannot handle straight
Diesel oil and coker gas oil are evaporated, technological deficiency is apparent.
For conduction oil as a kind of excellent heat transfer medium, it is necessarily becoming for industrial technology development to substitute traditional mode of heating
Gesture.Its ideal composition is the high aromatic hydrocarbons of thermal stability, and thermal stability is improved with the increase of arene content.According to ingredient and system
Industrial process difference is made, conduction oil can be divided into synthesis type conduction oil and mineral type conduction oil.China is to the need of conduction oil at present
Continuous increase is asked, but heat conduction oil tech is still at an early stage, therefore most of there is still a need for import, conduction oil notch is larger.
Patent CN106398764A discloses a kind of diesel oil post-processing method, and raw material is catalytic cracking diesel oil, coking bavin
One or more of oil and straight-run diesel oil, are extracted the condensed-nuclei aromatics in diesel oil with polar solvent, obtained tapped oil
Hydrogenated cracking handles to obtain kerosene and naphtha；Refined diesel oil and small part vapour are obtained after hydrogenated refinement treatment of raffinating oil
Oil.The raw materials technology is adaptable, but energy consumption and hydrogen-consuming volume are big, complex process, and obtained diesel cetane-number is relatively low；
Patent CN103805247A discloses a kind of combined technical method for processing poor ignition quality fuel, and step is poor ignition quality fuel
Hydro-upgrading, arenes selectivity open loop are carried out first；Liquid product carries out Aromatics Extractive Project, and the aromatic component extracted enters catalysis
Cracker carries out catalytic cracking reaction, obtains gas, catalytic gasoline and catalytic diesel oil, catalytic diesel oil is recycled into plus hydrogen changes
Qualitative response device.The technique can maximumlly produce high-knock rating gasoline, can effectively reduce diesel and gasoline ratio, but technological process is answered
Miscellaneous, liquid receives relatively low, benefit unobvious；
Patent CN103214332A discloses a kind of side that light aromatics and high-quality oil product are produced by catalytic cracking diesel oil
Method, step are：Catalytic cracking diesel oil with extraction solvent is stripped, obtains being rich in the tapped oil of polycyclic aromatic hydrocarbon and rich in alkane
Hydrocarbon is raffinated oil；Tapped oil is subjected to hydrofinishing under hydrogenation conditions and is hydrocracked production light aromatics, higher octane
It is worth gasoline fraction.The catalytic cracking diesel oil of low value is converted into the light aromatics and high-octane rating of high value by the process
Gasoline realizes high value added utilization, but is only capable of processing catalytic cracking diesel oil, and hydrogen consumption is higher.
Straight-run diesel oil, coker gas oil and catalytic cracking diesel oil common feature after hydrofinishing are naphthene content height, ten
Six alkane values are low, can only be handled at present by overhydrocracking technique, and energy consumption and hydrogen consume higher, complex process, and effect is not
It is preferable.If by dehydrogenating technology, the cycloalkane selective dehydrogenation in hydrofining diesel oil is generated into aromatic hydrocarbons, by post-processing
To heat conduction oil base oil and high cetane number diesel oil, and a large amount of high-purity hydrogens of by-product, then for diesel oil processing open one it is new
Approach.
Invention content
The technical problems to be solved by the invention are that overcome the deficiencies of the prior art and provide a kind of hydrofining diesel oil height attached
The value added process utilized.
In order to solve the above technical problems, the present invention provides a kind of processes of diesel oil high value added utilization.This method
Diesel oil after middle hydrofinishing carries out cycloalkane in a hydrogen atmosphere first by being equipped with the dehydrogenation reactor of noble metal catalyst
Selective dehydrogenation reacts, and the liquid product after dehydrogenation enters Aromatics Extractive Project unit, and output of raffinating oil, tapped oil enters rectifying list
Member, the final purpose for realizing production heat conduction oil base oil co-production high cetane number diesel oil.Specifically comprise the following steps：
(1) enter heat exchanger after the diesel raw material after hydrofinishing and hydrogen mixing, enter ring after exchanging heat with dehydrogenation product
Dehydrating alkanes reactor, under the action of dehydrogenation, initial ring paraffin selectivity dehydrogenation reaction obtains dehydrogenation product, reaction
Condition is as follows：420~500 DEG C of reactor temperature, reaction pressure are 2~6MPa, hydrocarbon raw material weight (hourly) space velocity (WHSV) is 0.5~3h-1、
Hydrogen hydrocarbon volume ratio is 500:1~1000~1；Preferred reaction conditions are as follows：430~450 DEG C of reactor temperature, reaction pressure are
3~5MPa, hydrocarbon raw material weight (hourly) space velocity (WHSV) are 1~2h-1, hydrogen hydrocarbon volume ratio be 600:1~800~1；
(2) dehydrogenation product of step (1) carries out gas-liquid phase separation through hp flash drum and stabilizer respectively, wherein, high pressure
Flash tank gas-phase product part is used as recycle hydrogen, and partly as periodic off-gases, liquid product enters stabilizer, top gaseous phase production
Object liquefied gas speeds to put, and bottom of towe liquid product enters Aromatics Extractive Project unit and carries out Aromatics Extractive Project, and solvent is furfural, and overhead product is height
Cetane number diesel oil, tower bottom product are arene content>90% BTX aromatics；
(3) tower bottom product of step (2) enters rectification cell and is cut, the high fragrant solvent naphtha of overhead extraction, side take-off
Heat conduction oil base oil, the bottomsstream are a small amount of kettle raffinate.
The process of diesel oil high value added utilization according to the present invention, the diesel oil are straight after hydrofinishing
Evaporate one or more of diesel oil, coker gas oil and catalytic cracking diesel oil；
The process of diesel oil high value added utilization according to the present invention, the fore-running of the heat conduction oil base oil
Point：280~290 DEG C, the end point of distillation：Density at 346~356 DEG C, 20 DEG C：0.92~1.01g/cm3, open flash point 165~176
DEG C, kinematic viscosity at 40 DEG C：8~11mm2/ s, acid value：<0.01mg KOH/g, condensation point：<-30℃.
Present invention process method has the following advantages compared with prior art：(1) adaptability to raw material is strong, can handle plus hydrogen is smart
Straight-run diesel oil, coker gas oil or catalytic cracking diesel oil one or more of mixed diesels therein after system；(2) diesel oil is realized
High value added utilization.By to the diesel oil middle ring paraffin selectivity dehydrogenation reaction after hydrofinishing, and pass through post processing and obtain
The high-purity hydrogen of high value, high cetane number diesel oil (improving 5~20 units compared with raw material Cetane number), heat conduction oil base oil and
High virtue solvent naphtha, improves the added value of raw material while reducing diesel and gasoline ratio, new technology is provided for diesel oil comprehensive utilization
Support.
Description of the drawings
Fig. 1 is the process flow chart of the process of diesel oil high value added utilization of the present invention.
In figure：1st, the diesel oil after hydrofinishing；2nd, new hydrogen；3rd, raw material pumps；4th, heat exchanger；5th, heating furnace；6th, recycle hydrogen pressure
Contracting machine；7th, dehydrogenation reactor；8th, hp flash drum；9th, high-purity hydrogen；10th, stabilizer；11st, liquefied gas；12nd, furfural；13rd, aromatic hydrocarbons
Extraction unit；14th, high cetane number diesel oil；15th, rectification cell；16th, high fragrant solvent naphtha；17th, heat conduction oil base oil；18th, kettle is residual
Liquid
Specific embodiment
Further technical scheme of the present invention is further illustrated with reference to the accompanying drawings and embodiments.
As shown in Figure 1, diesel raw material 1 after hydrofinishing after heat exchanger 4 and dehydrogenation product heat exchange with new hydrogen and cycle
Hydrogen 2 mixes, and heated stove 5 enters dehydrogenation reactor 7 after heating and carries out cycloalkane selective dehydrogenation reaction.Dehydrogenation product is through heat exchange
Enter hp flash drum 7 after device 4 and raw material heat exchange and carry out gas-liquid separation, a gas phase part is mixed through circulating hydrogen compressor 6 and new hydrogen
Enter dehydrogenation reactor after conjunction, a part of high-purity hydrogen 9 exports.Liquid phase enters stabilizer by bottom of towe, and gas phase condensation gas 11 speeds to put,
Liquid phase enters Aromatics Extractive Project unit 13 and carries out Aromatics Extractive Project, and solvent furfural 12 is entered by tower top, raffinated oil as high cetane number bavin
Oil 14, tapped oil enters rectification cell 15 and is cut, the high fragrant solvent naphtha 16 of overhead extraction, side take-off heat conduction oil base oil
17, bottom of towe produces a small amount of kettle raffinate 18.
Examples 1 to 4
Cycloalkane dehydrogenation reactor described in the process is fixed bed reactors.Wherein, cycloalkane catalysis dehydrogenation
Agent is the aluminium oxide catalyst of noble-metal-supported.Reactor feed is upper entering and lower leaving, and gas-phase product group is analyzed using chromatography of gases
Into using chromatograph-mas spectrometer analysis product liquid composition.
Hydrofining diesel oil raw material composition and evaluation result are shown in Table 1 and table 2. respectively used in Examples 1 to 4
The diesel raw material property of 1 hydrofinishing of table
2 technology assessment condition of table and result
From Examples 1 to 4 as can be seen that the process of diesel oil high value added utilization of the present invention, passes through dehydrogenation
Low value is effectively added hydrogen by reaction treatment hydrofining diesel oil, the selective cycloalkanes by diesel oil into aromatic hydrocarbons
Refined diesel oil is transformed into heat conduction oil base oil, high cetane number diesel oil and the high-purity hydrogen of high added value, and product yield is high, work
Skill flow is simple, and benefit is apparent, realizes the high value added utilization of diesel oil.
Claims (4)
1. a kind of process of diesel oil high value added utilization, it is characterised in that：Include the following steps：
(1) enter heat exchanger after the diesel raw material after hydrofinishing and hydrogen mixing, enter cycloalkane after exchanging heat with dehydrogenation product
Dehydrogenation reactor, under the action of dehydrogenation, initial ring paraffin selectivity dehydrogenation reaction obtains dehydrogenation product；Cycloalkane selects
The reaction condition of selecting property dehydrogenation reaction is as follows：420~500 DEG C of reactor temperature, reaction pressure are 2~6MPa, hydrocarbon raw material
Weight (hourly) space velocity (WHSV) is 0.5~3h-1, hydrogen hydrocarbon volume ratio be 500:1~1000~1；
(2) dehydrogenation product of step (1) carries out gas-liquid phase separation through hp flash drum and stabilizer respectively, wherein, high pressure flash
Tank gas-phase product part is used as recycle hydrogen, and partly as periodic off-gases, liquid product enters stabilizer, top gaseous phase product liquid
Change gas to speed to put, bottom of towe liquid product enters Aromatics Extractive Project unit and carries out Aromatics Extractive Project, and solvent is furfural, and overhead product is high by 16
Alkane value diesel oil, tower bottom product are arene content>90% BTX aromatics；
(3) tower bottom product of step (2) enters rectification cell and is cut, the high fragrant solvent naphtha of overhead extraction, side take-off heat conduction
Oil base oil, the bottomsstream are a small amount of kettle raffinate.
2. the process of diesel oil high value added utilization described in accordance with the claim 1, it is characterised in that：The cycloalkane choosing
The reaction condition of selecting property dehydrogenation reaction is：430~450 DEG C of reactor temperature, reaction pressure are 3~5MPa, hydrocarbon raw material weight
When air speed be 1~2h-1, hydrogen hydrocarbon volume ratio be 600:1~800~1.
3. the process of diesel oil high value added utilization described in accordance with the claim 1, it is characterised in that：Wherein step (1) institute
The diesel oil stated is one or more of straight-run diesel oil, coker gas oil and catalytic cracking diesel oil.
4. the process of diesel oil high value added utilization described in accordance with the claim 1, it is characterised in that：The heat conduction oil base
The physical data of plinth oil is as follows：Initial boiling point：280~290 DEG C, the end point of distillation：346~356 DEG C, 165~176 DEG C of open flash point, 40
DEG C when kinematic viscosity：8~11mm2/ s, acid value：<0.1mg KOH/g.
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| CN201711470143.9A CN108165309A (en) | 2017-12-29 | 2017-12-29 | A kind of process of diesel oil high value added utilization |
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| CN201711470143.9A CN108165309A (en) | 2017-12-29 | 2017-12-29 | A kind of process of diesel oil high value added utilization |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4676885A (en) * | 1986-05-28 | 1987-06-30 | Shell Oil Company | Selective process for the upgrading of distillate transportation fuel |
| CN106047404A (en) * | 2016-07-08 | 2016-10-26 | 中海油天津化工研究设计院有限公司 | Combined technique for improving yield of high-octane gasoline by using inferior catalytic cracking diesel |
| CN107163984A (en) * | 2017-06-19 | 2017-09-15 | 中海油天津化工研究设计院有限公司 | A kind of method that poor ignition quality fuel produces high-knock rating gasoline |
| CN107189816A (en) * | 2017-06-19 | 2017-09-22 | 中海油天津化工研究设计院有限公司 | It is a kind of that the combined technical method for producing light aromatics is maximized by hydrogenated diesel oil |
-
2017
- 2017-12-29 CN CN201711470143.9A patent/CN108165309A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4676885A (en) * | 1986-05-28 | 1987-06-30 | Shell Oil Company | Selective process for the upgrading of distillate transportation fuel |
| CN106047404A (en) * | 2016-07-08 | 2016-10-26 | 中海油天津化工研究设计院有限公司 | Combined technique for improving yield of high-octane gasoline by using inferior catalytic cracking diesel |
| CN107163984A (en) * | 2017-06-19 | 2017-09-15 | 中海油天津化工研究设计院有限公司 | A kind of method that poor ignition quality fuel produces high-knock rating gasoline |
| CN107189816A (en) * | 2017-06-19 | 2017-09-22 | 中海油天津化工研究设计院有限公司 | It is a kind of that the combined technical method for producing light aromatics is maximized by hydrogenated diesel oil |
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Application publication date: 20180615 |