CN107841333B - Method and corresponding crude oil for pour point depression of crude oil - Google Patents
Method and corresponding crude oil for pour point depression of crude oil Download PDFInfo
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- CN107841333B CN107841333B CN201711234668.2A CN201711234668A CN107841333B CN 107841333 B CN107841333 B CN 107841333B CN 201711234668 A CN201711234668 A CN 201711234668A CN 107841333 B CN107841333 B CN 107841333B
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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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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Abstract
The present invention relates to a kind of method for pour point depression of crude oil, the method includes: to make the thermal cracking of crude oil from oily phase transfer to intending in equal phase structure in the thermal cracking system using the methanol intervention crude oil of supercriticality；The thermal cracking trend of crude oil is controlled by kinetics, so that accelerating the C in crude oil under low temperature18~C30The alkyl of mixed alkanes is broken, and is inhibited the condensation reaction in thermal cracking, is realized the permanent reduction of condensation point of crude oil.The present invention also provides a kind of crude oil.Using in the invention for pour point depression of crude oil method and corresponding crude oil, by the either shallow thermal cracking for carrying out crude oil in supercritical methanol solvent, alkane component corresponding to selectivity fracture wax, to reduce the condensation point of crude oil permanently to save the cost of crude oil pipeline transport and subsequent processing；And since condensation reaction is inhibited, race's composition distribution of crude oil remains unchanged substantially.
Description
Technical field
The present invention relates to the technical field of crude oil more particularly to pour point depression of crude oil, in particular to a kind of for pour point depression of crude oil
Method and corresponding crude oil.
Background technique
C18~C30Linear paraffin, branched paraffin and belt length side chain monocyclic naphthenes mixture be known as paraffin, also referred to as
“C18~C30Mixed alkanes ".Solubility of the wax in crude oil declines with the reduction of temperature.Wax is brilliant under the conditions of certain temperature
It is precipitated and forms tridimensional network in crude oil, so that crude oil be made to lose flowability, temperature at this time is known as the solidification of crude oil
Point.Crude oil in China is largely high-content wax high freezing point oil, this brings difficulty to the exploitation of petroleum or pipeline.Change former
The mobility of oil, that is, the freezing point of reduction crude oil have become current important research topic.
The method that tradition reduces crude oil freezing point has physics pour point depression method, chemical pour-point depression method and chemical/physical pour point depression method.Physics
Method is mainly heat-treated, it inhibits the precipitation of wax crystalline substance in such a way that done site by site heats.Heat treatment method construction investment is high, fuel
Consumption is big, waste of energy, and (Xue Yi, Dou Dan different heating condition are to the Niger greatly for light fraction evaporation consumption in non-closed process
The influence Petroleum Engineering Construction 2015,41,66. of certain pour point depression of crude oil effect).Chemical method has emulsification pour point depression method, suspension conveying method
With pour-point depressant pour point depression method, the application of pour-point depressant pour point depression method is the most universal among these.This method is by changing the development course of wax crystalline substance, dividing
The crystal and obstruction of slack wax form reticular structure to reduce the condensation point of crude oil and viscosity, and then improve the mobile performance of crude oil
(Zhou Hao, Zhao Dezhi, Dai Yongchuan, Shi Weiwei grand celebration high-wax oil depression effeCt evaluate petrochemical industry Journal of Chinese Universities
2011,24,44；Li Weijia, Liangping, the Li Kehua high-wax oil chemical pour-point depression mechanism of action and influence factor Speciality Petrochemicals
Progress 2009,10,28；The synthesis of Li Kaixiang, Zhu Yugao crude oil with high solidifying point pour-point depressant and performance study present age chemical industry 2016,45,
2508).However, the crude oil to the carbon number distribution of high carbowax or wax compared with concentration, the sensitivity of pour-point depressant are poor.Also, depression effeCt
It is influenced simultaneously by wax content and crude oil race composition.The presence of above-mentioned factor brings the selection of pour-point depressant and depression effeCt
Adverse effect.
The presence of wax component is to cause the raised fundamental factor of condensation point of crude oil, if it is possible to destroy C18~C30Alkane mixing
The molecular structure of object, then the condensation point of crude oil irreversibly will be reduced permanently.Thermal cracking is to promote hydrocarbons structure that weight occurs
The effective ways of group.The cracking kinetics data reported according to document, petroleum mixture including crude oil and heavy oil
Thermal cracking mechanism can be found in Fig. 1.
As shown in Figure 1, the aliphatic chain (free or aromatic side chain) in hydrocarbon mixture is first under the conditions of lower temperature
The C-C key fracture of activation energy about 330kJ/mol first occurs.Being formed by fatty carbon radicals can be by other aliphatic chain
Take hydrogen by force and alkyl fracture is completed in β fracture (release light alkene).The either fracture of C-C or its subsequent reactions causes C18
~C30The diminution of aliphatic chain scale advantageously reduces condensation point (Pajak, J.Hydrogen the transfer from of crude oil
decalin to coal macerals.Fuel Process.Technol.1991,27,203；Sabbe,M.K.；
Vandeputte,A.G.； Reyniers,M.F.；Speybroeck,V.V.；Waroquier,M.；Marin,G.B.Ab
initio thermochemistry and kinetics for carbon-centered radical addition and
β-scission reactions.J.Phys.Chem.A 2007,111, 8416；Speybroeck,V.V.；Hemelsoet,
K.；Waroquier,M.；Marine,G.B.Reactivity and aromaticity of polyaromatics in
radical cyclization reactions.Int.J.Quantum Chem.2004,96,568；Hunter,K. C.；
East,A.L.L.Properties of C-C bonds in nalkanes:Relevance to cracking
mechanisms.J. Phys.Chem.A 2002,106,1346；Xiao,Y.T.；Longo,J.M.；Hieshima,G.B.；
Hill,R.J. Understanding the kinetics and mechanisms of hydrocarbon thermal
cracking:An ab initio approach.Ind.Eng.Chem.Res.1997,36,4033；Speybroeck,V.V.；
Neck,D.V.；Waroquier,M.S.； Saeys,W.M.；Marin,G.B.Ab initio study of radical
addition reactions:Addition of a primary ethylbenzene radical to ethene(I)
.J.Phys.Chem.A 2000,104,10939).At the same time, fatty carbon radicals can also be by taking hydrogen shape by force to aromatic ring
At aromatic carbon free radical.Aromatic carbon free radical is by coupling from each other, and the light alkene discharged with alkyl fracture process
Free radical addition, cyclisation and dehydrogenation complete condensation reaction (Leininger, J.P.； Minot,C.；Lorant,F.；Behar,
F.Density functional theory investigation of competitive free-Radical
processes during the thermal cracking of methylated polyaromatics:Estimation
of kinetic parameters.J.Phys.Chem.A 2007,111,3082；Hemelsoet,K.；Moran,D.；
Speybroeck,V. V.；Waroquier,M.；Radom,L.An assessment of theoretical procedures
for predicting the thermochemistry and kinetics of hydrogen abstraction by
methyl radical from benzene.J.Phys. Chem.A 2006,110,8942).Due to virtue required for being condensed
Carbon radicals and light alkene are broken dependent on alkyl, therefore condensation can regard the secondary counter of alkyl fracture as under cryogenic conditions
It answers.
Under the conditions of higher temperature, aromatic carbon free radical required for being condensed can pass through activation energy about 474kJ/mol's
Aromatic ring direct dehydrogenation and obtain.At this point, alkyl fracture and condensation reaction become reaction in parallel.And since Arrhenius is imitated
It answers, condensation reaction gradually occupies dominant advantage for being broken at high temperature with respect to alkyl.
For the either shallow thermal cracking for the purpose of pour point depression of crude oil, cracking should carry out at low temperature under ideal conditions.
On the one hand it can guarantee the preferential generation of alkyl fracture, on the other hand inhibit the progress of secondary condensation.However crude oil is at high temperature
Viscosity minimum also can only achieve 10-3P a · s .By the constraint that reaction system height glues, the fatty carbon generated by the fracture of C-C key
Free radical is easy to directly quench (Alomair, O. by situ couple；Elsharkawy,A.；Alkandari,H.A
viscosity prediction model for Kuwaiti heavy crude oils at elevated
temperatures.J Pet Sci Technol.2014,120,102).And subsequent fatty carbon radicals are to other aliphatic chains
The dynamics of bimolecular hydrogen abstraction reaction be similarly subjected to high viscous limitation.In order to which the alkyl for completing wax ingredient is disconnected under cryogenic conditions
It splits, cracking generally requires the reaction time extremely grown, and undesirable condensation secondary response will significantly occur in the process.Just because of
This, it then follows when conventional thermal cracking technique carries out pour point depression of crude oil, decline of the condensation point of crude oil in extremely limited range be in fact with
Oil product Fraction distribution becomes weight integrally as cost.
Summary of the invention
The purpose of the present invention is overcoming the above-mentioned prior art, crude oil can be selectively promoted by providing one kind
C preferentially occurs in thermal cracking process18~C30The alkyl fracture of mixed alkanes inhibits to be condensed and realize condensation point of crude oil and drop simultaneously
The low method for pour point depression of crude oil and corresponding crude oil.
To achieve the goals above, of the invention as follows for the method for pour point depression of crude oil and corresponding crude oil:
The present invention provides a kind of method for pour point depression of crude oil, the method includes:
Using supercriticality methanol intervention crude oil thermal cracking system in, make the thermal cracking of crude oil from oily phase transfer to
To intend in equal phase structure, the thermodynamic parameter of the methanol of the supercriticality includes: 370~400 DEG C of temperature, density 0.25~
0.30g/cm3；
The thermal cracking trend of crude oil is controlled by kinetics, so that accelerating the C in crude oil under low temperature18~C30Mix alkane
The alkyl of hydrocarbon is broken, and is inhibited the condensation reaction in thermal cracking, is realized the permanent reduction of condensation point of crude oil.
Preferably, the methanol of the supercriticality and the mass ratio of crude oil are 3:1~4:1 under normal temperature conditions.
Preferably, the thermal cracking time of the crude oil is 5~15min.
The present invention also provides a kind of method for pour point depression of crude oil, the method includes:
Methanol and crude oil is added；
High-purity N2Purging；
It heats up and stirs；
It keeps the temperature and stirs after being warming up to reaction temperature, it is anti-that the crude oil carries out thermal cracking in the methanol of supercriticality
It answers, the thermodynamic parameter of the methanol of the supercriticality includes: 370~400 DEG C of temperature, 0.25~0.30g/cm of density3；
Terminate reaction.
Preferably, the methanol of the supercriticality and the mass ratio of crude oil are 3:1~4:1 under normal temperature conditions；Institute
The addition volume of the methanol stated at normal temperature is the 30%~50% of reactor volume.
Preferably, the heat cracking reaction time of the crude oil is 5~15min.
Preferably, the method specifically includes:
Crude oil and methanol are added in the reactor；
Use high-purity N2Purging is with the air in metathesis reactor；
Closed reactor is started to warm up since room temperature with the rate of 10~15 DEG C/min, maintains stirring in the process；
5~15min is kept after reaching reaction temperature；
Air blast cooling mode terminates reaction.
Preferably, the method further include: clean reaction kettle as solvent using methylene chloride and collect product, the production
After object is generated without solid coke, evaporative removal methylene chloride then repeatedly extracts removal methanol, the original after obtaining pour point depression with water
Oil.
The present invention provides a kind of crude oil, the crude oil is the crude oil by the method treated pour point depression.
Preferably, the condensation point of the crude oil is between 6.5 DEG C~22.5 DEG C.
Using in the invention for pour point depression of crude oil method and corresponding crude oil, by supercritical methanol solvent
Carry out crude oil either shallow thermal cracking, selectivity be broken wax corresponding to alkane component, thus permanently reduce crude oil condensation point with
Save the cost of crude oil pipeline transport and subsequent processing；And since condensation reaction is inhibited, the race of crude oil forms distribution
Substantially it remains unchanged.
Detailed description of the invention
Fig. 1 is crude oil or heavy oil heat cracking reaction mechanism schematic diagram.
Fig. 2 is the general flow chart of the method for pour point depression of crude oil of the invention.
Specific embodiment
It is further to carry out combined with specific embodiments below in order to more clearly describe technology contents of the invention
Description.Method for pour point depression of crude oil of the invention, method described therein includes
Using supercriticality methanol intervention crude oil thermal cracking system in, make the thermal cracking of crude oil from oily phase transfer to
To intend in equal phase structure, the thermodynamic parameter of the methanol of the supercriticality includes: 370~400 DEG C of temperature, density 0.25~
0.30g/cm3；
The thermal cracking trend of crude oil is controlled by kinetics, so that accelerating the C in crude oil under low temperature18~C30Mix alkane
The alkyl of hydrocarbon is broken, and is inhibited the condensation reaction in thermal cracking, is realized the permanent reduction of condensation point of crude oil.
Wherein, the methanol of the supercriticality and the mass ratio of crude oil are 3:1~4:1 under normal temperature conditions；It is described
Crude oil the thermal cracking time be 5~25min, preferably 5~15min.
A kind of method for pour point depression of crude oil of the invention, as shown in Fig. 2, the method includes:
Methanol and crude oil is added；
High-purity N2Purging；
It heats up and stirs；
It keeps the temperature and stirs after being warming up to reaction temperature, it is anti-that the crude oil carries out thermal cracking in the methanol of supercriticality
It answers, the thermodynamic parameter of the methanol of the supercriticality includes: 370~400 DEG C of temperature, 0.25~0.30g/cm of density3；
Terminate reaction.
Wherein, the methanol of the supercriticality and the mass ratio of crude oil are 3:1~4:1 under normal temperature conditions；It is described
Methanol addition volume at normal temperature be the 30%~50% of reactor volume；The heat cracking reaction time of the crude oil is
5~15min.
Wherein, the method specifically includes:
Crude oil and methanol are added in the reactor；
Use high-purity N2Purging is with the air in metathesis reactor；
Closed reactor is started to warm up since room temperature with the rate of 10~15 DEG C/min, maintains stirring in the process；
5~15min is kept after reaching reaction temperature；
Air blast cooling mode terminates reaction.
Wherein, the method further include: reaction kettle is cleaned as solvent using methylene chloride and collects product, the product
After no solid coke generates, evaporative removal methylene chloride then repeatedly extracts removal methanol, the original after obtaining pour point depression with water
Oil.
The present invention provides a kind of crude oil, the crude oil is the crude oil by the method treated pour point depression.
Wherein, the condensation point of the crude oil is between 6.5 DEG C~22.5 DEG C.
Reaction based on supercritical methanol/crude oil mixed system phase structure and diffusional environment and cracking of crude oil is dynamic
Mechanical characteristics, the present invention provides a kind of methods that the intervention using supercritical methanol solvent carries out pour point depression of crude oil.
Major technique of the invention is according to as follows:
Certain thermodynamic state supercritical methanol (370~400 DEG C of temperature, 0.25~0.30g/cm of density3) intervention
May make cracking of crude oil system to enter, diffusional environment is superior to intend equal phase structure；
Since thermal cracking controls approach response dynamics Controlling, the raising of hydrocarbon radical reaction efficiency, so that low from diffusion
The lower crude oil institute content of wax ingredient (C of temperature18~C30Mixed alkanes) alkyl fracture can be rapidly completed；
Condensation reaction is the secondary response of alkyl fracture under low temperature, substantially foreshortens to 5~15min the time required to alkyl fracture
So that condensation reaction is effectively suppressed.
That is, it is right that selectivity is broken wax institute by the either shallow thermal cracking for carrying out crude oil in supercritical methanol solvent
The alkane component answered, to reduce the condensation point of crude oil permanently to save the cost of crude oil pipeline transport and subsequent processing；
Since condensation reaction is inhibited, race's composition distribution of crude oil remains unchanged substantially.
Method provided by the invention and product are specifically described below by way of two embodiments.
Embodiment 1:
Crude oil is produced as crude oil sample using the high condensation point China grand celebration of high wax, carries out pour point depression processing.
The fundamental property of crude oil is as shown in table 1:
1 Daqing crude oil fundamental property of table
The determination of freezing point establishing criteria SY/T 0541-2009 of crude oil and pour point depression product is implemented, and the measurement of race's composition is according to mark
Quasi- SY/T 5119-2016 is implemented, and the measurement establishing criteria SY/T 7550-2012 of wax content is implemented.
Specific implementation steps are as follows:
It is separately added into methanol and crude oil in a kettle；
Methanol additional amount is the 25% of reaction kettle volume, and the density of control methanol at reaction conditions is 0.25g/cm3, first
The mass ratio of pure and mild crude oil at normal temperature is 3:1；
Reaction kettle is closed after high pure nitrogen purges displaced air, then with the gradient increased temperature of 15 DEG C/min；
Stop heating after reaching predetermined cracking temperature reaction 15min, and reaction kettle is placed in terminate in air blast cooling and is reacted；
In preheating and thermal cracking process, speed of agitator maintains 800rpm always；
After the completion of cracking operation, reaction kettle is cleaned as solvent using methylene chloride and collects product, products therefrom is true through filtering
After recognizing no solid coke generation, methylene chloride is removed using rotary evaporation first, is then repeatedly extracted and is gone as extractant using water
Except solvent methanol, pour point depression crude oil is obtained.
Final gained pour point depression crude oil is for race's composition, condensation point, wax content analysis.
After reacting 15min under the conditions of cracking temperature is respectively 370,380,390 and 400 DEG C, the property of pour point depression product is such as
Shown in table 2.
Influence of 2 cracking temperature of table to pour point depression product fundamental property obtained by crude oil in supercritical methanol mild cracking
By data in table 2 as it can be seen that reaction temperature for pour point depression have significantly affect.
After mild cracking 15min under the conditions of 400 DEG C, the wax content in crude oil declines from raw material value 24.51wt%
To 17.42 wt%.The condensation point of crude oil drops to 6.5 DEG C from 28.4 DEG C after processing, and condensation point reduces amplitude and reaches 21.9 DEG C.
Embodiment 2:
Crude oil is equally produced as crude oil sample using the solidifying Chinese grand celebration of high wax height, carries out pour point depression processing.
The fundamental property of crude oil is as shown in table 1.
The measurement establishing criteria of the condensation point of crude oil and pour point depression product, race's composition and wax content is the same as example 1.
Specific implementation steps are as follows:
It is separately added into methanol and crude oil in a kettle；
Methanol additional amount is the 30% of reaction kettle volume, and the density of control methanol at reaction conditions is 0.30g/cm3, first
The mass ratio of pure and mild crude oil at normal temperature is 4:1；
Reaction kettle through high pure nitrogen purge displaced air after it is closed, then with the gradient increased temperature of 15 DEG C/min to 400 DEG C simultaneously
Start timing, stop heating immediately after reaching the setting reaction time, then is placed in terminate in air blast cooling by reaction kettle and react；
In preheating and cracking process, speed of agitator maintains 800rpm always；
After the completion of cracking operation, reaction kettle is cleaned as solvent using methylene chloride and collects product, products therefrom is true through filtering
After recognizing no solid coke generation, methylene chloride is removed using rotary evaporation first, is then repeatedly extracted and is gone as extractant using water
Except solvent methanol.Final gained pour point depression product is for race's composition, condensation point and wax content analysis.
After reaching 400 DEG C of reaction temperature 5,15 and 25min of reaction, the property of pour point depression product is as shown in table 3.
Influence of 3 reaction time of table to pour point depression product fundamental property obtained by crude oil in supercritical methanol mild cracking
By listed experimental result in table 3 as it can be seen that soaking periods equally with influence and have optimal value to depression effeCt.
Under supercritical methanol thermodynamic state and operating condition used by testing, reaction 15min can reach most
Excellent depression effeCt.
Using in the invention for pour point depression of crude oil method and corresponding crude oil, by supercritical methanol solvent
Carry out crude oil either shallow thermal cracking, selectivity be broken wax corresponding to alkane component, thus permanently reduce crude oil condensation point with
Save the cost of crude oil pipeline transport and subsequent processing；And since condensation reaction is inhibited, the race of crude oil forms distribution
Substantially it remains unchanged.
In this description, the present invention is described with reference to its specific embodiment.But it is clear that can still make
Various modifications and alterations are without departing from the spirit and scope of the invention.Therefore, the description and the appended drawings should be considered as illustrative
And not restrictive.
Claims (9)
1. a kind of method for pour point depression of crude oil, which is characterized in that the method includes:
In thermal cracking system using the methanol intervention crude oil of supercriticality, keep the thermal cracking of crude oil equal from oily phase transfer to intending
In phase structure, the thermodynamic parameter of the methanol of the supercriticality includes: 370~400 DEG C of temperature, and density 0.25~
0.30g/cm3, the methanol of the supercriticality and the mass ratio of crude oil are 3:1~4:1 under normal temperature conditions；
The thermal cracking trend of crude oil is controlled by kinetics, so that accelerating the C in crude oil under low temperature18~C30The alkane of mixed alkanes
Base fracture, inhibits the condensation reaction in thermal cracking, realizes the permanent reduction of condensation point of crude oil.
2. the method according to claim 1 for pour point depression of crude oil, which is characterized in that the thermal cracking time of the crude oil
For 5~15min.
3. a kind of method for pour point depression of crude oil, which is characterized in that the method includes:
Methanol and crude oil is added；
High-purity N2Purging；
It heats up and stirs；
It keeping the temperature and stirs after being warming up to reaction temperature, the crude oil carries out heat cracking reaction in the methanol of supercriticality,
The thermodynamic parameter of the methanol of the supercriticality includes: 370~400 DEG C of temperature, 0.25~0.30g/cm of density3；
Terminate reaction.
4. the method according to claim 3 for pour point depression of crude oil, which is characterized in that the methanol of the supercriticality
Mass ratio with crude oil is 3:1~4:1 under normal temperature conditions；The addition volume of the methanol at normal temperature is reactor volume
25%~30%.
5. the method according to claim 3 for pour point depression of crude oil, which is characterized in that the heat cracking reaction of the crude oil
Time is 5~15min.
6. the method according to claim 3 for pour point depression of crude oil, which is characterized in that the method specifically includes:
Crude oil and methanol are added in the reactor；
Use high-purity N2Purging is with the air in metathesis reactor；
Closed reactor is started to warm up since room temperature with the rate of 10~15 DEG C/min, maintains stirring in the process；
5~15min is kept after reaching reaction temperature；
Air blast cooling mode terminates reaction.
7. the method according to claim 3 for pour point depression of crude oil, which is characterized in that the method further include: with two
Chloromethanes is that solvent cleans reaction kettle and collects product, after the product is generated without solid coke, evaporative removal solvent dichloromethane
Alkane then repeatedly extracts removal methanol, the crude oil after obtaining pour point depression with water.
8. a kind of crude oil, which is characterized in that the crude oil is to pass through method according to any one of claim 1 to 7
The crude oil of treated pour point depression.
9. crude oil according to claim 8, which is characterized in that the condensation point of the crude oil between 6.5 DEG C~22.5 DEG C it
Between.
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| CN101077980A (en) * | 2006-05-26 | 2007-11-28 | 华东理工大学 | Method for preparing light oil from supercritical water modified vacuum residuum |
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| CN102676205A (en) * | 2012-05-29 | 2012-09-19 | 华东理工大学 | Method for improving thermal cracking of heavy oil in sub (ultra) critical water |
| CN205368255U (en) * | 2015-12-31 | 2016-07-06 | 中国石油天然气股份有限公司 | Semicontinuous device of mink cell focus lightization in overcritical solvent environment |
| CN106987265A (en) * | 2017-04-10 | 2017-07-28 | 华东理工大学 | The processing method of mink cell focus dehesion based on supercritical water |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9505678B2 (en) * | 2014-05-12 | 2016-11-29 | Saudi Arabian Oil Company | Process to produce aromatics from crude oil |
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2017
- 2017-11-30 CN CN201711234668.2A patent/CN107841333B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077980A (en) * | 2006-05-26 | 2007-11-28 | 华东理工大学 | Method for preparing light oil from supercritical water modified vacuum residuum |
| CN101935542A (en) * | 2010-09-15 | 2011-01-05 | 华东理工大学 | Heavy hydrocarbon modifying method |
| CN102676205A (en) * | 2012-05-29 | 2012-09-19 | 华东理工大学 | Method for improving thermal cracking of heavy oil in sub (ultra) critical water |
| CN205368255U (en) * | 2015-12-31 | 2016-07-06 | 中国石油天然气股份有限公司 | Semicontinuous device of mink cell focus lightization in overcritical solvent environment |
| CN106987265A (en) * | 2017-04-10 | 2017-07-28 | 华东理工大学 | The processing method of mink cell focus dehesion based on supercritical water |
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