CN105132014A - Method for applying multiple biological active agents to desulfurization of coking diesel oil - Google Patents
Method for applying multiple biological active agents to desulfurization of coking diesel oil Download PDFInfo
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Abstract
The invention discloses a method for applying multiple biological active agents to desulfurization of coking diesel oil. The method comprises steps as follows: (1), choline inositol composite powder or choline inositol composite pieces are added to the coking diesel oil, the mixture is heated and stirred by a magnetic stirring apparatus and react for 60-100 min, and coking diesel oil is taken out and cooled to the room temperature; (2), insulin is added to the coking diesel oil, and then the coking diesel oil is placed in a constant-temperature water bath environment and is heated and stirred at constant temperature; (3), a cholic acid active agent is added to the coking diesel oil, and the coking diesel oil is placed in the constant-temperature water bath environment and is heated and stirred at the constant temperature for 1-24 h; (4), a catalyst and an oxidizing agent are added to the coking diesel oil successively, and the coking diesel oil, the catalyst and the oxidizing agent have a catalytic oxidation reaction for 50-100 min; (5), an extraction agent is added in a volume ratio of the extraction agent to the coking diesel oil being 1:1, the mixture is stirred by the magnetic stirring apparatus for 5-10 min, poured into a separating funnel and left to stand for 20 min, and a diesel oil layer is collected. According to desulfurization refining with the method, the reaction conditions are mild, environmental protection is realized, the desulfurization rate is high, and the coking diesel oil has remarkable yield and is light in color and smell.
Description
Technical field
The present invention relates to a kind of coker gas oil desulfurization technology, be specifically related to the method for the coker gas oil desulfurization of high desulfurization rate.
Background technology
Along with the enhancing of people's environmental consciousness, people are increasingly strict to sulfur content of fuel oil standard-required, and comparatively strict new regulation has all been formulated for the sulphur content in oil fuel in countries in the world.U.S.'s regulation diesel oil sulphur content in 2006 reduces to 15 μ g/g by 500 μ g/g; And the Europe V standard of sulphur content 10 μ g/g has been implemented in Europe in 2009; Japan is the advanced country producing clean gasoline, performed JISK2202 gasoline standard regulation, and within 2005, Japanese gasoline standard restriction sulphur content is 50ppm, and national sulphur content of seeking unity of action was the super low-sulfur oil standard of 10ppm in 2009.In China, derv fuel oil and gasoline implemented integrally European quality standard in 1 day July in 2005, and 2010 all up to standard, and the sulphur content in regulation gasoline is less than 150 μ g/g, and the sulphur content in diesel oil is less than 350 μ g/g.Some line cities such as Beijing, Shanghai, Guangzhou perform Europe superscript accurate IV, and the sulphur content in regulation gasoline and diesel oil is less than 50 μ g/g.And at present, sulphur content index limits is reduced to 10ppm by the 50ppm of fourth stage by up-to-date " state five " standard, reduces 80%, implement in Beijing and Shanghai at present, before the end of the year 2017, whole nation supply meets automobile-used vapour, the diesel oil of " state five " standard.Therefore, domestic vehicle fuel will enter sulphur content and be less than the low-sulfur epoch of 50 μ g/g.In the face of increasingly strict sulfur content of fuel oil standard and market to the great demand of low-sulfur clean fuel oil, various countries are caused to be devoted to the research of various desulfurization technology one after another.
Along with deepening continuously of Petroleum Processing Technology, an important deep processing method of residual oil carries out coking, mainly contains autoclave coking and delayed coking two kinds at present.Coker gas oil is the product that residual oil obtains through coking.Coker gas oil occupies sizable ratio in the finished diesel fuel output of China, accounts for 10% of solar oil output.Second-rate without refining coker gas oil, containing non-hydrocarbon compounds such as a large amount of unsaturated hydrocarbons, more sulphur, nitrogen, oxygen, not only black but also smelly, and the stability of diesel oil is poor, gum level is high, colourity and insolubles content higher.A large amount of analysis and research show, the sulfocompound in coker gas oil mainly contains elementary sulfur, hydrogen sulfide, mercaptan, thioether, thiophene, thionaphthene (BT), dibenzothiophene (DBT) etc.Wherein, thiophene sulphur compound accounts for more than 85% of coker gas oil total sulfur, and BT and DBT accounts for more than 70% of thiophene-based.Therefore, that studies thiophene-type sulfide removes the emphasis becoming desulfurizing oil.Wherein elementary sulfur, hydrogen sulfide, mercaptan isoreactivity sulphur compound, have stronger corrosion failure effect to refining equipment.Elementary sulfur is a kind of fusing point 113 DEG C, water insoluble and be dissolved in the solid of organic solvent, has good dissolving power in the oil, but temperature higher than 115 DEG C time, can with some hydrocarbon reaction, generate new sulfide and hydrogen sulfide; Hydrogen sulfide is colourless and has the gas of rotten egg smell, and severe toxicity, slightly water-soluble, be soluble in oil product, have very strong reducing power and corrosive power, the hydrosulphuric acid formed in water is weak diprotic acid.Mercaptan comprises alkyl sulfhydryl, cycloalkyl mercaptan and aryl mercaptan, boiling point and water-soluble ratio low with the alcohol of carbon number, be soluble in ethanol and ether.Mercaptan is except there being disgusting foul smell, or a kind of oxidation inducer, makes the unstable component accelerated oxidation in gasoline and generates colloid, thus quality of gasoline is deteriorated.Although the inactive sulfur such as thioether and thiophene compound is lower to refining equipment corrosion, the very strong material of corrodibility can be generated in combustion.The feature of disulphide and polysulfide is that chemically reactive constantly increases along with the increase stability of number of sulfur atoms constantly declines.When number of sulfur atoms is greater than more than 3, its character is close with elementary sulfur.Heat is easily decomposed into thioether, elemental sulfur, mercaptan and alkene.The direct use of these diesel oil, does not only meet China to the sulphur content regulation in oil fuel, and serious environment pollution, the serious threat mankind's is healthy.Therefore, coker gas oil can use after must refining.
At present, the desulfurization technology of domestic and international oil fuel is mainly divided into hydrogenating desulfurization technology and the large class of non-hydrodesulfurization two.Hydrogenating desulfurization technology produces low-sulfur diesel-oil, and significantly can reduce coker gas oil sulphur, nitrogen and colloid equal size, sweetening effectiveness is good, obtains the fine-quality diesel oil meeting national standard; But large owing to investing, tooling cost high (180 yuan/t), is used widely for general in Large-scale Refinery, and middle-size and small-size refinery not only limited fund, moreover hydrogen source is not enough, limits the application of the method at middle-size and small-size refinery.
Non-hydrodesulfurizationof of Diesel Fuel Refining mainly comprises adsorption desulfurize, abstraction desulfurization, complexing desulfurization, biological desulphurization, oxidation sweetening etc.The fuel oil of traditional acid-alkali refining method process is difficult to reach new low sulphur specifications, moreover technique itself also exists the problems such as pollution, seriously corroded.Because the problem of biological process desulfurization technology in desulfurization rate and stability is not solved preferably, so biological process desulfurization also fails to embody its clear superiority; Catalytic oxidation desulfurization technology is lower because of the gentle production cost of its operational condition, is subject to very much the welcome of middle-size and small-size refinery.Therefore, carry out the research of coker gas oil Desulfurization Technology, a kind of method developing non-hydrogenation desulfuration purification coker gas oil is newly imperative.
Wherein, oxidation sweetening (ODS) technology reaction conditions is gentle, technique is simple, non-hydrogen operates, process cost is low, safety and environmental protection, facility investment is few, also higher desulfuration efficiency is had to the oil-source rock correlation that shortening is difficult to remove, the requirement of ultra-deep desulfurization can be reached, thus oxidation style is called as green desulfurization technique geared to the 21st century, become a new study hotspot in recent years.Oxidation sweetening refers under strong oxidizer effect, the thioether that oil product Semi-polarity is lower and thiophene sulfocompounds are oxidized to the higher sulfoxide of polarity and sulfone compound, these sulfide absorbs Sauerstoffatom and adds moment of dipole, thus add the solvability in polar solvent, be removed by solvent extraction again, to reach desulfurization object.At present, selective oxidation desulfurization technology is gentle with its processing condition, and the features such as sweetening effectiveness is obvious, receive the very big concern of oil refining industry.
Oxygenant used at present in the catalytic oxidation process of coker gas oil mainly contains hydrogen peroxide, O
3, air, oil insoluble oxidation agent etc.; Organic acid, inorganic heteropolyacid, light or metal oxide etc. is used to be catalyzer; In order to improve desulfuration efficiency, also carry out oxidation sweetening in conjunction with some supplementary meanss, as ultrasound oxidation technology method, plasma oxidation etc.In the process that the sulfone and sulfoxide of sulfide in diesel oil through being oxidized generation are removed by extraction, conventional extraction agent mainly contains methyl-sulphoxide, acetonitrile, N-Methyl pyrrolidone (NMP), N, dinethylformamide (DMF), furfural, Nitromethane 99Min., quadrol etc., research shows these organic solvents and sulfone class polar phase seemingly, can well by the sulfone class extracting and separating in diesel oil after oxidation out.The oxidative desulfurization techniques of extensively research both at home and abroad mainly comprises hydrogen peroxide oxidation desulfurization, Oxygen Catalytic Oxidation desulfurization, ultrasound oxidation technology desulfurization and Photochemical Oxidative Desulfurization of Fluidized etc., wherein because of H at present
2o
2have that oxidisability is strong, oxygenolysis thing receives much concern without advantages such as harm to environment, apply wider in oxidation sweetening is studied.
In recent years, Non-hydrogenation Desulfurization Technique of Fuel Oil develops rapidly, the method is under the condition of catalyzer, and the thioether in oxidation removal coker gas oil, mercaptan and thiophene sulfides, produce excellent sweetening effectiveness, thus reach decolouring, deodorization, de-slag, thus improve the object of diesel oil stability, in addition gentle operational condition, low production cost, environmentally friendly production process, more and more by the concern of being domestic and international investigator.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of desulfuration purification reaction conditions gentleness, environmental protection, desulfurization degree are high, coker gas oil yield significantly and the light multiple biologically active agent of look shallow taste is applied to the method for coker gas oil desulfurization.
The present invention adopts following technical scheme to solve the problems of the technologies described above:
Multiple biologically active agent is applied to the method for coker gas oil desulfurization, comprises the following steps:
(1), pre-treatment: choline inositol composite powder or composite sheet are added in coker gas oil by 0.04-0.1g/ml, in choline inositol composite powder or composite sheet, choline and inositol mass ratio respectively account for 50%, heat with magnetic stirring apparatus and stir, temperature is 36 DEG C-38 DEG C, mixing speed is 20rpm, reaction 1-24 hour;
(2), by 0.05-1.0mg/ml, Cholic acids promoting agent is added in the coker gas oil of step (1) gained, then be placed in water bath with thermostatic control environment thermostatically heating to stir, Heating temperature is 36.5 DEG C-38 DEG C, reacting by heating 1-24 hour, and mixing speed is 20-40rpm;
(3), Regular Insulin add in the coker gas oil of step (2) gained, be then placed in water bath with thermostatic control environment thermostatically heating and stir, Heating temperature is 36.5-38 DEG C, reacting by heating 1-24 hour, and mixing speed is 20-40rpm; Described Regular Insulin is powder ampoule agent for injection Regular Insulin or injection shape Regular Insulin, and the addition of powder ampoule agent for injection Regular Insulin is 0.01-0.10mg/ml; The volume ratio of injection shape Regular Insulin and coker gas oil is 2: 100-5: 100;
(4), catalyzer and oxygenant successively add in the coker gas oil after step (3) process, catalyzer is trichoroacetic acid(TCA) or formic acid, oxygenant to be mass concentration be 30% superoxol; The volume ratio of coker gas oil, catalyzer and oxygenant is 10: 2: 1-10: 4: 4, in magnetic stirring apparatus, carry out catalytic oxidation, and the reaction times is 50-100min, and temperature is 50 DEG C-80 DEG C, and stirring velocity is 40rpm;
(5) add extraction agent at 1: 1, by volume, extraction agent is DMF or furfural, uses magnetic stirrer 5-10min, and stirring velocity is 40rpm, then pours separating funnel into, leaves standstill 20min, collects diesel oil layer.
Cholic acids activator in described step (2) is cholic acid, cholate, deoxycholate, Ursodeoxycholic Acid Tablets, ursodesoxycholic acid capsule, ursodesoxycholic acid soft capsule, Septochol, Hyodeoxycholic Acid or glycocholic acid.
Choline in described choline inositol composite powder or composite sheet also can be choline chloride 60.
The water bath with thermostatic control environment of described step (2) and step (3) all adopts water bath with thermostatic control magnetic stirring apparatus, and power is 40w.
Compared with prior art, the invention has the advantages that:
1, technical process is simple, and operation is simple;
2, the method is applied to coker gas oil desulfuration purification reaction conditions gentleness, environmental protection, and sweetening effectiveness is obvious, and as clear as crystal light yellow diesel yield is remarkable.
Embodiment
Below in conjunction with embodiment to the detailed description of the invention, but do not form the restriction to the claims in the present invention protection domain.
Embodiment 1:
Weighing 0.4g choline inositol composite powder adds in 10ml coker gas oil, in choline inositol composite powder, choline and inositol mass ratio respectively account for 50%, put into beaker together, be placed in DF-101S instant-heating-type constant-temperature heating magnetic stirring apparatus, temperature is 36 DEG C, mixing speed is 20rpm, reacts and carries out pre-treatment in 1 hour.Under normal temperature, Regular Insulin is added in above-mentioned coker gas oil, Regular Insulin is powder ampoule agent for injection Regular Insulin, its addition is 0.01mg/ml, then be placed in water bath with thermostatic control environment thermostatically heating to stir, Heating temperature is 36.5 DEG C, reacting by heating 1 hour, the power of the magnetic stirring apparatus of constant temperature is 40w, and rotating speed is 20-40rpm; By 0.05mg/ml, cholic acid is added in above-mentioned coker gas oil under normal temperature, be then placed in water bath with thermostatic control environment thermostatically heating and stir, Heating temperature is 36.5 DEG C, reacting by heating 1 hour, water bath with thermostatic control environment all adopts water bath with thermostatic control magnetic stirring apparatus, and power is 40w, and rotating speed is 20rpm; Catalyzer and oxygenant are successively added in gained coker gas oil, and catalyzer is trichoroacetic acid(TCA), oxygenant to be mass concentration be 30% superoxol; Coker gas oil, catalyzer and oxygenant volume ratio are 10: 2: 1, then carry out catalytic oxidation in DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus, and the reaction times is 50min, and Heating temperature is 50 DEG C, and stirring velocity is 40rpm; Then, coker gas oil is taken out, after being cooled to room temperature, add extraction agent DMF again, the volume ratio of extraction agent and coker gas oil is 1: 1, use magnetic stirrer 5min again, stirring velocity is 40rpm, then pours separating funnel into, leave standstill 20min, collect diesel oil layer, and measure its volume, obtain diesel yield, it is 0.00513% that the diesel oil Sinie7039XR Single wavelength X-fluorescence sulphur content analyzer of collection is recorded sulphur content, and abstraction desulfurization rate is 98.18%, and diesel yield is 81%.
Embodiment 2:
Weighing 0.6g choline inositol composite sheet adds in 10ml coker gas oil, in composite sheet, choline or choline chloride 60 and inositol mass ratio respectively account for 50%, put into beaker together, be placed in DF-101S instant-heating-type constant-temperature heating magnetic stirring apparatus, temperature is 37 DEG C, mixing speed is 20rpm, reacts and carries out pre-treatment in 8 hours.Under normal temperature, Regular Insulin is added in above-mentioned coker gas oil, Regular Insulin is injection shape Regular Insulin, the volume ratio of Regular Insulin and coker gas oil is 3: 100, then be placed in water bath with thermostatic control environment thermostatically heating to stir, Heating temperature is 37 DEG C, reacting by heating 15 hours, the power of the magnetic stirring apparatus of constant temperature is 40w, and rotating speed is 30rpm; By 0.5mg/ml, Sodium cholic acid is added in coker gas oil under normal temperature, be then placed in water bath with thermostatic control environment thermostatically heating and stir, Heating temperature is 37 DEG C, reacting by heating 15 hours, water bath with thermostatic control environment all adopts water bath with thermostatic control magnetic stirring apparatus, and power is 40w, and rotating speed is 30rpm; Catalyzer and oxygenant are successively added in above-mentioned coker gas oil, and catalyzer is formic acid, oxygenant to be mass concentration be 30% superoxol; Coker gas oil, catalyzer and oxygenant volume ratio are 10: 2.5: 2, and be placed in DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus and carry out catalytic oxidation, the reaction times is 70min, and Heating temperature is 60 DEG C, and stirring velocity is 40rpm; Then, coker gas oil is taken out, after being cooled to room temperature, add extraction agent furfural again, the volume ratio of extraction agent and coker gas oil is 1: 1, then uses magnetic stirrer 7min, stirring velocity, for 40rpm pours separating funnel into again, leaves standstill 20min, collect diesel oil layer, and measure its volume, obtain diesel yield, it is 0.00436% that the diesel oil Sinie7039XR Single wavelength X-fluorescence sulphur content analyzer of collection is recorded its sulphur content, abstraction desulfurization rate is 98.95%, and diesel yield is 82%.
Embodiment 3:
Weighing 0.8g choline inositol composite powder adds in 10ml coker gas oil, in composite powder, choline and inositol mass ratio respectively account for 50%, put into beaker together, be placed in DF-101S instant-heating-type constant-temperature heating magnetic stirring apparatus, temperature is 37.5 DEG C, mixing speed is 20rpm, reacts and carries out pre-treatment in 16 hours.Under normal temperature, Regular Insulin is added in above-mentioned coker gas oil, Regular Insulin is injection shape Regular Insulin, the volume ratio of Regular Insulin and coker gas oil is 4: 100, then be placed in water bath with thermostatic control environment thermostatically heating to stir, Heating temperature is 37.5 DEG C, reacting by heating 20 hours, the power of the magnetic stirring apparatus of constant temperature is 40w, and rotating speed is 35rpm; By 0.7mg/ml, Ursodeoxycholic Acid Tablets is added in coker gas oil under normal temperature, be then placed in water bath with thermostatic control environment thermostatically heating and stir, Heating temperature is 37.5 DEG C, reacting by heating 20 hours, water bath with thermostatic control environment all adopts water bath with thermostatic control magnetic stirring apparatus, and power is 40w, and rotating speed is 35rpm; Catalyzer and oxygenant are successively added in coker gas oil, and catalyzer is trichoroacetic acid(TCA), oxygenant to be mass concentration be 30% superoxol; Coker gas oil, catalyzer and oxygenant volume ratio are 10: 3: 3, then carry out catalytic oxidation in DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus, and the reaction times is 90min, and Heating temperature is 70 DEG C, and stirring velocity is 40rpm; Then, coker gas oil is taken out, after being cooled to room temperature, add extraction agent DMF again, extraction agent and coker gas oil volume ratio are 1: 1, use magnetic stirrer 8min again, stirring velocity is 40rpm, then pours separating funnel into, leave standstill 20min, collect diesel oil layer, and measure its volume, obtain diesel yield, it is 0.00376% that the diesel oil Sinie7039XR Single wavelength X-fluorescence sulphur content analyzer of collection is recorded its sulphur content, and abstraction desulfurization rate is 99.55%, and diesel yield is 85%.
Embodiment 4:
Weighing 1.0g choline inositol composite sheet adds in 10ml coker gas oil, and in composite sheet, choline and inositol mass ratio respectively account for 50%, put into beaker together, be placed in DF-101S instant-heating-type constant-temperature heating magnetic stirring apparatus, temperature is 38 DEG C, and mixing speed is 20rpm, reacts and carries out pre-treatment in 24 hours.Under normal temperature, Regular Insulin is added in above-mentioned coker gas oil, Regular Insulin is powder ampoule agent for injection Regular Insulin, its addition is 0.1mg/ml, then be placed in water bath with thermostatic control environment thermostatically heating to stir, Heating temperature is 38 DEG C, reacting by heating 24 hours, and water bath with thermostatic control environment all adopts water bath with thermostatic control magnetic stirring apparatus, power is 40w, and rotating speed is 40rpm; By 1mg/ml, Septochol is added in aforesaid coker gas oil under normal temperature, be then placed in water bath with thermostatic control environment thermostatically heating and stir, Heating temperature is 38 DEG C, reacting by heating 24 hours, water bath with thermostatic control environment all adopts water bath with thermostatic control magnetic stirring apparatus, and power is 40w, and rotating speed is 40rpm; Catalyzer and oxygenant are successively added in coker gas oil, and catalyzer is trichoroacetic acid(TCA), oxygenant to be mass concentration be 30% superoxol; Coker gas oil, catalyzer and oxygenant volume ratio are 10: 4: 4, then carry out catalytic oxidation in DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus, and the reaction times is 100min, Heating temperature 80 DEG C, and stirring velocity is 40rpm; Then, coker gas oil is taken out, after being cooled to room temperature, add extraction agent furfural again, the volume ratio of extraction agent and coker gas oil is 1: 1, then uses magnetic stirrer 10min, stirring velocity is 40rpm, then pours separating funnel into, leaves standstill 20min, collect diesel oil layer, and measure its volume, obtain diesel yield, it is 0.00348% that the diesel oil Sinie7039XR Single wavelength X-fluorescence sulphur content analyzer of collection is recorded its sulphur content, abstraction desulfurization rate is 99.83%, and diesel yield is 89%.
Claims (4)
1. many kinds of biologically active agents are applied to the method for coker gas oil desulfurization, it is characterized in that, comprise the following steps:
(1), pre-treatment: choline inositol composite powder or composite sheet are added in coker gas oil by 0.04-0.1g/ml, in choline inositol composite powder or composite sheet, choline and inositol mass ratio respectively account for 50%, heat with magnetic stirring apparatus and stir, temperature is 36 DEG C-38 DEG C, mixing speed is 20rpm, reaction 1-24 hour;
(2), by 0.05-1.0mg/ml, Cholic acids promoting agent is added in the coker gas oil of step (1) gained, then be placed in water bath with thermostatic control environment thermostatically heating to stir, Heating temperature is 36.5 DEG C-38 DEG C, reacting by heating 1-24 hour, and mixing speed is 20-40rpm;
(3), Regular Insulin add in the coker gas oil of step (2) gained, be then placed in water bath with thermostatic control environment thermostatically heating and stir, Heating temperature is 36.5-38 DEG C, reacting by heating 1-24 hour, and mixing speed is 20-40rpm; Described Regular Insulin is powder ampoule agent for injection Regular Insulin or injection shape Regular Insulin, and the addition of powder ampoule agent for injection Regular Insulin is 0.01-0.10mg/ml; The volume ratio of injection shape Regular Insulin and coker gas oil is 2: 100-5: 100;
(4), catalyzer and oxygenant successively add in the coker gas oil after step (3) process, catalyzer is trichoroacetic acid(TCA) or formic acid, oxygenant to be mass concentration be 30% superoxol; The volume ratio of coker gas oil, catalyzer and oxygenant is 10: 2: 1-10: 4: 4, in magnetic stirring apparatus, carry out catalytic oxidation, and the reaction times is 50-100min, and temperature is 50 DEG C-80 DEG C, and stirring velocity is 40rpm;
(5), by volume 1: 1 add extraction agent to step (4) process after coker gas oil in, extraction agent is DMF or furfural, use magnetic stirrer 5-10min, stirring velocity is 40rpm, then pours separating funnel into, leave standstill 20min, collect diesel oil layer.
2. multiple biologically active agent according to claim 1 is applied to the method for coker gas oil desulfurization, it is characterized in that, the Cholic acids activator in described step (2) is cholic acid, cholate, deoxycholate, Ursodeoxycholic Acid Tablets, ursodesoxycholic acid capsule, ursodesoxycholic acid soft capsule, Septochol, Hyodeoxycholic Acid or glycocholic acid.
3. multiple biologically active agent according to claim 1 is applied to the method for coker gas oil desulfurization, it is characterized in that, the choline in described choline inositol composite powder or composite sheet also can be choline chloride 60.
4. multiple biologically active agent according to claim 1 is applied to the method for coker gas oil desulfurization, it is characterized in that, the water bath with thermostatic control environment of described step (2) and step (3) all adopts water bath with thermostatic control magnetic stirring apparatus, and power is 40w.
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| CN102936516A (en) * | 2012-10-30 | 2013-02-20 | 陕西高新能源发展有限公司 | Diesel desulfuration method |
| US20130330677A1 (en) * | 2012-06-07 | 2013-12-12 | Engineered Carbon Solutions, Inc. | Coal paste for use as fuel and methods of using same |
| CN104498085A (en) * | 2014-12-24 | 2015-04-08 | 广西大学 | Intensified distillation method for crude oil or heavy crude oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130330677A1 (en) * | 2012-06-07 | 2013-12-12 | Engineered Carbon Solutions, Inc. | Coal paste for use as fuel and methods of using same |
| CN102936516A (en) * | 2012-10-30 | 2013-02-20 | 陕西高新能源发展有限公司 | Diesel desulfuration method |
| CN104498085A (en) * | 2014-12-24 | 2015-04-08 | 广西大学 | Intensified distillation method for crude oil or heavy crude oil |
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