CN102041018A - Processing method of coal and oil co-refining - Google Patents
Processing method of coal and oil co-refining Download PDFInfo
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- CN102041018A CN102041018A CN2009101879195A CN200910187919A CN102041018A CN 102041018 A CN102041018 A CN 102041018A CN 2009101879195 A CN2009101879195 A CN 2009101879195A CN 200910187919 A CN200910187919 A CN 200910187919A CN 102041018 A CN102041018 A CN 102041018A
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Abstract
The invention discloses a processing method of coal and oil co-refining. The method comprises the following steps: mixing a coal and oil co-refining raw material and a hydrogen-donor solvent, wherein the hydrogen-donor solvent comprises tetrahydronaphthalene or decahydronaphthalene, and the weight ratio of the coal and oil co-refining raw material to the hydrogen-donor solvent is (1:0.5)-(1:10); processing the mixture of the coal and oil co-refining raw material and the hydrogen-donor solvent for 0.2-5 hours at the pressure of 15-40 MPa and the temperature of 300-500 DEG C; separating solid impurities from the processed product; and then, fractionating. Compared with the prior art, in the method provided by the invention, a synergic effect exists between coal and heavy oil, the coal and oil co-refining effect is promoted, and the coal and heavy oil conversion rate is higher.
Description
Technical field
The present invention relates to a kind of coal and oil and be total to the treatment process, particularly coal of refining and the method for modifying that inferior heavy oil is refined altogether.
Background technology
At present, because petroleum resources are day by day exhausted, and Economic development constantly increases the demand of oil, and the price of oil goes up rapidly.And in the refining process of oil, the productive rate of residual oil is higher, is generally 40%-50%.In addition, more heavy crude is arranged in world's crude oil reserve, it forms the overwhelming majority is residual oil, and is the very high poor residuum of foreign matter content.
The industrialized method of handling these residual oil comprises at present: method or combined methods such as catalytic cracking, residual hydrogenation, delayed coking, viscosity breaking, solvent deasphalting.Along with residual oil is more and more inferior, sulphur, nitrogen and metals content impurity are more and more higher, and existing working method deals with all weak point; On the other hand, the energy inferior such as oil-sand, pitch, synthetic crude also enter into the ranks of refining of petroleum, need suitable method to handle the great energy of these reserves, alleviate the demand of social development to produce more light-end products.
CN200610026906.6 discloses a kind of method of preparing light oil from supercritical water modified vacuum residuum, in supercritical water, carries out the thermally splitting of vacuum residuum and handles.Though this method is carried out heat cracking reaction in supercritical water, compare with common thermal cracking process and reduced the coking side reaction, for inferior raw material, coking rate is still higher.
CN96102808.4 discloses a kind of method of gelatin liquefaction, and by coal dust, solvent and Catalyst Production coal slime, 350 to 480 ℃ of temperature, 20 to 200atm times reactions of pressure form liquiefied product with coal slime and coke(oven)gas.Liquiefied product is separated into liquefaction slurry and gas; Distillation liquefaction slurry forms liquefaction oil and solvent refined coal.Obtain liquid product though coal can be liquefied, the solid coal dust stops up easily, and transformation efficiency is not high.
Summary of the invention
At the deficiencies in the prior art, the invention provides the altogether treatment process of refining of a kind of coal and oil, the inventive method can effective elimination heavy oil and coal in impurity, obtain liquid product preferably.
Coal of the present invention and oil smelting method altogether comprise following content: coal and oil refine raw material altogether to be mixed with hydrogen supply dissolvent, hydrogen supply dissolvent comprises naphthane or perhydronaphthalene, the mixed weight ratio that coal and oil refine raw material and hydrogen supply dissolvent altogether is 1: 0.5～1: 10, coal was handled 0.2～5 hour down for 300～500 ℃ at pressure 15～40MPa and temperature with the mixture that oil refines raw material and hydrogen supply dissolvent altogether, handled and carried out the fractionation processing after product is isolated solid impurity.
Coal of the present invention and oil are total in the smelting method, described coal and oil refine in the raw material altogether, oil can be the residual oil of various crude oil, and in various oil-sands, pitch and the synthetic crude etc. one or more, coal can be one or more in various coals such as brown coal, sub-bituminous coal and the high volatile coal etc., also can be two or more mixture of above-mentioned raw materials.
Coal of the present invention and oil are total in the smelting method, described treatment condition are the supercritical state of hydrogen supply dissolvent or the condition of subcritical state (promptly near criticality), hydrogen supply dissolvent can refine the coking precursor thorough mixing in the raw material altogether and provide hydrogen in coking precursor scission reaction with coal and oil under this condition, prevent its coking, and then reduce coking rate.
Coal of the present invention and oil are total in the smelting method, and the refining ratio of mixing of coal is 2%-50% (accounting for oil quality per-cent).
Coal of the present invention and oil are total in the smelting method, can also add entry in reaction system, and the add-on of water can be 0.1 times～10 times that coal and oil refine raw material weight altogether.Water can generate hydrogen with the reactions such as coke in the reaction system under reaction conditions, under the high pressure-temperature condition, the hydrogen that generates can react with the hydrogen supply dissolvent that loses hydrogen, makes the hydrogen supply dissolvent that loses hydrogen recover hydrogen supply capacity, thereby can reduce the consumption of hydrogen supply dissolvent and improve reaction efficiency.Water and hydrogen supply dissolvent have formed the coordinated effect.
Coal of the present invention and oil are total in the smelting method, the hydrogen supply dissolvent that can adopt method such as fractionation will comprise superfluous hydrogen supply dissolvent in the post reaction mixture or lose hydrogen separates, can directly recycle after the separation, or recycle after replenishing fresh hydrogen supply dissolvent, or recycle through after the conventional hydrogenation process.
Coal of the present invention and oil are total in the smelting method, conversion unit can use this area popular response device, and as continuously stirred tank reactor (CSTR) (CSTR), tank reactor etc. intermittently, reaction process is carried out agitation as appropriate, the air atmosphere that can be aided with lower concentration in the reactor is to increase reaction effect.
Coal of the present invention and oil are total to smelting method in the supercritical state of hydrogen supply dissolvent or near carrying out under the critical phase conditions, hydrogen supply dissolvent and coal and the oily fused effect and the reaction effect of coking precursor in the raw material of refining have altogether been improved, reduced the coking tendency, strengthened reaction effect simultaneously, improved the ability that removes impurity, can handle coal more inferior and oil and refine raw material altogether.Hydrogen supply dissolvent and water use simultaneously, can reach the coordinated effect, make hydrogen supply dissolvent can partly recover hydrogen supply capacity under response behaviour, reduce the consumption of hydrogen supply dissolvent, improve reaction effect.
The transformation efficiency of coal and heavy oil is higher, the transformation efficiency when all being higher than independent hydrogenation liquefaction of coal and heavy oil and hydrocracking.
Have synergistic effect between coal and the heavy oil, many when giving birth to olefiant total amount than independent reconstructed coal and heavy oil, the existence of coal also promotes removing of metallic element in the heavy oil (as Ni, V).Simultaneously, heavy oil can be used as the solvent of coal, the concentration of dilution solid phase coal.
Description of drawings
Fig. 1 is that coal of the present invention and oil are total to a kind of concrete process flow diagram of smelting method.
Embodiment
Below in conjunction with the drawings and specific embodiments further to being described.
As shown in Figure 1, coal and oil refine altogether raw material through with the identical pre-treatment of common process after, mix with additive (additive comprises hydrogen supply dissolvent and water etc.), then after the material heating, enter CSTR (continuously stirred tank reactor (CSTR)), pressurize, heat up and begin and stir rotating speed 800 commentaries on classics/min, be forced into 15～40MPa, be warming up to 300～500 ℃.Reacted product enters separator after isolating solid impurity after filtration, and gas phase is separated with liquid phase, and the solid impurity that filters to isolate etc. can burn or as the raw material of needle coke, liquid phase enters separation column and fractionates out corresponding product.Separation column is isolated the hydrogen supply dissolvent of various products and surplus or is lost the hydrogen supply dissolvent of hydrogen.Product after the fractionation can further be handled as required.
Embodiment-1
The mixing raw material of Tahe residual oil and Ningxia brown coal (the refining ratio of mixing of coal be account for the residual oil quality 35%) with naphthane join motionless mixer, (keep excessive naphthane, the weight ratio that coal and oil refine raw material and naphthane altogether is 1: 6), after the material heating, enter CSTR (continuously stirred tank reactor (CSTR)), pressurize, heat up and begin and stir, rotating speed 800 commentaries on classics/min, be forced into 20MPa, be warming up to 400 ℃, the reaction times is 3h.Reacted product enters separator after filtering, and gas phase is separated with liquid phase, and the solid impurity that filters to isolate etc. can burn or as the raw material of producing needle coke, liquid phase enters separation column.Separation column is isolated various products and superfluous hydrogen supply dissolvent.Superfluous hydrogen supply dissolvent can recycle.Reaction effect sees Table 1.
Embodiment-2
With Tahe residual oil and Ningxia brown coal be mixed into raw material (the refining ratio of mixing of coal be account for the residual oil quality 5%), step same embodiment-1, hydrogen supply dissolvent is a perhydronaphthalene, coal and oil refine raw material altogether and the hydrogen supply dissolvent weight ratio is 1: 2, and reaction pressure is 35MPa, and temperature of reaction is 450 ℃, reaction times is that (CSTR is the continuously feeding discharging to 0.5h, reaction times is the material mean residence time), after method processing of the present invention, reaction result sees Table 2.
Embodiment-3
Press the identical method of embodiment 2, add water simultaneously, the weight ratio that water and coal and oil refine raw material altogether is 1: 1, and reaction result sees Table 2.
Comparative example
The method identical with embodiment 2 only makes water, do not use hydrogen supply dissolvent, and reaction result sees Table 2.
Table 1 embodiment 1 reaction result
Table 2 embodiment 2,3 and comparative example reaction result
Claims (6)
1. a coal is total to the treatment process of refining with oil, it is characterized in that: coal and oil refine raw material altogether to be mixed with hydrogen supply dissolvent, hydrogen supply dissolvent comprises naphthane or perhydronaphthalene, the mixed weight ratio that coal and oil refine raw material and hydrogen supply dissolvent altogether is 1: 0.5～1: 10, coal was handled 0.2～5 hour down for 300～500 ℃ at pressure 15～40MPa and temperature with the mixture that oil refines raw material and hydrogen supply dissolvent altogether, handled and carried out the fractionation processing after product is isolated solid impurity.
2. in accordance with the method for claim 1, it is characterized in that: coal and oil refine in the raw material altogether, grease separation one or more in residual oil, oil-sand, pitch and synthetic crude, and coal is selected from one or more in brown coal, sub-bituminous coal and the high volatile coal.
3. in accordance with the method for claim 1, it is characterized in that: coal and oil are total in the smelting method, and by accounting for oil quality per-cent, the refining ratio of mixing of coal is 2%-50%.
4. in accordance with the method for claim 1, it is characterized in that: add entry in reaction system, the add-on of water is 0.1 times～10 times that coal and oil refine raw material weight altogether.
5. in accordance with the method for claim 1, it is characterized in that: adopt fractionated method will comprise that the hydrogen supply dissolvent of superfluous hydrogen supply dissolvent or mistake hydrogen separates in the post reaction mixture, directly recycle after the separation, or recycle after replenishing fresh hydrogen supply dissolvent, or recycle through after the hydrogenation process.
6. it is characterized in that in accordance with the method for claim 1: conversion unit uses continuously stirred tank reactor (CSTR) or tank reactor intermittently.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567319A (en) * | 2014-10-11 | 2016-05-11 | 中国石油化工股份有限公司 | Method for processing heavy oil |
| CN106732672A (en) * | 2017-02-23 | 2017-05-31 | 中国石油大学(华东) | It is a kind of to load catalyst with base of molybdenum for the coal that kerosene floating bed hydrogenation is refined altogether |
Citations (3)
| 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 |
| JP2008297466A (en) * | 2007-05-31 | 2008-12-11 | Japan Energy Corp | Method for cracking hydrocarbon oil |
| CN101553553A (en) * | 2006-10-31 | 2009-10-07 | 雪佛龙美国公司 | Process for upgrading heavy hydrocarbon oils |
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- 2009-10-16 CN CN200910187919.5A patent/CN102041018B/en active Active
Patent Citations (3)
| 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 |
| CN101553553A (en) * | 2006-10-31 | 2009-10-07 | 雪佛龙美国公司 | Process for upgrading heavy hydrocarbon oils |
| JP2008297466A (en) * | 2007-05-31 | 2008-12-11 | Japan Energy Corp | Method for cracking hydrocarbon oil |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567319A (en) * | 2014-10-11 | 2016-05-11 | 中国石油化工股份有限公司 | Method for processing heavy oil |
| CN105567319B (en) * | 2014-10-11 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of method for handling mink cell focus |
| CN106732672A (en) * | 2017-02-23 | 2017-05-31 | 中国石油大学(华东) | It is a kind of to load catalyst with base of molybdenum for the coal that kerosene floating bed hydrogenation is refined altogether |
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