CN102041018B - Processing method of coal and oil co-refining - Google Patents
Processing method of coal and oil co-refining Download PDFInfo
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- CN102041018B CN102041018B CN200910187919.5A CN200910187919A CN102041018B CN 102041018 B CN102041018 B CN 102041018B CN 200910187919 A CN200910187919 A CN 200910187919A CN 102041018 B CN102041018 B CN 102041018B
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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, be generally 40%-50%.In addition, have more heavy crude in world's crude oil reserve, it forms the overwhelming majority is residual oil, and is the poor residuum that foreign matter content is very high.
The industrialized method of processing these residual oil comprises at present: method or the 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 has dealt with 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 process 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 processes.Although the method is carried out heat cracking reaction in supercritical water, compare and reduced coking side reaction with common thermal cracking process, 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, by coal slime and coke(oven)gas, 350 to 480 ℃ of temperature, under pressure 20 to 200atm, reaction forms liquiefied product.Liquiefied product is separated into liquefaction slurry and gas; Distillation liquefaction slurry forms liquefaction oil and solvent refined coal.Although coal can be liquefied and obtains liquid product, solid coal dust easily stops up, and transformation efficiency is not high.
Summary of the invention
For 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 good liquid product.
Coal of the present invention and oil altogether smelting method comprise following content: coal and oil refine raw material altogether to be mixed with hydrogen supply dissolvent, hydrogen supply dissolvent comprises naphthane or perhydronaphthalene, it is 1: 0.5～1: 10 with the mixed weight ratio of hydrogen supply dissolvent that coal and oil refine raw material altogether, the mixture that coal and oil refine raw material and hydrogen supply dissolvent is altogether processed 0.2～5 hour at 300～500 ℃ of pressure 15～40MPa and temperature, after processing product separation goes out solid impurity, carries out fractionation processing.
Coal of the present invention and oil are total in smelting method, described coal and oil refine in raw material altogether, oil can be the residual oil of various crude oil, and one or more in various oil-sands, pitch and synthetic crude etc., coal can be various coals as one or more in brown coal, sub-bituminous coal and high volatile coal etc., can be also two or more mixture of above-mentioned raw materials.
Coal of the present invention and oil are total in smelting method, described treatment condition are the supercritical state of hydrogen supply dissolvent or the condition of subcritical state (approaching criticality), under this condition, hydrogen supply dissolvent can fully mix to be incorporated in coking precursor scission reaction with coal and oily coking precursor of refining altogether in raw material provides hydrogen, prevent its coking, and then reduce coking rate.
Coal of the present invention and oil are total in 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 smelting method, can also in reaction system, add water, and the add-on of water can be 0.1 times～10 times that coal and oil refine raw material weight altogether.Water can react and generate hydrogen with coke in reaction system etc. under reaction conditions, under high pressure-temperature condition, the hydrogen generating 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 coordinated effect.
Coal of the present invention and oil are total in smelting method, in reacted mixture, can adopt the methods such as fractionation that the hydrogen supply dissolvent that comprises superfluous hydrogen supply dissolvent or mistake hydrogen is carried out to separation, after separation, can use by direct circulation, or recycle after supplementing fresh hydrogen supply dissolvent, or recycle after conventional hydrogenation process.
Coal of the present invention and oil are total in 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, in reactor, can be aided with the air atmosphere of lower concentration, 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 approach under critical phase conditions and carries out, hydrogen supply dissolvent and coal and oily fused effect and the reaction effect of coking precursor in raw material of refining have altogether been improved, reduced coking tendency, strengthened reaction effect simultaneously, improved the ability of imurity-removal, can process coal more inferior and oil and refine altogether raw material.Hydrogen supply dissolvent and water are used simultaneously, can reach 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 during all higher than coal and the independent hydrogenation liquefaction of heavy oil and hydrocracking.
Between coal and heavy oil, have synergistic effect, many while generating oily total amount than independent reconstructed coal and heavy oil, the existence of coal also promotes removing of metallic element in heavy oil (as Ni, V).Meanwhile, heavy oil can be used as the solvent of coal, the concentration of dilution solid phase coal.
Accompanying drawing explanation
Fig. 1 is that coal of the present invention and oil are total to a kind of concrete technology FB(flow block) 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 raw material altogether after the identical pre-treatment with common process, mix with additive (additive comprises hydrogen supply dissolvent and water etc.), then after heating material, enter CSTR (continuously stirred tank reactor (CSTR)), pressurize, heat up and start and stir, turn/min of rotating speed 800, be forced into 15～40MPa, be warming up to 300～500 ℃.Reacted product enters separator after being separated by filtration out solid impurity, gas phase and liquid phase is carried out separated, and the solid impurity filtering 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 fractionation can further be processed 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 residual oil quality 35%) with naphthane join motionless mixer, (keep excessive naphthane, the weight ratio that coal and oil refine raw material and naphthane is altogether 1: 6), after heating material, enter CSTR (continuously stirred tank reactor (CSTR)), pressurize, heat up and start and stir, turn/min of rotating speed 800, be forced into 20MPa, be warming up to 400 ℃, the reaction times is 3h.Reacted product enters separator after filtering, and gas phase and liquid phase is carried out separated, and the solid impurity filtering 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 is in Table 1.
Embodiment-2
Take Tahe residual oil and Ningxia brown coal be mixed into raw material (the refining ratio of mixing of coal as account for residual oil quality 5%), same embodiment-1 of step, hydrogen supply dissolvent is perhydronaphthalene, coal and oil refine altogether raw material and 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 continuously feeding discharging to 0.5h, reaction times is material mean residence time), after method of the present invention is processed, reaction result is in Table 2.
Embodiment-3
Press the method that embodiment 2 is identical, add water simultaneously, the weight ratio that water and coal and oil refine raw material is altogether 1: 1, and reaction result is in Table 2.
Comparative example
The method identical with embodiment 2, only makes water, does not use hydrogen supply dissolvent, and reaction result is in Table 2.
Table 1 embodiment 1 reaction result
| Heavy oil character in raw material | Coal character in raw material | Embodiment-1 liquid product | |
| Density (20 ℃), kgm -3 | 1007.8 | - | |
| Carbon residue, quality % | 18.3 | - | |
| Viscosity (100 ℃) mm 2·s -1 | 576.7 | - | |
| S, quality % | 2.5 | 1.3 | 0.9 |
| N, quality % | 0.4 | 1.3 | 0.08 |
| H/C | 0.82 | ||
| Ni，μg·g -1 | 38.6 | 17.9 | |
| V，μg·g -1 | 287.4 | 123.2 | |
| Colloid, quality % | 24.5 | 16.8 | |
| Bituminous matter, quality % | 13.4 | 7.0 |
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, it is 1: 0.5～1: 10 with the mixed weight ratio of hydrogen supply dissolvent that coal and oil refine raw material altogether, the mixture that coal and oil refine raw material and hydrogen supply dissolvent is altogether processed 0.2～5 hour at 300～500 ℃ of pressure 15～40MPa and temperature, after processing product separation goes out solid impurity, carries out fractionation processing.
2. in accordance with the method for claim 1, it is characterized in that: coal and oil refine in raw material altogether, one or more in residual oil, oil-sand, pitch and synthetic crude of grease separation, coal is selected from one or more in brown coal, sub-bituminous coal and high volatile coal.
3. in accordance with the method for claim 1, it is characterized in that: coal and oil are total in 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: in reaction system, add water, 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: in reacted mixture, adopt the method for fractionation that the hydrogen supply dissolvent that comprises superfluous hydrogen supply dissolvent or mistake hydrogen is carried out to separation, after separated, direct circulation is used, or recycle after supplementing fresh hydrogen supply dissolvent, or recycle after hydrogenation process.
6. it is characterized in that in accordance with the method for claim 1: conversion unit use continuously stirred tank reactor (CSTR) or intermittently tank reactor.
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