CN103756700A - Method for improving quality of low-temperature tar during coal pyrolysis - Google Patents
Method for improving quality of low-temperature tar during coal pyrolysis Download PDFInfo
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- CN103756700A CN103756700A CN201410039002.1A CN201410039002A CN103756700A CN 103756700 A CN103756700 A CN 103756700A CN 201410039002 A CN201410039002 A CN 201410039002A CN 103756700 A CN103756700 A CN 103756700A
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Abstract
The invention provides a method for improving the quality of pyrolysis tar during co-pyrolysis of low-temperature coal tar and coal. According to the novel preparation method, the low-temperature coal tar or the distillation residues of the low-temperature coal tar are added into the feed coal for co-pyrolysis to obtain tar and gaseous hydrocarbon products, wherein the mass ratio of the low-temperature coal tar or the distillation residues of the low-temperature coal tar to the feed coal is (0.5 to 100) to (20 to 100), and the reaction conditions are that the pyrolysis temperature is 400-800 DEG C and the pyrolysis time is 0-90 minutes. Through the method, the yields of the pyrolysis tar and pyrolysis gas are increased, the content of light components with high added values in the pyrolysis tar is greatly increased, and the problems of processing and utilization of heavy pyrolysis tar are solved.
Description
Technical field
The present invention relates to pyrolysis of coal technology, be specifically related to a kind of pyrolysis of coal technology that improves semi coking tar quality.
Background technology
In the face of the significant challenge of China's energy development, and current domestic conventional primary energy source is under-supply, especially the situation of the serious dependence on import of communications and transportation fuel has become the bottleneck of restriction China Economic development, add China take coal as main energy structure, how high-efficiency cleaning rationally utilizes non-renewable coal resources to become the task of top priority.The main path of existing coal prepare liquid fuel has: direct liquefaction, indirect liquefaction, pyrolysis etc.Pyrolysis has the features such as technique is simple, mild condition, less investment, low production cost than other coal conversion approach.Especially for the low middle low-rank coal of metamorphic grade, there is economically incomparable value.
Now to improve pyrolytic tar productive rate and quality as the technique of object mainly contains pre-treatment, catalyse pyrolysis, change pyrolysis atmosphere, pyrolysis etc. is coupled.As China Patent Publication No. CN102229810A, this patent discloses a kind of method of coal tar extraction-pyrolyzing coal, and the method utilizes coal tar to extract coal, extracts rear copyrolysis or coal is isolated to independent pyrolysis, has improved the productive rate of pyrolytic tar.China Patent Publication No. CN102746861A, a kind of method for pyrolysis that passes into fusel and improve oily productive rate is disclosed, the method is steam by fusel preheating, by fusel steam or after mixing with carrier gas, pass into pyrolysis reactor, the pyrolysis product of fusel combines with the free radical fragment that pyrolysis of coal generates, and has improved oily yield.China Patent Publication No. CN102161904A, a kind of method of utilizing aromatization of hydrocarbons and pyrolysis of coal coupling to improve tar yield is disclosed, the method take hydro carbons as reaction atmosphere replaces traditional pure hydrogen atmosphere, by the method for aromizing and pyrolysis coupling, improved tar yield.China Patent Publication No. CN1224043A, the method of tar-increasing and water-reducing in a kind of pyrolysis of coal and coking is disclosed, the method is take brown coal and bituminous coal as raw material, add certain plastic waste (comprising polyethylene, polypropylene, polyvinyl chloride, polystyrene) to pass into rare gas element or coke-oven gas, carry out pyrolysis of coal and coking, the coal-tar middle oil content of gained product liquid increases, and moisture reduces.China Patent Publication No. CN101747922A discloses a kind of to be rich in the method for methane mixed gas as reaction atmosphere raising fluidized bed pyrolysis tar yield, the method is passed into the mixing tank that is rich in methane by fluidized-bed bottom, after activation, as fluidizing agent, improved the productive rate of pyrolytic tar.
But the problems such as traditional pyrolytic process ubiquity tar yield is low, poor quality.The processing method of a small amount of coalite tar or its distillation residue and coal copyrolysis there is not yet bibliographical information.
Summary of the invention
The present invention is directed to the deficiency of traditional pyrolytic process, a kind of processing method of utilizing a small amount of coalite tar or its distillation residue and coal copyrolysis is provided, realized pyrolytic tar productive rate, especially the raising of tar quality.
The object of the invention is to be achieved through the following technical solutions:
This coalite tar or its distillation residue and coal copyrolysis improve the method for pyrolytic tar quality, comprise the following steps:
(1) preparation of raw material
To feed coal carry out fragmentation, screening, standby after dry, coal powder size after treatment with 10-1000 μ m for better;
By coalite tar distillation, get distillation residue standby.
(2) mixing of raw material
Coalite tar or its distillation residue are evenly mixed with feed coal, and tar, coal mass ratio are 0.5:100～20:100.
Be preferably 1:100～10:100.
(3) pyrolysis
The mixture of being prepared by step (2) on pyrolysis reactor carries out pyrolytic reaction, obtains product liquid, pyrolysis gas, semicoke, and product liquid is oil-water mixture.Temperature of reaction is 400～800 ℃, and the residence time is 0～90min.
Better temperature of reaction is 450～700 ℃, and the best is 600 ℃;
Preferably the residence time is 1-60min, and most optimal retention time is 30min.
(4) dehydration
The product liquid dehydration that step (3) is obtained obtains low-temperature pyrolyzed coal tar.
(5) distillation
The low-temperature pyrolyzed coal tar that step (4) is obtained distills, and obtains distillate product, and residue and coal carry out copyrolysis.
Wherein, raw materials used coal is one or more in peat, brown coal, bituminous coal.
Pyrolysis reactor comprises fixed bed, fluidized-bed, ebullated bed.
The present invention compared to the prior art tool has the following advantages:
(1) significantly improved productive rate and the quality of pyrolyzing coal tar, can effectively solve that the coal-based liquefaction cost of China is high, productive rate is low, inferior problem;
(2) raw materials used pyrolyzing coal tar or its heavy component are pyrolysis of coal product, have reduced production cost, and applicable suitability for industrialized production;
(3) simple, the mild condition, easy to operate of production technique.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
Now in conjunction with the accompanying drawings and embodiments, the present invention is described in detail, but enforcement of the present invention is not limited only to this.
The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1:
Feed coal is selected peat.
After the coal dust that reaches granularity requirements 10-1000 μ m after broken, screening, grinding is mixed according to mass ratio 100:1 with coalite tar, be placed on pyrolysis reactor fixed bed and carry out pyrolytic reaction, temperature of reaction is 600 ℃, and the residence time is 30min.Dehydration of tar can adopt centrifuge dehydration.
Tar yield exceeds 1.79% compared with the calculated value of two kinds of independent pyrolysis of raw material, and normal hexane solvend productive rate exceeds calculated value 2.98%.
Embodiment 2:
Feed coal is brown coal.
After the coal dust that reaches granularity requirements 10-1000 μ m after broken, screening, grinding is mixed according to mass ratio 100:3 with coalite tar, be placed on pyrolysis reactor fluidized-bed and carry out pyrolytic reaction, temperature of reaction is 600 ℃, and the residence time is 30min.Dehydration of tar can adopt centrifuge dehydration.
Tar yield exceeds 1.36% compared with the calculated value of two kinds of independent pyrolysis of raw material, and normal hexane solvend productive rate exceeds calculated value 3.53%.
Embodiment 3:
Feed coal is bituminous coal.
After the coal dust that reaches granularity requirements 10-1000 μ m after broken, screening, grinding is mixed according to mass ratio 100:5 with coalite tar, be placed on pyrolysis reactor and carry out pyrolytic reaction, temperature of reaction is 600 ℃, and the residence time is 30min.Dehydration of tar can adopt centrifuge dehydration.
Tar yield exceeds 0.91% compared with the calculated value of two kinds of independent pyrolysis of raw material, and normal hexane solvend productive rate exceeds calculated value 3.64%.
Embodiment 4:
Feed coal is brown coal and bitumionus coal each 50%.
After the coal dust that reaches granularity requirements 10-1000 μ m after broken, screening, grinding is mixed according to mass ratio 100:5 with coalite tar distillation residue, be placed on pyrolysis reactor and carry out pyrolytic reaction, temperature of reaction is 600 ℃, and the residence time is 30min.Dehydration of tar can adopt centrifuge dehydration.
Tar yield exceeds 0.78% compared with the calculated value of two kinds of independent pyrolysis of raw material, and normal hexane solvend productive rate exceeds calculated value 3.05%.
Embodiment 5:
All the other, are placed on pyrolysis reactor and carry out pyrolytic reaction after the coal dust that reaches granularity requirements after broken, screening, grinding is mixed according to mass ratio 100:5 with coalite tar distillation residue with embodiment 4, and temperature of reaction is 500 ℃, and the residence time is 30min.Tar yield exceeds 1.22% compared with the calculated value of two kinds of independent pyrolysis of raw material, and normal hexane solvend productive rate exceeds calculated value 3.31%.
Embodiment 6
All the other are with embodiment 1, and the preparation method of the distillation residue of coalite tar is with embodiment 4.
After the coal dust that reaches granularity requirements after broken, screening, grinding is mixed according to mass ratio 100:5 with coalite tar distillation residue, be placed on pyrolysis reactor and carry out pyrolytic reaction, temperature of reaction is 700 ℃, and the residence time is 30min.Tar yield exceeds 1.04% compared with the calculated value of two kinds of independent pyrolysis of raw material, and normal hexane solvend productive rate exceeds calculated value 2.78%.
Embodiment 7:
All the other, are placed on pyrolysis reactor and carry out pyrolytic reaction after the coal dust that reaches granularity requirements after broken, screening, grinding is mixed according to mass ratio 100:5 with coalite tar with embodiment 2, and temperature of reaction is 600 ℃, and the residence time is 10min.Tar yield exceeds 0.62% compared with the calculated value of two kinds of independent pyrolysis of raw material, and normal hexane solvend productive rate exceeds calculated value 1.64%.
Embodiment 8:
All the other are with embodiment 3, and the preparation method of the distillation residue of coalite tar is with embodiment 4.
After the coal dust that reaches granularity requirements after broken, screening, grinding is mixed according to mass ratio 100:5 with coalite tar distillation residue, be placed on pyrolysis reactor and carry out pyrolytic reaction, temperature of reaction is 600 ℃, and the residence time is 60min.Tar yield exceeds 1.19% compared with the calculated value of two kinds of independent pyrolysis of raw material, and normal hexane solvend productive rate exceeds calculated value 2.94%.
By embodiment 1～embodiment 8 results, can be found out that coal and coalite tar or its distillation residue copyrolysis all can improve the content of normal hexane solvend in tar yield and tar.Illustrate that method for pyrolysis provided by the invention can improve tar and quality when distillation residue are utilized.
Above-described embodiment is preferably embodiment of the present invention, but embodiments of the present invention are not restricted to the described embodiments.Other are any does not depart from the distortion of doing under the present invention's spirit and principle, all should think protection scope of the present invention.
Claims (8)
1. a method that improves pyrolysis of coal semi coking tar quality, is characterized in that, the method comprises the following steps:
(A) to feed coal, carry out after fragmentation, screening, drying treatment standby;
(B) coalite tar is distilled, collect distillation residue;
(C) feed coal of being prepared by step (A) mixes with distillation residue prepared by coalite tar or step (B); The mass ratio of coalite tar or distillation residue and feed coal is 0.5:100～20:100;
(D) mixture of being prepared by step (C) carries out pyrolysis on pyrolysis reactor, obtains gas-liquid-solid three-phase product, and gaseous product is that pyrolysis gas, solid product are that semicoke, product liquid are tar and water;
(E) product liquid step (D) being obtained, by dehydration of tar, obtains pyrolytic tar;
(F) pyrolytic tar step (E) being obtained distills, and distillate is tar light oil product, and distillation residue can supply step (C) to recycle.
2. according to a kind of method that improves pyrolysis of coal semi coking tar quality claimed in claim 1, it is characterized in that, the feed coal described in step (A) is one or more in peat, brown coal, bituminous coal.
3. according to a kind of method that improves pyrolysis of coal semi coking tar quality claimed in claim 1, it is characterized in that, it is 10-1000 μ m that step (A) is processed rear coal particle size scope.
4. according to a kind of method that improves pyrolysis of coal semi coking tar quality claimed in claim 1, it is characterized in that, in step (C), the mass ratio of coalite tar or distillation residue and feed coal is 1:100～10:100.
5. according to a kind of method that improves pyrolysis of coal semi coking tar quality claimed in claim 1, it is characterized in that, in step (D), pyrolytical condition is: 400～800 ℃ of temperature of reaction, the residence time 0～90min.
6. according to a kind of method that improves pyrolysis of coal semi coking tar quality claimed in claim 1, it is characterized in that, in step (D), pyrolytical condition is: 450～700 ℃ of temperature of reaction, the residence time 1～60min.
7. according to a kind of method that improves pyrolysis of coal semi coking tar quality claimed in claim 1, it is characterized in that, in step (D), pyrolytical condition is: 600 ℃ of temperature of reaction; The residence time is 30min.
8. according to a kind of method that improves pyrolysis of coal semi coking tar quality claimed in claim 1, it is characterized in that, the pyrolysis reactor described in step (D) comprises fixed bed, fluidized-bed, ebullated bed.
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Cited By (6)
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|---|---|---|---|---|
| CN104479711A (en) * | 2014-11-26 | 2015-04-01 | 湖南科技大学 | Method for improving yield of pyrolysis coal tar of low-rank coals |
| CN107557038A (en) * | 2016-06-30 | 2018-01-09 | 神华集团有限责任公司 | The copyrolysis method and pyrolytic reaction system of a kind of coal and sticky carbonaceous material |
| CN109207176A (en) * | 2017-06-29 | 2019-01-15 | 神华集团有限责任公司 | Pyrolysis installation, pyrolysis system and method for pyrolysis |
| CN113214874A (en) * | 2021-05-26 | 2021-08-06 | 西京学院 | Method for kerosene co-catalytic pyrolysis-semicoke catalytic gasification |
| CN113831927A (en) * | 2021-10-25 | 2021-12-24 | 西安建筑科技大学 | Method for improving yield of low-metamorphic coal pyrolysis tar by utilizing biomass |
| CN114479891A (en) * | 2021-12-30 | 2022-05-13 | 北京鑫源寰宇环保科技有限公司 | Organic waste resource utilization treatment method |
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| CN102108301A (en) * | 2009-12-24 | 2011-06-29 | 中国石油化工股份有限公司 | Method for producing high-yield tar by pyrolyzing coal |
| CN102851054A (en) * | 2012-09-21 | 2013-01-02 | 中国科学技术大学 | C2-C9 chemical product produced from biomass, its preparation method and application |
| CN103788969A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Combined process for co-pyrolysis of coal and petroleum refining by-product |
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Patent Citations (4)
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| JP2009203336A (en) * | 2008-02-27 | 2009-09-10 | Jfe Engineering Corp | Method for producing fuel gas from thermally cracked oil from biomass, and method for producing tar |
| CN102108301A (en) * | 2009-12-24 | 2011-06-29 | 中国石油化工股份有限公司 | Method for producing high-yield tar by pyrolyzing coal |
| CN102851054A (en) * | 2012-09-21 | 2013-01-02 | 中国科学技术大学 | C2-C9 chemical product produced from biomass, its preparation method and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479711A (en) * | 2014-11-26 | 2015-04-01 | 湖南科技大学 | Method for improving yield of pyrolysis coal tar of low-rank coals |
| CN104479711B (en) * | 2014-11-26 | 2016-05-25 | 湖南科技大学 | A kind of method that improves low-order coal pyrolyzing coal tar yield |
| CN107557038A (en) * | 2016-06-30 | 2018-01-09 | 神华集团有限责任公司 | The copyrolysis method and pyrolytic reaction system of a kind of coal and sticky carbonaceous material |
| CN109207176A (en) * | 2017-06-29 | 2019-01-15 | 神华集团有限责任公司 | Pyrolysis installation, pyrolysis system and method for pyrolysis |
| CN113214874A (en) * | 2021-05-26 | 2021-08-06 | 西京学院 | Method for kerosene co-catalytic pyrolysis-semicoke catalytic gasification |
| CN113831927A (en) * | 2021-10-25 | 2021-12-24 | 西安建筑科技大学 | Method for improving yield of low-metamorphic coal pyrolysis tar by utilizing biomass |
| CN114479891A (en) * | 2021-12-30 | 2022-05-13 | 北京鑫源寰宇环保科技有限公司 | Organic waste resource utilization treatment method |
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