CN101993702A - Method for enhancing pyrolysis desulfurization rate of coal - Google Patents
Method for enhancing pyrolysis desulfurization rate of coal Download PDFInfo
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- CN101993702A CN101993702A CN2010105679364A CN201010567936A CN101993702A CN 101993702 A CN101993702 A CN 101993702A CN 2010105679364 A CN2010105679364 A CN 2010105679364A CN 201010567936 A CN201010567936 A CN 201010567936A CN 101993702 A CN101993702 A CN 101993702A
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- pyrolysis
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- sulfur
- semicoke
- sulphur content
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Abstract
The invention discloses a method for enhancing the pyrolysis desulfurization rate of coal, which is characterized in that the method comprises the following steps of: a, putting the medium/high sulfur coal with sulfur content of 1.5%-4.5% into a fixed bed reactor; b, introducing inert gas mixed with H2S scavenger into the fixed bed reactor as pyrolysis atmosphere, wherein the mixing volume of the H2S scavenger is 3-5% of the volume of the mixed gas; carrying out the pyrolysis on the high sulfur coal in the condition that the pyrolysis pressure is 0.1-1.0 Mpa, the pyrolysis heating rate is 10 DEG C/min, the final temperature is 500-600 DEG C, and the final temperature remains for 5-10 minutes, wherein the carbocoal obtained by the pyrolysis can serve as a clean low-sulfur solid fuel. Ethylene is added as the scavenger of the sulfocompound H2S in the pyrolysis atmosphere to restrain the secondary solid sulfur reaction. The method for enhancing pyrolysis desulfurization rate of coal enhances the pyrolysis desulfurization rate of coal and the productive rate of the carbocoal, and greatly reduces the sulfur content of the carbacoal.
Description
Technical field
The present invention relates to the coal processing technology, specifically, relate to a kind of method that improves the coal pyrolysis desulfurization degree and then obtain the low-sulfur semicoke.
Background technology
The pyrolysis of coal is a kind of processing technology that improves the coal comprehensive utilization ratio, also is a kind of desulfurization before combustion technology of effective medium-high sulfur coal.The pyrolysis desulfurization of so-called coal heats coal exactly under secluding air or inert atmosphere, the organic matter in the coal partially decomposes forming semicoke, and thermolysis also takes place the sulfur-bearing functional group in the coal simultaneously, generates H
2S overflows with pyrolysis gas, thereby obtains the low-sulfur semicoke, and this low-sulfur semicoke can be used as clean smokeless solid fuel, and the rare gas element that uses is nitrogen or argon gas usually.Common physics washing can only partly remove inorganic sulfur, and the pyrolysis desulfurization of coal belongs to chemical desulfurization before combustion method, not only can remove inorganic sulfur, also can remove the organosulfur in the coal.But, exist the secondary desulfurization reaction in the pyrolysis desulfurization process of coal, as the H of desulfurization primary product
2S can with the organic matter generation secondary desulfurization reaction (non-patent literature in the coal, " Effect of mineral on sulfur behavior during pressurized coal pyrolysis ", Fuel Processing Technology 2004,863 – 871), be exactly that sulphur in the coal is reuptaked by the coal organic matter again after thermolysis, form new C-S chemical bond, generating the difficult more thiophenic sulfur that decomposes is trapped in the semicoke, greatly reduce the pyrolysis desulfurization effect of coal, this becomes one of key issue that needs to be resolved hurrily in the pyrolysis of coal sulfur removal technology.In addition, the pyrolysis desulfurization technology of coal mainly is to be target to obtain clean low-sulfur semicoke product, so the yield of semicoke and the sulphur content in the semicoke all are to weigh the important indicator of pyrolysis of coal process efficiency.
Summary of the invention
Purpose of the present invention supplies a kind of H that stops the sulphur in the coal to generate just after thermo-cracking in order to solve existing weak point in the above-mentioned prior art
2The organic novel method that the secondary desulfurization reaction takes place in S and other sulfur-containing radicals and the coal, promptly a kind of method that improves the pyrolysis desulfurization efficient of coal can obtain higher semi-coke yield simultaneously.
Specifically, method of the present invention is by adding ethene as H in pyrolysis system
2S captures agent, the H that pyrolysis is produced
2S in time is converted into stable sulfocompound, and this sulfocompound can the secondary desulfurization reaction not take place with coal is organic, but overflows with pyrolysis gas, promotes H simultaneously on kinetics
2S is shifted to gas phase by solid phase, thereby can improve the pyrolysis desulfurization efficient of coal greatly.
Its theoretical foundation is following addition reaction:
As ethene and H
2Addition reaction takes place and generates sulfur alcohol in S, and sulfur alcohol can the secondary desulfurization reaction not take place with the coal organic matter, thereby improves the pyrolysis desulfurization efficient of coal.
Purpose of the present invention can realize by following technical solution:
Method of the present invention comprises the steps:
A, at first with sulphur content be 1.5% ~ 4.50%, granularity places fixed-bed reactor less than the coal of 3mm;
B, in fixed-bed reactor, feed and be mixed with H
2S captures the rare gas element of agent as pyrolysis atmosphere, wherein said H
2The mixed volume by volume that S captures agent is 3 ~ 5% of an above-mentioned mixed gas volume; In synthesis pressure is that 0.1 ~ 1.0Mpa, pyrolysis temperature rise rate are that 10 ℃/min, whole temperature are 500 ~ 600 ℃, and under the condition of whole temperature stop 5 ~ 10min coal is carried out pyrolysis, and pyrolysis obtains semicoke, is a kind of low-sulfur solid fuel of cleaning.
H described in the present invention
2It is ethene that S captures agent, adds ethene as sulfocompound H in pyrolysis atmosphere
2S captures agent, is used to suppress the secondary desulfurization reaction, improves the pyrolysis desulfurization efficient of coal and improves char yeild, reduces the semicoke sulphur content greatly.Fixed-bed reactor are selected the fixed-bed reactor of this area general type for use.The mensuration establishing criteria of sulphur content is JJG 1006-2005 in coal and the semicoke.Rare gas element of the present invention is rare gas element type conventional in this area, i.e. nitrogen.
Beneficial effect of the present invention is as follows:
The present invention compares with the pyrolysis desulfurization of coal under pure inert atmosphere or secluding air condition has following advantage: pure inert gas pyrolysis gained semicoke sulphur content reduces the semicoke sulphur content greatly, pyrolysis desulfurization efficient improves greatly, the productive rate of clean semicoke is higher than feeding, and H
2S captures agent regeneration easily.
Embodiment
The present invention is further described below with reference to embodiment:
Embodiment 1
Get total sulphur content and be 2.75%, granularity adds fixed-bed reactor less than the high sulphur coal 20g of Datong District of 3mm, feeding pressure is 1MPa, flow is that (the mixed gas volume consists of N for the mixed gas of 300ml/min
2: C
2H
4=95:5); Temperature rise rate with 10 ℃/min is heated to 600 ℃, and temperature stops 10min eventually.The pyrolysis result is a semi-coke yield 86.5%, and the semicoke sulphur content is reduced to 1.2%, sulphur content reduced rate (desulfurization degree) 56.4%; As a comparison, the pyrolysis result that the same terms feeds the 300ml/min pure nitrogen gas down is a semi-coke yield 74%, semicoke sulphur content 1.9%, and semicoke sulphur content reduced rate is 30.9%.Under above-mentioned pyrolytical condition, add volume ratio in the pyrolysis gas and be 5% ethene as H
2S captures agent, and semi-coke yield is improved 12.5%, and desulfurization degree improves 25.5%.
Embodiment 2
Get total sulphur content and be 2.75%, granularity adds fixed-bed reactor less than the high sulphur coal 20g of Datong District of 2mm, feeding pressure is 0.1MPa, flow is that (the mixed gas volume consists of N for the mixed gas of 300ml/min
2: C
2H
4=95:5); Temperature rise rate with 10 ℃/min is heated to 600 ℃, and temperature stops 10min eventually.The pyrolysis result is a semi-coke yield 81.5%, and the semicoke sulphur content is reduced to 1.5%, and sulphur content reduced rate (desulfurization degree) is 45.5%; As a comparison, the pyrolysis result that the same terms feeds the 300ml/min pure nitrogen gas down is a semi-coke yield 73%, semicoke sulphur content 1.8%, and semicoke sulphur content reduced rate is 34.5%.Under above-mentioned pyrolytical condition, it is that 5% ethene is as H that pyrolysis gas adds volume ratio
2S captures agent, and semi-coke yield is improved 8.5%, and desulfurization degree improves 11%.
Embodiment 3
Get total sulphur content and be 2.75%, granularity adds fixed-bed reactor less than the high sulphur coal 20g of Datong District of 2.5mm, feeding pressure is 1MPa, flow is that (the mixed gas volume consists of N for the mixed gas of 300ml/min
2: C
2H
4=95:5); Temperature rise rate with 10 ℃/min is heated to 500 ℃, and temperature stops 10min eventually.The pyrolysis result is a semi-coke yield 89%, and the semicoke sulphur content is reduced to 1.3%, and sulphur content reduced rate (desulfurization degree) is 52.3%; As a comparison, the pyrolysis result that the same terms feeds the 300ml/min pure nitrogen gas down is a semi-coke yield 78%, semicoke sulphur content 2.1%, and semicoke sulphur content reduced rate is 23.6%.Under above-mentioned pyrolytical condition, it is that 5% ethene is as H that pyrolysis gas adds volume ratio
2S captures agent, and semi-coke yield is improved 11%, and desulfurization degree improves 28.7%.
Embodiment 4
Get total sulphur content and be 2.75%, granularity adds fixed-bed reactor less than the high sulphur coal 20g of Datong District of 3mm, feeding pressure is 1MPa, flow is that (the mixed gas volume consists of N for the mixed gas of 300ml/min
2: C
2H
4=97:3); Temperature rise rate with 10 ℃/min is heated to 600 ℃.The pyrolysis result is a semi-coke yield 81.5%, and the semicoke sulphur content is reduced to 1.7%, and sulphur content reduced rate (desulfurization degree) is 38.1%; As a comparison, the pyrolysis result that the same terms feeds the 300ml/min pure nitrogen gas down is a semi-coke yield 74%, semicoke sulphur content 1.9%, and semicoke sulphur content reduced rate is 30.9%.Under above-mentioned pyrolytical condition, it is that 3% ethene is as H that pyrolysis gas adds volume ratio
2S captures agent, and semi-coke yield is improved 7.5%, and desulfurization degree improves 7.2%.
Embodiment 5
Get total sulphur content and be 3.78%, granularity adds fixed-bed reactor less than the Yanzhou high sulphur coal 20g of 2mm, feeding pressure is 1MPa, flow is that (the mixed gas volume consists of N for the mixed gas of 300ml/min
2: C
2H
4=95:5); Temperature rise rate with 10 ℃/min is heated to 550 ℃.The pyrolysis result is a semi-coke yield 75.5%, and the semicoke sulphur content is reduced to 2.1%, and sulphur content reduced rate (desulfurization degree) is 44.4%; As a comparison, the pyrolysis result that the same terms feeds the 300ml/min pure nitrogen gas down is a semi-coke yield 58%, semicoke sulphur content 3.0%, and semicoke sulphur content reduced rate is 20.6%.Under above-mentioned pyrolytical condition, it is that 5% ethene is as H that pyrolysis gas adds volume ratio
2S captures agent, and semi-coke yield is improved 17.5%, and desulfurization degree improves 23.8%.
Embodiment 6
Get total sulphur content and be 2.75%, granularity adds fixed-bed reactor less than the high sulphur coal 20g of Datong District of 2mm, feeding pressure is 1MPa, flow is that (the mixed gas volume consists of N for the mixed gas of 300ml/min
2: C
2H
4=95:5); Temperature rise rate with 10 ℃/min is heated to 600 ℃, and temperature stops 5min eventually.The pyrolysis result is a semi-coke yield 87.4%, and the semicoke sulphur content is reduced to 1.3%, sulphur content reduced rate (desulfurization degree) 52.7%; As a comparison, the pyrolysis result that the same terms feeds the 300ml/min pure nitrogen gas down is a semi-coke yield 76%, semicoke sulphur content 2.0%, and semicoke sulphur content reduced rate is 27.3%.Under above-mentioned pyrolytical condition, add volume ratio in the pyrolysis gas and be 5% ethene as H
2S captures agent, and semi-coke yield is improved 11.4%, and desulfurization degree improves 25.4%.
Claims (1)
1. method that improves the coal pyrolysis desulfurization degree, it is characterized in that: described method comprises the steps:
A, at first with sulphur content be 1.5% ~ 4.5%, granularity places fixed-bed reactor less than the coal of 3mm;
B, in fixed-bed reactor, feed and be mixed with H
2S captures the rare gas element of agent as pyrolysis atmosphere, wherein said H
2The mixed volume by volume that S captures agent is 3 ~ 5% of an above-mentioned mixed gas volume; In synthesis pressure is that 0.1 ~ 1.0Mpa, pyrolysis temperature rise rate are that 10 ℃/min, whole temperature are 500 ~ 600 ℃, and under the condition of whole temperature stop 5 ~ 10min coal is carried out pyrolysis, obtains semicoke, wherein said H
2It is ethene that S captures agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105912796A (en) * | 2016-04-19 | 2016-08-31 | 中国科学院青岛生物能源与过程研究所 | Low-rank coal pyrolysis characteristic parameter and semicoke combustion characteristic parameter obtaining method |
| CN107267198A (en) * | 2017-08-11 | 2017-10-20 | 南京康鑫成生物科技有限公司 | A kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil |
| CN107541229A (en) * | 2016-06-24 | 2018-01-05 | 上海梅山钢铁股份有限公司 | A kind of coke and coking process of adapted superelevation sulphur content coking coal |
| CN115216318A (en) * | 2022-07-19 | 2022-10-21 | 沈阳化工大学 | Medium-high sulfur coal pyrolysis desulfurization method |
-
2010
- 2010-12-01 CN CN2010105679364A patent/CN101993702A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 刘全润: "煤的热解转化和脱硫研究", 《中国优秀博硕士学位论文全文数据库（博士） 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105912796A (en) * | 2016-04-19 | 2016-08-31 | 中国科学院青岛生物能源与过程研究所 | Low-rank coal pyrolysis characteristic parameter and semicoke combustion characteristic parameter obtaining method |
| CN105912796B (en) * | 2016-04-19 | 2019-04-02 | 中国科学院青岛生物能源与过程研究所 | The acquisition methods of low-order coal pyrolysis characteristics parameter and its coal-char combustion characterisitic parameter |
| CN107541229A (en) * | 2016-06-24 | 2018-01-05 | 上海梅山钢铁股份有限公司 | A kind of coke and coking process of adapted superelevation sulphur content coking coal |
| CN107267198A (en) * | 2017-08-11 | 2017-10-20 | 南京康鑫成生物科技有限公司 | A kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil |
| CN115216318A (en) * | 2022-07-19 | 2022-10-21 | 沈阳化工大学 | Medium-high sulfur coal pyrolysis desulfurization method |
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Application publication date: 20110330 |