CN102041128B - Chemical deashing method for coal - Google Patents

Chemical deashing method for coal Download PDF

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CN102041128B
CN102041128B CN 201010571741 CN201010571741A CN102041128B CN 102041128 B CN102041128 B CN 102041128B CN 201010571741 CN201010571741 CN 201010571741 CN 201010571741 A CN201010571741 A CN 201010571741A CN 102041128 B CN102041128 B CN 102041128B
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deliming
acid
coal
chemical
solution
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CN102041128A (en
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蒋伟
李晓蓉
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Yibin Tianyuan Group Co Ltd
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Yibin Tianyuan Group Co Ltd
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Abstract

The invention discloses a chemical deashing method for coal, belonging to the technical field of clean coal. A novel deashing acid solution is adopted for deashing coal and is a mixed acid of hydrofluoric acid and at least one other inorganic acid, wherein the mass percentage content of the hydrofluoric acid is 5-30%, the mass percentage content of other inorganic acids is 10-40%, and total acid concentration is 10-40%; during acid leaching, the mass ratio of the deashing acid solution to the raw material coal is (1-6):1, reaction temperature is 10-80DEG C, and the process of acid leaching lasts for 4-24 hours; and meanwhile, after exhaust gas and scouring water, generated in a defluorination processing, are graded and reused and a waste mixed acid solution is repeatedly reused, a lime solution is adopted for absorption. The method provided by the invention is suitable for deashing larger coal particles of which the diameter is 1-5mm, and can achieve a better deashing effect. A moderate reaction condition is adopted to ensure that the deashing mixed acid containing hydrofluoric acid is difficult to volatilize, so that energy consumption and cost are lowered and environmental pollution is lightened at the same time.

Description

A kind of chemical deliming method of coal
Technical field
The present invention relates to a kind of high-purity preparation of coal method, be specifically related to a kind of chemical deliming method of coal.
Background technology
The rich coal resources of China, great variety of goods, but inorganic mineral (ash content) content is higher, thereby limited in industrial widespread use in certain degree.Particularly coal is used for the application in the fields such as oil engine in carbon electrode manufacturing, graphite product, gac, high temperature lubricating, oil replacement, and pit ash content has been proposed high requirement.Also there are the large problem of cost consumption in the storage of ash coal, transportation.Therefore, the exploitation of the deliming technology of coal becomes the clean coal technology that obtains broad research for a long time.
At present, the ash removal from raw coal method for preparing high-purity coal, super clean coal mainly is divided into Physical, chemical deliming method, physical chemistry deliming method three major types.
Wherein, chemical method has the characteristics of thorough, the applicable face width of deliming, thereby occupies critical role in producing the technique of super clean coal.The chemical deliming method has hydrofluoric acid method, acid-base method, melting alkali leaching process, chemical coal technology etc., ash content can be down to about 0.5% when effect is better, but because complex process, cost is high, and its development is restricted.
When adopting the chemical method deliming, the granularity of general requirement feed coal is thinner, and raw coal size is thinner, and the deliming rate is higher, and cleans ash almost reduces with being lowered into of raw material granularity is linear.
Present pickling chemical deliming technology, the general nitration mixture that adopts HF or hydrofluoric acid containing, to the proposition of raw material granularity and ash content high requirement, producing of super clean coal, the general nitration mixture of hydrofluoric acid containing that adopts is not higher than 10% to ash oontent, be preferably in below 3.0%, the feed coal of particle diameter below 1mm carries out deliming.
The advantage that it has been generally acknowledged that chemical method is the grinding rate that feed coal needn't reach monomer dissociation, and the effect of deliming is not limited by the raw material pit ash.But in fact present pickling chemical deliming method has still proposed high requirement to the particle fineness of feed coal for guaranteeing the deliming effect, is conducive to like this acid solution can fully contact with the coal surface, and the micropore that diffuses into rapidly coal carries out deliming.But coal is milled down to a certain degree can increase energy consumption, and will bring difficulty to subsequent disposal such as filtration, washings, and significant loss is large, has reduced production efficiency.Because the de-ash coal granularity is meticulous, caused the limitation of its range of application simultaneously.
Summary of the invention
The chemical deliming method that the purpose of this invention is to provide the low coal of the high production cost of a kind of production efficiency that addresses the above problem.
The technical scheme that the present invention solves the problems of the technologies described above is: a kind of chemical deliming method of coal, adopt following steps: feed coal is mixed with the deliming acid solution carry out acid-leaching reaction, after the reaction with deliming product and solution separating, obtain deliming product and waste mixed acid liquid, the deliming product is washed, then the deliming product is dried, deliming product after the oven dry carries out defluorinate to be processed, the repeatedly reuse of waste mixed acid liquid, described deliming acid solution is the nitration mixture of hydrofluoric acid and at least a other mineral acids, and wherein, the quality percentage composition of hydrofluoric acid is 5%-30%, the quality percentage composition of other mineral acids is 10-40%, and total acid concentration is 10-40%.
As preferably: the quality percentage composition of hydrofluoric acid is 8%-15%, and the quality percentage composition of other mineral acids is 10-20%.
As preferably: described other mineral acids are at least a in hydrochloric acid, nitric acid, the sulfuric acid.
As preferably: during acid-leaching reaction, the physique of deliming acid solution and feed coal is than being (1-6): 1, and temperature of reaction is 10-80 ℃, leaching time 4-24 hour, so-called physique ratio, i.e. ratio between the quality of the volume of deliming acid solution and feed coal.
Further: during acid-leaching reaction, the deliming acid solution is (2-4) with the physique ratio of feed coal: 1, and temperature of reaction is 20-60 ℃, leaching time is 6-12 hour.
As preferably: the waste gas that produces when defluorinate is processed, adopt lime solution to absorb processing.
As preferably: after the washing, behind the washing water grading recycle, add lime and process, behind the clarification filtration, discharge.
As preferably: waste mixed acid liquid repeatedly after the reuse, adds lime and processes, and extracts filtering emission behind the Calcium Fluoride (Fluorspan).
Beneficial effect of the present invention is: the one, through great many of experiments, adopted the nitration mixture prescription of new hydrofluoric acid containing, make it go for the deliming that particle diameter is the larger coal particle of 1-5mm, simultaneously can reach preferably deliming effect, ash oontent can be no more than 5.0% coal deliming after ash oontent drop to below 0.9%.From the angle of heat transfer, mass transfer, momentum transfer, the granularity of coal is thinner, and surface-area is larger, more is beneficial to sour deliming reaction.Present technique is in conjunction with coal characteristics, explore deliming mechanism by great many of experiments, obtained being applicable to the reaction conditions of large particle diameter coal (1-5mm) deliming, and by changing reaction conditions, can obtain low ash (Ad<2.0%) even Carbon from Ultra-low-ash Coal (Ad<1.0%), and in deliming, sulphur content is reduced to below 2.0%, so that deliming efficient improves, ature of coal obtains deep purifying;
The 2nd, adopted gentle reaction conditions, make the deliming nitration mixture of hydrofluoric acid containing not volatile, take full advantage of, reduce energy consumption, alleviated environmental pollution when having saved cost;
The 3rd, recycle, waste gas is absorbed for the classification of the waste water that produces in the present technique production process, waste mixed acid liquid, adopt at last lime to process, further alleviated environmental pollution, environmental friendliness.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
A kind of chemical deliming method of coal, the step that adopts is: be 1-5mm with particle diameter, ash oontent is that 4.9% contain culm and deliming solution carry out the acid-leaching reaction deliming under 10 ℃ of temperature, reaction times is 4 hours, deliming solution is the nitration mixture of hydrofluoric acid and hydrochloric acid, wherein fluohydric acid content is 5%, content of hydrochloric acid is 10%, behind the acid-leaching reaction with deliming product and solution separating, obtain deliming product and waste mixed acid liquid, behind the oven dry deliming product, in calcining furnace, the deliming product is carried out defluorinate and process, adopt simultaneously lime solution to absorb calciner emission, the deliming waste mixed acid repeatedly after the reuse, adds lime and processes, and extracts the Calcium Fluoride (Fluorspan) filtering emission, behind the washing water grading recycle, add lime and process, behind the clarification filtration, discharge.The ash oontent of the de-ash coal that obtains at last is 0.9%.
Embodiment 2
A kind of chemical deliming method of coal, the step that adopts is: be 1-5mm with particle diameter, ash oontent is that 4.9% contain culm and deliming solution carry out the acid-leaching reaction deliming under 80 ℃ of temperature, reaction times is 24 hours, deliming solution is the nitration mixture of hydrofluoric acid and hydrochloric acid, wherein fluohydric acid content is 30%, content of hydrochloric acid is 40%, behind the acid-leaching reaction with deliming product and solution separating, obtain deliming product and waste mixed acid liquid, behind the oven dry deliming product, in calcining furnace, the deliming product is carried out defluorinate and process, adopt simultaneously lime solution to absorb calciner emission, the deliming waste mixed acid repeatedly after the reuse, adds lime and processes, and extracts the Calcium Fluoride (Fluorspan) filtering emission, behind the washing water grading recycle, add lime and process, behind the clarification filtration, discharge.The ash oontent of the de-ash coal that obtains at last is 0.5%.
Embodiment 3
A kind of chemical deliming method of coal, the step that adopts is: be 1-5mm with particle diameter, ash oontent be 4.9% contain culm and deliming solution carries out the acid-leaching reaction deliming under temperature 60 C, reaction times is 12 hours, deliming solution is the nitration mixture of hydrofluoric acid and hydrochloric acid, wherein fluohydric acid content is 15%, content of hydrochloric acid is 20%, behind the acid-leaching reaction with deliming product and solution separating, obtain deliming product and waste mixed acid liquid, behind the oven dry deliming product, in calcining furnace, the deliming product is carried out defluorinate and process, adopt simultaneously lime solution to absorb calciner emission, the deliming waste mixed acid repeatedly after the reuse, adds lime and processes, and extracts the Calcium Fluoride (Fluorspan) filtering emission, behind the washing water grading recycle, add lime and process, behind the clarification filtration, discharge.The ash oontent of the de-ash coal that obtains at last is 0.6%.
Embodiment 4
A kind of chemical deliming method of coal, the step that adopts is: be 1-5mm with particle diameter, ash oontent be 4.9% contain culm and deliming solution carries out the acid-leaching reaction deliming under temperature 60 C, reaction times is 12 hours, deliming solution is hydrofluoric acid, the nitration mixture of hydrochloric acid and nitric acid, wherein fluohydric acid content is 15%, content of hydrochloric acid is 10%, nitric acid content is 10%, behind the acid-leaching reaction with deliming product and solution separating, obtain deliming product and waste mixed acid liquid, behind the oven dry deliming product, the deliming product carried out defluorinate in calcining furnace and process, adopt simultaneously lime solution to absorb calciner emission, the deliming waste mixed acid is repeatedly after the reuse, adding lime processes, extract the Calcium Fluoride (Fluorspan) filtering emission, behind the washing water grading recycle, add lime and process, behind the clarification filtration, discharge.The ash oontent of the de-ash coal that obtains at last is 0.52%.
Embodiment 5
A kind of chemical deliming method of coal, the step that adopts is: be 1-5mm with particle diameter, ash oontent be 4.9% contain culm and deliming solution carries out the acid-leaching reaction deliming under temperature 60 C, reaction times is 12 hours, deliming solution is hydrofluoric acid, hydrochloric acid, nitration mixture, wherein fluohydric acid content is 20%, content of hydrochloric acid is 8%, nitric acid content is 2%, sulfuric acid content is 5%, behind the acid-leaching reaction with deliming product and solution separating, obtain deliming product and waste mixed acid liquid, behind the oven dry deliming product, the deliming product carried out defluorinate in calcining furnace and process, adopt simultaneously lime solution to absorb calciner emission, the deliming waste mixed acid is repeatedly after the reuse, adding lime processes, extract the Calcium Fluoride (Fluorspan) filtering emission, behind the washing water grading recycle, add lime and process, behind the clarification filtration, discharge.The ash oontent of the de-ash coal that obtains at last is 0.61%.
Embodiment 6
A kind of chemical deliming method of coal, the step that adopts is: be 1-5mm with particle diameter, ash oontent be 4.9% contain culm and deliming solution carries out the acid-leaching reaction deliming under temperature 60 C, reaction times is 12 hours, deliming solution is hydrofluoric acid, nitration mixture, wherein fluohydric acid content is 15%, nitric acid content is 7%, sulfuric acid content is 10%, behind the acid-leaching reaction with deliming product and solution separating, obtain deliming product and waste mixed acid liquid, behind the oven dry deliming product, the deliming product carried out defluorinate in calcining furnace and process, adopt simultaneously lime solution to absorb calciner emission, the deliming waste mixed acid is repeatedly after the reuse, adding lime processes, extract the Calcium Fluoride (Fluorspan) filtering emission, behind the washing water grading recycle, add lime and process, behind the clarification filtration, discharge.The ash oontent of the de-ash coal that obtains at last is 0.53%.

Claims (8)

1. the chemical deliming method of a coal, adopt following steps: feed coal is mixed with the deliming acid solution carry out acid-leaching reaction, after the reaction with deliming product and solution separating, obtain deliming product and waste mixed acid liquid, the deliming product is washed, then the deliming product is dried, deliming product after the oven dry carries out defluorinate to be processed, the repeatedly reuse of waste mixed acid liquid is characterized in that, described deliming acid solution is the nitration mixture of hydrofluoric acid and at least a other mineral acids, wherein, the quality percentage composition of hydrofluoric acid is 5%-30%, and the quality percentage composition of other mineral acids is 10-40%, and total acid concentration is 10-40%.
2. the chemical deliming method of a kind of coal according to claim 1, it is characterized in that: the quality percentage composition of hydrofluoric acid is 8%-15%, the quality percentage composition of other mineral acids is 10-20%.
3. the chemical deliming method of a kind of coal according to claim 1 is characterized in that: described other mineral acids are at least a in hydrochloric acid, nitric acid, the sulfuric acid.
4. the chemical deliming method of a kind of coal according to claim 1 is characterized in that: during acid-leaching reaction, the physique of deliming acid solution and feed coal is than being (1-6): 1, and temperature of reaction is 10-80 ℃, leaching time 4-24 hour.
5. the chemical deliming method of a kind of coal according to claim 4 is characterized in that: during acid-leaching reaction, the physique of deliming acid solution and feed coal is than being (2-4): 1, and temperature of reaction is 20-60 ℃, leaching time is 6-12 hour.
6. the chemical deliming method of a kind of coal according to claim 1 is characterized in that: the waste gas that produces when defluorinate is processed, adopt lime solution to absorb processing.
7. the chemical deliming method of a kind of coal according to claim 1 is characterized in that: after the washing, behind the washing water grading recycle, add lime and process, behind the clarification filtration, discharge.
8. the chemical deliming method of a kind of coal according to claim 1 is characterized in that: waste mixed acid liquid repeatedly after the reuse, adds lime and processes, and extracts filtering emission behind the Calcium Fluoride (Fluorspan).
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Cited By (1)

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CN104891470A (en) * 2015-04-17 2015-09-09 石家庄新华能源环保科技股份有限公司 Method for high-temperature removal of coal powder ash

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CN103421567A (en) * 2013-01-10 2013-12-04 泸州兰良水泥有限公司 Pure coal and production method thereof
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CN104774635A (en) * 2015-03-27 2015-07-15 陕西省石油化工研究设计院 Treatment method for acid washing and deashing of coal liquefaction residue
CN105154165B (en) * 2015-07-10 2017-05-31 江苏徐矿能源股份有限公司 A kind of method for reducing ash content in ash coal mud
CN105670731B (en) * 2016-02-19 2018-07-20 山东省计量科学研究院 A method of carrying out overcritical deliming using five-membered ring structure amidino groups reunion amidine
CN107478667A (en) * 2016-11-15 2017-12-15 西安科技大学 A kind of deliming processing method applied to XRD test analysis coal samples
CN106867619A (en) * 2017-03-30 2017-06-20 韩越秦 A kind of sour coupled desulfurization method of coal
CN107573978A (en) * 2017-10-19 2018-01-12 兖矿集团有限公司 Chemical method prepares the removing system and method for acid-soluble mineral in ultra-clean coal
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CN110272772B (en) * 2019-08-05 2021-02-19 中南大学 Preparation method of ultra-pure anthracite
CN111250021A (en) * 2020-01-22 2020-06-09 中国矿业大学 Environment-friendly fine coal chemical deashing equipment and method

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CN104891470A (en) * 2015-04-17 2015-09-09 石家庄新华能源环保科技股份有限公司 Method for high-temperature removal of coal powder ash
CN104891470B (en) * 2015-04-17 2019-04-30 石家庄新华能源环保科技股份有限公司 A kind of method of high temperature removal coal powder fraction

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Application publication date: 20110504

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Denomination of invention: A Chemical Deashing Method for Coal

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