CN106433851A - Method for desulfurizing high-sulfur coal through microwaves and peracetic acid aid - Google Patents
Method for desulfurizing high-sulfur coal through microwaves and peracetic acid aid Download PDFInfo
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- CN106433851A CN106433851A CN201610915597.1A CN201610915597A CN106433851A CN 106433851 A CN106433851 A CN 106433851A CN 201610915597 A CN201610915597 A CN 201610915597A CN 106433851 A CN106433851 A CN 106433851A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/02—Treating solid fuels to improve their combustion by chemical means
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/36—Applying radiation such as microwave, IR, UV
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Abstract
The invention discloses a method for desulfurizing high-sulfur coal through microwaves and a peracetic acid aid. The method comprises steps as follows: a coal sample, glacial acetic acid and hydrogen peroxide are mixed in a certain proportion and react in a microwave environment, a product obtained through the reaction is filtered, washed and dried, and finally, low-sulfur coal is obtained. According to the method, the microwaves are taken as main reaction power, oxidative acid is taken as a reaction aid, organic sulfur and inorganic sulfur in coal are removed, the industrial property of coal is ensured basically not to be changed, coal property damage is smaller, the reaction conditions are easy to realize, the controllability is high, the investment cost is lower, the reaction waste liquid is easy to treat, the applicability is high, and the method is a coal desulfurizing method easy to popularize.
Description
Technical field
The present invention relates to a kind of method of coal desulfurization before combustion, particularly a kind of using microwave combined oxidisability auxiliary agent
Coal desulfurization before combustion method.
Background technology
China is the country for mining and applying coal in the world earliest.Even to this day, China remain in the world exploitation and
The most country of application coal resources.Simultaneously as the petroleum and natural gas resource of China is relatively fewer, coal is in China once
Occupy very important status in energy consumption structure, proportion is up to 75%.Even low in coal industry situation in recent years
Under conditions of fan, new forms of energy concept and application theory emerge in an endless stream, leading position of the coal in China's energy resource structure is still difficult dynamic
Shake and will continue to keep for a long time.And in the application of coal, be thermal power plant provide power be one of its main uses, by
This and the coal of consumption of directly being burnt accounts for the 50% of coal total burn-off, this ratio is equally difficult to change at short notice.
Sulfur is a kind of chemical composition of generally existing in coal, and its presence is extremely disadvantageous for the utilization of coal.One
Aspect, the thermal coal for using for directly burning, the sulphur content contained by it can be with SO2And H2The form of S sulfides is discharged into greatly
In gas, the presence in an atmosphere of these sulfur-containing smoke gas is the principal element to form " acid rain "；Meanwhile, the sour gas that in the air contains
Body also can cause major injury to the respiratory tract of human body and skin.On the other hand, for the coal as coking and chemical industry purposes,
The presence of sulphur content also can be had undesirable effect to its coking capacity, caking property etc., and application performance is deteriorated.Generally, coal is pressed
Sulfur-bearing rate can be divided into low-sulfur coal（<1%）, medium sulphur coal（2%~3%）And sulphur coal（>3%）.And in the coal resources of China, high-quality
Coal reserves are relatively fewer and increasingly reduce；High-sulfur coal reserves has accounted for 1/3rd of raw coal gross reserves or so, accounts for raw coal product
The 16.67% of amount, and this ratio will continue rising.At the same time, relevant minimizing SO2Discharge capacity, improve the ecological environment
Cry increasingly strengthens, and the necessity and urgency of coal desulfurization causes the research of sulfur removal technology to be increasingly becoming coal field section to major in
The vital task that closes.
Coal desulfurization before combustion refers to coal before burning is utilized, in advance the sulphur content in removing coal, reducing or
The sulfurous gas content that coal discharges in combustion is eliminated, so as to reduce pollution.In general, the desulfurization before combustion work of coal
Skill mainly has Physical desulfurization, chemical method desulfurization, bacterial desulfurization and Electrochemistry Desulfurization etc..
Microwave desulfurization is to carry out pretreatment to coal in the way of microwave irradiation, then again with flotation or the mode of washing and filtering
Carry out coal, a kind of detached desulfurization means of sulfur.
Microwave is a kind of form of electric field and magnetic field checker energy transmission, is in inside the dielectric medium in microwave field
Induct or intrinsic dipole, ceaselessly upset shake in the electromagnetic field of checker.Frequency due to this checker
Very high, dipole, during this frequency of response does high frequency rotational, is hindered by inertia, elasticity and friction, and
Generation connects electrical loss, i.e. microwave energy and decays, and material is by the microwave energy for absorbing for heat energy, and the degree for heating depends on ore deposit
The different dielectric property of thing component.Simultaneously as the thermal coefficient of expansion difference of different minerals, then produce between different minerals group separating surface
Heat is strained, and then crack occurs.Research shows, sulfide mineral is much better than to the response ratio coal of microwave, quartz etc., therefore permissible
Make by way of microwave heating between sulphide ore and coal, to produce crack and then removed by crushing dissociation.
Research shows, pyrite can show good floatability when surface occurs mild oxidation, and completely fresh
Surface and highly oxidized surface can then make pyrite lose floatability.The irradiation of microwave can make the sulfur in coal occur to oxidation state
The trend of conversion, so that pyrite is effectively suppressed in floatation process.Meanwhile, the irradiation of microwave divides to the big of coal itself
Minor structure does not cause obvious impact, is only the mass loss for generating part, i.e. volatile matters loss, therefore to coking capacity
Little Deng coal index impact, for the desulfurization of coal for coking, microwave treatment shows good application prospect.
Additionally, when microwave in acid or alkaline environment with oxidisability auxiliary agent collective effect when, by the organic sulfur in coal and can solve
From for soluble sulphate, so as to reach the purpose of removing organic sulfur.
At present, the detailed mechanism of microwave desulfurization is still not clear, still without practicable microwave desulfurization method in reality
Central it is applied.
Content of the invention
It is an object of the invention to provide a kind of method that utilization microwave carries out desulfurization under peracetic acid system, in order to more
Deficiency of the current coal washing technique in terms of desulfurized effect is mended, improves cleaned coal quality, advance clean coal utilization.
For realizing above-mentioned technical purpose, the technical solution of the present invention is as follows.
A kind of sulfur method of microwave combined peracetic acid auxiliary agent to sulphur coal, the sulfur method be follow these steps to into
Row：
（1）Sulphur coal is dried as former state to air-dried state, is ground to standby less than 0.2mm granularity；
（2）Peracetic acid soln is prepared with quartz container, want in process for preparation to be sufficiently stirred for Glass rod in mixing, single-point is mixed
Sum velocity not should be greater than 0.1L/min, and medicament mixing is continued to be sufficiently mixed with the coal sample for preparing after finishing, and uses motor stirrer
10-15min is sufficiently stirred for being thoroughly mixed moistening with the rotating speed of 350-500r/min；
（3）After will be equipped with mixing, the quartz container of sample is put in microwave reactor, is carried out microwave irradiation at ambient pressure, and is compareed
Sample deionized water after penetrating carries out vacuum filtration, washs to filtrate pH value less than 8.0, after sample be put into 75 DEG C of constant temperature dry
Case drying obtains low-sulfur coal to air-dried state.
Wherein, the sulphur coal is Anthracite, and the volatile matters of its dry ash free basis are done in the range of 7.0%-10.0%
The hydrogen content of dry ash free basis is in 3.5%-5.0%；The peracetic acid be with 3:Glacial acetic acid and peroxide that 1 volume ratio is formulated
Change hydrogen, solution is 1 with the solid-to-liquid ratio of coal sample:14；The power of the microwave is 750W, and exposure time is 4-6min；Described is micro-
The reaction chamber of ripple reactor is that acid resistance corrosion pipeline is connected with outdoor wide open space, in course of reaction in microwave reaction chamber
Temperature control is at 140 ± 10 DEG C；Described carry out microwave irradiation at ambient pressure, after irradiation first by sample be placed in moving air cool down
To room temperature, and with clear water, remaining reaction promoter is diluted to after 3 times of volumes and carries out vacuum filtration, washing；The sulphur coal warp
After desulfurization process, inorganic sulfur removal rate therein is more than 90%, and organic sulfur removal rate is in 10%-23%.
Sulfur method of above-mentioned the provided a kind of microwave combined peracetic acid auxiliary agent of invention to sulphur coal, with prior art
Compare, one be microwave reaction precision requirement relatively low, be easily achieved on equipment；Two is that microwave reaction itself is relatively gentleer, instead
Answer process easily controllable；Three be reacted component of effluent based on acetic acid, Pollutant Treatment is relatively simple；Four is this method pair
Inorganic sulfur and organic sulfur in coal all has excellent removal effect, and after testing, inorganic sulfur removal rate is more than 90%, organic sulfur removal
Rate, in 10%-23%, is effective supplement of existing desulfurization washing process.
Specific embodiment
Hereinafter the specific embodiment of the present invention is further illustrated.
Embodiment 1
Implement a kind of sulfur method of microwave combined peracetic acid auxiliary agent to sulphur coal, the comprising the following steps that of the sulfur method：
Step one, will dry be ground to the high-sulfur coal sample after air-dried state standby less than 0.2mm particle size fraction；
Step 2, by glacial acetic acid（CH3COOH）And hydrogen peroxide（H2O2）With 3:1 volume ratio is made into peracetic acid soln, prepares
During want while mixing while be sufficiently stirred for Glass rod, single-point mixing velocity not should be greater than 0.1L/min；
Step 3, using high temperature resistant quartz container, ground coal sample is mixed with peracetic acid soln, solid-to-liquid ratio be:14, use
Agitator makes coal sample be thoroughly mixed with solution and moistening with the continuously stirred 10-15min of the rotating speed of 350-500r/min；
Step 4：The container for filling reactant is placed in microwave reactor, and microwave irradiation, microwave work(is carried out under atmospheric pressure environment
Rate is 700W, and exposure time is that 4min, the temperature control in microwave reaction chamber exists（140±10）DEG C in irradiation process, use
The reaction chamber of microwave reactor is connected by the pipeline of acid resistance corrosion with outdoor wide open space, in order to exclude reactor off-gas；
After step 5, microwave irradiation terminate, reaction vessel is placed in ventilating air environment and is slowly cooled to room temperature, and use clear water
After being diluted to 3 times of volumes, with vacuum filtration machine sucking filtration, and continuous deionized water rinses coal sample during sucking filtration, until filter
Liquid pH value stops washing after being less than 8.0；
Step 6, the coal sample by sucking filtration, after washing are put into 75 DEG C of constant temperature oven dryings to air-dried state, that is, obtain low-sulfur
Coal.
The above, simply one simple application example of the present invention, not makees to the technology application scope of the present invention any
Limit, as long as the change done of claim under this invention and claims or modification, should all belong to patent of the present invention culvert
Within the scope of lid.
Claims (7)
1. sulfur method of a kind of microwave combined peracetic acid auxiliary agent to sulphur coal, the sulfur method is to follow these steps to carry out
's：
（1）Sulphur coal is dried as former state to air-dried state, is ground to standby less than 0.2mm granularity；
（2）Peracetic acid soln is prepared with quartz container, want in process for preparation to be sufficiently stirred for Glass rod in mixing, single-point is mixed
Sum velocity not should be greater than 0.1L/min, and medicament mixing is continued to be sufficiently mixed with the coal sample for preparing after finishing, and uses motor stirrer
10-15min is sufficiently stirred for being thoroughly mixed moistening with the rotating speed of 350-500r/min；
（3）After will be equipped with mixing, the quartz container of sample is put in microwave reactor, is carried out microwave irradiation at ambient pressure, and is compareed
Sample deionized water after penetrating carries out vacuum filtration, washs to filtrate pH value less than 8.0, after sample be put into 75 DEG C of constant temperature dry
Case drying obtains low-sulfur coal to air-dried state.
2. the sulfur method according to claims 1, the sulphur coal is Anthracite, the volatilization of its dry ash free basis
Divide in the range of 7.0%-10.0%, the hydrogen content of dry ash free basis is in 3.5%-5.0%.
3. the sulfur method according to claims 1, the peracetic acid be with 3:The ice second that 1 volume ratio is formulated
Acid and hydrogen peroxide, solution is 1 with the solid-to-liquid ratio of coal sample:14.
4. the sulfur method according to claims 1, the power of the microwave is 750W, exposure time be.
5. the sulfur method according to claims 1, the reaction chamber of described microwave reactor is acid resistance corrosion pipeline
It is connected with outdoor wide open space, the temperature control in course of reaction in microwave reaction chamber is at 140 ± 10 DEG C.
6. the sulfur method according to claims 1, described carry out microwave irradiation at ambient pressure, first sample is put after irradiation
It is cooled to room temperature in moving air, and with clear water, remaining reaction promoter is diluted to after 3 times of volumes and carries out vacuum filtration, wash
Wash.
7. the sulfur method according to claims 1, the sulphur coal after desulfurization process, inorganic sulfur removal rate therein
More than 90%, organic sulfur removal rate is in 10%-23%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610915597.1A CN106433851A (en) | 2016-10-21 | 2016-10-21 | Method for desulfurizing high-sulfur coal through microwaves and peracetic acid aid |
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| CN201610915597.1A CN106433851A (en) | 2016-10-21 | 2016-10-21 | Method for desulfurizing high-sulfur coal through microwaves and peracetic acid aid |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107513449A (en) * | 2017-10-19 | 2017-12-26 | 河北工程大学 | A kind of technique of coal desulfurization before combustion |
| CN107903981A (en) * | 2017-11-23 | 2018-04-13 | 安徽理工大学 | The method that desulfurizing agent and desulfurizing agent United microwave carry out coal desulfurization |
| CN110527578A (en) * | 2019-09-30 | 2019-12-03 | 山西焦煤集团有限责任公司 | A kind of method that microwave-assisted halogen simple substance carries out big partial size coal desulfurization |
| CN110527577A (en) * | 2019-09-30 | 2019-12-03 | 山西焦煤集团有限责任公司 | A kind of technique that microwave-assisted halogen simple substance carries out big partial size coal desulfurization |
| CN112194736A (en) * | 2020-09-24 | 2021-01-08 | 长春工业大学 | Method for preparing chitosan oligosaccharide by microwave-peroxide coupling degradation of chitosan |
| CN113728076A (en) * | 2019-04-24 | 2021-11-30 | 杰富意钢铁株式会社 | Method for producing low-sulfur coal |
| CN113748186A (en) * | 2019-04-24 | 2021-12-03 | 杰富意钢铁株式会社 | Method for producing low-sulfur coal |
| RU2780625C1 (en) * | 2019-04-24 | 2022-09-28 | ДжФЕ СТИЛ КОРПОРЕЙШН | Method for producing coal with a low sulphur content |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107513449A (en) * | 2017-10-19 | 2017-12-26 | 河北工程大学 | A kind of technique of coal desulfurization before combustion |
| CN107903981A (en) * | 2017-11-23 | 2018-04-13 | 安徽理工大学 | The method that desulfurizing agent and desulfurizing agent United microwave carry out coal desulfurization |
| CN113728076A (en) * | 2019-04-24 | 2021-11-30 | 杰富意钢铁株式会社 | Method for producing low-sulfur coal |
| CN113748186A (en) * | 2019-04-24 | 2021-12-03 | 杰富意钢铁株式会社 | Method for producing low-sulfur coal |
| US20220220404A1 (en) * | 2019-04-24 | 2022-07-14 | Jfe Steel Corporation | Low-sulfur coal production method |
| RU2780625C1 (en) * | 2019-04-24 | 2022-09-28 | ДжФЕ СТИЛ КОРПОРЕЙШН | Method for producing coal with a low sulphur content |
| RU2790043C1 (en) * | 2019-04-24 | 2023-02-14 | ДжФЕ СТИЛ КОРПОРЕЙШН | Method for preparation of carbon with low sulfur content |
| CN110527578A (en) * | 2019-09-30 | 2019-12-03 | 山西焦煤集团有限责任公司 | A kind of method that microwave-assisted halogen simple substance carries out big partial size coal desulfurization |
| CN110527577A (en) * | 2019-09-30 | 2019-12-03 | 山西焦煤集团有限责任公司 | A kind of technique that microwave-assisted halogen simple substance carries out big partial size coal desulfurization |
| CN112194736A (en) * | 2020-09-24 | 2021-01-08 | 长春工业大学 | Method for preparing chitosan oligosaccharide by microwave-peroxide coupling degradation of chitosan |
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Application publication date: 20170222 |