CN110527578A - A kind of method that microwave-assisted halogen simple substance carries out big partial size coal desulfurization - Google Patents
A kind of method that microwave-assisted halogen simple substance carries out big partial size coal desulfurization Download PDFInfo
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- CN110527578A CN110527578A CN201910945201.1A CN201910945201A CN110527578A CN 110527578 A CN110527578 A CN 110527578A CN 201910945201 A CN201910945201 A CN 201910945201A CN 110527578 A CN110527578 A CN 110527578A
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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
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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
- C10L9/06—Treating solid fuels to improve their combustion by chemical means by oxidation
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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 present invention relates to Desulphurization Technology for Coal field, method that specifically a kind of microwave-assisted halogen simple substance carries out big partial size coal desulfurization, it is intended to solve the low technical problem of existing big partial size coal desulfurization method desulfurization degree.Successively the following steps are included: S1, by raw coal by broken, screening process, obtain partial size >=1mm coal sample；S2, configuration pharmacy response: halogen simple substance is dissolved in the water, stablizing solution is formed, obtains desulphurization reaction medicament；S3, the coal sample that step S1 is obtained is mixed with the obtained pharmacy response of step S2, the mass ratio of pharmacy response and coal sample is 2:1 ~ 20:1, obtains mixed reactant；S4, it the obtained mixed reactant of step S3 is placed under microwave radiates, microwave frequency is 300 ~ 2500MHz, and microwave irradiation power is 300 ~ 1000W, and microwave treatment time is 0.5 ~ 10min, and pressure is normal pressure；S5, the obtained coal sample of step S4 is filtered, is washed, obtaining low-sulfur coal sample.
Description
Technical field
The present invention relates to Desulphurization Technology for Coal field, it is de- that specifically a kind of microwave-assisted halogen simple substance carries out big partial size coal
The method of sulphur.
Background technique
As China continues to increase Coal Energy Source consumption intensity, Coal Quality structure numerous imbalances, high-sulfur coal exists
The SO generated in industrial utilization2、SO3, can not only corrode equipment and pipeline, influence equipment life, it is often more important that can seriously pollute
Atmosphere, welding, while also will greatly affect the quality of the industrial products such as downstream coke, steel.Therefore, sulphur content contains in coal
Amount height is the principal element that environmental pollution and restriction coal comprehensive high-efficiency utilize during causing coal utilization.
Currently, Desulphurization Technology for Coal be broadly divided into combustion before, combustion neutralize combustion after desulfurization.Desulfurization is in coal combustion process in combustion
Middle removing sulfide.Desulfurization refers to the sulfide in removing flue gas after combustion.For sulphur coal, latter two desulfurization technology is not only
There is desulfurization pressure is big, the problem of higher cost, while also there is in industrial application itself limitation, for example, extensively
The desulfurization technology of coking high-sulfur cleaned coal applied to steel industry.Not only cost is relatively low for desulfurization before combustion, and desulfurization degree is high, while can pole
The big self-value and application range for improving coal.As country is to the continuous improvement of environmental requirement and Coal Quality structure
Increasingly decline, the economy of coal enterprise, environmental and social benefits can be greatly improved in the high-sulfur desulfurization before coal combustion technology of economical and efficient.
There are mainly three types of methods at present for desulfurization before coal: physical method, chemical method, bioanalysis.Wherein, chemical method can not only take off
Except pyritic sulfur most of in coal, the organic sulfur of more difficult removing in coal can also be removed, it is most potential.Existing chemical desulfurization method
Have very much, such as alkali doctor treatment, hydrogen reduction doctor treatment, oxidation sweetening method etc..Most commonly used oxidation sweetening method is wherein studied to press
According to the difference of oxidant species used in laboratory, ozone/oxygen gas oxidizing process, peroxide acid oxidation, high volence metal ion oxygen can be divided into
Change method etc..But the above method all has a problem that: for partial size be greater than 0.1mm coal sample, desulfurization degree is lower, all 10% with
Under, greatly limit the promotion and application prospect of desulfurization technology.Therefore, the big efficient organic sulfur removal of partial size Coal Economy is researched and developed
Method is of great practical significance.
Summary of the invention
Present invention seek to address that the technical problem that existing big partial size coal desulfurization method desulfurization degree is low.For this purpose, the present invention mentions
A kind of method that microwave-assisted halogen simple substance carries out big partial size coal desulfurization out.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of method that microwave-assisted halogen simple substance carries out big partial size coal desulfurization, successively the following steps are included:
S1, raw coal is passed through into broken, screening process, obtains partial size >=1mm coal sample；
S2, configuration pharmacy response: halogen simple substance is dissolved in the water, stablizing solution is formed, obtains pharmacy response；
S3, the coal sample that step S1 is obtained is mixed with the obtained pharmacy response of step S2, the mass ratio of pharmacy response and coal sample is
2:1 ~ 20:1 obtains mixed reactant；
S4, it the obtained mixed reactant of step S3 is placed under microwave radiates, microwave frequency is 300 ~ 2500MHz, microwave
Radiant power is 300 ~ 1000W, and microwave treatment time is 0.5 ~ 10min, and pressure is normal pressure；
S5, the obtained coal sample of step S4 is filtered, is washed, obtaining low-sulfur coal sample.
Further, there are also step S6 after step S5: the original in low-sulfur coal sample replacement step S1 that step S5 is obtained
Coal, repetitive operation step S1 ~ step S5 is several times.
Further, in step sl, raw coal is processed into partial size is 1 ~ 6mm.
Preferably, the halogen simple substance is elementary chlorine or bromine simple substance.It is further preferred that the halogen simple substance is bromine list
Matter, pharmacy response are bromine water, and bromine water concentration is 1 ~ 3%.
The beneficial effects of the present invention are:
The present invention provides a kind of method that microwave-assisted halogen simple substance carries out big partial size coal desulfurization, will using halogen oxidant
Mercaptan, thioether and thiophene-based organic sulfur compound in coal are oxidized to sub- maple class first (can refer to Fig. 1 ~ Fig. 4, wherein in Fig. 1
X represent halogen), then sub- maple class is continued oxidation and generates sulfonate radical, the water soluble ions such as sulfate radical by halogen simple substance, is passed through
Filter, washing, organic sulfur in coal compound is removed.Halogen simple substance is not only with higher de- in organic sulfur in coal removing application
Sulphur rate, while halogen simple substance and its derivative have price low, it is easy to operate, it is easy purchase, the advantages that stability is high.In addition,
The present invention takes full advantage of that microwave itself is quick, uniform, selective and to polar molecule or polarizable molecule special work
Principle, not only substantially reduces the reaction time of halogen simple substance oxidation sweetening, while it is de- to greatly improve the oxidation of halogen simple substance
Sulphur effect.
Detailed description of the invention
Fig. 1 is the reaction process signal of halogen simple substance oxidation mercaptan, thioether and thiophene-based organic sulfur compound of the invention
Figure；
Fig. 2 is bromine simple substance and sulfide reaction process schematic diagram of the invention；
Fig. 3 is elementary chlorine and sulfide reaction process schematic diagram of the invention；
Fig. 4 is elemental iodine and sulfide reaction process schematic diagram of the invention.
Specific embodiment
Method of the invention is described in detail below by several specific embodiments:
Embodiment 1:
S1, Gaoyang coal 100g is chosen as raw coal, be crushed, sieved, guarantee that partial size in 1 ~ 6mm, obtains coal sample；Here coal
For partial size preferably in the range of 1 ~ 6mm, the desulfuration efficiency within the scope of this is more excellent, in other embodiments, if partial size > 6mm is also
It can.
S2, configuration pharmacy response: bromine simple substance is dissolved in the water, and the bromine aqueous solution that mass concentration is 3% is formed, as de-
Reaction of Salmon-Saxl medicament；Here, the preferred 1%-3% of the concentration of bromine water, the concentration within the scope of this not only can guarantee reaction rate, but also can be not
Guarantee the completeness of desulfurization under the premise of wasting bromine water, wherein 3% is most preferred concentration value, also optional in other embodiments
1% or 1.5% or 2% or 2.5% is selected, as long as halogen solutions, so that it may carry out desulfurization, concentration is to influence the completeness and effect of desulfurization
Rate, this is also exactly the reason of the claim of this application is not defined concentration；
S3, the coal sample that step S1 is obtained is mixed with the obtained bromine aqueous solution of step S2, the mass ratio of bromine aqueous solution and coal sample is
5:1 obtains mixed reactant；Here mass ratio mainly to guarantee that coal sample can soak in a liquid, guarantees the thorough of desulfurization
Property, in other embodiments, 2:1 or 10:1 or 15:1 or 20:1 also may be selected；
S4, it the obtained mixed reactant of step S3 is placed under microwave radiates, microwave frequency 2450MHz, microwave radiation
Power is 300W, and microwave treatment time 1.5min, pressure is normal pressure；In other embodiments, microwave frequency may be selected 300
MHz or 1000 MHz or 1500 MHz or 2000 MHz or 2500 MHz, microwave irradiation power are 500W or 700W or 1000W,
Microwave treatment time is 0.5min or 5min or 10min；
S5, the obtained coal sample of step S4 is filtered, is washed, obtaining low-sulfur coal sample.
The total sulphur content in coal, which is measured, according to high-temp combustion coulomb method is reduced to 1.63% from 2.13%, desulfurization degree 23.47%.
Embodiment 2:
The raw coal in low-sulfur coal sample replacement step S1 that the step S5 of embodiment one is obtained, repetitive operation S1 ~ S5 five times, obtains
Low-sulfur coal sample.
The total sulphur content in coal, which is measured, according to high-temp combustion coulomb method falls below 0.19% from 2.13%, desulfurization degree 91.08%.
It is as follows that coal sample repeats the corresponding desulfurization degree of reaction times:
| Test reaction times | 1 time | 2 times | 3 times | 4 times | 5 times |
| Desulfurization degree % | 23.47 | 43.66 | 56.34 | 74.65 | 91.08 |
Embodiment 3:
S1, Gaoyang coal 100g is chosen as raw coal, be crushed, sieved, guarantee that partial size in 1 ~ 6mm, obtains coal sample；Here coal
For partial size preferably in the range of 1 ~ 6mm, the desulfuration efficiency within the scope of this is more excellent, in other embodiments, if partial size > 6mm is also
It can.
S2, configuration pharmacy response: elementary chlorine is dissolved in the water, and the chlorine water solution that mass concentration is 2% is formed, as de-
Reaction of Salmon-Saxl medicament；Here, the preferred 0.5%-2% of the concentration of chlorine water, the concentration within the scope of this not only can guarantee reaction rate, but also can be
The completeness for guaranteeing desulfurization under the premise of chlorine water is not wasted, wherein 2% is most preferred concentration value, can also in other embodiments
Selection 0.5% or 1% or 1.5%；
S3, the coal sample that step S1 is obtained is mixed with the chlorine water solution that step S2 is obtained, the mass ratio of chlorine water solution and coal sample is
5:1 obtains mixed reactant；Here mass ratio mainly to guarantee that coal sample can soak in a liquid, guarantees the thorough of desulfurization
Property, in other embodiments, 2:1 or 10:1 or 15:1 or 20:1 also may be selected；
S4, it the obtained mixed reactant of step S3 is placed under microwave radiates, microwave frequency 2450MHz, microwave radiation
Power is 300W, and microwave treatment time 3min, pressure is normal pressure；In other embodiments, 300 MHz may be selected in microwave frequency
Or 1000 MHz or 1500 MHz or 2000 MHz or 2500 MHz, microwave irradiation power are 500W or 700W or 1000W, microwave
The processing time is 1.5min or 5min or 10min；
S5, the obtained coal sample of step S4 is filtered, is washed, obtaining low-sulfur coal sample.
The total sulphur content in coal, which is measured, according to high-temp combustion coulomb method is reduced to 1.71% from 2.13%, desulfurization degree 19.71%.
From embodiment 1 and embodiment 3 as can be seen that carrying out big partial size desulfurization using microwave-assisted halogen simple substance of the invention
Method can greatly improve desulfurization degree.
It can be concluded that, the present invention is provided to the low-sulfur coal sample of the 5th step generation of sulfur method, replacement step from embodiment 2
Raw coal in S1 carries out repeatedly repeatedly, desulfurization degree can be made higher and higher.
Claims (5)
1. a kind of method that microwave-assisted halogen simple substance carries out big partial size coal desulfurization, which is characterized in that successively include following step
It is rapid:
S1, raw coal is passed through into broken, screening process, obtains partial size >=1mm coal sample；
S2, configuration pharmacy response: halogen simple substance is dissolved in the water, stablizing solution is formed, obtains pharmacy response；
S3, the coal sample that step S1 is obtained is mixed with the obtained pharmacy response of step S2, the mass ratio of pharmacy response and coal sample is
2:1 ~ 20:1 obtains mixed reactant；
S4, it the obtained mixed reactant of step S3 is placed under microwave radiates, microwave frequency is 300 ~ 2500MHz, microwave
Radiant power is 300 ~ 1000W, and microwave treatment time is 0.5 ~ 10min, and pressure is normal pressure；
S5, the obtained coal sample of step S4 is filtered, is washed, obtaining low-sulfur coal sample.
2. the method that a kind of microwave-assisted halogen simple substance according to claim 1 carries out big partial size coal desulfurization, feature
Be: there are also step S6 after step S5: the raw coal in low-sulfur coal sample replacement step S1 that step S5 is obtained, repetitive operation step
Rapid S1 ~ step S5 is several times.
3. the method that a kind of microwave-assisted halogen simple substance according to claim 2 carries out big partial size coal desulfurization, feature
Be: in step sl, it is 1 ~ 6mm that raw coal, which is processed into partial size,.
4. the method that a kind of microwave-assisted halogen simple substance according to claim 3 carries out big partial size coal desulfurization, feature
Be: the halogen simple substance is elementary chlorine or bromine simple substance.
5. the method that a kind of microwave-assisted halogen simple substance according to claim 4 carries out big partial size coal desulfurization, feature
Be: the halogen simple substance is bromine simple substance, and pharmacy response is bromine water, and bromine water concentration is 1 ~ 3%.
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Citations (6)
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|---|---|---|---|---|
| US4305726A (en) * | 1979-12-21 | 1981-12-15 | Brown Jr George E | Method of treating coal to remove sulfur and ash |
| CN102295969A (en) * | 2011-07-27 | 2011-12-28 | 北京科技大学 | Method having high removal rate and costing little time for simultaneous removal of sulfur and arsenic in sulfur coal |
| US20120031232A1 (en) * | 2010-08-03 | 2012-02-09 | Xiaodi Huang | Method and Apparatus For Coproduction of Pig Iron and High Quality Syngas |
| CN106433851A (en) * | 2016-10-21 | 2017-02-22 | 太原理工大学 | Method for desulfurizing high-sulfur coal through microwaves and peracetic acid aid |
| CN106867619A (en) * | 2017-03-30 | 2017-06-20 | 韩越秦 | A kind of sour coupled desulfurization method of coal |
| CN108728201A (en) * | 2018-06-22 | 2018-11-02 | 山西焦煤集团有限责任公司 | A kind of micro ware auxiliary catalysis ozone liquid phase oxidation sulphur coal sulfur method |
-
2019
- 2019-09-30 CN CN201910945201.1A patent/CN110527578A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4305726A (en) * | 1979-12-21 | 1981-12-15 | Brown Jr George E | Method of treating coal to remove sulfur and ash |
| US20120031232A1 (en) * | 2010-08-03 | 2012-02-09 | Xiaodi Huang | Method and Apparatus For Coproduction of Pig Iron and High Quality Syngas |
| CN102295969A (en) * | 2011-07-27 | 2011-12-28 | 北京科技大学 | Method having high removal rate and costing little time for simultaneous removal of sulfur and arsenic in sulfur coal |
| CN106433851A (en) * | 2016-10-21 | 2017-02-22 | 太原理工大学 | Method for desulfurizing high-sulfur coal through microwaves and peracetic acid aid |
| CN106867619A (en) * | 2017-03-30 | 2017-06-20 | 韩越秦 | A kind of sour coupled desulfurization method of coal |
| CN108728201A (en) * | 2018-06-22 | 2018-11-02 | 山西焦煤集团有限责任公司 | A kind of micro ware auxiliary catalysis ozone liquid phase oxidation sulphur coal sulfur method |
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Application publication date: 20191203 |