CN108611153A - A kind of method of organic sulfur compound in removing bituminous coal - Google Patents
A kind of method of organic sulfur compound in removing bituminous coal Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002802 bituminous coal Substances 0.000 title claims abstract description 18
- 150000002898 organic sulfur compounds Chemical class 0.000 title claims abstract description 10
- 239000003245 coal Substances 0.000 claims abstract description 82
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 239000005864 Sulphur Substances 0.000 claims abstract description 25
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 24
- 230000023556 desulfurization Effects 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000002604 ultrasonography Methods 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000002817 coal dust Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000052 vinegar Substances 0.000 abstract 1
- 235000021419 vinegar Nutrition 0.000 abstract 1
- 125000001741 organic sulfur group Chemical group 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 235000001508 sulfur Nutrition 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 3
- 239000003830 anthracite Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000003077 lignite Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000004021 humic acid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910003252 NaBO2 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000329 molecular dynamics simulation Methods 0.000 description 1
- 238000000324 molecular mechanic Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010181 polygamy Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- -1 therefore Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C10L2290/38—Applying an electric field or inclusion of electrodes in the apparatus
-
- 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
- C10L2290/60—Measuring or analysing fractions, components or impurities or process conditions during preparation or upgrading of a fuel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Treating Waste Gases (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
A kind of method of organic sulfur compound in removing bituminous coal, it is therefore an objective to which desulfurization effect is good, rate of sulphur expulsion is fast；The present invention first takes granularity 8mm coal samples below to divide 7 parts of isodose, retains 1 part, remaining 6 parts are fitted into ceramic disk after sodium hydroxide solution impregnates and are put by several times in ultrasound microwave chemical reactor and carry out microwave frequency modulation irradiation test respectively；It is separately added into after irradiation in hydrogen peroxide and impregnates, impregnated in vinegar；It chemically examines coal sample sulfur content and compared with the portion of reservation, selects out the highest microwave frequency value of desulfuration efficiency；It is respectively put into alkaline electrolyte again, electrolyzer power source uses high frequency pulse dc square wave power, selects voltage 3V, per square meter electrode 400A electric currents；It is electrolysed under selection different electrical power frequency, selects the highest supply frequency of desulfuration efficiency；According to production line batch desulfurization in selected microwave frequency value, electrolyzer power source voltage, electric current and frequency.
Description
Technical field
The invention belongs to technical field of desulfurization, and in particular to a kind of more technologies, the combined removing organic sulfur in coal of more means
And the method for attached production high-purity hydrogen.
Background technology
Coal is the macromolecule condensed polymer of the highly cross-linked non-matter of three dimensions, and the core of coal molecule basic structural unit is
It is condensed aromatic proton, is the irregularities being connected to around basic structural unit, is the existence form of oxygen, ammonia, sulphur；In other words,
Coal is the polymer of three-phase material, and is the compound of organic matter and inanimate matter.So coal is the compound of organic matter and inanimate matter
Object.Sulphur in coal can be divided into the organic sulfur of the impurity inorganic sulfur of physics incorporation and the component part of coal according to existing forms.It is inorganic
Sulphur is mainly sulfide, sulfate and a small amount of elemental sulfur.Organic sulfur in coal is a series of general name of sulfur-containing organic functional groups,
It is broadly divided into two parts：A part is the sulfur-bearing low molecular compound for including in the extract that available organic solvent extracting obtains；
Another part is in the basic structural unit that coal is incorporated in C-S keys（Coal macromolecule skeleton）On organic sulfur.Generally, in coal
Organic sulfur mainly include mercaptan sulfide and disulphide, thiophene, sulfoxide and sulfone etc..Sulphur be in coal main accompanying elements it
One, directly burning when the oxygen sulfur compound that discharges and the fine particle for being enriched plurality of heavy metal be environmental pollution it is most outstanding because
Element.The difference of Coal-forming Plants source and the condition of coal formation causes answering for coal specific diversity and coal fundamental property in coal generating process
Polygamy can be divided into peat, four major class of lignite, bituminous coal and anthracite according to the different humic coals of degree of coalification.Main point used in coal
Class index includes indicating the dry ash free basis volatile matter Vdaf of degree of coalification, for distinguishing anthracite, bituminous coal and lignite；Or it indicates
The cohesiveness index of technologic properties of coal energy.Bituminous coal is the coal that nature is most important, distribution is most wide, reserves are maximum and kind is most,
It is the raw material of coking, oil refining, gasification, low temperature distillation and chemical industry etc., fuel can also be directly used as, bituminous coal can be also used for
Fuel cell, catalyst or carrier, soil conditioner, filtering agent, construction material adsorbent handle waste water etc..The degree of coalification of bituminous coal
Less than anthracite be higher than lignite, because burning when cigarette more than due to gain the name.Because the humic acid in bituminous coal has been completely reformed into more complicated
Neutral humus, therefore, bituminous coal cannot make acid, aqueous slkali dyeing.General bituminous coal has different degrees of gloss, most
In light and shade alternate ribbons shape.Appearance is in black, and hardness is larger, and real density is higher（1.20~1.45g/cm3）.Bituminous coal phosphorus content is
75%-90%, without free humic acid.It is most of that there is caking property；Calorific value is higher.Flame is long when burning and thickness, most
Energy coking, density about 1.2-1.5, volatile matter about 10-40%, relative density 1.25-1.35, calorific value about 27170-37200 kilojoule/
Kilogram（6500-8900 kilocalories/kilogram）.The medium referred to as metabituminous coal of volatile content, it is lower to be referred to as ub-bituminous coal.How effectively
Removing organic sulfur in coal compound, be always a problem.
Invention content
Purpose of the present invention is to overcome the shortcomings of above-mentioned prior art, provide that a kind of desulfurization effect is good, rate of sulphur expulsion is fast and can
The method of organic sulfur compound in the removing bituminous coal of co-producing hydrogen.
The present invention uses different organic solvents continuous extraction, passes through x-ray photoelectron spectroscopy（XPS）To coal sample and different extractions
Excess is analyzed, and with quantum chemistry, molecular mechanics, molecular dynamics, covers support Caro and the micro- excellent method computational theory of free energy,
It combines the swarming fitting result of energy to judge organic sulfur type according to S2P, the content of different organic sulfurs is known according to swarming area, is sentenced
Break different organic sulfur compound removal effects, and preserves these data.
A kind of method of organic sulfur compound in removing bituminous coal, it is characterized in that：
（1）It takes coal sample to carry out preproduction-type test, finds out suitable microwave frequency；
1）Take granularity to divide 7 parts of isodose in 8mm coal samples below, retain 1 part, remaining 6 parts be separately immersed in it is a concentration of
In 500mol/l sodium hydroxide solutions；Stirring separation soaking liquid and dries coal sample for several times, after 2 hours；
2）Coal sample after 6 parts of drying is respectively charged into the ceramic disk of uncovered, the ultrasound for being put into frequency and power adjustable by several times is micro-
Microwave frequency modulation irradiation test is carried out in wave chemical reactor：In 0.5-3GHZ；3-9GHZ；In tri- frequency bands of 9-18 GHZ, often
It is given in frequency range and selects two frequencies, 6 parts of coal samples are respectively adopted 6 frequencies and irradiate respectively once, and each irradiation time is 4 minutes；
3）Coal sample after irradiation is collected respectively in 6 vials, is separately added into a concentration of 5% hydrogen peroxide and is impregnated and stir
It mixes five minutes, encasing bottleneck with qualitative filter paper at a slow speed pours out hydrogen peroxide；It is separately added into again in vial in a concentration of 5% acetic acid
Immersion is stirred for five minutes, and encasing bottleneck with qualitative filter paper at a slow speed pours out acetic acid；The coal sample in distilled water flushing bottle is used again, is used
Coal sample is taken out and is dried by qualitative filter paper filtering at a slow speed；
4）The sulfur content that coal sample is chemically examined using constant sulphur appliance, six parts crossed the portion of reservation and using different frequency radiation treatment by
One chemical examination, and list is compared, and the highest microwave frequency value of desulfuration efficiency is selected out；
（2）Select suitable decomposition voltage, Faradaic current and supply frequency in electrolytic cell；
1）The minimum coal sample of microwave irradiation is crossed and constant sulphur appliance chemical examination sulfur content is divided into 6 parts again, is respectively put into alkaline electro
It solves in liquid, the NaOH mass fractions 10% and liquid of alkaline electrolyte consolidate mass ratio 10：1；Then according to water quality in alkaline electrolyte
NiCl is added in the 0.1% of amount2As catalyst, kodalk is added as reduction according still further to water quality in alkaline electrolyte 1.5%
Agent；
2）Electrolyzer power source uses high frequency pulse dc square wave power, first selectes voltage 3V, according still further in electrolytic cell any one
The area meter of electrode needs electric current 400A per square meter electrode；Then supply frequency is adjusted, adjusting range is 1khz-100khz, high
Frequency pulse current will produce electromagnetic wave, be conducive to be electrolysed.6 different supply frequencies are selected, after being electrolysed 4 minutes under each frequency
Coal sample is taken out, it is multiple with clear water flushing coal sample again after being washed respectively with a concentration of 5% hydrogen peroxide and a concentration of 5% acetic acid, it dries
It is chemically examined respectively with constant sulphur appliance after dry, selects out the highest supply frequency of desulfuration efficiency；
（3）Upper production line batch desulfurization；
1）Coal dust is broken to granularity 8mm and is stirred 2 hours hereinafter, being immersed in a concentration of 500mol/l sodium hydroxide solutions, is drained
Soak simultaneously dries coal；
2）It is packed into uncovered ceramic vessel, is put into ultrasound microwave chemical reactor according to preceding method（1）The selected frequency of institute into
Row microwave frequency modulation irradiates, and irradiation time is 4-5 minutes；
3）Be added a concentration of 5% hydrogen peroxide stir 5-6 minutes after hydrogen peroxide is taken out；Add a concentration of 5% acetic acid stirring 5-6
Acetic acid is taken out after minute；With being dried after distilled water flushing；
4）It is put into produced alkaline electrolyte, carries out electrolytic desulfurization；The NaOH mass fractions 10% and liquid of alkaline electrolyte
Gu mass ratio 10：1；NiCl is added according to 0.1% of water quality in alkaline electrolyte2As catalyst, according still further to alkaline electrolyte
Kodalk is added as reducing agent in the 1.5% of middle water quality；
5）Electrolyzer power source uses high frequency pulse dc square wave power, voltage 3V to need electric current 400A to select according to every square meter electrode
Select current value；According to preceding method（2）The selected supply frequency of institute is electrolysed 4-5 minute, then respectively with a concentration of 5% hydrogen peroxide with
It is rinsed with clear water after a concentration of 5% acetic acid washing.
Alkaline electrolyte is stirred in the water for pour into 50kg using the NaOH of 5kg, and the NiCl of 50g is added2With
The NaBO of 750g2▪4H2O is stirred evenly.Constant sulphur appliance uses XKDL--3000A type intelligent integrated constant sulphur appliances, to chemically examine the sulfur-bearing of coal
Amount.
The key of organic sulfur in coal removing is the fracture of C-S keys, and C-S keys are more stablized in thiophene-based organic sulfur, micro-
Easy fracture is not allowed under wave effect, therefore thiophene-based organic sulfur relative amount increases after microwave irradiation.By apply size and
The extra electric field that direction is suitable for, C-S is entirely possible in thiophene-based organic sulfur is pulled off, and organic sulfur in coal form and content will
It changes.Therefore the power supply of electrolytic cell is done using a frequency tunable high-frequency pulse direct current square wave power.
By the microwave irradiation and electrolyzer electric chemical test of Frequency Adjustable, while understanding molecular structure of coal, grasp
The microwave frequency and power and irradiation time of removing organic sulfur compound；Also voltage, the electric current that electrolyzer power source should use have been grasped
And used square wave frequency.There are two key areas on production line, and first is microwave irradiation area.Microwave irradiation（Chamber）Instead
Device is answered to be divided into upper layer and lower layer, upper layer is uniformly mobile coal seam by microwave irradiation；There is slurries flowing in lower layer（Neither inhale wave and energy
Steady temperature）, microwave can play fuel factor to coal desulfurization and non-thermal effect two acts on.Second be electrolytic cell electrolysis zone.
Bottom of electrolytic tank has the big axis of stirring；Top has in the electrode insertion groove of drum type, there is diaphragm seals between positive and negative anodes；Electrode
Being close to has two ultrasonic vibration sticks；Reduction cell cover plate is closed with groove body by sealing strip,（Ensure air tight under a certain pressure）, in slot
For NaoH alkaline solutions, liquid level keeps certain distance with cover board.
Alkali object and organic sulfur in coal and inorganic substances occur oxidation reaction and generate solable matter, achieve the purpose that desulfurization；
The reduction and desulfurization material for using sodium borohydride as coal can implement reduction reaction at normal temperatures and pressures；The activity generated with electrolytic anode
Oxygen is oxidant, organic sulfur in coal is oxidized to sulfoxide and sulfone, sulfone in the presence of alkali, is hydrolyzed to the sulphur that can be dissolved in water in water
Acid group or sulfate.Under alkaline condition, in cathode circular response occurs for NaBO2 and NaBH4 when electrolysis, NaBH4, occurs with coal
Reduction reaction, and output high-purity hydrogen, electrolyte can be recycled.In electrolytic cell Inner electrolysis coal can there are four types of state, Gu
The particle of state, the solvents of liquid, the negative ions of gaseous H2 and plasmoid.Along with power supply is high frequency arteries and veins at this time
Direct current square wave power is rushed, the frequency moment ten thousand of electromagnetic wave becomes, and by multiple dissociation and redox reaction, reassembles into new shape
State detaches the sulphur combination producing sodium sulfate salt of organic sulfur out.
When coal carries out reduction reaction in alkaline electrolyte, hydrogen is generated in cathode.The method that nitrogen displacement can be used will
Hydrogen releases, and by pressure-variable adsorption, collects high-purity hydrogen, and reuse nitrogen, has saved cost, is conducive to the de- of coal
Sulphur works.
The method advantages of simple of the removing organic sulfur in coal compound of the present invention is effective, and rate of sulphur expulsion is fast, the used time is short, desulfurization effect
Fruit is good；But also coal can be generated hydrogen in cathode when reduction reaction in alkaline electrolyte and use the method that nitrogen is replaced by hydrogen
Gas releases, and by pressure-variable adsorption, collects high-purity hydrogen, and reuse nitrogen, has saved cost, be conducive to the desulfurization of coal
Work.
Specific implementation mode
1. coal sample is taken to carry out preproduction-type test, suitable microwave frequency is found out；
（1）It takes granularity to divide 7 parts, every part of 500g of isodose in 8mm coal sample 3500g below, retains 1 part, remaining 6 parts are soaked respectively
Bubble is in a concentration of 500mol/l sodium hydroxide solutions；Stirring separation soaking liquid and dries coal sample for several times, after 2 hours.
（2）Coal sample after 6 parts of drying is respectively charged into the ceramic disk of uncovered, is put into the super of frequency and power adjustable by several times
Microwave frequency modulation irradiation test is carried out in sound microwave chemical reactor：In 0.5-3GHZ；3-9GHZ；Tri- frequency bands of 9-18 GHZ
In, it is given in every frequency range and selects two frequencies, 6 parts of coal samples are respectively adopted 6 frequencies and irradiate respectively once, and each irradiation time is 4 points
Clock；
（3）Coal sample after irradiation is collected respectively in 6 vials, is separately added into a concentration of 5% hydrogen peroxide and is impregnated and stir
It mixes five minutes, encasing bottleneck with qualitative filter paper at a slow speed pours out hydrogen peroxide；It is separately added into again in vial in a concentration of 5% acetic acid
Immersion is stirred for five minutes, and encasing bottleneck with qualitative filter paper at a slow speed pours out acetic acid；The coal sample in distilled water flushing bottle is used again, is used
Coal sample is taken out and is dried by qualitative filter paper filtering at a slow speed；
（4）The sulfur content that coal sample is chemically examined using constant sulphur appliance, six parts that the portion and use different frequency radiation treatment of reservation are crossed
It chemically examines one by one, and list is compared, selects out the highest microwave frequency value of desulfuration efficiency；
2. selecting suitable decomposition voltage, Faradaic current and supply frequency in electrolytic cell
（1）The minimum coal sample of microwave irradiation is crossed and constant sulphur appliance chemical examination sulfur content is divided into 6 parts again, is respectively put into alkaline electro
It solves in liquid, the NaOH mass fractions 10% and liquid of alkaline electrolyte consolidate mass ratio 10：1；Then according to water quality in alkaline electrolyte
NiCl is added in the 0.1% of amount2As catalyst, kodalk is added as also according still further to 1.5% of water quality in alkaline electrolyte
Former agent；
（2）Electrolyzer power source uses high frequency pulse dc square wave power, first selectes voltage 3V, according still further in electrolytic cell any one
The areal calculation of electrode goes out electric current, needs 400A electric currents per square meter electrode；In 1khz--100khz adjusting ranges select 6 not
Coal sample is taken out after being electrolysed 4 minutes under each frequency, is washed respectively with a concentration of 5% hydrogen peroxide and a concentration of 5% acetic acid by same frequency
It is multiple with clear water flushing coal sample again after washing, it is chemically examined respectively with constant sulphur appliance after drying, selects out the highest power supply of desulfuration efficiency
Frequency；
3. production line batch desulfurization
（1）Coal dust is broken to granularity 8mm and is stirred 2 hours hereinafter, being immersed in a concentration of 500mol/l sodium hydroxide solutions, is drained
Soak simultaneously dries coal；
（2）It is packed into uncovered ceramic vessel, is put into ultrasound microwave chemical reactor according to preceding method（1）The selected frequency of institute into
Row microwave frequency modulation irradiates, and irradiation time is 4-5 minutes；
（3）Be added a concentration of 5% hydrogen peroxide stir 5-6 minutes after hydrogen peroxide is taken out；Add a concentration of 5% acetic acid stirring 5-
Acetic acid is taken out after 6 minutes；With being dried after distilled water flushing；
（4）It is put into produced alkaline electrolyte, carries out electrolytic desulfurization；The NaOH mass fractions 10% of alkaline electrolyte and
Liquid consolidates mass ratio 10：1；NiCl is added according to 0.1% of water quality in alkaline electrolyte2As catalyst, according still further to alkaline electrolysis
Kodalk is added as reducing agent in the 1.5% of water quality in liquid；
（5）Electrolyzer power source uses high frequency pulse dc square wave power, voltage 3V to need electric current 400A to select according to every square meter electrode
Select current value；According to preceding method（2）The selected supply frequency of institute is electrolysed 4-5 minute, then respectively with a concentration of 5% hydrogen peroxide with
It is rinsed with clear water after a concentration of 5% acetic acid washing.
The sulfur content of coal is chemically examined using XKDL--3000A type intelligent integrated constant sulphur appliances, 1 part of reservation certain coal mine cleaned coal contains
Organic sulfur 2.72%, sulphur takes off to 1.67% after being handled by production line, and desulfurization effect is fairly obvious.It can using the method that nitrogen is replaced
It is 99.9% to produce purity, a concentration of 23% or more hydrogen.
Claims (3)
1. a kind of method of organic sulfur compound in removing bituminous coal, it is characterized in that：
（1）It takes coal sample to carry out preproduction-type test, finds out suitable microwave frequency；
1）Take granularity to divide 7 parts of isodose in 8mm coal samples below, retain 1 part, remaining 6 parts be separately immersed in it is a concentration of
In 500mol/l sodium hydroxide solutions；Stirring separation soaking liquid and dries coal sample for several times, after 2 hours；
2）Coal sample after 6 parts of drying is respectively charged into the ceramic disk of uncovered, the ultrasound for being put into frequency and power adjustable by several times is micro-
Microwave frequency modulation irradiation test is carried out in wave chemical reactor：In 0.5-3GHZ；3-9GHZ；In tri- frequency bands of 9-18 GHZ, often
It is given in frequency range and selects two frequencies, 6 parts of coal samples are respectively adopted 6 frequencies and irradiate respectively once, and each irradiation time is 4 minutes；
3）Coal sample after irradiation is collected respectively in 6 vials, is separately added into a concentration of 5% hydrogen peroxide and is impregnated and stir
It mixes five minutes, encasing bottleneck with qualitative filter paper at a slow speed pours out hydrogen peroxide；It is separately added into again in vial in a concentration of 5% acetic acid
Immersion is stirred for five minutes, and encasing bottleneck with qualitative filter paper at a slow speed pours out acetic acid；The coal sample in distilled water flushing bottle is used again, is used
Coal sample is taken out and is dried by qualitative filter paper filtering at a slow speed；
4）The sulfur content that coal sample is chemically examined using constant sulphur appliance, six parts crossed the portion of reservation and using different frequency radiation treatment by
One chemical examination, and list is compared, and the best microwave frequency value of desulfuration efficiency is selected out；
（2）Select suitable decomposition voltage, Faradaic current and supply frequency in electrolytic cell；
1）The minimum coal sample of microwave irradiation is crossed and constant sulphur appliance chemical examination sulfur content is divided into 6 parts again, is respectively put into alkaline electro
It solves in liquid, the NaOH mass fractions 10% and liquid of alkaline electrolyte consolidate mass ratio 10：1；Then according to water quality in alkaline electrolyte
NiCl is added in the 0.1% of amount2As catalyst, kodalk is added as also according still further to 1.5% of water quality in alkaline electrolyte
Former agent；
2）Electrolyzer power source uses high frequency pulse dc square wave power, voltage 3V is first selected, according still further to electrode area in electrolytic cell
Electric current is calculated, 400A galvanometer are pressed per square meter electrode；6 supply frequencies are selected within the scope of 1khz-100khz；Each frequency
Lower electrolysis took out coal sample after 4 minutes, was rushed again with clear water after being washed respectively with a concentration of 5% hydrogen peroxide and a concentration of 5% acetic acid
Coal washing sample is multiple, is chemically examined respectively with constant sulphur appliance after drying, and desulfuration efficiency optimal power supply frequency is selected out；
（3）Production line batch desulfurization；
1）Coal dust is broken to granularity 8mm and is stirred 2 hours hereinafter, being immersed in a concentration of 500mol/l sodium hydroxide solutions, is drained
Soak simultaneously dries coal；
2）It is packed into uncovered ceramic vessel, is put into ultrasound microwave chemical reactor according to preceding method（1）It selectes best micro-
Wave frequency rate carries out microwave frequency modulation irradiation, and irradiation time is 4-5 minutes；
3）Be added a concentration of 5% hydrogen peroxide stir 5-6 minutes after hydrogen peroxide is taken out；Add a concentration of 5% acetic acid stirring 5-6
Acetic acid is taken out after minute；With being dried after distilled water flushing；
4）It is put into produced alkaline electrolyte, carries out electrolytic desulfurization；The NaOH mass fractions 10% and liquid of alkaline electrolyte
Gu mass ratio 10：1；NiCl is added according to 0.1% of water quality in alkaline electrolyte2As catalyst, according still further to alkaline electrolyte
Kodalk is added as reducing agent in the 1.5% of middle water quality；
5）Electrolyzer power source uses high frequency pulse dc square wave power, voltage 3V to need 400A galvanometer according to every square meter electrode
Calculate current value；According to preceding method（2）Selected optimal power supply frequency is electrolysed 4-5 minutes, then respectively with a concentration of 5%
It is rinsed with clear water after hydrogen peroxide and the washing of a concentration of 5% acetic acid.
2. the method for removing organic sulfur compound in bituminous coal as described in claim 1, it is characterized in that alkaline electrolyte is to use 5kg
NaOH pour into the water of 50kg and stir, add the NiCl of 50g2With the NaBO of 750g2▪4H2O is stirred evenly.
3. the method for removing organic sulfur compound in bituminous coal as claimed in claim 1 or 2, it is characterized in that constant sulphur appliance uses XKDL--
3000A type intelligent integrated constant sulphur appliances.
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| CN115074164A (en) * | 2022-05-07 | 2022-09-20 | 塔里木大学 | Integrated cleaning and removing method for key harmful elements in hard-to-float bituminous coal |
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