CN107573978A - Chemical method prepares the removing system and method for acid-soluble mineral in ultra-clean coal - Google Patents
Chemical method prepares the removing system and method for acid-soluble mineral in ultra-clean coal Download PDFInfo
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- CN107573978A CN107573978A CN201710979531.3A CN201710979531A CN107573978A CN 107573978 A CN107573978 A CN 107573978A CN 201710979531 A CN201710979531 A CN 201710979531A CN 107573978 A CN107573978 A CN 107573978A
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- acid
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- 239000003245 coal Substances 0.000 title claims abstract description 172
- 238000000034 method Methods 0.000 title claims abstract description 113
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 45
- 239000011707 mineral Substances 0.000 title claims abstract description 45
- 239000000126 substance Substances 0.000 title claims abstract description 25
- 238000005554 pickling Methods 0.000 claims abstract description 125
- 239000002253 acid Substances 0.000 claims abstract description 88
- 230000008569 process Effects 0.000 claims abstract description 57
- 230000008676 import Effects 0.000 claims abstract description 40
- 238000007599 discharging Methods 0.000 claims abstract description 33
- 235000021110 pickles Nutrition 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 46
- 238000000227 grinding Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- 239000002455 scale inhibitor Substances 0.000 claims description 9
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 7
- 239000011297 pine tar Substances 0.000 claims description 7
- 229940068124 pine tar Drugs 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000004021 humic acid Substances 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229920001732 Lignosulfonate Polymers 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 46
- 235000010755 mineral Nutrition 0.000 description 40
- 239000003250 coal slurry Substances 0.000 description 26
- 239000003513 alkali Substances 0.000 description 21
- 235000011121 sodium hydroxide Nutrition 0.000 description 21
- 238000003756 stirring Methods 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 16
- 229910052665 sodalite Inorganic materials 0.000 description 16
- 238000012545 processing Methods 0.000 description 13
- 239000002956 ash Substances 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 238000003828 vacuum filtration Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003818 cinder Substances 0.000 description 4
- 239000010459 dolomite Substances 0.000 description 4
- 229910000514 dolomite Inorganic materials 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
The invention provides the removing system and method that a kind of chemical method prepares acid-soluble mineral in ultra-clean coal, the removing system includes：Micronization processes device；The micronization processes device is provided with resolution coal sample import and the first additive import；The first filter that charging aperture is connected with the discharging opening of the micronization processes device；The first acid dip pickle that micronizing coal sample import is connected with the discharging opening of first filter；First acid dip pickle is provided with the second additive import；The second filter that charging aperture is connected with the discharging opening of first acid dip pickle；Second filter exports provided with the first pickling coal sample.Compared with prior art, system and method provided by the invention can effectively remove acid-soluble mineral, and sour dosage is few and will not introduce difficult acid.Test result indicates that system and method removing calcium ion concentration provided by the invention is improved to 300ppm~500ppm by 200ppm；The dry basis ash content that pickling coal sample after removing prepares UCC is reduced to 0.4%~0.6% by 0.8%~1.2%.
Description
Technical field
The present invention relates to coal deep process technology field, is to be related to chemical method to prepare acid in ultra-clean coal more specifically
The removing system and method for the solvable mineral of property.
Background technology
At present, large-scale developing and utilizing for coal brings severe environmental destruction and pollutant emission problem, coal
Purifying utilize of charcoal faces immense pressure and challenge.Purifying utilize of coal in China quickly grows, various new coal gasification
Technology is applied converts field in coal, and large-scale coal liquifaction, coal-ethylene glycol, coal-to-olefin device have been enter into the Industrial demonstration stage.
Although China has grasped the core technology of multinomial coal-cleaning utilization, coal-cleaning utilization integral level is not high, develop by
The limitation of technology, policy and fund.
Ultra-clean coal (Ultra Clean Coal, abbreviation UCC) is the Filter Tuber For Clean Coal that content of ashes is no more than 1%, is to wash
Cleaned coal is raw material, is made by Chemical cleaning, separation and filtering production.UCC is a kind of alternative energy source, biggest market potentiality be
Diesel oil substitute and heavy oil on generating, steamer, truck and train, make coal resources efficiently, clean utilization, meet the energy and environmental protection will
Ask.Since last century, the developed country such as Australia, Japan and Britain both participates in the research and exploitation of UCC technologies.At present,
UCC technology of preparing includes Physical and chemical method, wherein chemical method mainly have hydrogen fluoride, acid-base method, molten caustic soda percolation,
Chemical coal technology etc..The external technology developed that succeeds has Australian Auscoal techniques (existing Yan coal Australia UCC technologies), U.S.
State's Gravimelt techniques etc..In the world, UCC technical researches last longer, but the precedent without technology commercial development, Yan coal
Australia UCC technical research achievements maintain the leading position.
Australian Auscoal techniques (existing Yan coal Australia UCC technologies) prepare UCC technologies, i.e.,：Coal sample is through sodium hydroxide alkali
The silica in coal ash, alumina and its derivative, at high temperature dissolving generation silicate solutions and sodalite solid are sunk in liquid resolution
Form sediment；Be continuing with sulfuric acid or hydrochloric acid and coal in remaining NaOH, while dissolve sodalite and other impurity；It is more that surface is washed with water
Remaining sulfuric acid and sulfate, prepares UCC.Using Australian Auscoal techniques, the resolution of conventional alkali lye and acid solution washing,
The ash content of part coal can be removed to less than 1%, but UCC preparation technologies requirement：Clay content is high in fluorine in coal composition
Up to more than 60%；Iron oxide, calcium oxide and titanium oxide total amount are less than 20% in coal ash.
Adaptability of the UCC technologies to Coal rank is prepared in order to improve chemical method, it is cleared up in alkali lye by many research units
After carried out different acid elutions and processing method, but all suffer from the problems such as sour dosage is larger, acid pickle processing is difficult；Such as US aluminum
Acid elution prepares UCC, and the hydrogen fluorine of Univ Melbourne Australia's exploitation to sulfuric acid, the nitric acid of industry company exploitation twice respectively
The acid elution of acid, hydrofluoric acid and nitric acid nitration mixture prepares UCC.Therefore, acid elution method how is improved, is improved to different minerals in coal
Matter disposal ability, sour dosage is reduced, it is in the urgent need to address at present to avoid the difficult sour introducing such as hydrofluoric acid, hydrochloric acid, nitric acid
Technical problem.
The content of the invention
In view of this, it is an object of the invention to provide a kind of chemical method to prepare the de- of acid-soluble mineral in ultra-clean coal
Except system and method, system and method provided by the invention can effectively remove acid-soluble mineral, and sour dosage is few and will not draw
Enter difficult acid.
The invention provides the removing system that a kind of chemical method prepares acid-soluble mineral in ultra-clean coal, including：
Micronization processes device；The micronization processes device is provided with resolution coal sample import and the first additive import；
The first filter that charging aperture is connected with the discharging opening of the micronization processes device；
The first acid dip pickle that micronizing coal sample import is connected with the discharging opening of first filter；First acid
Cleaning device is provided with the second additive import；
The second filter that charging aperture is connected with the discharging opening of first acid dip pickle；Second filter is set
There is the outlet of the first pickling coal sample.
Preferably, the micronization processes device is selected from vibromill, Ball-stirring mill or airflow milling.
Preferably, second filter is additionally provided with the outlet of the first acid solution.
Preferably, in addition to：
The second acid device that the import of pickling coal sample is connected with the first pickling coal sample outlet of second filter；Institute
State the second acid device and be provided with the 3rd additive import；
The 3rd filter that charging aperture is connected with the discharging opening of the described second acid device；3rd filter is set
There is the outlet of the second pickling coal sample.
It is including following present invention also offers the removal methods that a kind of chemical method prepares acid-soluble mineral in ultra-clean coal
Step：
A) resolution coal sample is subjected to micronization processes in the presence of grinding aid and water, then filtered through first time, obtain micro mist
Change coal sample；
B) the micronizing coal sample for obtaining step a) carries out first time pickling in the presence of dilute sulfuric acid and promoter for pickling, then passes through
Second of filtering, obtains the first pickling coal sample.
Preferably, grinding aid described in step a) is included in triethanolamine, triisopropanolamine, aphthenic acids, pine tar and graphite
One or more；
The dosage of the grinding aid is the 0.04%~0.1% of resolution coal sample dosage.
Preferably, the requirement of micronization processes described in step a) is to be crushed to below 0.08mm.
Preferably, promoter for pickling is made up of dispersant and scale inhibitor described in step b)；
The dispersant includes the one or more in lignosulfonates, naphthalene sulfonic salt and humic acid sulfonate；
The scale inhibitor includes ATMP, hydroxy ethylene diphosphonic acid, PAPE and water
Solve the one or more in HPMA.
Preferably, the pH value of first time pickling described in step b) is 0.5~1.5, and temperature is 20 DEG C~30 DEG C, and the time is
40min~80min.
Preferably, the step b) also includes：
The first obtained pickling coal sample is subjected to second of pickling in the presence of dilute sulfuric acid and promoter for pickling, then through third time
Filtering, obtains the second pickling coal sample.
It is described the invention provides the removing system and method that a kind of chemical method prepares acid-soluble mineral in ultra-clean coal
Removing system includes：Micronization processes device；The micronization processes device is provided with resolution coal sample import and the first additive enters
Mouthful；The first filter that charging aperture is connected with the discharging opening of the micronization processes device；Be micronized coal sample import with it is described
The first connected acid dip pickle of the discharging opening of first filter；First acid dip pickle is provided with the second additive import；Enter
The second filter that material mouth is connected with the discharging opening of first acid dip pickle；Second filter is provided with the first pickling
Coal sample exports.Compared with prior art, system and method provided by the invention can effectively remove acid-soluble mineral, sour dosage
Less and difficult acid will not be introduced.Test result indicates that system and method provided by the invention removing calcium ion concentration by
200ppm is improved to 300ppm~500ppm；Pickling coal sample after removing prepares UCC dry basis ash content by 0.8%~1.2% drop
As little as 0.4%~0.6%；Processing be particularly suitable for use in containing the more coal of the mineral such as kaolin, dolomite, calcite.
Brief description of the drawings
Fig. 1 is the knot that chemical method provided in an embodiment of the present invention prepares the removing system of acid-soluble mineral in ultra-clean coal
Structure schematic diagram；
Fig. 2 is that the chemical method that the embodiment of the present invention 1 provides prepares the removing system of acid-soluble mineral in ultra-clean coal
Structural representation.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention,
The every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, belongs to this hair
The scope of bright protection.
The invention provides the removing system that a kind of chemical method prepares acid-soluble mineral in ultra-clean coal, including：
Micronization processes device；The micronization processes device is provided with resolution coal sample import and the first additive import；
The first filter that charging aperture is connected with the discharging opening of the micronization processes device；
The first acid dip pickle that micronizing coal sample import is connected with the discharging opening of first filter；First acid
Cleaning device is provided with the second additive import；
The second filter that charging aperture is connected with the discharging opening of first acid dip pickle；Second filter is set
There is the outlet of the first pickling coal sample.
Referring to Fig. 1, Fig. 1 is the de- of acid-soluble mineral in chemical method provided in an embodiment of the present invention preparation ultra-clean coal
Except the structural representation of system.Wherein, 1 is micronization processes device, and 2 be the first filter, and 3 be the first acid dip pickle, and 4 are
Second filter.
In the present invention, the micronization processes device is used to resolution coal sample carrying out micronization processes.In the present invention,
The resolution coal sample is the coal sample after alkali lye resolution processing；The process that the present invention clears up processing to the alkali lye does not have special limit
System, the technical scheme of processing is cleared up using alkali lye well known to those skilled in the art.
In the present invention, the micronization processes device is preferably selected from vibromill, Ball-stirring mill or airflow milling, more preferably stirs
Mix mill.In the present invention, the micronization processes device is provided with the import of resolution coal sample, the first additive import and discharging opening；Institute
The import of resolution coal sample is stated to be used to resolution coal sample being delivered in micronization processes device；The first additive import is used to help
Grinding agent and water are delivered in micronization processes device；The discharging opening of the micronization processes device is used for after micronization processes
It is micronized coal slurry discharge.
The present invention carries out micronization processes using said apparatus, by shearing and extruding, can destroy the inner pore of coal cinder,
The water that wetting quantity is separated out in the inner pore of coal cinder is forced, on the one hand destroys in alkali lye resolution the sodalite crystalline particle formed, separately
On the one hand influence of the water to the pH value degree of accuracy in acid cleaning process in local hole is reduced, so as to effectively avoid silica gel from separating out, simultaneously
Reduce absorption of the silica gel in hole, removal effect of the increase pickling to element silicon.Also, the micronization processes through particular requirement
Afterwards, the sodalite crystalline particle formed can be further destroyed in alkali lye resolution, increases sodalite reaction contact area, reduces alkali
Liquid clears up parcel of the organic matter to crystallization sodalite, improves the conversion ratio of sodalite, promotes sodalite pickling dissolution.
In the present invention, first filter is used to be filtered micronizing coal slurry to remove filtrate, obtains micro-
Efflorescence coal sample.The present invention is not particularly limited to first filter, it is preferred to use well known to those skilled in the art true
Empty pumping and filtering device.In the present invention, first filter is provided with charging aperture and discharging opening；First filter enters
Material mouth is connected with the discharging opening of the micronization processes device；The discharging opening of first filter is used for will be micro- after filtering
Efflorescence coal sample is discharged.
In the present invention, first acid dip pickle is used to micronizing coal sample carrying out pickling.In the present invention, described
Pickling reactor of one acid dip pickle preferably with stirring.In the present invention, first acid dip pickle is provided with micronizing coal
Sample import, the second additive import and discharging opening；The micronizing coal sample import and the discharging opening phase of first filter
Even；The second additive import is used to dilute sulfuric acid and promoter for pickling being delivered in the first acid dip pickle；First pickling
The discharging opening of device is used to discharge the pickling coal slurry after pickling.
The present invention using said apparatus carry out pickling, can it is few in sour dosage and do not introduce it is difficult acid on the premise of, have
Effect removing acid-soluble mineral, so as to further obtain low grey ultra-clean coal.
In the present invention, second filter is used to be filtered pickling coal slurry is dissolved with acid-soluble to remove
The acid solution of mineral, obtain pickling coal sample.The present invention is not particularly limited to second filter, it is preferred to use ability
Vacuum filtration equipment known to field technique personnel.In the present invention, second filter is provided with charging aperture, the first pickling coal
Sample exports and the outlet of the first acid solution；The discharging opening phase of the charging aperture of second filter and first acid dip pickle
Even；The first pickling coal sample is exported for the pickling coal sample after filtering to be discharged；First acid solution is exported for inciting somebody to action
The discharge of the acid solution dissolved with acid-soluble mineral being filtrated to get.
In the present invention, the removing system of acid-soluble mineral preferably also includes in the chemical method preparation ultra-clean coal：
The second acid device that the import of pickling coal sample is connected with the first pickling coal sample outlet of second filter；Institute
State the second acid device and be provided with the 3rd additive import；
The 3rd filter that charging aperture is connected with the discharging opening of the described second acid device；3rd filter is set
There is the outlet of the second pickling coal sample.
In the present invention, second acid dip pickle is used to pickling coal sample carrying out second of pickling.In the present invention, institute
State pickling reactor of second acid dip pickle preferably with stirring.In the present invention, second acid dip pickle is provided with pickling
Coal sample import, the 3rd additive import and discharging opening；The pickling coal sample import and the first pickling of second filter
Coal sample outlet is connected；The 3rd additive import is used to dilute sulfuric acid and promoter for pickling being delivered in the second acid dip pickle；Institute
The discharging opening for stating the second acid dip pickle is used to discharge the pickling coal slurry after second of pickling.
The present invention carries out second of pickling using said apparatus, acid-soluble mineral can be further removed, so as to obtain
The lower ultra-clean coal of ash content；The present invention considers sour dosage and pickling effect, using white picking.
In the present invention, the 3rd filter is used to be filtered the pickling coal slurry after second of pickling to remove
Acid solution dissolved with acid-soluble mineral, obtain the second pickling coal sample.The present invention is to the 3rd filter without spy
Different limitation, it is preferred to use vacuum filtration equipment well known to those skilled in the art.In the present invention, the 3rd filter is set
There are charging aperture, the outlet of the second pickling coal sample and the outlet of the second acid solution；The charging aperture of 3rd filter and described the
The discharging opening of two acid dip pickles is connected；The second pickling coal sample is exported for the second pickling coal sample after filtering to be discharged；Institute
The second acid solution is stated to export for the acid solution dissolved with acid-soluble mineral being filtrated to get to be discharged.
It is including following present invention also offers the removal methods that a kind of chemical method prepares acid-soluble mineral in ultra-clean coal
Step：
A) resolution coal sample is subjected to micronization processes in the presence of grinding aid and water, then filtered through first time, obtain micro mist
Change coal sample；
B) the micronizing coal sample for obtaining step a) carries out first time pickling in the presence of dilute sulfuric acid and promoter for pickling, then passes through
Second of filtering, obtains the first pickling coal sample.
Resolution coal sample is carried out micronization processes by the present invention in the presence of grinding aid and water first, then is filtered through first time,
Obtain being micronized coal sample.In the present invention, the resolution coal sample is the coal sample after alkali lye resolution processing；The present invention is to the alkali lye
The process of resolution processing is not particularly limited, and the technical scheme that processing is cleared up using alkali lye well known to those skilled in the art is
Can.In the present invention, the coal sample after alkali lye resolution processing, the mineral matter in its coal mainly include sodalite, dolomite, side
The silicate of Xie Shi and adsorption, aluminate, wherein sodalite content are about 60%~80%, dolomite and calcite content
About 10%~15%, silicate, the aluminate content of adsorption are about 5%~10%.
Resolution coal sample is carried out micronization processes by the present invention in the presence of grinding aid and water, obtains being micronized coal slurry.At this
In invention, the grinding aid preferably includes the one or more in triethanolamine, triisopropanolamine, aphthenic acids, pine tar and graphite,
More preferably triethanolamine, aphthenic acids and pine tar.In the preferred embodiment of the invention, the grinding aid is that mass ratio is 1：1：
1 triethanolamine, aphthenic acids and pine tar.The present invention is not particularly limited to the source of the grinding aid, using art technology
Above-mentioned triethanolamine known to personnel, triisopropanolamine, aphthenic acids, the commercial goods of pine tar and graphite.In the present invention,
The dosage of the grinding aid preferably clears up the 0.04%~0.1% of coal sample dosage, more preferably 0.06%.
In the present invention, the mass ratio of the resolution coal sample and water is preferably 1：(1~2), more preferably 1：1.25.
In the present invention, the device of the micronization processes is preferably selected from vibromill, Ball-stirring mill or airflow milling, more preferably
Ball-stirring mill.In the present invention, the requirement of the micronization processes is preferably to be crushed to below 0.08mm, is more preferably crushed to
Below 0.074mm.In the preferred embodiment of the invention, the device of the micronization processes is vertical mixing mill；It is described vertical
The rotating speed of Ball-stirring mill is preferably 100r/min~200r/min, more preferably 150r/min；When grinding of the vertical mixing mill
Between be preferably 20min~40min, more preferably 30min.
The present invention carries out micronization processes using said apparatus and grinding aid, by shearing and extruding, can destroy coal cinder
Inner pore, force the water that wetting quantity is separated out in the inner pore of coal cinder, on the one hand destroy the sodalite knot that is formed in alkali lye resolution
Brilliant particle, influence of the water to the pH value degree of accuracy in acid cleaning process in local hole is on the other hand reduced, so as to effectively avoid silica gel
Separate out, while reduce absorption of the silica gel in hole, removal effect of the increase pickling to element silicon.Also, through the micro- of particular requirement
After efflorescence processing, the sodalite crystalline particle formed, increase sodalite reaction contact surface can be further destroyed in alkali lye resolution
Product, parcel of the alkali lye resolution organic matter to crystallization sodalite is reduced, improve the conversion ratio of sodalite, promote sodalite pickling molten
Go out.
After obtaining the micronizing coal slurry, obtained micronizing coal slurry is carried out first time filtering by the present invention, obtains micro mist
Change coal sample.The present invention is not particularly limited to the device of first time filtering, it is preferred to use well known to those skilled in the art
It is filtered by vacuum equipment；Purpose is to remove the filtrate in micronizing coal slurry, and it is to be micronized coal sample to obtain filter cake.
After obtaining the micronizing coal sample, the present invention is by obtained micronizing coal sample in the presence of dilute sulfuric acid and promoter for pickling
First time pickling is carried out, then is filtered through second, obtains the first pickling coal sample.Source and concentration of the present invention to the dilute sulfuric acid
It is not particularly limited, it is preferred to use mass concentration well known to those skilled in the art is 4% dilute sulfuric acid.In the present invention, institute
It is preferably 1 to state dilute sulfuric acid and the mass ratio of resolution coal sample in step a)：(1.25~2), more preferably 1：1.5.
In the present invention, the promoter for pickling is preferably made up of dispersant and scale inhibitor.In the present invention, described point
Powder preferably includes the one or more in lignosulfonates, naphthalene sulfonic salt and humic acid sulfonate, more preferably naphthalene system
Sulfonate.The present invention is not particularly limited to the source of the dispersant, using well known to those skilled in the art above-mentioned wooden
The commercial goods of plain sulfonate, naphthalene sulfonic salt and humic acid sulfonate.In the present invention, the dosage of the dispersant is excellent
Elect as and the 0.05%~1% of coal sample dosage, more preferably 0.0625% is cleared up in step a).
In the present invention, the scale inhibitor preferably includes ATMP, hydroxy ethylene diphosphonic acid, more
One or more in first alcohol phosphate and HPMA, more preferably ATMP and polyalcohol phosphoric acid
Ester.In the preferred embodiment of the invention, the scale inhibitor is that mass ratio is 2：1 ATMP and polynary
Alcohol phosphate.The present invention is not particularly limited to the source of the scale inhibitor, on well known to those skilled in the art
State the commercial goods of ATMP, hydroxy ethylene diphosphonic acid, PAPE and HPMA i.e.
Can.In the present invention, the mass ratio of the scale inhibitor and dispersant is preferably (0.1~0.5)：1, more preferably 0.3：1.
Obtained micronizing coal sample is carried out first time pickling by the present invention in the presence of dilute sulfuric acid and promoter for pickling, obtains acid
Coal washing is starched.In the present invention, pickling reactor of the device of the first time pickling preferably with stirring；Ensure whole pickling
Process is carried out under conditions of stirring.In the present invention, the pH value of the first time pickling is preferably 0.5~1.5, more preferably
1.The present invention meets above-mentioned requirements for the pH value of guarantee first time acid cleaning process, it is preferred to use the sulphur that mass concentration is 40% is added dropwise
Acid solution.In the present invention, the temperature of the first time pickling is 20 DEG C~30 DEG C, more preferably 25 DEG C；The first time pickling
Time be preferably 40min~80min, more preferably 60min.
The present invention carries out first time pickling using said apparatus and promoter for pickling, can be few in sour dosage and introduce difficulty
On the premise of reason acid, acid-soluble mineral are effectively removed, so as to further obtain low grey ultra-clean coal.
After obtaining the pickling coal slurry, obtained pickling coal slurry is carried out second and filtered by the present invention, obtains the first pickling
Coal sample.The present invention is not particularly limited to the device of second of filtering, it is preferred to use well known to those skilled in the art true
Empty pumping and filtering device；Purpose is to remove the acid solution dissolved with acid-soluble mineral in pickling coal slurry, and it is the to obtain filter cake
One pickling coal sample.
In the present invention, the step b) preferably also includes：
The first obtained pickling coal sample is subjected to second of pickling in the presence of dilute sulfuric acid and promoter for pickling, then through third time
Filtering, obtains the second pickling coal sample.In the present invention, the dilute sulfuric acid and promoter for pickling and the phase described in above-mentioned technical proposal
Together, will not be repeated here.
In the present invention, pickling reactor of the device of second of pickling preferably with stirring；Ensure whole acid
Journey is washed to carry out under conditions of stirring.In the present invention, the process of second of pickling and the process phase of first time pickling
Together, it is therefore an objective to further removing acid-soluble mineral, so as to further obtain low grey ultra-clean coal；The present invention considers sour use
Amount and pickling effect, using white picking.
In the present invention, the process of the third time filtering is identical with the process of second of filtering, it is therefore an objective to removes
Acid solution dissolved with acid-soluble mineral, it is the second pickling coal sample to obtain filter cake, be will not be repeated here.
It is described the invention provides the removing system and method that a kind of chemical method prepares acid-soluble mineral in ultra-clean coal
Removing system includes：Micronization processes device；The micronization processes device is provided with resolution coal sample import and the first additive enters
Mouthful；The first filter that charging aperture is connected with the discharging opening of the micronization processes device；Be micronized coal sample import with it is described
The first connected acid dip pickle of the discharging opening of first filter；First acid dip pickle is provided with the second additive import；Enter
The second filter that material mouth is connected with the discharging opening of first acid dip pickle；Second filter is provided with the first pickling
Coal sample exports.Compared with prior art, system and method provided by the invention can effectively remove acid-soluble mineral, sour dosage
Less and difficult acid will not be introduced.Test result indicates that system and method provided by the invention removing calcium ion concentration by
200ppm is improved to 300ppm~500ppm；Pickling coal sample after removing prepares UCC dry basis ash content by 0.8%~1.2% drop
As little as 0.4%~0.6%；Processing be particularly suitable for use in containing the more coal of the mineral such as kaolin, dolomite, calcite.
In addition, removal methods technique provided by the invention is simple, energy consumption is low, relevant device and auxiliary agent are easy to get, improving cost
It is low, subtractive process clean environment firendly, be advantageous to promote and develop in this area.
In order to further illustrate the present invention, it is described in detail below by following examples.Following examples of the present invention
Resolution coal sample used is the Xinglongzhuang coal after alkali lye resolution processing, and its basic ature of coal and ash content composition are as shown in table 1~2.
The Xinglongzhuang coal coal industry analysis result of table 1
| Moisture | Ash content | Volatile matter |
| Mad% | Ad% | Vdaf% |
| 3.32 | 8.00 | 37.18 |
The Xinglongzhuang ash content of coal analysis result (mass content, %) of table 2
| Al2O3 | SiO2 | Fe2O3 | CaO | MgO | Na2O | K2O | TiO2 | SO3 |
| 34.66 | 40.54 | 4.86 | 6.87 | 2.57 | 0.87 | 0.38 | 1.58 | 5.93 |
The alkali lye of Xinglongzhuang coal clears up processing procedure：By the Xinglongzhuang coal dust prepared (granularity is less than 1mm) 309g, water
735g, sodium hydroxide 156g are mixed evenly in beaker, obtain coal-alkali mixed liquor；Then by obtained coal-alkali mixed liquor
Move into autoclave, 240 DEG C are heated to from room temperature with 2 DEG C/min speed, after constant temperature 20min, with 4 DEG C/min speed
Be cooled to 90 DEG C, by be filtered by vacuum remove filtrate, by filter cake in 50 DEG C of drying boxes forced air drying 6h, obtain at alkali lye resolution
Xinglongzhuang coal sample 320g after reason.
Embodiment 1
Referring to Fig. 2, the chemical method that Fig. 2, which is the embodiment of the present invention 1, to be provided prepares acid-soluble mineral in ultra-clean coal
The structural representation of removing system.Wherein, 1 is micronization processes device, and 2 be the first filter, and 3 be the first acid dip pickle, 4
It is the second acid dip pickle for the second filter, 5,6 be the 3rd filter.
The course of work that the chemical method that embodiment 1 provides prepares the removing system of acid-soluble mineral in ultra-clean coal is specific
For：
(1) cancel solution coal sample 80g, add grinding aid 0.048g, wherein each 0.016g of triethanolamine, aphthenic acids, pine tar, add
Add water 100g, grind 30min in rotating speed 150r/min vertical mixing mills, be crushed to below 0.074mm, obtain being micronized coal
Slurry；Obtained micronizing coal slurry is subjected to vacuum filtration again and removes filtrate, it is to be micronized coal sample that filter cake, which is made,.
The total pore volume about 0.04mL/g of resolution coal sample is tested using nitrogen adsorption instrument；It is crushed to below 0.74mm, total hole
Volume is reduced to about 0.01mL/g.
(2) obtained micronizing coal sample is added into the acid with stirring equipped with the dilute sulfuric acid 120g that mass concentration is 4%
Reactor is washed, addition naphthalene sulfonic salt 0.05g, ATMP 10mg, PAPE 5mg, is stirred anti-
Should；The sulfuric acid solution 56.23g that mass concentration is 40% is added dropwise simultaneously, is 1 to coal slurry pH value is mixed, constant temperature stirs at 25 DEG C
60min is reacted, obtains pickling coal slurry；Obtained pickling coal slurry is subjected to vacuum filtration separation again and is dissolved with acid-soluble mineral
Acid solution, it is the first pickling coal sample to obtain filter cake.
The acid-soluble mineral (in terms of calcium ion) dissolved after testing in acid solution are 300ppm.
(3) the first obtained pickling coal sample is added and carries what is stirred equipped with the dilute sulfuric acid 120g that mass concentration is 4%
Pickling reactor, addition naphthalene sulfonic salt 0.05g, ATMP 10mg, PAPE 5mg, adjusts pH value
For 1, the constant temperature stirring reaction 60min at 25 DEG C, pickling coal slurry is obtained；Obtained pickling coal slurry is subjected to vacuum filtration separation again
Acid solution dissolved with acid-soluble mineral, it is the second pickling coal sample to obtain filter cake.
The acid-soluble mineral (in terms of calcium ion) dissolved after testing in acid solution are 500ppm.
Comparative example
The removing of acid-soluble mineral is carried out according to Australian Auscoal techniques：
(1) cancel solution coal sample 80g, it is anti-to add the pickling with stirring equipped with the dilute sulfuric acid 120g that mass concentration is 4%
Kettle is answered, is stirred reaction；The sulfuric acid solution 47.28g that mass concentration is 40% is added dropwise simultaneously, is 1 to coal slurry pH value is mixed,
Constant temperature stirring reaction 60min at 25 DEG C, obtains pickling coal slurry；Obtained pickling coal slurry is carried out into vacuum filtration separation again to be dissolved with
The acid solution of acid-soluble mineral, it is the first pickling coal sample to obtain filter cake.
(3) the first obtained pickling coal sample is added and carries what is stirred equipped with the dilute sulfuric acid 120g that mass concentration is 4%
Pickling reactor, regulation pH value is 1, the constant temperature stirring reaction 60min at 25 DEG C, obtains pickling coal slurry；The pickling that will be obtained again
Coal slurry carries out acid solution of the vacuum filtration separation dissolved with acid-soluble mineral, and it is the second pickling coal sample to obtain filter cake.
The acid-soluble mineral (in terms of calcium ion) dissolved after testing in acid solution are 200ppm.
The second acid that the first pickling coal sample and the second pickling coal sample, the comparative example provided using the embodiment of the present invention 1 is provided
Coal washing sample prepares ultra-clean coal by chemical method respectively, and detailed process is as follows：
Second pickling coal sample is added into 50% ethanol water 160g, mixing coal slurry is moved into autoclave, from room
Temperature is heated to 260 DEG C with 2 DEG C/min speed, and after constant temperature 5min, reactor is from boosting to about 8MPa, then the speed with 4 DEG C/min
Degree is cooled to room temperature, removes filtrate by being filtered by vacuum, obtains filter cake；By obtained filter cake, air blast is done in 50 DEG C of drying boxes again
Dry 6h, dry UCC is prepared.
The UCC being prepared is subjected to ash analysis, the results showed that, the first pickling coal sample that the embodiment of the present invention 1 provides
The UCC dry basis ash contents being prepared are 0.6%, the UCC butts that the second pickling coal sample that the embodiment of the present invention 1 provides is prepared
Ash content is 0.52%, and the UCC dry basis ash contents that the second pickling coal sample that comparative example provides is prepared are 1.16%.
The described above of the disclosed embodiments, professional and technical personnel in the field are enable to realize or using the present invention.It is right
A variety of modifications of these embodiments will be apparent for those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with principles disclosed herein and features of novelty
Most wide scope.
Claims (10)
1. a kind of chemical method prepares the removing system of acid-soluble mineral in ultra-clean coal, including：
Micronization processes device；The micronization processes device is provided with resolution coal sample import and the first additive import；
The first filter that charging aperture is connected with the discharging opening of the micronization processes device；
The first acid dip pickle that micronizing coal sample import is connected with the discharging opening of first filter；The first pickling dress
The second additive import is installed；
The second filter that charging aperture is connected with the discharging opening of first acid dip pickle；Second filter is provided with the
One pickling coal sample exports.
2. removing system according to claim 1, it is characterised in that the micronization processes device is selected from vibromill, stirred
Mix mill or airflow milling.
3. removing system according to claim 1, it is characterised in that it is acid molten that second filter is additionally provided with first
Liquid exports.
4. removing system according to claim 1, it is characterised in that also include：
The second acid device that the import of pickling coal sample is connected with the first pickling coal sample outlet of second filter；Described
Two acid devices are provided with the 3rd additive import；
The 3rd filter that charging aperture is connected with the discharging opening of the described second acid device；3rd filter is provided with the
Diacid coal washing sample exports.
5. a kind of chemical method prepares the removal methods of acid-soluble mineral in ultra-clean coal, comprise the following steps：
A) resolution coal sample is subjected to micronization processes in the presence of grinding aid and water, then filtered through first time, obtain being micronized coal
Sample；
B) the micronizing coal sample for obtaining step a) carries out first time pickling in the presence of dilute sulfuric acid and promoter for pickling, then through second
Secondary filtering, obtain the first pickling coal sample.
6. removal methods according to claim 5, it is characterised in that grinding aid described in step a) include triethanolamine,
One or more in triisopropanolamine, aphthenic acids, pine tar and graphite；
The dosage of the grinding aid is the 0.04%~0.1% of resolution coal sample dosage.
7. removal methods according to claim 5, it is characterised in that the requirement of micronization processes is broken described in step a)
It is broken to below 0.08mm.
8. removal methods according to claim 5, it is characterised in that promoter for pickling is by dispersant and knot described in step b)
Scale inhibitors form；
The dispersant includes the one or more in lignosulfonates, naphthalene sulfonic salt and humic acid sulfonate；
It is poly- that the scale inhibitor includes ATMP, hydroxy ethylene diphosphonic acid, PAPE and hydrolysis
One or more in maleic anhydride.
9. removal methods according to claim 5, it is characterised in that the pH value of first time pickling is described in step b)
0.5~1.5, temperature is 20 DEG C~30 DEG C, and the time is 40min~80min.
10. according to the removal methods described in any one of claim 5~9, it is characterised in that the step b) also includes：
The first obtained pickling coal sample is subjected to second of pickling in the presence of dilute sulfuric acid and promoter for pickling, then through third time mistake
Filter, obtains the second pickling coal sample.
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Cited By (2)
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| CN110272772A (en) * | 2019-08-05 | 2019-09-24 | 中南大学 | A kind of ultrapure anthracitic preparation method |
| CN111040819A (en) * | 2018-10-12 | 2020-04-21 | 国家能源投资集团有限责任公司 | Ash removal method for solid carbonaceous material |
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