JPH03294391A - Additive for coal-water slurry - Google Patents
Additive for coal-water slurryInfo
- Publication number
- JPH03294391A JPH03294391A JP9684690A JP9684690A JPH03294391A JP H03294391 A JPH03294391 A JP H03294391A JP 9684690 A JP9684690 A JP 9684690A JP 9684690 A JP9684690 A JP 9684690A JP H03294391 A JPH03294391 A JP H03294391A
- Authority
- JP
- Japan
- Prior art keywords
- water
- coal
- slurry
- acid
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002002 slurry Substances 0.000 title claims abstract description 46
- 239000000654 additive Substances 0.000 title claims abstract description 23
- 230000000996 additive effect Effects 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 36
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007717 redox polymerization reaction Methods 0.000 claims abstract description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 abstract 1
- 239000003245 coal Substances 0.000 description 21
- -1 alkali metal salts Chemical class 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 239000011970 polystyrene sulfonate Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SAESCDGAKWEZRD-UHFFFAOYSA-N formaldehyde;triazin-4-amine Chemical compound O=C.NC1=CC=NN=N1 SAESCDGAKWEZRD-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical class C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- ONUXAGYOFJLIQM-UHFFFAOYSA-N 2-ethenylnaphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=C(C=C)C=CC2=C1 ONUXAGYOFJLIQM-UHFFFAOYSA-N 0.000 description 1
- OBNZQBVPDZWAEB-UHFFFAOYSA-N 2-phenylprop-1-ene-1-sulfonic acid Chemical compound OS(=O)(=O)C=C(C)C1=CC=CC=C1 OBNZQBVPDZWAEB-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 235000006173 Larrea tridentata Nutrition 0.000 description 1
- 244000073231 Larrea tridentata Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229960002126 creosote Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003476 subbituminous coal Substances 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
Description
【発明の詳細な説明】
１！上ム杜凰光災
本発明は、石炭水スラリーに添加されて、スラリーの流
動性および安定性を向上する添加剤に関する。[Detailed description of the invention] 1! The present invention relates to an additive that is added to a coal-water slurry to improve the fluidity and stability of the slurry.
従】ｌ幻１
石油価格の高騰やエネルギー資源の多様化の観点から、
近年、石炭の利用が注目されている。Illusion 1 From the perspective of soaring oil prices and diversification of energy resources,
In recent years, the use of coal has attracted attention.
石炭は固体燃料でありハンドリングの点で難点があるの
で、これを微粉砕して水スラリーとすることが提案され
てきた。石炭を水スラリーとすることによりパイプ輸送
が可能となり、液体燃料と同様に取り扱うことができる
が、輸送効率を向上するために高濃度化することが必要
となる。しかし、石炭をそのまま水中に分散しただけで
は５０％以上の高濃度スラリーを得ることは困難であり
、また、静置しておくと石炭粉体が沈降して不均一にな
り貯蔵安定性の点で問題がある。Since coal is a solid fuel and is difficult to handle, it has been proposed to pulverize it into a water slurry. By turning coal into a water slurry, it becomes possible to transport it through pipes and handle it in the same way as liquid fuel, but it is necessary to increase the concentration to improve transport efficiency. However, it is difficult to obtain a slurry with a high concentration of 50% or more by simply dispersing coal in water, and if left to stand still, the coal powder will settle and become non-uniform, resulting in poor storage stability. There is a problem.
そこで、スラリー中に添加剤を混合して高濃度化および
分散安定性を改善することが提案されてきている。この
ような添加剤としては、たとえば、ポリスチレンスルホ
ン酸塩、ナフタレンスルホン酸塩のホルマリン縮合物な
どが用いられている。Therefore, it has been proposed to mix additives into the slurry to increase the concentration and improve dispersion stability. As such additives, for example, formalin condensates of polystyrene sulfonates and naphthalene sulfonates are used.
また、ポリスチレンスルホン酸塩等の芳香族環またはト
リアジン環を有するスルホン酸系重合体とα、β−不飽
和カルボン酸系重合体との２成分系（特開昭６０−６０
１９１号公報）、ポリスチレンスルホン酸塩等とα、β
−不飽和カルボン酸系重合体との２成分系（特開昭６０
−２５００９５号公報）、ポリスチレンスルホン酸塩、
α、β−不飽和カルボン酸系重合体、アルキレンオキシ
ドが付加されたポリエーテルとの３成分系（特開昭６３
−３５６９４号公報）などが報告されている・これらの
添加剤を用いて石炭水スラリーは実用化されたが、長期
間にわたる実機運転の結果、石炭水スラリーにソフト凝
集の発生する場合が見られ、ハンドリング性に支障をき
たすという新たな問題が発生した。In addition, a two-component system (JP-A-60-60
No. 191), polystyrene sulfonate, etc. and α, β
-Two-component system with unsaturated carboxylic acid polymer (JP-A-60
-250095), polystyrene sulfonate,
Three-component system of α,β-unsaturated carboxylic acid polymer and polyether to which alkylene oxide is added (JP-A-63
Coal-water slurry has been put into practical use using these additives, but as a result of long-term actual machine operation, soft agglomeration has been observed in the coal-water slurry. , a new problem arose that affected handling.
が しよ゛とする
本発明は、石炭水スラリーにおけるソフト凝集を抑制し
、実機におけるハンドリング性を円滑にする石炭水スラ
リー用添加剤を提供するものである。The present invention aims to provide an additive for coal-water slurry that suppresses soft agglomeration in coal-water slurry and facilitates handling in actual equipment.
３１Ｒ月１腹
本発明の石炭水スラリー用添加剤は、還元剤として次亜
リン酸または次亜リン酸塩を単量体に対して１〜１５モ
ル％使用し、酸化剤として過硫酸塩を用いるレドックス
重合により製造された重量平均分子量２０，０００以下
の水溶性アクリル系重合体を含むことを特徴とする。The additive for coal water slurry of the present invention uses 1 to 15 mol% of hypophosphorous acid or hypophosphite based on the monomer as a reducing agent, and persulfate as an oxidizing agent. It is characterized by containing a water-soluble acrylic polymer having a weight average molecular weight of 20,000 or less produced by redox polymerization.
以下、本発明について詳細に説明するが、説明の便宜上
、本発明の必須成分である上記の水溶性アクリル系重合
体を（Ａ）成分と呼ぶ。The present invention will be described in detail below, but for convenience of explanation, the above-mentioned water-soluble acrylic polymer, which is an essential component of the present invention, will be referred to as component (A).
（Ａ）成分の水溶性アクリル系重合体は、重量平均分子
量が２０，０００以下のものが好適であり、好ましくは
１０００〜２０，０００である。分子量が２０．０００
を超えると、石炭水スラリーの流動性が不良となるので
好ましくない。また、（Ｂ）成分の重合体は酸型でも塩
型でもよく、中和の程度も特に制限はなく、添加剤の所
望の性状に合せて適宜選択される。塩として用いられる
場合は、リチウム、ナトリウム、カリウムなどのアルカ
リ金属塩、マグネシウム、カルシウムなどのアルカリ土
類金属塩、アンモニウム塩および有機アミン塩が適当で
あり、好ましくはナトリウム、カリウムまたはアンモニ
ウム塩である。The water-soluble acrylic polymer as component (A) preferably has a weight average molecular weight of 20,000 or less, preferably 1000 to 20,000. Molecular weight is 20.000
If it exceeds , the fluidity of the coal-water slurry becomes poor, which is not preferable. The polymer of component (B) may be either an acid type or a salt type, and the degree of neutralization is not particularly limited and is appropriately selected depending on the desired properties of the additive. When used as a salt, alkali metal salts such as lithium, sodium, potassium, alkaline earth metal salts such as magnesium, calcium, ammonium salts and organic amine salts are suitable, preferably sodium, potassium or ammonium salts. .
本発明のアクリル系重合体としては、特定の製法で製造
されたものが用いられ、還元剤として次亜リン酸または
その塩を単量体に対して１〜１５モル％使用し、酸化剤
として過硫酸塩を用いるレドックス重合により製造され
たものを用いる。The acrylic polymer of the present invention is manufactured by a specific manufacturing method, and hypophosphorous acid or its salt is used as a reducing agent in an amount of 1 to 15 mol% based on the monomer, and as an oxidizing agent, One produced by redox polymerization using persulfate is used.
次亜リン酸塩としては、次亜リン酸ナトリウムが代表的
である。過硫酸塩としては、過硫酸カリウム、過硫酸ア
ンモニウム、過硫酸ナトリウム等が用いられる。A typical hypophosphite is sodium hypophosphite. As the persulfate, potassium persulfate, ammonium persulfate, sodium persulfate, etc. are used.
レドックス重合において、還元剤の使用量が１モル％よ
り少ないと、得られるアクリル系重合体の分子量が高く
なりすぎる傾向がある。In redox polymerization, if the amount of reducing agent used is less than 1 mol %, the molecular weight of the resulting acrylic polymer tends to be too high.
一方、１５モル％より多く使用しても分子量の低下に対
して顕著な効果がなく、また、経済性の点でも好ましく
ない。On the other hand, even if it is used in an amount exceeding 15 mol %, there is no significant effect on lowering the molecular weight, and it is also unfavorable from the economic point of view.
酸化剤の使用量は、単量体に対して０．３〜５モル％が
好ましい。The amount of the oxidizing agent used is preferably 0.3 to 5 mol% based on the monomer.
（イ）酸化剤と（ロ）還元剤とは、モル比で（イ）／（
ロ） ＝ ２／１〜１／２０の範囲で使用することが好
ましい、また、このレドックス触媒系に、さらに過酸化
水素を、（い）過硫酸塩と（ろ）過酸化水素との比率が
モル比で（い）／（ろ） ： １０／１〜１／２の範囲
で使用することもできる。(a) The oxidizing agent and (b) the reducing agent have a molar ratio of (i)/(
b) It is preferable to use hydrogen peroxide in the range of 2/1 to 1/20, and hydrogen peroxide is further added to this redox catalyst system so that the ratio of (i) persulfate to (filtration) hydrogen peroxide is It can also be used in a molar ratio of (i)/(ro): 10/1 to 1/2.
重合で用いられるアクリル系単量体としては、アクリル
酸、メタクリル酸が好ましく、また、これらと共重合し
うる他の水溶性ビニル系単量体を共重合させることもで
きる。（メタ）アクリル酸と共重合しうる単量体として
は、イタコン酸、フマル酸、マレイン酸、ヒドロキシエ
チル（メタ）アクリレート、ヒドロキシメチル（メタ）
アクリレート、ヒドロキシプロピル（メタ）アクリレー
ト、（メタ）アクリルアミド、２−アクリルアミド−２
−メチルプロパンスルホン酸、スチレンスルホン酸等が
挙げられる。なお、上記記載中で例えば（メタ）アクリ
ル酸とあるのは、「アクリル酸またはメタクリル酸」を
意味する。The acrylic monomer used in the polymerization is preferably acrylic acid or methacrylic acid, and other water-soluble vinyl monomers that can be copolymerized with these can also be copolymerized. Monomers that can be copolymerized with (meth)acrylic acid include itaconic acid, fumaric acid, maleic acid, hydroxyethyl (meth)acrylate, and hydroxymethyl (meth)acrylate.
Acrylate, hydroxypropyl (meth)acrylate, (meth)acrylamide, 2-acrylamide-2
-Methylpropanesulfonic acid, styrenesulfonic acid, etc. In addition, in the above description, for example, (meth)acrylic acid means "acrylic acid or methacrylic acid".
これら単量体は酸の形で重合に供するのが好ましいが、
得られる重合体の性能に差しつがえない範囲で、塩の形
で重合に供してもよい。These monomers are preferably subjected to polymerization in the form of acids,
It may be used in the polymerization in the form of a salt, as long as it does not affect the performance of the resulting polymer.
上記のようなアクリル系水溶性単量体、酸化剤および還
元剤を使用して重合反応を行なうことにより、（Ｂ）成
分のアクリル系水溶性重合体が得られ、特にポリアクリ
ル酸またはその塩が好ましい。By carrying out a polymerization reaction using the above-mentioned water-soluble acrylic monomer, oxidizing agent, and reducing agent, the water-soluble acrylic polymer of component (B) can be obtained, especially polyacrylic acid or its salt. is preferred.
重合方法１条件等は特に限定されず、例えば公知の溶液
重合の手法を用いることができる。The conditions of the polymerization method 1 are not particularly limited, and for example, a known solution polymerization method can be used.
単量体濃度は、１〜６０重量％の範囲が好適であり、１
０〜４５重量％が好ましい。The monomer concentration is preferably in the range of 1 to 60% by weight, and 1 to 60% by weight.
0 to 45% by weight is preferred.
重合温度は、酸化剤および還元剤の種類によっても異な
るが、一般には、４０〜１００℃の範囲内で実施でき、
６０〜１００℃が好ましい。The polymerization temperature varies depending on the type of oxidizing agent and reducing agent, but generally it can be carried out within the range of 40 to 100 ° C.
60-100°C is preferred.
重合時間は、通常４〜１０時間で十分である。Polymerization time of 4 to 10 hours is usually sufficient.
重合反応を行う雰囲気は、空気でも窒素、二酸化炭素等
の不活性ガス雰囲気でも良いが、窒素雰囲気が好ましい
。The atmosphere in which the polymerization reaction is carried out may be air or an inert gas atmosphere such as nitrogen or carbon dioxide, but a nitrogen atmosphere is preferable.
本発明の添加剤においては、上記（Ａ）成分に、以下の
ＣＢ）成分を併用することが好ましい。In the additive of the present invention, it is preferable to use the following component CB) in combination with the component (A).
（Ｂ）分子内に芳香族環またはトリアジン環およびスル
ホン酸基を有する水溶性スルホン酸系重合体。(B) A water-soluble sulfonic acid polymer having an aromatic ring or triazine ring and a sulfonic acid group in the molecule.
（Ｂ）成分の水溶性スル示ン酸系重合体としては、ベン
ゼン環、ナフタレン環等の芳香族環またはトリアジン環
とスルホン酸基とを有するものが用いられ、その具体例
としては、ポリ芳香族スルホン酸またはその塩、芳香族
スルホン酸ホルムアルデヒド縮金物またはその塩、アミ
ノトリアジンホルムアルデヒド縮金物スルホン酸または
その塩などが挙げられる。As the water-soluble sulfonic acid-based polymer of component (B), those having an aromatic ring such as a benzene ring or a naphthalene ring or a triazine ring and a sulfonic acid group are used. Examples include sulfonic acids or salts thereof, aromatic sulfonic acid formaldehyde condensed metal products or salts thereof, aminotriazine formaldehyde condensed metal sulfonic acids or salts thereof, and the like.
ポリ芳香族スルホン酸またはその塩は、重合性芳香族ス
ルホン酸（モノマー）を重合ないしは他のモノマーと共
重合することにより得られ、また、芳香族重合体（ポリ
マー）をスルホン化し、必要により中和することによっ
ても得られ、ポリスチレンスルホン酸またはその塩が好
適である。重合性芳香族スルホン酸の具体例としては、
スチレンスルホン酸、α−メチルスチレンスルホン酸、
メチル核置換スチレンスルホン酸、ビニルナフタレンス
ルホン酸が挙げられる。ポリスチレン、ポリα−メチル
スチレン等の芳香族重合体のスルホン化は、常法により
適当なスル・ホン化剤、例えば無水硫酸、クロルスルホ
ン酸などを用いて行なうことができる。Polyaromatic sulfonic acids or salts thereof can be obtained by polymerizing or copolymerizing a polymerizable aromatic sulfonic acid (monomer) with other monomers, and can also be obtained by sulfonating an aromatic polymer (polymer) and, if necessary, neutralizing it. Polystyrene sulfonic acid or a salt thereof is preferred. Specific examples of polymerizable aromatic sulfonic acids include:
Styrene sulfonic acid, α-methylstyrene sulfonic acid,
Examples include methyl nucleus-substituted styrene sulfonic acid and vinylnaphthalene sulfonic acid. Sulfonation of aromatic polymers such as polystyrene and poly-α-methylstyrene can be carried out in a conventional manner using a suitable sulfonating agent such as sulfuric anhydride or chlorosulfonic acid.
ポリ芳香族スルホン酸（塩）のスルホン化度は、７５〜
１００％が好ましく、より好ましくは８０〜９５％であ
る。ポリ芳香族スルホン酸（塩）の重量平均分子量は、
２ 、０００以上が好適であり、好ましくは約ｓ、ｏｏ
ｏ〜８０，０００である。The degree of sulfonation of polyaromatic sulfonic acid (salt) is 75 to
100% is preferable, more preferably 80-95%. The weight average molecular weight of polyaromatic sulfonic acid (salt) is
2,000 or more is suitable, preferably about s,oo
o~80,000.
芳香族スルホン酸のホルムアルデヒド縮金物またはその
塩としては、重量平均分子量７００以上のものが好適で
あり、好ましくは８００〜５，０００である。この芳香
族スルホン酸としては、ベンゼンスルホン酸、短鎖アル
キルベンゼンスルホン酸、ナフタレンスルホン酸、短鎖
アルキルナフタレンスルホン酸、フェノールスルホン酸
。The formaldehyde condensate of aromatic sulfonic acid or its salt has a weight average molecular weight of 700 or more, preferably 800 to 5,000. Examples of the aromatic sulfonic acid include benzenesulfonic acid, short-chain alkylbenzenesulfonic acid, naphthalenesulfonic acid, short-chain alkylnaphthalenesulfonic acid, and phenolsulfonic acid.
ナフトールスルホン酸、クレオソート油スルホン化物な
どが挙げられる。Examples include naphtholsulfonic acid and creosote oil sulfonates.
アミノトリアジンホルムアルデヒド縮金物のスルホン化
物またはその塩は、アミノ−８−トリアジン化合物１例
えばメラミン、ヘキサメチロールメラミン、アヤトグア
ナミン、ベンゾグアナミン等とホルムアルデヒドとの縮
重合反応生成物を、さらにスルホン化して得られたスル
オン化物またはその塩であり、重量平均分子量が７００
以上のものが好適であり、好ましくは８００〜５，００
０の範囲である。The sulfonated product of aminotriazine formaldehyde condensate or its salt is obtained by further sulfonating the condensation reaction product of amino-8-triazine compound 1, such as melamine, hexamethylolmelamine, ayatoguanamine, benzoguanamine, etc., and formaldehyde. It is a sulfonide or its salt, and has a weight average molecular weight of 700.
The above is suitable, preferably 800 to 5,000
The range is 0.
（Ｂ）成分の水溶性スルホン酸系重合体は、酸型でも塩
型でもよいが、スルホン酸基の半分以上が中和されたも
のが好ましい。このような重合体の塩としては、リチウ
ム、ナトリウム、カリウムなどのアルカリ金属塩、マグ
ネシウム、カルシウムなどのアルカリ土類金属塩、アン
モニウム塩および有機アミン塩が適当であり、好ましく
はナトリウム、カリウムおよびアンモニウムの各塩であ
る。The water-soluble sulfonic acid polymer as component (B) may be either an acid type or a salt type, but it is preferably one in which half or more of the sulfonic acid groups are neutralized. Suitable salts of such polymers include alkali metal salts such as lithium, sodium and potassium, alkaline earth metal salts such as magnesium and calcium, ammonium salts and organic amine salts, preferably sodium, potassium and ammonium salts. each salt.
（Ａ）成分と（Ｂ）成分を併用する場合、これらは（Ａ
）／（Ｂ）＝０．１／９９．９〜２５／７５の範囲で併
用することが好適であり、好ましくは１／９９〜２０／
８０の範囲である。この範囲で両成分を併用することに
より、よりいっそうの相剰効果が発揮される。When using component (A) and component (B) together, these are (A)
)/(B)=0.1/99.9 to 25/75, preferably 1/99 to 20/
The range is 80. By using both components together within this range, even more mutually beneficial effects can be exhibited.
（Ａ）成分の水溶性アクリル系重合体の量が０．１／９
９．９より少ないと、石炭水スラリーのソフト凝集を抑
制できない、一方、（Ａ）成分の量が２５７７５より多
い場合は、石炭水スラリーの流動性は向上するものの、
ハードパックを形成しやすくなる。The amount of water-soluble acrylic polymer as component (A) is 0.1/9
If the amount is less than 9.9, soft agglomeration of the coal water slurry cannot be suppressed, while if the amount of component (A) is more than 25775, the fluidity of the coal water slurry will improve,
It becomes easier to form hard packs.
本発明の石炭水スラリー用添加剤は、 （Ａ）。The additive for coal water slurry of the present invention is (A).
（Ｂ）両成分が酸型か塩型かにより、そのｐＨを酸性か
らアルカリ性まで広範囲に変えることができるが、高ア
ルカリ性領域において添加効果が大きく発揮されること
から、添加後のスラリーのｐＨを９以上とすることが望
ましい。(B) Depending on whether the two components are acid-type or salt-type, the pH can be varied over a wide range from acidic to alkaline, but since the addition effect is greatest in the highly alkaline region, the pH of the slurry after addition is It is desirable to set it to 9 or more.
上記の添加剤を添加、混合することにより、高濃度石炭
水スラリーが得られる１石炭水スラリー中への添加量は
、０．１〜３．０重量％が好適である。A high concentration coal water slurry is obtained by adding and mixing the above additives.The amount added to the coal water slurry is preferably 0.1 to 3.0% by weight.
本発明の石炭水スラリーでは、スラリーの粘度指数が０
．５〜１．０、好ましくは０．７〜０．９となるように
スラリー調製をするとよい、スラリーの粘度指数がこれ
よりも低いとソフト凝集が増加し、また、逆に高くなる
とダイラタント流動を示すようになり、スラリーを静置
保存したときにハードパックを形成する傾向が強くなる
。In the coal water slurry of the present invention, the viscosity index of the slurry is 0.
．． It is recommended to prepare the slurry so that the viscosity index is 5 to 1.0, preferably 0.7 to 0.9.If the viscosity index of the slurry is lower than this, soft aggregation will increase, and if it is higher, dilatant flow will be inhibited. When the slurry is stored stationary, it has a strong tendency to form hard packs.
本発明の添加剤は、褐炭、亜瀝青炭、瀝青炭、無煙炭な
どの各種石炭のスラリーに適用できる。The additive of the present invention can be applied to slurries of various coals such as brown coal, subbituminous coal, bituminous coal, and anthracite coal.
スラリー中の石炭粒度は、実質的に１■−以上のものが
無ければ使用できるが、一般に粒度が小さくなるほど水
スラリーの分散安定性が良くなる傾向があるので、２０
０メツシユパス（約７４ｇｍ以下）５０重量％以上のも
のが好ましく、特に６５〜９５重量％の範囲にあるもの
が好ましい。The coal particle size in the slurry can be used as long as it does not have a particle size of 1- or more, but generally speaking, the smaller the particle size, the better the dispersion stability of the water slurry.
0 mesh pass (approximately 74 gm or less) is preferably 50% by weight or more, and particularly preferably in the range of 65 to 95% by weight.
石炭水スラリーは、乾式粉砕法または湿式粉砕法により
石炭を粉砕して水スラリー化することにより得ることが
でき、添加剤は最終水スラリーに含まれるように適宜の
工程で分散することができる。たとえば、乾式粉砕法で
石炭微粉体を得た場合は、添加剤を水に溶解または分散
させ、これに石炭微粉体を加えて適当な混合装置により
高濃度水スラリーを調製すればよい。The coal-water slurry can be obtained by pulverizing coal to form a water slurry using a dry pulverization method or a wet pulverization method, and the additives can be dispersed in an appropriate step so as to be included in the final water slurry. For example, when fine coal powder is obtained by dry pulverization, the additives may be dissolved or dispersed in water, and the fine coal powder may be added thereto to prepare a highly concentrated water slurry using an appropriate mixing device.
また、湿式粉砕法を採用する場合は、湿式粉砕に用いる
水中に添加剤を予め分散するようにしてもよいし、湿式
粉砕中もしくは粉砕後に分散するようにしてもよい。Furthermore, when a wet pulverization method is employed, the additives may be dispersed in advance in the water used for wet pulverization, or may be dispersed during or after wet pulverization.
また、本発明の（Ａ） 、 （Ｂ）両成分に加えて、ジ
シクロペンタジェン重合体のスルホン化物、アニオン界
面活性剤、ノニオン界面活性剤、アルカリ剤などを石炭
水スラリー中に添加することもできる。In addition to both components (A) and (B) of the present invention, a sulfonated dicyclopentadiene polymer, an anionic surfactant, a nonionic surfactant, an alkali agent, etc. may be added to the coal water slurry. You can also do it.
アニオン界面活性剤としては、アルキルベンゼンスルホ
ン酸、ポリオキシエチレンアルキルエーテル硫酸塩など
が例示される。Examples of anionic surfactants include alkylbenzene sulfonic acids and polyoxyethylene alkyl ether sulfates.
ノニオン界面活性剤としては、ポリオキシエチレンアル
キルエーテル、ポリオキシエチレンアルキルフェニルエ
ーテル、ポリオキシエチレン脂肪酸アミド、ポリエチレ
ンオキシド−ポリプロピレンオキシド等のアルキレンオ
キシド重合体、ポリエチレンイミンにプロピレンオキシ
ドとエチレンオキシドを付加して得られるポリエーテル
などが挙げられる６
アルカリ剤としては、水酸化ナトリウム、水酸化カリウ
ムなどが好適に使用でき、これらはスラリー製造の任意
の段階で添加できる。Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid amide, alkylene oxide polymers such as polyethylene oxide-polypropylene oxide, and polyethylene imine obtained by adding propylene oxide and ethylene oxide. Examples of the alkaline agent include sodium hydroxide, potassium hydroxide, etc., and these can be added at any stage of slurry production.
見尻勿麦米
本発明の石炭水スラリー用添加剤によれば、特定の水溶
性アクリル系重合体を使用することにより、石炭水スラ
リーにおけるソフト凝集を抑制し、実機におけるハンド
リング性を改善することができる。According to the additive for coal-water slurry of the present invention, by using a specific water-soluble acrylic polymer, soft agglomeration in the coal-water slurry can be suppressed and handling properties in actual equipment can be improved. Can be done.
本発明の添加剤の作用機構について充分に解明されてい
ないが、一般にソフト凝集は粒子間ポテンシャルの第２
極少に白米すると言われている点を考慮すると１本発明
の水溶性アクリル系重合体により粒子間反発力（立体的
反発力および電気的反発力）が高められ、第２極少が浅
くなったものと思われる。さらに、本発明の水溶性アク
リル系重合体２・こ（Ｂ）成分の水溶性スルホン酸系重
合体を併用することにより、上記の粒子間反発力が相乗
的に高められると考えられる。Although the mechanism of action of the additive of the present invention has not been fully elucidated, soft aggregation is generally caused by the second phase of the interparticle potential.
Taking into account the fact that it is said that the rice is polished to a minimum, the water-soluble acrylic polymer of the present invention increases the interparticle repulsion (steric repulsion and electrical repulsion), and the second one has a shallow minimum repulsion. I think that the. Furthermore, it is thought that by using the water-soluble acrylic polymer 2 of the present invention and the water-soluble sulfonic acid polymer of component (B) in combination, the above-mentioned interparticle repulsion force is increased synergistically.
スー」Ｌ二釘
ステンレス製ボールを充填率５０％で収容する６Ｍ（内
径１９ｃ■）のステンレス製ボールミルに。This is a 6M (inner diameter 19cm) stainless steel ball mill that accommodates "Sue" L two-nail stainless steel balls at a filling rate of 50%.
所定量の（ム）成分、（Ｂ）成分、水、粒径３ｍ■以下
に粉砕したマウントソーレー炭を仕込んだ後、６５ｒｐ
ｍで回転させ、レーザー回折型粒度分布計でスラリーの
粒度（７４μ園以下の粒子の数）を測定しながら、７４
μ■以下の粒子の量が８０％になるまで粉砕した。After adding a predetermined amount of component (M), component (B), water, and Mount Thorley charcoal crushed to a particle size of 3 m or less, 65 rpm was added.
74 m while measuring the particle size (number of particles of 74 μm or less) of the slurry with a laser diffraction particle size analyzer.
The powder was ground until the amount of particles smaller than μ■ was 80%.
粉砕後、ボールミル中からスラリーを取り出し、ホモミ
キサーにより４０００ｒｐ馬で１０分間撹拌したのち、
スラリーのソフト凝集性を評価した。After pulverization, the slurry was taken out from the ball mill and stirred for 10 minutes at 4000 rpm using a homomixer.
The soft cohesiveness of the slurry was evaluated.
なお、スラリーの石炭濃度は、粘度が約１０００ｃｐに
なるように調整し、粘度はハーグの粘度計により１００
ｓｅｃ−ｄｏｗｎ時の粘度を測定した。The coal concentration of the slurry was adjusted so that the viscosity was approximately 1000 cp, and the viscosity was determined to be 100 cp using a Hague viscometer.
The viscosity at sec-down was measured.
次に、次式によりスラリーの粘度指数を算出したところ
、後記表−３に示した各スラリーはいずれも０．７〜０
．９の範囲にあった。Next, the viscosity index of the slurry was calculated using the following formula, and it was found that each slurry shown in Table 3 below was 0.7 to 0.
．． It was in the 9 range.
粘度指数＝ ｎτ −Ωｎτ
Ｊｌｎ’ｙｌ−ｊＩｎＹ＊
γｌ ＠ ７８−’時のずれ速度
γ、 ： １００ｓ−’時のずれ速度
τ１： ７ ！ｌ−１時のずれ応力
τ、 ： １００ｓ−１時のずれ応力
以下、ソフト凝集性の評価法、使用石炭の性状分析値（
表−１）、（Ａ）成分の合成法ならびに性状、（Ｂ）成
分の性状（表−２）、（Ａ）および（Ｂ）成分を添加し
た石炭水スラリーの評価結果を順次に示す。Viscosity index = nτ -Ωnτ Jln'yl-jInY* γl @ Shear velocity γ at 78-': Shear velocity τ1 at 100 s-': 7! Shear stress τ at l-1: less than shear stress at 100 s-1, soft cohesion evaluation method, property analysis value of coal used (
Table 1), the synthesis method and properties of component (A), the properties of component (B) (Table 2), and the evaluation results of the coal water slurry to which components (A) and (B) were added are shown in sequence.
（１）ソフト凝集性の評価法
２５０膳Ωの広口びんにスラリーを入れ２５℃で１０日
間静置したのち、１６メツシユのふるい上にあけた際の
ふるい上の量（スラリー全量に対する重量％）より、ソ
フト凝集性を判定した。(1) Soft cohesiveness evaluation method: Put the slurry in a 250Ω wide-mouth bottle, let it stand at 25°C for 10 days, and then pour it onto a 16-mesh sieve.The amount on the sieve (% by weight based on the total amount of slurry) Soft cohesiveness was determined.
（２）マウントソーレー炭の性状分析値表−１
（３） （Ａ）成分の合成
以下の３つの（Ａ）成分、Ａ−１，Ａ−２，Ａ−３を合
成し、分子量を測定した。(2) Table of property analysis values for Mount Sorley charcoal-1 (3) Synthesis of (A) components The following three (A) components, A-1, A-2, and A-3, were synthesized and their molecular weights were measured. did.
（ｉ）Ａ−１の合成
撹拌機、温度計、還流管、窒素導入
管、Ｙ字滴下管を備えた１１の５つロ
セバラブルフラスコに、蒸留水９７ｇを仕込み、窒素を
流入して撹拌しながら
９０℃まで昇温する。これに、蒸留水
１３５ｇに過硫酸カリウム４．８６ｇ（対モノマー０．
５モル％）と、８０％アクリル酸水溶液３２４ｇに次亜
リン酸ナトリウム１水和物１５．２６ｇ（対モノマー４
モル％）を溶解した溶液とを、それぞれ３時間かけて
連続滴下した後、さらに、９０℃で３時間熟成を行った
。ついで、４８％水酸化ナトリウム水溶液３００．を添
加して中和した。(i) Synthesis 97 g of distilled water is charged into a 5-piece rose variable flask (No. 11) equipped with a stirrer, a thermometer, a reflux tube, a nitrogen introduction tube, and a Y-shaped dropping tube as shown in A-1, and nitrogen is introduced into the flask and stirred. While heating, raise the temperature to 90°C. To this, 4.86 g of potassium persulfate was added to 135 g of distilled water (0.8 g of potassium persulfate (relative to the monomer).
5 mol%) and 15.26 g of sodium hypophosphite monohydrate (based on monomer 4) in 324 g of 80% acrylic acid aqueous solution.
% by mole) were continuously added dropwise over a period of 3 hours, and then aged at 90° C. for 3 hours. Then, 300% of a 48% aqueous sodium hydroxide solution was added. was added to neutralize.
得られたポリマー溶液は、固形分
４０．１％であり１重量平均分子量は５７００であった
。The obtained polymer solution had a solid content of 40.1% and a weight average molecular weight of 5,700.
（ｉｔ）Ａ−２の合成
撹拌機、温度計、還流管、窒素導入
管、Ｙ字滴下管を備えたＩＱの５つロ
セパラブルフラスコに、蒸留水２０５ｇを仕込み、窒素
を流入して撹拌しながら
９０℃まで昇温する。これに、蒸留水
１２０ｇに過硫酸カリウム４．３２ｇ（対七ツマー０．
５モル％）と、８０％アクリル酸水溶液２８８ｇに次亜
リン酸ナトリウム１水和物４０．７ｇ（対モノマー１２
モル％）を溶解した溶液とを、それぞれ３時間かけて
連続滴下した後、さらに、９０℃で３時間熟成を行った
。ついで、４８％水酸化ナトリウム水溶液２６７ｇを添
加して中和した。(it) Pour 205 g of distilled water into IQ's 5-separable flask equipped with A-2's synthesis stirrer, thermometer, reflux tube, nitrogen inlet tube, and Y-shaped dropping tube, and then add nitrogen and stir. While heating, raise the temperature to 90°C. To this, 120 g of distilled water and 4.32 g of potassium persulfate (0.7 g of potassium persulfate) were added.
5 mol%) and 40.7 g of sodium hypophosphite monohydrate (to monomer 12 g) to 288 g of 80% acrylic acid aqueous solution
% by mole) were continuously added dropwise over a period of 3 hours, and then aged at 90° C. for 3 hours. Then, 267 g of 48% aqueous sodium hydroxide solution was added to neutralize.
得られたポリマー溶液は、固形分
３５．４％であり、重量平均分子量は１８００であった
。The obtained polymer solution had a solid content of 35.4% and a weight average molecular weight of 1,800.
（ｉｎ） Ａ−３の合成
撹拌機、温度計、還流管、窒素導入
管、Ｙ字滴下管を備えたＩＱの５つロ
セパラブルフラスコに、蒸留水２３９ｇを仕込み、窒素
を流入して撹拌しながら
９０℃まで昇温する。これに、蒸留水
１２０ｇに過硫酸カリウム４．３２ｇ（対モノマー０．
５モル％）と、８０％アクリル酸水溶液２８８ｇに次亜
リン酸ナトリウム１水和物６．７８ｇ（対モノマー２モ
ル％）を溶解した溶液とを、それぞれ３時間かけて
連続滴下した後、さらに、９０℃で３時間熟成を行った
。ついで、４８％水酸化ナトリウム水溶液２６７ｇを添
加して中和した。(in) Pour 239 g of distilled water into an IQ five-separable flask equipped with an A-3 synthetic stirrer, a thermometer, a reflux tube, a nitrogen introduction tube, and a Y-shaped dropping tube, then introduce nitrogen and stir. While heating, raise the temperature to 90°C. To this, 4.32 g of potassium persulfate was added to 120 g of distilled water (0.0 g of potassium persulfate (relative to monomer).
5 mol%) and a solution of 6.78 g of sodium hypophosphite monohydrate (2 mol% of monomer) dissolved in 288 g of 80% acrylic acid aqueous solution were each continuously added dropwise over 3 hours, and then , aging was performed at 90°C for 3 hours. Then, 267 g of 48% aqueous sodium hydroxide solution was added to neutralize.
得られたポリマー溶液は、固形分 ３３．２％であり、重量平均分子量は １５０００であった。The obtained polymer solution has a solid content of 33.2%, and the weight average molecular weight is It was 15,000.
（以下余白）(Margin below)
Claims (1)
を単量体に対して１〜１５モル％使 用し、酸化剤として過硫酸塩を用いるレ ドックス重合により製造された重量平均 分子量２０，０００以下の水溶性アクリル系重合体を含
むことを特徴とする高濃度石炭 水スラリー用添加剤。 ２、下記（Ｂ）成分を併用する請求項１記載の添加剤。 （Ｂ）分子内に芳香族環またはトリアジン環およびスル
ホン酸基を有する水溶性スル ホン酸系重合体 ３、上記（Ｂ）成分がポリスチレンスルホン酸またはそ
の塩である請求項２記載の添加剤。 ４、上記（Ａ）成分と（Ｂ）成分とを重量比で（Ａ）／
（Ｂ）＝２５／７５〜０．１／９９．９の範囲で含有す
る請求項２または３に記載の添加剤。[Claims] 1. (A) By redox polymerization using 1 to 15 mol% of hypophosphorous acid or hypophosphite salt based on the monomer as a reducing agent and persulfate as an oxidizing agent. An additive for a highly concentrated coal-water slurry, comprising a produced water-soluble acrylic polymer having a weight average molecular weight of 20,000 or less. 2. The additive according to claim 1, in which the following component (B) is used in combination. 3. The additive according to claim 2, wherein (B) is a water-soluble sulfonic acid polymer 3 having an aromatic ring or a triazine ring and a sulfonic acid group in the molecule, and the component (B) is polystyrene sulfonic acid or a salt thereof. 4. The weight ratio of the above (A) component and (B) component is (A)/
The additive according to claim 2 or 3, containing (B) in the range of 25/75 to 0.1/99.9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9684690A JP2847131B2 (en) | 1990-04-11 | 1990-04-11 | Additive for coal water slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9684690A JP2847131B2 (en) | 1990-04-11 | 1990-04-11 | Additive for coal water slurry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03294391A true JPH03294391A (en) | 1991-12-25 |
| JP2847131B2 JP2847131B2 (en) | 1999-01-13 |
Family
ID=14175871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9684690A Expired - Fee Related JP2847131B2 (en) | 1990-04-11 | 1990-04-11 | Additive for coal water slurry |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2847131B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007537341A (en) * | 2004-05-12 | 2007-12-20 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for removing sulfur-containing end groups |
-
1990
- 1990-04-11 JP JP9684690A patent/JP2847131B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007537341A (en) * | 2004-05-12 | 2007-12-20 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for removing sulfur-containing end groups |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2847131B2 (en) | 1999-01-13 |
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