CN1570042A - Hydrophilic and lipophilic type water coalite slurry additive and its preparation method - Google Patents
Hydrophilic and lipophilic type water coalite slurry additive and its preparation method Download PDFInfo
- Publication number
- CN1570042A CN1570042A CN200410014921.XA CN200410014921A CN1570042A CN 1570042 A CN1570042 A CN 1570042A CN 200410014921 A CN200410014921 A CN 200410014921A CN 1570042 A CN1570042 A CN 1570042A
- Authority
- CN
- China
- Prior art keywords
- acid
- kilograms
- amphiphilic
- sodium
- preparation
- 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 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 56
- 239000000654 additive Substances 0.000 title claims description 45
- 230000000996 additive effect Effects 0.000 title claims description 43
- 238000002360 preparation method Methods 0.000 title claims description 32
- 239000000047 product Substances 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 26
- 238000006482 condensation reaction Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- 238000006243 chemical reaction Methods 0.000 claims description 43
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 34
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 238000006277 sulfonation reaction Methods 0.000 claims description 29
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 25
- 239000004202 carbamide Substances 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 24
- -1 quinhydrones Chemical compound 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 238000005516 engineering process Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 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 claims description 17
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 15
- 159000000000 sodium salts Chemical class 0.000 claims description 12
- 229960004279 formaldehyde Drugs 0.000 claims description 11
- 235000019256 formaldehyde Nutrition 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 9
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 239000001488 sodium phosphate Substances 0.000 claims description 7
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 235000011008 sodium phosphates Nutrition 0.000 claims description 5
- 229940124530 sulfonamide Drugs 0.000 claims description 5
- 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 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001896 cresols Chemical class 0.000 claims description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 4
- 229940095064 tartrate Drugs 0.000 claims description 4
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 3
- 229950011260 betanaphthol Drugs 0.000 claims description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 229940100630 metacresol Drugs 0.000 claims description 3
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 3
- 229940045998 sodium isethionate Drugs 0.000 claims description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 2
- 229940074391 gallic acid Drugs 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 150000007513 acids Chemical class 0.000 abstract description 4
- 229920000877 Melamine resin Polymers 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 125000003368 amide group Chemical group 0.000 abstract 1
- 239000012263 liquid product Substances 0.000 abstract 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003245 coal Substances 0.000 description 51
- 238000012545 processing Methods 0.000 description 36
- 235000013877 carbamide Nutrition 0.000 description 27
- 238000001556 precipitation Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 description 14
- 239000013049 sediment Substances 0.000 description 13
- 238000002407 reforming Methods 0.000 description 9
- 238000011160 research Methods 0.000 description 9
- 150000001912 cyanamides Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical class C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003250 coal slurry Substances 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- 239000004021 humic acid Substances 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical class OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 3
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 239000011970 polystyrene sulfonate Substances 0.000 description 3
- 229960002796 polystyrene sulfonate Drugs 0.000 description 3
- 229950000244 sulfanilic acid Drugs 0.000 description 3
- 239000012991 xanthate Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000009798 Shen-Fu Substances 0.000 description 2
- 229920005550 ammonium lignosulfonate Polymers 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 235000019357 lignosulphonate Nutrition 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005552 sodium lignosulfonate Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- KHDYBVQANLNECY-UHFFFAOYSA-N 1-hydroxyethanesulfonic acid;sodium Chemical compound [Na].CC(O)S(O)(=O)=O KHDYBVQANLNECY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920005646 polycarboxylate Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Images
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a slurry addition agent and method for making same, which consists of, carrying out sulphonation to 1.0-10.0 wt% melamine, mixing with 8.0-20.0 wt% of sulfaminic acid (salt), 1.5-20.0 wt% of phenol and its derivative, 1.0-5.0% of compound containing amide groups for condensation reaction by the regulation of acids and alkali, recapitalizing to obtain liquid product, and preparing the powder form product through spray drying.
Description
Technical field the invention belongs to field of fine chemical, specially refers to a kind of amphiphilic slurries additive agent and preparation method thereof.
The background technology coal water slurry is a kind of coal based fluid fuel of early 1980s exploitation, and characteristics are to pollute the liquid starting material low, that efficient is high, flowability is strong, clean.It is that a kind of coal dust that certain particle size is distributed is scattered in high-concentration coal/aqueous dispersion of making in the water medium (65～70% coal, 29～34% water and less than 1% chemical additive), coal water slurry had both kept the coal original physical characteristics, have the same mobile and stable of image-stone oil again, at aspect such as transportation, storage, pumping and materialization burning and incendiary to regulate aspects such as control all close with oil.In actual applications, 2.lt coal water slurry energy is equivalent to the energy of 1t oil, but cost is far below oil.Aspect environmental protection, because that coal dust reduces through the sulfur of washing own and ash content is about 40%, again because coal water slurry boiler low about 200 ℃ of temperature when burn than coal firing boiler, nitrogen oxide emission is reduction significantly also, has obviously purified air.China is an oil-poor big country of rich coal, thus COAL-WATER SLURRY TECHNOLOGY apply for advancing China's coal for replacing oil and improving environmental quality significant.
The preparation of high-concentration coal-water slurry is influenced by several factors, and selection is suitable, additive prepares one of key factor of high density, low viscosity coal water slurry beyond doubt efficiently.The preparation coal water slurry need be added minor amounts of additives to reduce viscosity of coal-water slurry, improves concentration, the rheological of coal water slurry and the stability that improves coal slurry.For many years, the country of each main developing water coal slurry all drops into the new variety that a large amount of human and material resources are developed additive.External company relatively more outstanding in Study on Additive work has: Nippon grease company, Kao company, Lion company and Com company etc.At present, external slurries additive agent mainly adopts
[1-2]: (1) high condensation degree naphthalene sulfonic acid condensate; (2) vinylformic acid and other Acrylic Acid Monomer copolymerization, molecular weight control is in certain limit
[3](3) polyolefin series is as the polymkeric substance sodium salt of toxilic acid and all kinds of cyclopentadiene, poly styrene sulfonate series
[4](4) sulfonated lignin
[5](5) humate and sulfonated humic acid salt series; (6) carboxylate salt and series of phosphate: as many cyclic polycarboxylic acids, polycarboxylate, polyphosphoric acid salt, hydroxy-benzoic acid polymkeric substance sodium salt etc.; (7) non-ionic dispersing agent: oxyethane series of surfactants or the like.Wherein, naphthalene sulfonic acidformaldehyde condensation product (NSF) and poly styrene sulfonate (PSS) etc. have all been realized suitability for industrialized production.Domestic scientific worker passes through research and the effort of decades, naphthalenesulfonate formaldehyde condensation compound in also successively developing
[6], humate
[7-8], better performances such as ethylene oxide type additive, and be that raw material has carried out modification and composite to the lignin series products, thereby synthesized cheap additive to make waste liquid
[9-10]China compares with external slurries additive agent technology, also there is a certain distance, particularly disperseing the viscosity reduction properties, under the situation of not considering dispersion agent ton slurry expense, home products hangs down 2-3% than external product on slurrying concentration, therefore, the basic purpose of China's exploitation slurries additive agent is to consider following two factors simultaneously: (1) improves the utilising efficiency of dispersion agent, promptly keep the existing cost of anionic dispersing agents, improve its performance, reduce consumption; Under the prerequisite that maintenance non-ionic dispersing agent consumption is few and performance is good, reduce its cost.(2) in conjunction with the additive of corresponding efficient, inexpensive, the wide adaptability of coal character (mainly being the coal on ground such as Shanxi, Shan and the Inner Mongol) exploitation of building extensive pulp mill raw material from now on.
Reference:
1.Zeki?Aktas，E.Ted?Woodburn.Effect?of?addition?of?surface?active?agent?on?the?viscosity?of?a?highconcentration?slurry?of?a?low-rank?British?coal?in?water[J].Fuel?Processing?Technology，2000，62：1-15
2. Guo is according to ice, Wu Guoguang. the present Research of slurries additive agent and development trend [J]. clean coal technology, 2001,7 (1): 32-343.Kain William S, Staker Donald D.Amides of polycarboxylic acids as rheological additives for coal-waterslurries[P] .US 5082469,1992
4.Ljusberg-Wahren?Helena.Coal-water?dispersion?agent[P].US?4957511，1990
5.Dilling?Peter.Ammonium?lignosulfonates[P].US?4670482，1987
6. Xu Jiang Hua, Fang Xiumin, the river is bright. naphthalene sulfonic acid formaldehyde condensation polymer synthetic and in the application [J] of slurries additive agent kind. Huainan Mining Industry College's journal, 1996,16 (3): 46-51,87
7. Zhengization peace, He Genliang, Yang Ping. humic acid additives for water-coal slurry and preparation method [P]. application number: 99115929.2,1999; Publication number CN 1298927A, 2001
8. Pan's phase minister in ancient times, Ceng Fan, Fu Xiaoyan. relation research (1) dispersing property of humic-acid kind slurries additive agent performance and its fraction and the relation [J] of fraction. coal conversion, 1999,22 (1): 38-42
9. Bai Chengzhi, Li Hanxu. the ammonium salt process black liquid is produced the research [J] of slurries additive agent. environmental engineering, 2001,19 (6): 48-49
10. Zhu's book is complete, king ancestral, Hu Kunmo etc. composite slurries additive agent technology [P]. and application number: 96120601.2,1996; Publication number: CN 11550001A, 1997
Summary of the invention the objective of the invention is to overcome the deficiencies in the prior art, and a kind of dispersiveness and stability, adaptable efficient, inexpensive amphiphilic slurries additive agent and preparation method thereof of improving is provided.
A kind of amphiphilic slurries additive agent provided by the present invention and preparation method thereof, this slurries additive agent is reddish-brown liquid or pulvis, and is soluble in water, wherein both contained lipophilicity group-(CN), contain hydrophilic radical (NH again
2,-OH and-SO
3Na etc.), and its weight-average molecular weight Mw is 2000～39000, and number-average molecular weight Mn is 200～10000, and chemical general formula is:
In the formula, m, n, o, p, q are the polymerization degree (5≤m≤90; 5≤n≤90; 1≤o≤20; 2≤p≤40; 2≤q≤60); D is aniline sulfonic acid and sodium salt thereof, 4-amino-1,3-phenyl disulfonic acid and sodium salt thereof, 4-kharophen Phenylsulfonic acid and sodium salt thereof; E is phenol and derivative thereof, as phenol, dihydroxyphenyl propane, bisphenol S, p-cresol, meta-cresol, cresols, Resorcinol, quinhydrones, catechol, naphthyl alcohol or 2-Naphthol etc.; F is the amino cyano group urea of methyl alcohol, Dyhard RU 100, benzoguanamine, amino-cyanobenzene, trimeric cyanamide etc. is contained the amphiphilic group (as contains lipophilicity group-CN and hydrophilic radical-NH
2Or-CONH
2Deng) compound; G is the compound of phosphinylidyne-containing amine groups such as urea or toluol sulfonamide; R=-H ,-CH
2-CH
2CH
2,-(CH
2)
n,-CH
2(CH
3)
nDeng.
The concrete technology of above-mentioned amphiphilic slurries additive agent is as follows:
1. raw material and prescription (massfraction):
Trimeric cyanamide: 1.0～10.0%;
Sulphonating agent: 1.0～15.0%;
Aniline sulfonic acid (salt): 8.0～20.0%;
Phenol and derivative thereof: 1.5～20.0%;
The compound of phosphinylidyne-containing amine group: 0.5～8.5%;
The compound that contains the amphiphilic group: 1.0～5.0%;
Condensing agent: 6.0～40.0%;
Acid regulator: 0.05～3.5%;
Alkaline conditioner: 0.1～8.5%;
Water: 15～65%.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: trimeric cyanamide sulfonation, condensation reaction and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) trimeric cyanamide sulfonation: promptly earlier trimeric cyanamide and water are added in the reactor, after stirring, the pH value of reaction system is transferred to 9.0～13.5, adding sulphonating agent, heat temperature raising to 75～95 ℃ afterreaction 0.5～2.5h with alkaline conditioner.
(2) condensation reaction: the compound and the water adding of aniline sulfonic acid (salt), phenol and derivative thereof, the compound that contains the amphiphilic group and phosphinylidyne-containing amine group are equipped with in the reactor of (1) step sulfonation reaction product, after stirring, with acid-base modifier the pH value of reaction system is transferred to 3.0～7.0, behind heat temperature raising to 65～100 ℃, in 1.0～2.5h, drip condensing agent, behind reaction 0.5～2.5h, add alkaline conditioner the pH value in the above-mentioned system is transferred to 8.0～9.0, react 2.0～6.0h down at 65～100 ℃.
(3) alkalescence is reformed: utilize alkaline conditioner that the pH value in the above-mentioned system is transferred to 9.0～12.0, cooling discharge behind reaction 1.0～4.0h under 70～100 ℃ promptly gets powder-like product by spraying drying.
In this technology, aniline sulfonic acid (salt) is Sulphanilic Acid and sodium salt thereof, 4-amino-1, and 3-phenyl disulfonic acid and sodium salt thereof, 4-kharophen Phenylsulfonic acid and sodium salt thereof preferably use wherein one or more (containing two kinds) mixtures; Phenol and derivative thereof are preferably the mixture of one or more (containing two kinds) in phenol, dihydroxyphenyl propane, bisphenol S, p-cresol, meta-cresol, cresols, Resorcinol, quinhydrones, catechol, naphthyl alcohol or the 2-Naphthol; Condensing agent is preferably a kind of or the two mixture in formaldehyde, the Paraformaldehyde 96, and the massfraction of industrial formol concentration is 30～40%; Sulphonating agent is preferably the mixture of one or more (containing two kinds) in alpha-hydroxymethyl sodium sulfonate, α-sodium isethionate, α-hydroxypropyl azochlorosulfonate acid sodium, the α-hydroxyl sodium isopropyl xanthate, and the massfraction of its concentration is 10～75%; The compound that contains the amphiphilic group is preferably the amino cyano group urea of methyl alcohol, Dyhard RU 100, benzoguanamine, to the mixture of one or more (containing two kinds) in amino-cyanobenzene, the trimeric cyanamide; The compound of phosphinylidyne-containing amine group is preferably a kind of or the two mixture in urea, the toluol sulfonamide; Acid regulator is preferably the mixture of one or more (containing two kinds) in thionamic acid, sulfuric acid, phosphoric acid, nitric acid, phenylformic acid, gallic acid, Whitfield's ointment, citric acid, tartrate, oxysuccinic acid, toxilic acid, the succsinic acid, and add-on is 0.05～3.5%; Alkaline conditioner is the mixture of one or more (containing two kinds) in sodium hydroxide, potassium hydroxide, sodium phosphate, trisodium phosphate, two sodium polyphosphates, tripoly phosphate sodium STPP, sodium polyphosphate, the water glass, and add-on is 0.1～8.5%.
More than the raw material of each step and the massfraction summation of prescription be 100%.
Compared with prior art, the present invention introduces the amphiphilic group in the molecular structure of additive, has promptly both contained the lipophilicity group and (CN), has contained hydrophilic radical (NH again
2,-OH and-SO
3Na etc.), the weight-average molecular weight Mw of product is 2000～39000, number-average molecular weight Mn is 200～10000, and both contained linear chain structure on the molecular chain of product, contain branched structure again, therefore product of the present invention can form network-like structure, and then play good dispersion and stable double effects by the bonding action of amphiphilic group and the multipoint adsorption effect on the molecular chain in pulping process.The lipophilicity group can improve the hydrophobicity on coal surface, and then improves the contact angle of the coal of the little and difficult slurrying of some original contact angles, significantly improves effects on slurry making.In addition because the existence of lipophilicity group can stop sulfonic group attached in the back suction that coal grain surface forms in the chemisorption mode, and with water in the high volence metal ion effect produce water-insoluble, weaken these ionic detrimentally affects, and then reduce the consumption of medicament.And the molecular weight of product of the present invention is bigger, and has both contained linear chain structure on the molecular chain, contain branched structure again, can form multipoint adsorption on coal grain surface, make when additive concentration is low, also can obtain effects on slurry making preferably, thereby reduce the additive consumption.
The present invention has the following advantages and positively effect:
1. product tool of the present invention contains lipophilicity group-(CN), contain hydrophilic radical (NH again
2,-OH and-SO
3Na etc.), and have straight chain and branched structure on the molecular chain concurrently, so product of the present invention has good dispersion and effect such as stable, and adaptability is strong.
2. keeping on the basis of product performance, the present invention introduces the compound of phosphinylidyne-containing amine group such as urea in the preparation process of product, with the rigid structure of raising product; Reduced the formaldehyde content in the product simultaneously, reduced production cost, and eliminated formaldehyde pollution from preparation technology.
3. the present invention also adds an amount of phenol derivatives to improve the molecular weight of product in preparation technology, its weight-average molecular weight Mw is controlled in 2000～39000 scopes, thereby help improving The comprehensive performance, and then reduce the consumption of medicament in the pulping process.
4. production technique of the present invention is simple, and raw materials for production are easy to get, and are with short production cycle, reaction temperature and, required equipment is a conventional equipment, is convenient to existing chemical plant and practices midwifery.
Now the present invention is further elaborated in conjunction with the accompanying drawings for description of drawings:
Fig. 1 is according to a kind of process flow sheet of the present invention.
Embodiment as shown in Figure 1, the embodiments of the invention situation is as follows:
The processing step of embodiment 1 and order be as shown in Figure 1:
1. the raw material of present embodiment and prescription (unit-kilogram):
Trimeric cyanamide: 16 kilograms;
Alpha-hydroxymethyl sodium sulfonate (50% content): 45 kilograms;
Sodium sulfanilate: 120 kilograms;
Phenol: 66 kilograms;
Urea: 15 kilograms;
Dyhard RU 100: 20 kilograms;
Formaldehyde (37% content): 185 kilograms;
Thionamic acid: 1.0 kilograms;
The NaOH:8.5 kilogram;
Water: 523.5 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: trimeric cyanamide sulfonation, condensation reaction and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) trimeric cyanamide sulfonation: promptly earlier 16 kilograms of trimeric cyanamides and 73.5 kg water are added in the reactor, after stirring, with 3.25 kilograms of 40%NaOH solution the pH value of reaction system is transferred to 10.5, add 45 kilogram of 50% alpha-hydroxymethyl sodium sulfonate solution, heat temperature raising to 85 ℃ afterreaction 1.5h.
(2) condensation reaction: 120 kilograms of Sodium sulfanilates, 66 kilograms of phenol, 20 kilograms of Dyhard RU 100s and 15 kg urea and 437.3 kg water are added be equipped with in the reactor of (1) step sulfonation reaction product, after stirring, add 1.0 kilograms of thionamic acids the pH value of reaction system is transferred to 5.0, behind the heat temperature raising to 80 ℃, in 1.5h, drip 185 kilogram of 37% formaldehyde solution, behind the reaction 1.5h, add 6.0 kilograms of 40%NaOH solution the pH value in the above-mentioned system is transferred to 8.0, react 4.0h down at 90 ℃.
(3) alkalescence is reformed: add 12 kilograms of 40%NaOH solution the pH value in the above-mentioned system is transferred to 11.0, react 2.0 back cooling discharges down at 98 ℃, product of the present invention is a reddish-brown liquid, and weight-average molecular weight Mw is 5000, number-average molecular weight Mn is 800, promptly gets powder-like product by spraying drying.
The processing step of embodiment 2 and order be as shown in Figure 1:
1. the raw material of present embodiment and prescription (unit-kilogram):
Trimeric cyanamide: 23 kilograms;
Alpha-hydroxymethyl sodium sulfonate (40% content): 55 kilograms;
Sodium sulfanilate: 180 kilograms;
Phenol: 96 kilograms;
Urea: 50 kilograms;
Dyhard RU 100: 10 kilograms;
Formaldehyde (37% content): 320 kilograms;
Tartrate: 2.0 kilograms;
Alkaline conditioner (sodium hydroxide and sodium phosphate mixture, mass ratio 9: 1): 12 kilograms;
Water: 252 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: trimeric cyanamide sulfonation, condensation reaction and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) trimeric cyanamide sulfonation: promptly earlier 23 kilograms of trimeric cyanamides and double centner water are added in the reactor, after stirring, with 10 kilogram of 20% alkaline conditioner solution the pH value of reaction system is transferred to 13.0, add 55 kilogram of 40% alpha-hydroxymethyl sodium sulfonate solution, heat temperature raising to 90 ℃ afterreaction 1.0h.
(2) condensation reaction: 180 kilograms of Sodium sulfanilates, 96 kilograms of phenol, 10 kilograms of Dyhard RU 100s and 50 kg urea and 104 kg water are added be equipped with in the reactor of (1) step sulfonation reaction product, after stirring, add 2.0 kilograms of tartrate the pH value of reaction system is transferred to 4.5, behind the heat temperature raising to 75 ℃, in 1.0h, drip 320 kilogram of 37% formaldehyde solution, behind the reaction 1.0h, add 20 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 8.5, react 5h down at 85 ℃.
(3) alkalescence is reformed: add 30 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 10.5, cooling discharge behind reaction 3.0h under 95 ℃, product of the present invention is a reddish-brown liquid, weight-average molecular weight Mw is 2910, number-average molecular weight Mn is 350, promptly gets powder-like product by spraying drying.
The processing step of embodiment 3 and order be as shown in Figure 1:
1. the raw material of present embodiment and prescription (unit-kilogram):
Trimeric cyanamide: 12.5 kilograms;
Alpha-hydroxymethyl sodium sulfonate (30% content): 50 kilograms;
Sodium sulfanilate: double centner;
Phenol: 55 kilograms;
Urea: 6 kilograms;
The amino cyano group urea of methyl alcohol: 35 kilograms;
Formaldehyde (35% content): 145 kilograms;
Citric acid: 1.5 kilograms;
Alkaline conditioner (sodium hydroxide and tripoly phosphate sodium STPP mixture, mass ratio 19: 1): 10 kilograms;
Water: 585 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: trimeric cyanamide sulfonation, condensation reaction and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) trimeric cyanamide sulfonation: promptly earlier 12.5 kilograms of trimeric cyanamides and 150 kg water are added in the reactor, after stirring, with 10 kilogram of 20% alkaline conditioner solution the pH value of reaction system is transferred to 11.0, add 50 kilogram of 30% alpha-hydroxymethyl sodium sulfonate solution, heat temperature raising to 80 ℃ afterreaction 2.5h.
(2) condensation reaction: double centner Sodium sulfanilate, 55 kilograms of phenol, 35 kilograms of amino cyano group ureas of methyl alcohol and 6 kg urea and 395 kg water are added be equipped with in the reactor of (1) step sulfonation reaction product, after stirring, add 1.5 kilograms of citric acids the pH value of reaction system is transferred to 6.0, behind the heat temperature raising to 80 ℃, in 1.5h, drip 145 kilogram of 35% formaldehyde solution, behind the reaction 2.0h, add 15 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 8.2, react 3.0h down at 95 ℃.
(3) alkalescence is reformed: add 25 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 10.0, and cooling discharge behind reaction 1.0h under 100 ℃, product of the present invention is a reddish-brown liquid, and weight-average molecular weight Mw is 3600, and number-average molecular weight Mn is 600.
The processing step of embodiment 4 and order be as shown in Figure 1:
1. the raw material of present embodiment and prescription (unit-kilogram):
Trimeric cyanamide: 15 kilograms;
Alpha-hydroxymethyl sodium sulfonate (20% content): 80 kilograms;
Sodium sulfanilate: 85 kilograms;
Dihydroxyphenyl propane: 52 kilograms;
Urea: 5 kilograms;
The amino cyano group urea of methyl alcohol: 45 kilograms;
Formaldehyde (40% content): 150 kilograms;
Acid regulator (thionamic acid and phosphate mixture, mass ratio are 1: 1): 2.5 kilograms;
The NaOH:10.5 kilogram;
Water: 555 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: trimeric cyanamide sulfonation, condensation reaction and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) trimeric cyanamide sulfonation: promptly earlier 15 kilograms of trimeric cyanamides and 55 kg water are added in the reactor, after stirring, with 5 kilograms of 20%NaOH solution the pH value of reaction system is transferred to 10.5, add 80 kilograms of alpha-hydroxymethyl sodium sulfonate solution, heat temperature raising to 95 ℃ afterreaction 1.0h.
(2) condensation reaction: 85 kilograms of Sodium sulfanilates, 52 kilograms of dihydroxyphenyl propanes, 45 kilograms of amino cyano group ureas of methyl alcohol and 5 kg urea and 458 kg water are added be equipped with in the reactor of (1) step sulfonation reaction product, after stirring, with 2.5 kilograms of acid regulators the pH value of reaction system is transferred to 5.6, behind the heat temperature raising to 95 ℃, in 1.0h, drip 150 kilogram of 40% formaldehyde solution, behind the reaction 0.9h, add 15 kilograms of 20%NaOH solution the pH value in the above-mentioned system is transferred to 9.0, react 4.5h down at 95 ℃.
(3) alkalescence is reformed: add 32.5 kilograms of 20%NaOH solution the pH value in the above-mentioned system is transferred to 11.0, and cooling discharge behind reaction 1.0h under 99 ℃, product of the present invention is a reddish-brown liquid, and weight-average molecular weight Mw is 32000, and number-average molecular weight Mn is 5600.
The processing step of embodiment 5 and order be as shown in Figure 1:
1. the raw material of present embodiment and prescription (unit-kilogram):
Trimeric cyanamide: 25 kilograms;
α-sodium isethionate (60% content): 55 kilograms;
Sulphanilic Acid: 173 kilograms;
Phenol: 95 kilograms;
Toluol sulfonamide: 8.5 kilograms;
The amino cyano group urea of methyl alcohol: 20 kilograms;
Formaldehyde (37% content): 265 kilograms;
The NaOH:49.5 kilogram;
Water: 309 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: trimeric cyanamide sulfonation, condensation reaction and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) trimeric cyanamide sulfonation: promptly earlier 25 kilograms of trimeric cyanamides and 50 kg water are added in the reactor, after stirring, with 8.8 kilograms of 40%NaOH solution the pH value of reaction system is transferred to 12.5, add 55 kilograms of 60% α-hydroxyethylsulfonic acid sodium solutions, heat temperature raising to 75 ℃ afterreaction 2.5h.
(2) condensation reaction: 173 kilograms of Sulphanilic Acid, 95 kilograms of phenol, 20 kilograms of amino cyano group ureas of methyl alcohol and 8.5 kilograms of toluol sulfonamides and 184.7 kg water are added be equipped with in the reactor of (1) step sulfonation reaction product, with double centner 40%NaOH solution the pH value of reaction system is transferred to 7.0 immediately, after stirring, heat temperature raising to 80 ℃, in 2.5h, drip condensing agent, behind the reaction 1.5h, add 5.0 kilograms of 40%NaOH solution the pH value in the above-mentioned system is transferred to about 8.5, react 3.5h down at 98 ℃.
(3) alkalescence is reformed: add 10 kilograms of 40%NaOH solution the pH value in the above-mentioned system is transferred to 11.0, cooling discharge behind reaction 3.0h under 98 ℃, product of the present invention is a reddish-brown liquid, weight-average molecular weight Mw is 12000, number-average molecular weight Mn is 1520, promptly gets powder-like product by spraying drying.
The processing step of embodiment 6 and order be as shown in Figure 1:
1. the raw material of present embodiment and prescription (unit-kilogram):
Trimeric cyanamide: 20 kilograms;
Alpha-hydroxymethyl sodium sulfonate (65% content): 36 kilograms;
4-amino-1,3-phenyl disulfonic acid: 25 kilograms;
Sodium sulfanilate: 135 kilograms;
Phenol: 85 kilograms;
Urea: 20 kilograms;
Benzoguanamine: 10.5 kilograms;
Formaldehyde (37% content): 250 kilograms;
The NaOH:15.5 kilogram;
Water: 403 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: trimeric cyanamide sulfonation, condensation reaction and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) trimeric cyanamide sulfonation: promptly earlier 20 kilograms of trimeric cyanamides and 84.5 kg water are added in the reactor, after stirring, the pH value of reaction system is transferred to 12.8, add 36 kilogram of 65% alpha-hydroxymethyl sodium sulfonate solution with 3 kilograms of 50%NaOH solution, behind the heat temperature raising to 85 ℃, reaction 1.5h.
(2) condensation reaction: with 25 kilograms of 4-amino-1,3-phenyl disulfonic acid, 135 kilograms of Sodium sulfanilates, 85 kilograms of phenol, 10.5 kilograms of benzoguanamines and 20 kg urea and 303 kg water add and are equipped with in the reactor of (1) step sulfonation reaction product, with 10.5 kilograms of 50%NaOH solution the pH value of reaction system is transferred to 6.5 immediately, after stirring, heat temperature raising to 90 ℃, in 2.0h, drip condensing agent, behind the reaction 1.0h, add 3.5 kilograms of 50%NaOH solution the pH value in the above-mentioned system is transferred to 8.0, react 6.0h down at 90 ℃.
(3) alkalescence is reformed: add 14 kilograms of 50%NaOH solution the pH value in the above-mentioned system is transferred to 12.0, cooling discharge behind reaction 2.5h under 95 ℃, product of the present invention is a reddish-brown liquid, weight-average molecular weight Mw is 19370, number-average molecular weight Mn is 4720, promptly gets powder-like product by spraying drying.
The processing step of embodiment 7 and order be as shown in Figure 1:
1. the raw material of present embodiment and prescription (unit-kilogram):
Trimeric cyanamide: 45 kilograms;
Alpha-hydroxymethyl sodium sulfonate (55% content): 120 kilograms;
4-kharophen Phenylsulfonic acid: 15 kilograms;
Sodium sulfanilate: 160 kilograms;
Cresols: 25 kilograms;
Phenol: 75 kilograms;
Urea: 24 kilograms;
Dyhard RU 100: 10 kilograms;
Formaldehyde (37% content): 300 kilograms;
Alkaline conditioner (sodium hydroxide, sodium phosphate and dimerization sodium phosphate compound, mass ratio 8: 1: 1): 15 kilograms;
Water: 210 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: trimeric cyanamide sulfonation, condensation reaction and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) trimeric cyanamide sulfonation: promptly earlier 45 kilograms of trimeric cyanamides and 50 kg water are added in the reactor, after stirring, with 10 kilogram of 20% alkaline conditioner solution the pH value of reaction system is transferred to 11.5, add 120 kilograms of alpha-hydroxymethyl sodium sulfonate solution, heat temperature raising to 80 ℃ afterreaction 2.0h.
(2) condensation reaction: with 15 kilograms of 4-kharophen Phenylsulfonic acids, 160 kilograms of Sodium sulfanilates, 25 kilograms of cresolss, 75 kilograms of phenol, 10 kilograms of Dyhard RU 100s and 24 kg urea and double centner water add and are equipped with in the reactor of (1) step sulfonation reaction product, with 31.5 kilogram of 20% alkaline conditioner solution the pH value of reaction system is transferred to 6.0 immediately, after stirring, behind the heat temperature raising to 80 ℃, in 1.0h, drip 300 kilogram of 37% formaldehyde solution, behind the reaction 1.0h, add 8.5 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 8.7, react 5h down at 95 ℃.
(3) alkalescence is reformed: add 25 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 11.0, cooling discharge behind reaction 2.0h under 95 ℃, product of the present invention is a reddish-brown liquid, weight-average molecular weight Mw is 5100, number-average molecular weight Mn is 750, promptly gets powder-like product by spraying drying.
The processing step of embodiment 8 and order be as shown in Figure 1:
1. the raw material of present embodiment and prescription (unit-kilogram):
Trimeric cyanamide: 15 kilograms;
α-hydroxyl sodium isopropyl xanthate (50% content): 40 kilograms;
Sodium sulfanilate: 105 kilograms;
Dihydroxyphenyl propane: 22 kilograms;
Phenol: 35 kilograms;
Urea: 60.5 kilograms;
The amino cyano group urea of methyl alcohol: 23.5 kilograms;
Paraformaldehyde 96: 120 kilograms;
Sulfuric acid (50% content): 1.5 kilograms;
The NaOH:8.5 kilogram;
Water: 569 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: trimeric cyanamide sulfonation, condensation reaction and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) trimeric cyanamide sulfonation: promptly earlier 15 kilograms of trimeric cyanamides and double centner water are added in the reactor, after stirring, with 10 kilograms of 20%NaOH solution the pH value of reaction system is transferred to 11.6, add 40 kilograms of 50% α-hydroxyl sodium isopropyl xanthate solution, behind the heat temperature raising to 90 ℃, reaction 1.0h.
(2) condensation reaction: 105 kilograms of Sodium sulfanilates, 22 kilograms of dihydroxyphenyl propanes, 35 kilograms of phenol, 23.5 kilograms of amino cyano group ureas of methyl alcohol and 60.5 kg urea and 435 kg water are added be equipped with in the reactor of (1) step sulfonation reaction product, after stirring, transfer to about 5.7 with the pH value of 1.5 kilogram of 50% sulfuric acid reaction system, behind the heat temperature raising to 90 ℃, in 1.0h, slowly add 120 kilograms of Paraformaldehyde 96s, behind the reaction 1.0h, add 12.5 kilograms of 20%NaOH solution the pH value in the above-mentioned system is transferred to about 8.0, react 5.5h down at 90 ℃.
(3) alkalescence is reformed: add 20 kilograms of 20%NaOH solution the pH value in the above-mentioned system is transferred to 11.0, cooling discharge behind reaction 1.0h under 99 ℃, product of the present invention is a reddish-brown liquid, weight-average molecular weight Mw is 29500, number-average molecular weight Mn is 3560, promptly gets powder-like product by spraying drying.
Below for the performance situation of product of the present invention and with every performance comparable situation of like product:
Selecting ceremonial dress for royalty state, Shandong coal, Datong coal, Shan Xiwang village coal, Jincheng, Shanxi-Yangcheng high-quality anthracite, Shaanxi shenfu coal and waterside town eagle mountain, Guizhou coal for use is research object, after fragmentation, ore grinding, screening and grating, the moisture and the slurries additive agent that add calculated amount, can obtain the coal water slurry of different concns after stirring, utilize the NDJ-1 rotational viscosimeter to measure viscosity in aqueous coal slurries, and adopt excellent test method(s) to check the stability of coal water slurry.
The slurry performance of table 1 product relatively
| The coal water slurry performance | The embodiment product | |||||||
| ????1 | ????2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 | |
| Concentration (%) | ??66.8 | ????67.1 | ??66.9 | ??67.2 | ??66.7 | ??67.0 | ??66.9 | ??67.1 |
| Viscosity (mPaS) | ??735 | ????821 | ??792 | ??680 | ??713 | ??706 | ??739 | ??696 |
| Range estimation is mobile | Good | Good | Good | Good | Good | Good | Good | Good |
| Bleed rate (%) behind the 24h | ??0.7 | ????0.9 | ??1.0 | ??0.5 | ??0.6 | ??0.8 | ???0.9 | ??1.1 |
| Paste structure behind the 24h | There is not precipitation | There is not precipitation | There is not precipitation | There is not precipitation | There is not precipitation | There is not precipitation | There is not precipitation | There is not precipitation |
Annotate: with the Datong coal is research object, and embodiment product 3 and 4 feeds in raw material with liquid form, and adding dose is 0.6% (quality with the butt coal is a benchmark); Embodiment product 1,2,5,6,7 and 8 feeds in raw material with solid form, and adding dose is 0.18% (quality with the butt coal is a benchmark), 24.3 ℃ of room temperatures.
The pulping stability test of table 2 product
| Water coal slurry concentration (%) | Viscosity (mPaS) | Rod test (s) falls | ||||||||
| ????0 | ??1d | ??3d | ??7d | ??14d | ??28d | ??35d | 56d | 63d | ||
| ????66.9 | ????792 | ??1.2 | ??1.3 | ??1.6 | ??2.1 | ??15 | ??29 | ??56 | Can not be naturally on earth, no hard-caked sediment | Can not naturally on earth hard-caked sediment be arranged |
Annotate: with the Datong coal is research object, and embodiment product 3 is reinforced with liquid form, and adding dose is 0.6% (quality with the butt coal is a benchmark), room temperature 24.3-27.1 ℃
The relation of table 3 product consumption and pulping concentration
| Product consumption (%) | Concentration (%) | Viscosity (mPaS) | Mobile | Bleed rate (%) behind the 24h | Rod test (s) falls | ||
| ????0 | ????28d | ????56d | |||||
| ????0.2 | ????65.1 | ????861 | Good | ????0.9 | ????1.6 | ????32 | Can not be naturally on earth, no hard-caked sediment |
| ????0.4 | ????66.4 | ????796 | Good | ????0.7 | ????1.2 | ????28 | Can not be naturally on earth, no hard-caked sediment |
| ????0.6 | ????68.9 | ????816 | Good | ????0.9 | ????1.4 | ????30 | Can not be naturally on earth, no hard-caked sediment |
| ????0.8 | ????70.2 | ????857 | Good | ????1.1 | ????1.6 | ????35 | Can not be naturally on earth, no hard-caked sediment |
| ????1.0 | ????72.3 | ????938 | Good | ????0.7 | ????2.1 | ????43 | Can not be naturally on earth, a small amount of hard-caked sediment is arranged at the bottom |
Annotate: with the Datong coal is research object, and embodiment product 3 is reinforced with liquid form, and adding dose is benchmark with the quality of butt coal, room temperature 23.6-28.5 ℃.
From table 1-table 3 result as seen, product of the present invention has good dispersiveness and stable to coal water slurry, can satisfy the requirement of industrial slurrying.
The relation of table 4 product consumption and pulping concentration
| The coal water slurry performance | Slurries additive agent | ||||||
| Embodiment 3 | Sodium lignosulfonate | Calcium lignin sulphonate | Ammonium lignosulphonate | Naphthalene system | The propylene acid out | Humic acid | |
| Concentration (%) | ????66.9 | ??66.1 | ???66.0 | ????66.2 | ????66.5 | ???66.4 | ???66.1 |
| Viscosity (mPaS) | ????792 | ??1267 | ???1179 | ????1206 | ????961 | ???998 | ???987 |
| Range estimation is mobile | Good | Better | Better | Better | Good | Good | Good |
| Bleed rate (%) behind the 24h | ????1.0 | ???9.5 | ????10.5 | ????8.7 | ????3.1 | ???2.6 | ???2.5 |
| Paste structure behind the 24h | There is not precipitation | Soft precipitation | Soft precipitation | There is not precipitation | There is not precipitation | There is not precipitation | There is not precipitation |
Annotate: with the Datong coal is research object, and embodiment product 3 is reinforced with liquid form, and adding dose is 0.6%; The acrylic acid series additive is reinforced with liquid form, and adding dose is 1.0%; Naphthalene system, humic acid and three kinds of sulfonated lignin are reinforced with solid form, add dose and are respectively 0.6%, 0.6%, 1.0%, 1.0% and 1.0% (quality with the butt coal is a benchmark), room temperature 23.6-28.5 ℃.
From table 4 result as seen, the dispersiveness of product of the present invention, stability and cost performance obviously are better than other slurries additive agent, as naphthalene system, acrylic acid series, humic acid, sodium lignosulfonate, calcium lignin sulphonate and ammonium lignosulphonate etc.
The compatibility test of table 5 product
| The kind of coal | The coal water slurry performance | ||||||
| Concentration (%) | Viscosity (mPaS) | Mobile | Bleed rate (%) behind the 24h | Rod test (s) falls | |||
| ????0 | ????28d | ????56d | |||||
| Ceremonial dress for royalty state, Shandong coal | ??68.1 | ????735 | Good | ??0.8 | ????0.9 | ????23 | Can not be naturally on earth, no hard-caked sediment |
| The Datong coal | ??66.9 | ????792 | Good | ??1.0 | ????1.2 | ????29 | Can not be naturally on earth, no hard-caked sediment |
| Shan Xiwang village coal | ??66.1 | ????801 | Good | ??1.3 | ????1.5 | ????34 | Can not be naturally on earth, no hard-caked sediment |
| Jincheng, Shanxi-Yangcheng high-quality anthracite | ??70.0 | ????756 | Good | ??0.7 | ????0.8 | ????20 | Can not be naturally on earth, no hard-caked sediment |
| The Shaanxi shenfu coal | ??68.5 | ????823 | Good | ??1.7 | ????1.8 | ????41 | Can not be naturally on earth, no hard-caked sediment |
| Waterside town eagle mountain, Guizhou coal | ??70.5 | ????819 | Good | ??1.1 | ????1.6 | ????35 | Can not be naturally on earth, no hard-caked sediment |
Annotate: embodiment product 3 is reinforced with liquid form, and adding dose is 0.6% (quality with the butt coal is a benchmark), room temperature 24.5-30.5 ℃.From table 5 result as seen, the adaptation of product of the present invention is strong, can be used as the additive of different places of production feed coal slurrying.
Claims (11)
1. amphiphilic slurries additive agent and preparation method thereof, this slurries additive agent is reddish-brown liquid or pulvis, and is soluble in water, it is characterized in that: this additive had both contained the lipophilicity group and (CN), had contained hydrophilic radical (NH again
2,-OH and-SO
3Na etc.), and its weight-average molecular weight Mw is 2000～39000, and number-average molecular weight Mn is 200～10000, and chemical general formula is:
In the formula, m, n, o, p, q are the polymerization degree (5≤m≤90; 5≤n≤90; 1≤o≤20; 2≤p≤40; 2≤q≤60); D is aniline sulfonic acid and sodium salt thereof; E is phenol and derivative thereof; F is for containing amphiphilic group (lipophilicity group-CN and hydrophilic radical-NH
2Or-CONH
2Deng) compound; G is the compound of phosphinylidyne-containing amine group; R=-H ,-CH
2,-CH
2CH
2,-(CH
2)
n,-CH
2(CH
3)
n
2. the preparation method of amphiphilic slurries additive agent according to claim 1, it is characterized in that: its preparation technology comprises the steps: (1) trimeric cyanamide sulfonation in regular turn: promptly earlier trimeric cyanamide and water are added in the reactor, after stirring, with alkaline conditioner the pH value of reaction system is transferred to 9.0～13.5, add sulphonating agent, heat temperature raising to 75～95 ℃ afterreaction 0.5～2.5h; (2) condensation reaction: the compound and the water adding of aniline sulfonic acid (salt), phenol and derivative thereof, the compound that contains the amphiphilic group and phosphinylidyne-containing amine group are equipped with in the reactor of (1) step sulfonation reaction product, after stirring, with acid-base modifier the pH value of reaction system is transferred to 3.0～7.0, behind heat temperature raising to 65～100 ℃, in 1.0～2.5h, drip condensing agent, behind reaction 0.5～2.5h, add alkaline conditioner the pH value in the above-mentioned system is transferred to 8.0～9.0, react 2.0～6.0h down at 65～100 ℃; (3) alkalescence is reformed: utilize alkaline conditioner that the pH value in the above-mentioned system is transferred to 9.0～12.0, cooling discharge behind reaction 1.0～4.0h under 70～100 ℃ promptly gets powder-like product by spraying drying.
3. the preparation method of amphiphilic slurries additive agent according to claim 1 and 2 is characterized in that: these starting material comprise the composition of following massfraction proportioning:
Trimeric cyanamide: 1.0～10.0%;
Sulphonating agent: 1.0～15.0%;
Aniline sulfonic acid (salt): 8.0～20.0%;
Phenol and derivative thereof: 1.5～20.0%;
The compound of phosphinylidyne-containing amine group: 0.5～8.5%;
The compound that contains the amphiphilic group: 1.0～5.0%;
Condensing agent: 6.0～40.0%;
Acid regulator: 0.05～3.5%;
Alkaline conditioner: 0.1～8.5%;
Water: 15～65%.
4. the preparation method of amphiphilic slurries additive agent according to claim 1 and 2, it is characterized in that: the aniline sulfonic acid of employing (salt) is aniline sulfonic acid and sodium salt thereof, 4-amino-1, one or more in 3-phenyl disulfonic acid and sodium salt thereof, 4-kharophen Phenylsulfonic acid and the sodium salt thereof (containing two kinds) mixture.
5. the preparation method of amphiphilic slurries additive agent according to claim 1 and 2 is characterized in that: the phenol of employing and derivative thereof are the mixture of one or more (containing two kinds) in phenol, dihydroxyphenyl propane, bisphenol S, p-cresol, meta-cresol, cresols, Resorcinol, quinhydrones, catechol, naphthyl alcohol or the 2-Naphthol.
6. the preparation method of amphiphilic slurries additive agent according to claim 1 and 2 is characterized in that: the condensing agent of employing is a kind of or two kinds of mixtures in formaldehyde, the Paraformaldehyde 96, and the massfraction of industrial formol concentration is 30～40%.
7. the preparation method of amphiphilic slurries additive agent according to claim 1 and 2, it is characterized in that: the sulphonating agent of employing is the mixture of one or more (containing two kinds) in alpha-hydroxymethyl sodium sulfonate, α-sodium isethionate, α-hydroxypropyl azochlorosulfonate acid sodium, the different interior basic sodium sulfonate of α-hydroxyl, and the massfraction of its concentration is 10～75%.
8. the preparation method of amphiphilic slurries additive agent according to claim 1 and 2 is characterized in that: the compound that contains the amphiphilic group of employing is the amino cyano group urea of methyl alcohol, Dyhard RU 100, benzoguanamine, to the mixture of one or more (containing two kinds) in amino-cyanobenzene, the trimeric cyanamide.
9. the preparation method of amphiphilic slurries additive agent according to claim 1 and 2 is characterized in that: the compound of the phosphinylidyne-containing amine group of employing is a kind of or two kinds of mixtures in urea, the toluol sulfonamide.
10. the preparation method of amphiphilic slurries additive agent according to claim 1 and 2, it is characterized in that: the acid regulator of employing is the mixture of one or more (containing two kinds) in thionamic acid, sulfuric acid, phosphoric acid, nitric acid, phenylformic acid, gallic acid, Whitfield's ointment, citric acid, tartrate, oxysuccinic acid, toxilic acid, the succsinic acid, and add-on is 0.05～3.5%.
11. the preparation method of amphiphilic slurries additive agent according to claim 1 and 2, it is characterized in that: the alkaline conditioner of employing is the mixture of one or more (containing two kinds) in sodium hydroxide, potassium hydroxide, sodium phosphate, trisodium phosphate, two sodium polyphosphates, tripoly phosphate sodium STPP, sodium polyphosphate, the water glass, and add-on is 0.1～8.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410014921XA CN100430122C (en) | 2004-05-14 | 2004-05-14 | Hydrophilic and lipophilic type water coalite slurry additive and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410014921XA CN100430122C (en) | 2004-05-14 | 2004-05-14 | Hydrophilic and lipophilic type water coalite slurry additive and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1570042A true CN1570042A (en) | 2005-01-26 |
| CN100430122C CN100430122C (en) | 2008-11-05 |
Family
ID=34478675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200410014921XA Expired - Fee Related CN100430122C (en) | 2004-05-14 | 2004-05-14 | Hydrophilic and lipophilic type water coalite slurry additive and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100430122C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735870B (en) * | 2009-12-16 | 2013-06-19 | 北京海淀华煤水煤浆技术开发中心 | Coal water slurry additive and preparation method and application thereof |
| CN103980963A (en) * | 2014-05-27 | 2014-08-13 | 徐同威 | Coal water slurry additive and application thereof |
| CN108441272A (en) * | 2018-04-16 | 2018-08-24 | 李智 | A kind of slurries additive agent and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4722740A (en) * | 1982-09-30 | 1988-02-02 | Oxce Fuel Company | Dispersions of coal in water useful as a fuel |
| JPS6462393A (en) * | 1987-09-03 | 1989-03-08 | Dai Ichi Kogyo Seiyaku Co Ltd | Additive for coal-water slurry having high life and concentration |
| JP2783668B2 (en) * | 1990-11-01 | 1998-08-06 | 株式会社日本触媒 | Additive for coal-water slurry |
| CN1194802C (en) * | 2002-11-08 | 2005-03-30 | 华南理工大学 | Modified lignin sulfosalt dispersant of water coal slurry |
-
2004
- 2004-05-14 CN CNB200410014921XA patent/CN100430122C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735870B (en) * | 2009-12-16 | 2013-06-19 | 北京海淀华煤水煤浆技术开发中心 | Coal water slurry additive and preparation method and application thereof |
| CN103980963A (en) * | 2014-05-27 | 2014-08-13 | 徐同威 | Coal water slurry additive and application thereof |
| CN103980963B (en) * | 2014-05-27 | 2015-11-11 | 徐同威 | A kind of slurries additive agent and application thereof |
| CN108441272A (en) * | 2018-04-16 | 2018-08-24 | 李智 | A kind of slurries additive agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100430122C (en) | 2008-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1095074A (en) | The method of preparation and use high molecular weight acrylamide polymers | |
| CN1745048A (en) | High solids pumpable cement additives | |
| CN1625528A (en) | Method for determining the dissolution rate of a solid water treatment product | |
| CN1681747A (en) | Oligomeric dispersant | |
| CN1869105A (en) | Method of preparing mercaptopoly asparagic acid and chitin copolymer and use | |
| CN1704373A (en) | Use of polysaccharides for addition in mineral materials | |
| CN105154151A (en) | Coal water slurry additive and preparation method thereof | |
| CN1706769A (en) | Amino sulfonic acid water reducing agent with very low alkali content and its production process | |
| CN1193933C (en) | Method for producing magnesium hydroxide and its aqueous suspension | |
| CN101044103A (en) | Method for inerting impurities | |
| CN101225336A (en) | Alkali lignin-sulphonated acetone formaldehyde polycondensates coal water slurry additive and preparation method thereof | |
| CN1320084C (en) | Extra fine mud fuel and production thereof | |
| CN1570042A (en) | Hydrophilic and lipophilic type water coalite slurry additive and its preparation method | |
| CN85109233A (en) | The slurry that contains special oxyalkylated amino-polyether, the preparation of this coal/water slurry and the preparation technology of oxyalkylated amino-polyether | |
| CN1041431C (en) | Additive composition for coal-water slurry and coal-water slurry composition | |
| CN1025007C (en) | Process for preparing sulphonated dispersants | |
| CN1023813C (en) | Dispersing agent and solid fuel slurry composition containing same | |
| CN107010627A (en) | A kind of method that calcium carbide furnace gas dedusting ash, semi-coke end and pulverized limestone recycle production pelletizing carbide raw material | |
| CN107312581A (en) | The surface additive and its application process of a kind of biomass coal-water slurry | |
| CN1590524A (en) | Process for producing granular anionic surfactant | |
| CN1569723A (en) | Method for batch polymerization preparation of sulphamate composite high-efficiency water reducing agent and its acid and alkali | |
| CN1958947A (en) | Method of manufacturing paper | |
| CN1470464A (en) | Efficient water-saving phosphine-free water treatment chemical for environmental protection | |
| CN1730625A (en) | Liquid fuel additive | |
| CN113969197B (en) | Multi-copolymer dispersant based on humic acid, preparation method thereof and application thereof in coal water slurry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20050126 Assignee: Fujian Qingyuan Technology Co., Ltd. Assignor: Liu Minghua Contract record no.: 2012350000205 Denomination of invention: Hydrophilic and lipophilic type water coalite slurry additive and its preparation method Granted publication date: 20081105 License type: Exclusive License Record date: 20121228 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Liu Minghua Document name: payment instructions |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Chen Wen Document name: Notice of termination of patent |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081105 Termination date: 20200514 |