JP2860390B2 - Method for producing super heavy oil emulsion fuel - Google Patents
Method for producing super heavy oil emulsion fuelInfo
- Publication number
- JP2860390B2 JP2860390B2 JP8531325A JP53132596A JP2860390B2 JP 2860390 B2 JP2860390 B2 JP 2860390B2 JP 8531325 A JP8531325 A JP 8531325A JP 53132596 A JP53132596 A JP 53132596A JP 2860390 B2 JP2860390 B2 JP 2860390B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- salt
- heavy oil
- surfactant
- parts
- 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.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 title claims description 60
- 239000000295 fuel oil Substances 0.000 title claims description 48
- 239000000446 fuel Substances 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000002245 particle Substances 0.000 claims description 63
- -1 alkyl phenol Chemical compound 0.000 claims description 52
- 150000003839 salts Chemical class 0.000 claims description 49
- 239000002736 nonionic surfactant Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 31
- 230000001186 cumulative effect Effects 0.000 claims description 23
- 239000011777 magnesium Substances 0.000 claims description 23
- 239000002734 clay mineral Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000003945 anionic surfactant Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 239000003093 cationic surfactant Substances 0.000 claims description 11
- 239000011362 coarse particle Substances 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 10
- 229920005610 lignin Polymers 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 6
- 229920005615 natural polymer Polymers 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001059 synthetic polymer Polymers 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical class [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 235000012245 magnesium oxide Nutrition 0.000 claims description 2
- 235000001465 calcium Nutrition 0.000 claims 1
- 235000011116 calcium hydroxide Nutrition 0.000 claims 1
- 235000013980 iron oxide Nutrition 0.000 claims 1
- 159000000014 iron salts Chemical class 0.000 claims 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims 1
- 235000001055 magnesium Nutrition 0.000 claims 1
- 235000012254 magnesium hydroxide Nutrition 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 description 23
- 150000003863 ammonium salts Chemical class 0.000 description 22
- 239000000178 monomer Substances 0.000 description 18
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 229910052783 alkali metal Inorganic materials 0.000 description 14
- 238000009826 distribution Methods 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 11
- 229910001919 chlorite Inorganic materials 0.000 description 10
- 229910052619 chlorite group Inorganic materials 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 229920001477 hydrophilic polymer Polymers 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 159000000003 magnesium salts Chemical class 0.000 description 9
- 239000010455 vermiculite Substances 0.000 description 9
- 229910052902 vermiculite Inorganic materials 0.000 description 9
- 235000019354 vermiculite Nutrition 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 159000000007 calcium salts Chemical class 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 7
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- 229910000280 sodium bentonite Inorganic materials 0.000 description 7
- 229940080314 sodium bentonite Drugs 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002169 ethanolamines Chemical class 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229910052901 montmorillonite Inorganic materials 0.000 description 5
- 229910021647 smectite Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 159000000001 potassium salts Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 230000027455 binding Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
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- 150000005846 sugar alcohols Polymers 0.000 description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- CTTJWXVQRJUJQW-UHFFFAOYSA-N 2,2-dioctyl-3-sulfobutanedioic acid Chemical class CCCCCCCCC(C(O)=O)(C(C(O)=O)S(O)(=O)=O)CCCCCCCC CTTJWXVQRJUJQW-UHFFFAOYSA-N 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
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- 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
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
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- 244000215068 Acacia senegal Species 0.000 description 1
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- 241001474374 Blennius Species 0.000 description 1
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- 229910021532 Calcite Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000004373 Pullulan Substances 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
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- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- UDHMTPILEWBIQI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 UDHMTPILEWBIQI-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 235000010494 karaya gum Nutrition 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000009149 molecular binding Effects 0.000 description 1
- SYVVGUDDZLRTJR-UHFFFAOYSA-N n-(propylsulfonylmethyl)prop-2-enamide Chemical compound CCCS(=O)(=O)CNC(=O)C=C SYVVGUDDZLRTJR-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- JCBJVAJGLKENNC-UHFFFAOYSA-N potassium;ethoxymethanedithioic acid Chemical compound [K+].CCOC(S)=S JCBJVAJGLKENNC-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940067741 sodium octyl sulfate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- VQOXUMQBYILCKR-UHFFFAOYSA-N tridecaene Natural products CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003170 water-soluble synthetic polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- 229910021493 α-cristobalite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/328—Oil emulsions containing water or any other hydrophilic phase
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
Description
【発明の詳細な説明】 技術分野 本発明は、火力発電用燃料として使用し得る水中油滴
型の超重質油エマルション燃料の製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing an oil-in-water type super heavy oil emulsion fuel that can be used as a fuel for thermal power generation.
背景技術 超重質油エマルション燃料を、乳化剤、安定化剤、流
動化剤等の添加剤とともに用いると安定なエマルション
燃料が得られることはよく知られており、エマルション
燃料組成物に用いられる様々な優れた乳化剤等が開発さ
れている(特開平1−185394号公報、米国特許第502467
6号明細書、特開平1−313595号公報)。しかし、これ
らの乳化剤、安定化剤、流動化剤等の添加剤を使用して
も、超重質油エマルション燃料中の超重質油の濃度は高
々77重量%であるとされている。安定で流動性のある超
重質油エマルション燃料は取扱いが容易であり、超重質
油濃度が高ければ高いほど、水による熱量の損失が少な
くなるため、得られるエマルション燃料としての価値は
高くなる。また、高い超重質油濃度を有する超重質油エ
マルションは、必要に応じて希釈して使用できる点でも
有利である。BACKGROUND ART It is well known that a stable emulsion fuel can be obtained by using an ultra-heavy oil emulsion fuel together with additives such as an emulsifier, a stabilizer, and a fluidizing agent. Emulsifiers and the like have been developed (JP-A-1-185394, U.S. Pat. No. 502467)
No. 6, specification, JP-A-1-313595). However, even when these emulsifiers, stabilizers, fluidizers and other additives are used, the concentration of the super heavy oil in the super heavy oil emulsion fuel is said to be at most 77% by weight. Stable and fluid ultra-heavy oil emulsion fuels are easy to handle, and the higher the ultra-heavy oil concentration, the less the loss of heat due to water, the higher the value of the resulting emulsion fuel. Further, the super heavy oil emulsion having a high super heavy oil concentration is advantageous in that it can be used after being diluted as necessary.
発明の開示 前記問題点に鑑みて、本発明の目的は、超重質油濃度
が高くかつ流動性があり、取扱いが容易で、しかも安定
な超重質油エマルション燃料を製造する方法を提供する
ことにある。DISCLOSURE OF THE INVENTION In view of the above problems, an object of the present invention is to provide a method for producing a super heavy oil emulsion fuel which has a high concentration of heavy oil, has fluidity, is easy to handle, and is stable. is there.
本発明の他の目的は前記方法により得られる超重質油
エマルション燃料を提供することにある。Another object of the present invention is to provide a super heavy oil emulsion fuel obtained by the above method.
従来は、エマルション燃料の高濃度化を考える場合、
粒子径分布を広くすることが必要であるとするのが技術
常識であった。Conventionally, when considering the high concentration of emulsion fuel,
It was common knowledge in the art that it was necessary to broaden the particle size distribution.
本発明者らは、前記問題点を解決すべく鋭意検討した
結果、エマルション中における超重質油の量、界面活性
剤の種類と量、及び攪拌力を特定な範囲となるように限
定し、粒子径分布をある範囲になるように特定すること
により超重質油濃度が77重量%を超えたところで、安定
なエマルションを得ることができることを発見した。本
発明はかかる発見に基づき完成するに至ったものであ
る。The present inventors have conducted intensive studies to solve the above problems, and as a result, limited the amount of the super heavy oil in the emulsion, the type and amount of the surfactant, and the stirring force to be in a specific range, By specifying the diameter distribution to be within a certain range, it was discovered that a stable emulsion could be obtained when the concentration of the heavy oil exceeded 77% by weight. The present invention has been completed based on such findings.
即ち、本発明の要旨は、 (1)(a)超重質油100重量部に対してHLB(親水性親
油性バランス)が13〜19のノニオン界面活性剤0.1〜0.6
重量部と水を超重質油に加え、均一な混合液を調製する
工程と、 (b)高剪断力による均一な混合液の機械的混合を行っ
て、10%累積粒子径が1.5〜8μm、50%累積粒子径が1
1〜30μm、90%累積粒子径が25〜150μmであり、かつ
150μm以上の粒子径を有する粗粒が全エマルション燃
料において3重量%以下を占める粒子径分布を有し、超
重質油濃度が76.5〜82.0重量%である超重質油エマルシ
ョン燃料を得る工程と、からなる超重質油エマルション
燃料の製造方法、 (2)工程(a)において、さらにアニオン界面活性剤
又はカチオン界面活性剤をノニオン界面活性剤の配合量
を超えない範囲で添加する。前記(1)記載の製造方
法、 (3)工程(a)において、さらに天然高分子及び合成
高分子からなる群より選択された高分子化合物、又は水
膨潤性粘土鉱物をノニオン界面活性剤の配合量を超えな
い範囲で添加する、前記(1)又は(2)記載の製造方
法、 (4)工程(a)において、さらに超重質油100重量部
に対してマグネシウム、カルシウム及び鉄の酸化物、マ
グネシウム、カルシウム及び鉄の水酸化物並びにマグネ
シウム、カルシウム及び鉄の塩からなる群より選ばれた
1種以上の化合物0.01〜0.5重量部を添加する、前記
(1)〜(3)いずれか記載の製造方法、 (5)機械的混合を1,000〜20,000s-1の剪断力で行う、
前記(1)〜(4)いずれか記載の製造方法、 (6)工程(b)の後に、さらに (c)工程(b)で得られた混合物を水又はHLBが13〜1
9の界面活性剤等の添加剤を含有する水により希釈し
て、得られる混合物の粘度(100s-1、25℃)を3000cp以
下に調製する工程 を有する、前記(1)〜(5)いずれか記載の製造方
法、 (7)超重質油濃度が78.0〜81.0重量%である前記
(1)〜(6)いずれか記載の製造方法、 (8)ノニオン海面活性剤がアルキルフェノールのアル
キレンオキシド付加物である前記(1)〜(7)いずれ
か記載の製造方法、 (9)アニオン界面活性剤がリグニンスルホン酸塩、リ
グニンスルホン酸とナフタリンスルホン酸のホルマリン
縮合物、又はそれらの塩、及びナフタリンスルホン酸塩
のホルマリン縮合物からなる群より選ばれた1種以上の
化合物である前記(2)記載の製造方法、並びに (10)前記(1)〜(9)いずれか記載の製造方法によ
り得られる、10%累積粒子径が1.5〜8μm、50%累積
粒子径が11〜30μm、90%累積粒子径が25〜150μmで
あり、かつ150μm以上の粒子径を有する粗粒が全エマ
ルション燃料において3重量%以下を示す粒子径分布を
有し、超重質油濃度が76.5〜82.0重量%である超重質油
エマルション燃料、に関する。That is, the gist of the present invention is as follows: (1) (a) a nonionic surfactant having an HLB (hydrophilic-lipophilic balance) of 13 to 19 with respect to 100 parts by weight of a super heavy oil;
Adding a weight part and water to the super heavy oil to prepare a uniform mixed solution; and (b) performing mechanical mixing of the uniform mixed solution by high shearing force to obtain a 10% cumulative particle size of 1.5 to 8 μm, 50% cumulative particle size is 1
1-30 μm, 90% cumulative particle size is 25-150 μm, and
Obtaining a super-heavy oil emulsion fuel in which coarse particles having a particle diameter of 150 μm or more have a particle diameter distribution occupying 3% by weight or less in the total emulsion fuel, and a super-heavy oil concentration of 76.5 to 82.0% by weight; (2) In step (a), an anionic surfactant or a cationic surfactant is further added in a range not to exceed the blending amount of the nonionic surfactant. (1) The production method according to (1), (3) In step (a), a polymer compound selected from the group consisting of a natural polymer and a synthetic polymer, or a water-swellable clay mineral is further blended with a nonionic surfactant. The production method according to the above (1) or (2), which is added in an amount not exceeding the amount, (4) in the step (a), an oxide of magnesium, calcium, and iron with respect to 100 parts by weight of the super heavy oil; The method according to any one of (1) to (3) above, wherein 0.01 to 0.5 part by weight of one or more compounds selected from the group consisting of hydroxides of magnesium, calcium and iron and salts of magnesium, calcium and iron are added. Manufacturing method, (5) mechanical mixing is performed with a shearing force of 1,000 to 20,000 s −1 ,
(1) The method according to any one of (1) to (4), (6) after step (b), (c) further mixing the mixture obtained in step (b) with water or HLB of 13 to 1;
9. The method according to any of (1) to (5) above, further comprising a step of diluting with water containing an additive such as a surfactant to adjust the viscosity of the resulting mixture (100 s −1 , 25 ° C.) to 3000 cp or less. (7) The method according to any one of the above (1) to (6), wherein the ultra-heavy oil concentration is 78.0 to 81.0% by weight, (8) the nonionic surfactant is an alkylphenol oxide adduct of an alkylphenol. (9) The method according to any one of the above (1) to (7), wherein the anionic surfactant is a lignin sulfonic acid salt, a formalin condensate of lignin sulfonic acid and naphthalene sulfonic acid, or a salt thereof, and naphthalene sulfone And (10) the method according to any one of (1) to (9), which is at least one compound selected from the group consisting of formalin condensates of acid salts. Coarse particles having a 10% cumulative particle size of 1.5 to 8 μm, a 50% cumulative particle size of 11 to 30 μm, a 90% cumulative particle size of 25 to 150 μm, and a particle size of 150 μm or more are 3% by weight in all emulsion fuels. % Of ultra-heavy oil emulsion fuel having a particle size distribution of not more than 76.5% by weight and an ultra-heavy oil concentration of 76.5 to 82.0% by weight.
図面の簡単な説明 図1は、実施例1で得られたエマルション燃料の粒子
径分布を示す図であり、及び 図2は、比較例1で得られたエマルション燃料の粒子
径分布を示す図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the particle size distribution of the emulsion fuel obtained in Example 1, and FIG. 2 is a diagram showing the particle size distribution of the emulsion fuel obtained in Comparative Example 1. is there.
発明を実施するための最良の形態 以下に本発明について詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
本発明に用いられる超重質とは、室温で固体又は半流
動状態のものであり、高温に加温しないと流動しない油
である。超重質油の具体例としては、下記のものが挙げ
られる。The super heavy used in the present invention is an oil that is in a solid or semi-fluid state at room temperature and does not flow unless heated to a high temperature. Specific examples of the super heavy oil include the following.
(1)石油系アスファルト類及びその混合物、 (2)石油系アスファルトの各種処理物、その中間製
品、残留物及びそれらの混合物、 (3)高温でも流動しない高流動点油又は原油、 (4)石油系タールピッチ及びその混合物、並びに (5)ビチューメン類(オリノコタール、アサバスカビ
チューメン)。(1) Petroleum-based asphalts and mixtures thereof; (2) Various processed products of petroleum-based asphalts, intermediate products, residues and mixtures thereof; (3) High pour point oil or crude oil which does not flow even at high temperatures; (4) Petroleum tar pitch and mixtures thereof, and (5) bitumens (orinoco tar, Athabasca bitumen).
本発明に使用される界面活性剤としては、HLBが13〜1
9のノニオン界面活性剤が好適に使用される。さらに、
アニオン界面活性剤又はカチオン界面活性剤をノニオン
界面活性剤の配合量を超えない範囲で加え、粒子に電荷
を与えて粒子同士の斥力を賦与することが好ましい。本
発明におけるHLB値とは、Griffin式により算出される親
水性−親油性バランスの略称である。すなわち、HLBと
は、親水性および親油性の両性質を有する媒体の親水性
と親油性の強度比を数値化して表した界面活性能の指標
であり、ここでは、Griffinらの経験値(W.C.Griffin,
“Kirk−Othmer Encyclopedia of Chemical Technolog
y,"3rd ed.,Vol.8,p.913−916,John−Wiley(1979))
を採用した。As the surfactant used in the present invention, HLB is 13 to 1
Nine nonionic surfactants are preferably used. further,
It is preferable to add an anionic surfactant or a cationic surfactant within a range not exceeding the compounding amount of the nonionic surfactant, to impart a charge to the particles and to impart repulsion between the particles. The HLB value in the present invention is an abbreviation for the hydrophilic-lipophilic balance calculated by the Griffin equation. That is, HLB is an index of surface activity that is expressed by numerically expressing the intensity ratio of hydrophilicity and lipophilicity of a medium having both hydrophilicity and lipophilicity. Here, the empirical value of Griffin et al. (WCGriffin ,
“Kirk-Othmer Encyclopedia of Chemical Technolog
y, "3rd ed., Vol. 8, p. 913-916, John-Wiley (1979))
It was adopted.
本発明に使用されるノニオン界面活性剤の例として
は、以下のものが挙げられる。Examples of the nonionic surfactant used in the present invention include the following.
(i)フェノール、m−クレゾール、ブチルフェノー
ル、ノニルフェノール、ジノニルフェノール、ドデシル
フェノール、p−クミルフェノール、ビスフェノールA
等のフェノール性水酸基を有する化合物のアルキレンオ
キシド付加物。(I) phenol, m-cresol, butylphenol, nonylphenol, dinonylphenol, dodecylphenol, p-cumylphenol, bisphenol A
And alkylene oxide adducts of compounds having a phenolic hydroxyl group.
(ii)アルキルフェノール、フェノール、m−クレゾー
ル、スチレン化フェノール、ベンジル化フェノール等の
フェノール性水酸基を有する化合物のホルマリン(ホル
ムアルデヒド)縮合物のアルキレンオキシド付加物。縮
合度の平均は1.2〜100、好ましくは2〜20である。(Ii) Alkylene oxide adducts of formalin (formaldehyde) condensates of compounds having a phenolic hydroxyl group such as alkylphenol, phenol, m-cresol, styrenated phenol, and benzylated phenol. The average degree of condensation is 1.2 to 100, preferably 2 to 20.
(iii)炭素数2〜50の一価の脂肪族アルコール及び/
又は一価の脂肪族アミンのアルキレンオキシド付加物。(Iii) monohydric aliphatic alcohol having 2 to 50 carbon atoms and / or
Or an alkylene oxide adduct of a monovalent aliphatic amine.
(iv)エチレンオキシド/プロピレンオキシド、エチレ
ンオキシド/ブチレンオキシド、エチレンオキシド/ス
チレンオキシド、エチレンオキシド/プロピレンオキシ
ド/ブチレンオキシド、及びエチレンオキシド/プロピ
レンオキシド/スチレンオキシドのブロック又はランダ
ム付加重合物。(Iv) Ethylene oxide / propylene oxide, ethylene oxide / butylene oxide, ethylene oxide / styrene oxide, ethylene oxide / propylene oxide / butylene oxide, and ethylene oxide / propylene oxide / styrene oxide block or random addition polymers.
(v)グリセリン、トリメチロールプロパン、ペンタエ
リスリトール、ソルビトール、サッカロース、ポリグリ
セリン、エチレングリコール、ポリエチレングリコー
ル、プロピレングリコール、ポリプロピレングリコール
等の多価アルコール、又はそれら多価アルコールと炭素
数8〜18の脂肪酸とのエステルのアルキレンオキシド付
加物。(V) polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, saccharose, polyglycerin, ethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol; or polyhydric alcohols and fatty acids having 8 to 18 carbon atoms. Alkylene oxide adduct of the ester of
(vi)エチレンジアミン、テトラエチレンジアミン、ポ
リエチレンイミン(分子量:600〜10000)等の複数個の
活性水素を有する多価アミンのアルキレンオキシド付加
物。(Vi) Alkylene oxide adducts of polyamines having a plurality of active hydrogens such as ethylenediamine, tetraethylenediamine, and polyethyleneimine (molecular weight: 600 to 10,000).
(vii)トリグリセライド型油脂1モルとグリセリン、
トリメチロールプロパン、ペンタエリスリトール、ソル
ビトール、サッカロース、エチレングリコール、分子量
1000以下のポリエチレングリコール、プロピレングリコ
ール、分子量1000以下のボリプロピレングリコールから
なる群から選ばれた1種又は2種以上の多価アルコール
及び/又は水0.1〜5モルとの混合物に、アルキレンオ
キシドを付加反応させた生成物。(Vii) 1 mol of triglyceride type fat and oil and glycerin,
Trimethylolpropane, pentaerythritol, sorbitol, saccharose, ethylene glycol, molecular weight
Addition of an alkylene oxide to a mixture of one or more polyhydric alcohols and / or 0.1 to 5 mol of water selected from the group consisting of polyethylene glycol of 1000 or less, propylene glycol, and polypropylene glycol of 1000 or less in molecular weight. The reacted product.
前記(i)〜(vii)の各ノニオン界面活性剤におい
て、アルキレンオキシドは、例えば、エチレンオキシ
ド、プロピレンオキシド、ブリレンオキシド、スチレン
オキシド、およびそれらの組み合わせである。In each of the nonionic surfactants (i) to (vii), the alkylene oxide is, for example, ethylene oxide, propylene oxide, brylene oxide, styrene oxide, or a combination thereof.
前記ノニオン界面活性剤の中でも、前記の(i)に記
載したものが好ましく、特にアルキルフェノールのアル
キレンオキシド付加物が好適である。本発明に用いられ
るノニオン界面活性剤のHLBは、通常13〜19、好ましく
は13.5〜15.5である。HLBが13未満又は19を越えている
ノニオン界面活性剤も使用することは可能であるが、安
定なエマルションを調製する点からHLBが13〜19の範囲
のものが好ましい。本発明においては、前記ノニオン界
面活性剤は単独で又は2種以上を混合して用いることが
できる。Among the nonionic surfactants, those described in the above (i) are preferable, and alkylene oxide adducts of alkylphenols are particularly preferable. The HLB of the nonionic surfactant used in the present invention is usually 13 to 19, preferably 13.5-15.5. Although a nonionic surfactant having an HLB of less than 13 or more than 19 can be used, an HLB in the range of 13 to 19 is preferable from the viewpoint of preparing a stable emulsion. In the present invention, the nonionic surfactants can be used alone or in combination of two or more.
本発明に用いられるアニオン界面活性剤としては以下
のものが挙げられる。Examples of the anionic surfactant used in the present invention include the following.
(i)ナフタリンスルホン酸塩、アルキルナフタリンス
ルホン酸塩、アルキルフェノールスルホン酸塩、アルキ
ルベンゼンスルホン酸塩等の芳香族環化合物のスルホン
酸塩又は芳香族環化合物のスルホン酸塩のホルマリン
(ホルムアルデヒド)縮合物。但し、ホルマリンの平均
縮合度は1.2〜100である。スルホン酸塩としてはアンモ
ニウム塩、モノエタノールアミン塩、ジエタノールアミ
ン塩、トリエタノールアミン塩、トリエチルアミン塩等
の低級アミン塩、ナトリウム塩、カリウム塩、マグネシ
ウム塩、カルシウム塩等のアルカリ金属塩又はアルカリ
土類金属塩等が例示できる。(I) A sulfonate of an aromatic ring compound such as a naphthalene sulfonate, an alkyl naphthalene sulfonate, an alkylphenol sulfonate, or an alkylbenzene sulfonate, or a formalin (formaldehyde) condensate of a sulfonate of an aromatic ring compound. However, the average degree of condensation of formalin is 1.2 to 100. Examples of the sulfonate include lower amine salts such as ammonium salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt and triethylamine salt, alkali metal salts such as sodium salt, potassium salt, magnesium salt and calcium salt or alkaline earth metals. Salts and the like can be exemplified.
(ii)リグニンスルホン酸、その塩、又はその誘導体、
リグニンスルホン酸とナフタリンスルホン酸、アルキル
ナフタリンスルホン酸等の芳香族化合物のスルホン酸と
のホルマリン(ホルムアルデヒド)縮合物及びその塩。
リグニンスルホン酸塩および芳香族化合物のスルホン酸
塩のいずれの場合も、塩としては、アンモニウム塩、モ
ノエタノールアミン塩、ジエタノールアミン塩、トリエ
タノールアミン塩、トリエチルアミン塩等の低級アミン
塩、ナトリウム塩、カリウム塩、マグネシウム塩、カル
シウム塩等のアルカリ金属塩又はアルカリ土類金属塩等
が例示できる。ホルマリンの平均縮合度は1.2〜50、好
ましくは2〜50である。リグニンの中では変性リグニ
ン、例えば1個以上のカルボキシル塩で置換された変性
リグニンが、特に高温で優れた性能を示す。(Ii) ligninsulfonic acid, a salt thereof, or a derivative thereof,
A formalin (formaldehyde) condensate of lignin sulfonic acid with a sulfonic acid of an aromatic compound such as naphthalene sulfonic acid or alkyl naphthalene sulfonic acid, and a salt thereof.
In any case of the lignin sulfonate and the sulfonate of the aromatic compound, the salts include lower amine salts such as ammonium salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt, triethylamine salt, sodium salt, and potassium salt. Examples thereof include alkali metal salts such as salts, magnesium salts, and calcium salts, and alkaline earth metal salts. The average degree of condensation of formalin is from 1.2 to 50, preferably from 2 to 50. Among lignins, modified lignins, for example, modified lignins substituted with one or more carboxyl salts, show excellent performance especially at high temperatures.
(iii)ポリスチレンスルホン酸又はその塩、及びスチ
レンスルホン酸と他の共重合性モノマーとの共重合体と
その塩。但し、数平均分子量は500〜50万、好ましくは2
000〜10万である。塩としてはアンモニウム塩、モノエ
タノールアミン塩、ジエタノールアミン塩、トリエタノ
ールアミン塩、トリエチルアミン塩等の低級アミン塩、
ナトリウム塩、カリウム塩、マグネシウム塩、カルシウ
ム塩等のアルカリ金属塩又はアルカリ土類金属塩等が例
示できる。ここで、共重合性モノマーの代表例として
は、アクリル酸、メタクリル酸、酢酸ビニル、アクリル
酸エステル、オレフィン、アリルアルコール及びそのエ
チレンオキシド付加物、アクリルアミドメチルプロピル
スルホン酸等が挙げられる。(Iii) Polystyrenesulfonic acid or a salt thereof, and a copolymer of styrenesulfonic acid and another copolymerizable monomer and a salt thereof. However, the number average molecular weight is 500 to 500,000, preferably 2
It is from 100,000 to 100,000. Salts include lower amine salts such as ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts and triethylamine salts,
Examples thereof include alkali metal salts such as sodium salt, potassium salt, magnesium salt, and calcium salt, and alkaline earth metal salts. Here, typical examples of the copolymerizable monomer include acrylic acid, methacrylic acid, vinyl acetate, acrylic acid ester, olefin, allyl alcohol and its ethylene oxide adduct, acrylamidomethylpropylsulfonic acid, and the like.
(iv)ジシクロペンタジエンスルホン酸重合物又はその
塩。重合物の数平均分子量は500〜50万、好ましくは200
0〜10万である。塩としては、アンモニウム塩、モノエ
タノールアミン塩、ジエタノールアミン塩、トリエタノ
ールアミン塩、トリエチルアミン塩等の低級アミン塩、
ナトリウム塩、カリウム塩、マグネシウム塩、カルシウ
ム塩等のアルカリ金属塩又はアルカリ土類金属塩等が例
示できる。(Iv) Dicyclopentadiene sulfonic acid polymer or a salt thereof. The number average molecular weight of the polymer is 500 to 500,000, preferably 200
It is 100,000 to 100,000. Salts include lower amine salts such as ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts;
Examples thereof include alkali metal salts such as sodium salt, potassium salt, magnesium salt, and calcium salt, and alkaline earth metal salts.
(v)無水マレイン酸及び/又は無水イタコン酸と他の
共重合性モノマーとの共重合体又はその塩。但し、数平
均分子量は500〜50万、好ましくは1500〜10万である。
塩としてはアンモニウム塩及びナトリウム塩、カリウム
塩等のアルカリ金属塩等が例示できる。ここで、共重合
性モノマーの代表例としては、エチレン、プロピレン、
ブチレン、ペンテン、ヘキセン、ヘプテン、オクテン、
ノネン、デセン、ウンデセン、ドデセン、トリデセン、
テトラデセン、ペンタデセン、ヘキサデセン等のオレフ
ィン類、スチレン、酢酸ビニル、アクリル酸エステル、
アクリル酸、メタクリル酸等が挙げられる。(V) A copolymer of maleic anhydride and / or itaconic anhydride with another copolymerizable monomer or a salt thereof. However, the number average molecular weight is 500 to 500,000, preferably 1500 to 100,000.
Examples of the salt include ammonium salts and alkali metal salts such as sodium salts and potassium salts. Here, as typical examples of the copolymerizable monomer, ethylene, propylene,
Butylene, pentene, hexene, heptene, octene,
Nonen, decene, undecene, dodecene, tridecene,
Olefins such as tetradecene, pentadecene and hexadecene, styrene, vinyl acetate, acrylate,
Examples include acrylic acid and methacrylic acid.
(vi)液状ポリブタジエンのマレイン化物及びその塩。
但し、原料の液状ポリブタジエンの数平均分子量は500
〜20万、好ましくは1000〜5万、マレイン化度はポリブ
タジエンを水に溶解させるのに必要な程度でよいが、好
ましくは40〜70%である。塩としては、アンモニウム塩
及びナトリウム塩、カリウム塩等のアルカリ金属塩等が
例示できる。(Vi) A maleated liquid polybutadiene and a salt thereof.
However, the number average molecular weight of the raw material liquid polybutadiene is 500
20200,000, preferably 1000-50,000, and the degree of maleation may be as high as required for dissolving polybutadiene in water, but is preferably 40-70%. Examples of the salt include ammonium salts and alkali metal salts such as sodium salts and potassium salts.
(vii)下記の(a)〜(h)からなる群より選択され
た、親水基を分子中に1個又は2個持つ、アニオン界面
活性剤。(Vii) An anionic surfactant having one or two hydrophilic groups in a molecule selected from the group consisting of the following (a) to (h).
(a)炭素数4〜18のアルコールの硫酸エステル塩。但
し、塩としては、アンモニウム塩、モノエタノールアミ
ン塩、ジエタノールアミン塩、トリエタノールアミン
塩、トリエチルアミン塩等の低級アミン塩、ナトリウム
塩、カリウム塩、マグネシウム塩、カルシウム塩等のア
ルカリ金属塩又はアルカリ土類金属塩等が例示できる。
その代表としては、ドデシル硫酸ナトリウム、オクチル
硫酸ナトリウム等が挙げられる。(A) A sulfate salt of an alcohol having 4 to 18 carbon atoms. However, examples of the salt include a lower amine salt such as an ammonium salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, and a triethylamine salt; an alkali metal salt such as a sodium salt, a potassium salt, a magnesium salt, and a calcium salt; Examples thereof include metal salts.
Typical examples thereof include sodium dodecyl sulfate and sodium octyl sulfate.
(b)炭素数4〜18のアルカンスルホン酸、アルケンス
ルホン酸及び/又はアルキルアリールスルホン酸又はそ
の塩。但し、塩としては、アンモニウム塩、モノエタノ
ールアミン塩、ジエタノールアミン塩、トリエタノール
アミン塩、トリエチルアミン塩等の低級アミン塩、ナト
リウム塩、カリウム塩、マグネシウム塩、カルシウム塩
等のアルカリ金属塩又はアルカリ土類金属塩等が例示で
きる。その代表例としては、ドデシルベンゼンスルホン
酸ナトリウム、ブチルナフタリンスルホン酸ナトリウ
ム、ドデカンスルホン酸ナトリウムが挙げられる。(B) Alkanesulfonic acid, alkenesulfonic acid and / or alkylarylsulfonic acid having 4 to 18 carbon atoms or a salt thereof. However, examples of the salt include a lower amine salt such as an ammonium salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, and a triethylamine salt; an alkali metal salt such as a sodium salt, a potassium salt, a magnesium salt, and a calcium salt; Examples thereof include metal salts. Representative examples include sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, and sodium dodecanesulfonate.
(c)活性水素を分子中に1個以上持つ化合物のアルキ
レンオキシド付加物の硫酸エステル又はリン酸エステル
及びそれらの塩。塩としては、アンモニウム塩、ナトリ
ウム塩、カリウム塩、マグネシウム塩、カルシウム塩等
のアルカリ金属塩又はアルカリ土類金属塩等が例示でき
る。その代表例としては、ポリオキシエチレン(3モ
ル)ノニルフェニルエーテルの硫酸エステルナトリウム
塩、ポリオキシエチレン(3モル)ドデシルエーテルの
リン酸エステルナトリウム塩が挙げられる。(C) Sulfate or phosphate esters of alkylene oxide adducts of compounds having one or more active hydrogens in the molecule and salts thereof. Examples of the salt include an alkali metal salt such as an ammonium salt, a sodium salt, a potassium salt, a magnesium salt, and a calcium salt or an alkaline earth metal salt. Typical examples thereof include sodium sulfate of polyoxyethylene (3 mol) nonylphenyl ether and sodium phosphate of polyoxyethylene (3 mol) dodecyl ether.
(d)炭素数4〜22の飽和又は不飽和脂肪酸のスルホコ
ハク酸エステル塩。但し、塩としては、アンモニウム
塩、ナトリウム塩、カリウム塩等のアルカリ金属塩等が
例示できる。その代表例としては、ジオクチルスルホコ
ハク酸のナトリウム塩、ジオクチルスルホコハク酸のア
ンモニウム塩、ジブチルスルホコハク酸のナトリウム塩
等が挙げられる。(D) A sulfosuccinate salt of a saturated or unsaturated fatty acid having 4 to 22 carbon atoms. However, examples of the salt include alkali metal salts such as ammonium salt, sodium salt, and potassium salt. Representative examples include sodium salts of dioctylsulfosuccinic acid, ammonium salts of dioctylsulfosuccinic acid, sodium salts of dibutylsulfosuccinic acid, and the like.
(e)アルキルジフェニルエーテルジスルホン酸又はそ
の塩。アルキル基は炭素数8〜18のアルキル基であり、
塩としてはアンモニウム塩、ナトリウム塩、カリウム
塩、マグネシウム塩、カルシウム塩等のアルカリ金属塩
又はアルカリ土類金属塩等が例示できる。(E) Alkyl diphenyl ether disulfonic acid or a salt thereof. The alkyl group is an alkyl group having 8 to 18 carbon atoms,
Examples of the salt include an alkali metal salt such as an ammonium salt, a sodium salt, a potassium salt, a magnesium salt, and a calcium salt or an alkaline earth metal salt.
(f)ロジン(又は樹脂酸)又はその塩。塩としてはア
ンモニウム塩、ナトリウム塩、カリウム塩等のアルカリ
金属塩等が例示できる。トールロジンと高級脂肪酸の混
合酸であるトール油混酸とその塩もこの中に含まれる。(F) Rosin (or resin acid) or a salt thereof. Examples of the salt include an alkali metal salt such as an ammonium salt, a sodium salt, and a potassium salt. Tall oil mixed acids, which are mixed acids of tall rosin and higher fatty acids, and salts thereof are also included in this.
(g)炭素数4〜18のアルカン脂肪酸又はアルケン脂肪
酸とその塩。塩としてはアンモニウム塩、ナトリウム
塩、カリウム塩等のアルカリ金属塩等が例示できる。(G) Alkane fatty acids or alkene fatty acids having 4 to 18 carbon atoms and salts thereof. Examples of the salt include an alkali metal salt such as an ammonium salt, a sodium salt, and a potassium salt.
(h)炭素数4〜22のアルキル基を有するα−スルホ脂
肪酸エステル塩及びその誘導体。塩としてはアンモニウ
ム塩、ナトリウム塩、カリウム塩、マグネシウム塩等の
アルカリ金属塩又はアルカリ土類金属塩等が例示でき
る。(H) α-sulfofatty acid ester salts having an alkyl group having 4 to 22 carbon atoms and derivatives thereof. Examples of the salt include an alkali metal salt such as an ammonium salt, a sodium salt, a potassium salt, and a magnesium salt or an alkaline earth metal salt.
前記に示したアニオン界面活性剤のうち、特にリグニ
ンスルホン酸塩やリグニンスルホン酸とナフタリンスル
ホン酸のホルマリン縮合物又はそれらの塩、及びナフタ
リンスルホン酸塩のホルマリン縮合物が総合的に粒子の
電荷供与に優れた性能を示すので好適である。本発明に
用いられるカチオン界面活性剤としては以下のものが挙
げられる。Among the anionic surfactants shown above, in particular, lignin sulfonic acid salt or a formalin condensate of lignin sulfonic acid and naphthalene sulfonic acid or a salt thereof, and a formalin condensate of naphthalene sulfonic acid salt collectively provide the charge of the particles. It is preferable because it shows excellent performance. Examples of the cationic surfactant used in the present invention include the following.
(i)炭素数4〜18のアルキルアミン及び/又はアルケ
ニルアミンを塩酸、酢酸等の無機酸及び/又は有機酸で
中和したアルキルアミン塩及び/又はアルケニルアミン
塩。(I) An alkylamine salt and / or alkenylamine salt obtained by neutralizing an alkylamine and / or alkenylamine having 4 to 18 carbon atoms with an inorganic acid and / or an organic acid such as hydrochloric acid and acetic acid.
(ii)下記一般式(A)、(B)、及び(C)で表され
る第4級アンモニウム塩。(Ii) Quaternary ammonium salts represented by the following general formulas (A), (B) and (C).
(但し、R1、R2、R3及びR4は、同一でも異なっていても
よく、それぞれ炭素数1〜18のアルキル基又はアルケニ
ル基、X-は、塩素イオン、臭素イオン等の対アニオンで
ある。) (但し、R1、R2、R3及びX-は前記と同じ意味を有す
る。) (但し、R5は炭素数8〜18のアルキル基又はアルケニル
基、R6はH原子又はメチル基、X-は前記と同じ意味を有
する。) (iii)下記一般式で表されるアルキルベタイン又はア
ルケニルベタイン。 (However, R 1 , R 2 , R 3 and R 4 may be the same or different, and each is an alkyl group or alkenyl group having 1 to 18 carbon atoms, and X − is a counter anion such as a chloride ion and a bromide ion. Is.) (However, R 1 , R 2 , R 3 and X − have the same meaning as described above.) (However, R 5 is an alkyl group or alkenyl group having 8 to 18 carbon atoms, R 6 is a H atom or a methyl group, and X − has the same meaning as described above.) (Iii) Alkyl betaine represented by the following general formula Or alkenyl betaine.
(但し、Rは炭素数8〜18のアルキル基又はアルケニル
基である。) (iv)下記一般式で表されるアルキルアミンオキシド又
はアルケニルアミンオキシド。 (However, R is an alkyl group or alkenyl group having 8 to 18 carbon atoms.) (Iv) An alkylamine oxide or alkenylamine oxide represented by the following general formula.
(但し、Rは前記と同じ意味を有する。) (v)下記一般式で表されるアルキルアラニン又はアル
ケニルアラニン。 (However, R has the same meaning as described above.) (V) Alkylalanine or alkenylalanine represented by the following general formula.
(但し、Rは前記と同じ意味を有する。) (vi)下記一般式(D)又は(E)で表されるジアミン
又はトリアミンのアルキレンオキシド付加物の重合体。 (However, R has the same meaning as described above.) (Vi) A polymer of an alkylene oxide adduct of a diamine or triamine represented by the following general formula (D) or (E).
(但し、Rは前記と同じ意味を有し、Y及びY′は、同
一でも異なっていてもよく、それぞれ一般式 C2H4OmH (但し、mは1〜50の数である) で表されるオキシエチレン類である。) (vii)下記一般式(F)又は(G)で表されるポリア
ミン塩。 (However, R has the same meaning as described above, and Y and Y ′ may be the same or different, and each has the general formula C 2 H 4 O m H (where m is a number of 1 to 50)) (Vii) A polyamine salt represented by the following general formula (F) or (G).
RNHC3H6NHX′ (F) RNH(C3H6NH)2X′ (G) (但し、Rは前記と同じ意味を有し、X′は塩酸、酢酸
等の無機酸又は有機酸である。) 本発明において、HLB(親水性親油性バランス)が13
〜19のノニオン界面活性剤の添加量は、超重質油100重
量部に対して、0.1〜0.6重量部、好ましくは0.1〜0.5重
量部、さらに好ましくは0.2〜0.4重量部である。ノニオ
ン界面活性剤の添加量が0.6重量部を超えると、油滴の
粒径が小さくなるため、所望の粒子径分布をもった本発
明のエマルションを得ることができなくなる。一方、添
加量が0.1重量部より少ないと油滴が大きくなりすぎ、
得られるエマルションの安定性も悪くなる。150μm以
上の粒子径を有する油滴が多く存在すると、エマルショ
ン燃料は完全燃焼できず、一部が未燃物として残留す
る。従って、150μm以上の粒子径を有する粗粒の量は
できるだけ少量であることが好ましい。RNHC 3 H 6 NHX ′ (F) RNH (C 3 H 6 NH) 2 X ′ (G) (where R has the same meaning as described above, and X ′ is an inorganic acid such as hydrochloric acid or acetic acid or an organic acid. In the present invention, HLB (hydrophilic-lipophilic balance) is 13
The addition amount of the nonionic surfactant is from 0.1 to 0.6 part by weight, preferably from 0.1 to 0.5 part by weight, more preferably from 0.2 to 0.4 part by weight, based on 100 parts by weight of the super heavy oil. When the amount of the nonionic surfactant exceeds 0.6 parts by weight, the emulsion of the present invention having a desired particle size distribution cannot be obtained because the particle size of the oil droplets becomes small. On the other hand, if the addition amount is less than 0.1 parts by weight, the oil droplets become too large,
The stability of the resulting emulsion is also poor. If there are many oil droplets having a particle diameter of 150 μm or more, the emulsion fuel cannot be completely burned, and a part of the emulsion fuel remains as unburned matter. Therefore, the amount of coarse particles having a particle diameter of 150 μm or more is preferably as small as possible.
本発明のエマルション燃料においては、ノニオン界面
活性剤が界面活性剤成分の主成分として用いられ、アニ
オン界面活性剤及びカチオン界面活性剤は、前記のよう
なノニオン界面活性剤が本来有する性質を阻害しない範
囲で、ノニオン界面活性剤に混合させることができる。
アニオン界面活性剤及びカチオン界面活性剤を添加する
ことにより、粒子が荷電されて、乳化滴同士の斥力が向
上するため得られるエマルションを安定させることがで
きる。ノニオン界面活性剤を、アニオン界面活性剤また
はカチオン界面活性剤と組み合わせて使用する場合、界
面活性剤の合計添加量は、ノニオン界面活性剤を単独で
使用する場合と同様に、超重質油100重量部に対して好
ましくは0.1〜0.6重量部、さらに好ましくは0.1〜0.5重
量部である。アニオン界面活性剤又はカチオン界面活性
剤の添加量は、ノニオン界面活性剤100重量部に対し
て、好ましくは100重量部以下、さらに好ましくは5〜3
0重量部である。本発明における水の添加量は、超重質
油100重量部に対して、好ましくは22〜31重量部、より
好ましくは22〜28重量部である。In the emulsion fuel of the present invention, the nonionic surfactant is used as a main component of the surfactant component, and the anionic surfactant and the cationic surfactant do not inhibit the properties inherent to the nonionic surfactant as described above. In a range, it can be mixed with a nonionic surfactant.
By adding an anionic surfactant and a cationic surfactant, the particles are charged and the repulsive force between the emulsified droplets is improved, so that the obtained emulsion can be stabilized. When a nonionic surfactant is used in combination with an anionic surfactant or a cationic surfactant, the total amount of the surfactant added is 100% by weight, as in the case of using the nonionic surfactant alone. The amount is preferably from 0.1 to 0.6 part by weight, more preferably from 0.1 to 0.5 part by weight, per part by weight. The addition amount of the anionic surfactant or the cationic surfactant is preferably 100 parts by weight or less, more preferably 5 to 3 parts by weight, based on 100 parts by weight of the nonionic surfactant.
0 parts by weight. In the present invention, the amount of water to be added is preferably 22 to 31 parts by weight, more preferably 22 to 28 parts by weight, based on 100 parts by weight of the heavy oil.
界面活性剤成分として前記のようなノニオン界面活性
剤を用いた系に、以下に例示する天然高分子、合成高分
子等の高分子化合物及び水膨潤性粘土鉱物を更に用いる
と、液滴の界面の粘性が増加して、安定な乳化滴を形成
するため、得られるエマルションは安定化する。本発明
に用いられる高分子化合物としては、天然物に由来する
親水性高分子等の天然高分子及び合成高分子が挙げられ
る。これらは工程(a)におけるノニオン界面活性剤の
配合量を超えない範囲で添加する。In a system using the above-mentioned nonionic surfactant as a surfactant component, a polymer compound such as a natural polymer or a synthetic polymer exemplified below and a water-swellable clay mineral are further used. The resulting emulsion is stabilized because the viscosity of the emulsion increases and stable emulsion droplets are formed. Examples of the polymer compound used in the present invention include natural polymers such as hydrophilic polymers derived from natural products and synthetic polymers. These are added within a range not exceeding the amount of the nonionic surfactant in step (a).
微生物を含む天然物に由来する親水性高分子として
は、下記の(A)微生物由来の親水性高分子、(B)植
物由来の親水性高分子、(C)動物由来の親水性高分子
及び(D)天然高分子誘導体からなる群より選ばれた1
種又は2種以上が挙げられる。この親水性高分子物質は
水に溶解又は分散して高い粘稠性又はゲル化性を示す。As hydrophilic polymers derived from natural products including microorganisms, the following (A) hydrophilic polymers derived from microorganisms, (B) hydrophilic polymers derived from plants, (C) hydrophilic polymers derived from animals, and (D) 1 selected from the group consisting of natural polymer derivatives
Species or two or more species. This hydrophilic polymer substance is dissolved or dispersed in water and exhibits high viscosity or gelling property.
(A)微生物由来の親水性高分子(多糖類) (a)キサンタンガム (b)プルラン (c)デキストラン (B)植物由来の親水性高分子(多糖類) (a)海藻由来 (i)寒天 (ii)カラギーナン (iii)ファーセレラン (iv)アルギン酸とその塩(Na,K,NH4,Ca,又はMg) (b)種子由来 (i)ローカストビーンガム (ii)グアーガム (iii)タラガム (iv)タマリンドガム (c)樹木(滲出物) (i)アラビアガム (ii)カラヤガム (iii)トラガントガム (d)果実由来 (i)ペクチン (C)動物由来の親水性高分子(蛋白質) (i)ゼラチン (ii)カゼイン (D)天然高分子誘導体 (i)カルボキシメチルセルロース等のセルロース誘導
体 (ii)加工澱粉 合成高分子としては、以下に示す水溶性合成高分子が
挙げられる。(A) Microorganism-derived hydrophilic polymer (polysaccharide) (a) Xanthan gum (b) Pullulan (c) Dextran (B) Plant-derived hydrophilic polymer (polysaccharide) (a) Seaweed-derived (i) Agar ( ii) carrageenan (iii) furceleran (iv) alginic acid and its salts (Na, K, NH 4 , Ca, or Mg) (b) from seed (i) locust bean gum (ii) guar gum (iii) tarara gum (iv) tamarind Gum (c) tree (exudate) (i) gum arabic (ii) gum karaya (iii) gum tragacanth (d) fruit-derived (i) pectin (C) animal-derived hydrophilic polymer (protein) (i) gelatin (ii) ) Casein (D) Natural polymer derivative (i) Cellulose derivative such as carboxymethyl cellulose (ii) Processed starch Examples of the synthetic polymer include the following water-soluble synthetic polymers.
(a)下記一般式で表されるアクリル酸及びその誘導体
のホモポリマー、及び他のモノマーとのコポリマー。(A) A homopolymer of acrylic acid and its derivative represented by the following general formula, and a copolymer with another monomer.
(但し、R′はH原子、メチル基又はエチル基を表し、
M1はH原子、又はNaイオン、Kイオン、Liイオン、NH4
イオンを表し、 (R′及びM1は前記と同じ意味を有する。) 及びこのモノマーと共重合可能なモノマー又はそのアン
モニウム塩、ナトリウム塩、カリウム塩、リチウム塩等
の塩とを共重合させることにより得られる2価の基を表
す。nは50〜100,000を表す。上記式のモノマーと共重
合可能なモノマーとしては、例えば、(無水)マレイン
酸、(無水)イタコン酸、α−オレフィン、アクリルア
ミド、ビニルスルホン酸、アリルスルホン酸、メタリル
スルホン酸、アクリルアミドメチルプロピルスルホン酸
及びそれらのアンモニウム塩、ナトリウム塩、カリウム
塩、リチウム塩等の塩、ジメチルアミノエチルメタアク
リレート、ジエチルアミノエチルメタアクリレート等の
ジアルキルアミノエチルメタアクリレート及びその塩又
は4級化物(塩酸、ジエチル硫酸、ジメチル硫酸)等が
挙げられる。) (b)下記一般式で表されるアクリルアミド及びその誘
導体のホモポリマー、及び他の共重合可能なモノマーと
コポリマー。 (However, R 'represents an H atom, a methyl group or an ethyl group,
M 1 is H atom, or Na ion, K ion, Li ion, NH 4
Represents an ion, (R ′ and M 1 have the same meanings as described above.) And 2 obtained by copolymerizing this monomer with a copolymerizable monomer or a salt thereof such as an ammonium salt, a sodium salt, a potassium salt, and a lithium salt. Represents a valence group. n represents 50 to 100,000. Examples of the monomer copolymerizable with the monomer of the above formula include (anhydride) maleic acid, (anhydride) itaconic acid, α-olefin, acrylamide, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, and acrylamidomethylpropylsulfone. Acids and their salts such as ammonium salt, sodium salt, potassium salt and lithium salt; dialkylaminoethyl methacrylate such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; and salts or quaternaries thereof (hydrochloric acid, diethyl sulfate, dimethyl Sulfuric acid) and the like. (B) Homopolymers of acrylamide and its derivatives represented by the following general formula, and copolymers with other copolymerizable monomers.
(但し、R″はH原子、又はC2H4OHを表し、 (R″は前記と同じ意味を有する。) 及びこのモノマーと共重合可能なモノマー又はそのアン
モニウム塩、ナトリウム塩、カリウム塩、リチウム塩等
の塩とを共重合させることにより得られる2価の基を表
し、nは50〜100,000を表す。上記式のモノマーと共重
合可能なモノマーとしては、例えば、ビニルスルホン
酸、アリルスルホン酸、メタリルスルホン酸、アクリル
アミドエチルプロピルスルホン酸、及びそれらのアンモ
ニウム塩、ナトリウム塩、カリウム塩、リチウム塩等の
塩、ジメチルアミノエチルメタアクリレート、ジエチル
アミノエチルメタアクリレート等のジアルキルアミノエ
チルメタアクリレート及びその塩又は4級化物(塩酸、
ジエチル硫酸、ジメチル硫酸等)、スチレン、炭素数2
〜18のα−オレフィン類、及びビニルアリルアルコール
が挙げられる。) (c)無水マレイン酸又は無水イタコン酸のホモポリマ
ー、及び下記一般式で表されるコポリマー。 (However, R ″ represents an H atom or C 2 H 4 OH, (R ″ has the same meaning as described above.) And a divalent group obtained by copolymerizing this monomer with a copolymerizable monomer or a salt thereof such as an ammonium salt, a sodium salt, a potassium salt, and a lithium salt. And n represents 50 to 100,000. Examples of monomers copolymerizable with the monomer of the above formula include vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, acrylamidoethyl propyl sulfonic acid, and ammonium salts thereof. , Sodium salts, potassium salts, salts such as lithium salts, dimethylaminoethyl methacrylate, dialkylaminoethyl methacrylate such as diethylaminoethyl methacrylate and salts or quaternary compounds thereof (hydrochloric acid,
Diethylsulfate, dimethylsulfate, etc.), styrene, carbon number 2
To 18 alpha-olefins, and vinyl allyl alcohol. (C) A homopolymer of maleic anhydride or itaconic anhydride and a copolymer represented by the following general formula.
M2−Z3 n (但し、M2は無水マレイン酸残基又は無水イタコン酸残
基を表し、Z3はエチレン、プロピレン、ブチレン、イソ
ブチレン、オクテン、デセン、ドデセン等のα−オレフ
ィン残基又はスチレン残基を表し、nは50〜100,000を
表す。M 2 -Z 3 n (where M 2 represents a maleic anhydride residue or itaconic anhydride residue, and Z 3 is an α-olefin residue such as ethylene, propylene, butylene, isobutylene, octene, decene, dodecene or Represents a styrene residue, and n represents 50 to 100,000.
(d)ポリビニルアルコール及び下記一般式で表される
コポリマー。(D) Polyvinyl alcohol and a copolymer represented by the following general formula.
(但し、Z4は酢酸ビニル残基又はスチレン残基を表し、
n′は30〜100,000を表す。) (e)ビニルピロリドンのホモポリマー及び下記一般式
で表されるコポリマー。 (However, Z 4 represents a vinyl acetate residue or a styrene residue,
n 'represents 30 to 100,000. (E) Vinylpyrrolidone homopolymers and copolymers represented by the following general formula:
(但し、Z5はビニルピロリドンモノマー、又はそのアン
モニウム塩、ナトリウム塩、カリウム塩、リチウム塩等
の塩と共重合可能なモノマー又はそのアンモニウム塩、
ナトリウム塩、カリウム塩、リチウム塩等の共重合させ
ることにより得られる2価の基を表し、ビニルピロリド
ンモノマーと共重合可能なモノマーまたはその塩の例と
しては、アクリルアミド、ビニルスルホン酸、メタリル
スルホン酸、無水マレイン酸、無水イタコン酸、及びそ
れらのアンモニウム塩、ナトリウム塩、カリウム塩、リ
チウム塩等の塩、スチレン、炭素数2〜18のα−オレフ
ィン等が挙げられる。nは50〜100,000を表す。) (f)分子量1万〜500万のポリアルキレンオキシド
(但し、エチレンオキシド95%以上)。5%以下のプロ
ピレンオキシド、ブチレンオキシド、スチレンオキシド
の各々のブロックポリマーやアルキルアリール基、アル
キル基等を分子中に持つものも含まれる。 (However, Z 5 is vinylpyrrolidone monomer or its ammonium salt, sodium salt, potassium salt, salt and copolymerizable monomer or its ammonium salt such as lithium salt,
Represents a divalent group obtained by copolymerization of a sodium salt, a potassium salt, a lithium salt or the like, and examples of a monomer copolymerizable with a vinylpyrrolidone monomer or a salt thereof include acrylamide, vinylsulfonic acid, and methallylsulfonic acid. Examples thereof include acids, maleic anhydride, itaconic anhydride, and salts thereof such as ammonium salts, sodium salts, potassium salts, and lithium salts, styrene, and α-olefins having 2 to 18 carbon atoms. n represents 50 to 100,000. (F) Polyalkylene oxide having a molecular weight of 10,000 to 5,000,000 (provided that ethylene oxide is 95% or more). It also includes those having 5% or less of propylene oxide, butylene oxide, and styrene oxide block polymers and those having an alkylaryl group, an alkyl group, or the like in the molecule.
本発明に用いられる水膨潤性粘土鉱物としては、以下
のものが挙げられる。Examples of the water-swellable clay mineral used in the present invention include the following.
本発明に使用される粘土鉱物は、高膨潤性の微細な粘
土鉱物であるが、本発明において高膨潤性粘土鉱物と
は、水中に粘土鉱物を懸濁させると水分子を多量に拘束
するものであり、粘度鉱物を乾燥物換算で水中に1重量
%懸濁した時の核磁気共鳴装置で測定した水分子の緩和
時間(T2)が900ミリ秒以下、好ましくは500ミリ秒以下
となるようなものをいう。緩和時間が900ミリ秒を越え
ると水の拘束力が弱くなり本発明の効果が不十分とな
る。また、微細な粘土鉱物とは平均粒径が100μm以下
である粘土鉱物をいう。粘度鉱物の平均粒径が100μm
を越えると水分子の拘束力が弱くなるのと同時に粘度鉱
物が沈降しやすくなるため、本発明の効果を十分発揮す
ることができなくなる。The clay mineral used in the present invention is a fine clay mineral having a high swelling property.In the present invention, a high swelling clay mineral means that when the clay mineral is suspended in water, a large amount of water molecules are restricted. And the relaxation time (T 2 ) of water molecules measured by a nuclear magnetic resonance apparatus when the viscous mineral is suspended at 1% by weight in water on a dry matter basis is 900 ms or less, preferably 500 ms or less. Something like that. If the relaxation time exceeds 900 milliseconds, the binding force of water becomes weak, and the effect of the present invention becomes insufficient. The fine clay mineral refers to a clay mineral having an average particle diameter of 100 μm or less. 100μm average particle size of viscous mineral
If the ratio exceeds the above range, the binding force of water molecules is weakened, and at the same time, the viscous mineral is liable to settle, so that the effect of the present invention cannot be sufficiently exhibited.
具体的には、例えばスメクタイト、バーミキュライ
ト、緑泥石等の高膨潤性で水分子の拘束力の強い微細な
粘土鉱物が本発明の範囲に含まれる。但し、これらの中
でもT2が900ミリ秒を超えるものは本発明には含まれな
い。さらに、米国ジョージア産のカオリンや一般のカオ
リン、タルク等は水分子の拘束力が弱いため、本発明の
範囲から除外される。Specifically, fine clay minerals such as smectite, vermiculite, chlorite and the like, which are highly swellable and have a strong binding force on water molecules, are included in the scope of the present invention. However, it is not included in the present invention that T 2 Among them exceeds 900 ms. Furthermore, kaolin, general kaolin, talc, and the like produced in Georgia, USA, are excluded from the scope of the present invention because of their weak water molecule binding force.
以下、本発明に用いられるスメクタイト、バーミキュ
ライト、緑泥石等の高膨潤性の微細な粘土鉱物について
詳細に説明する。Hereinafter, the highly swellable fine clay minerals such as smectite, vermiculite, and chlorite used in the present invention will be described in detail.
(A)スメクタイト(smectite)は、置換が広範囲に生
じ、層間に水分子を伴った種々のイオンが入るため、2
枚の四面シート及びその間に挟まれる1枚の八面体シー
ト(すなわち、2:1層)からなる複雑な化学組成を有す
る。具体的には、次のような一般式で表される。(A) Smectite has a wide range of substitution, and various ions with water molecules enter between layers.
It has a complex chemical composition consisting of four tetrahedral sheets and one octahedral sheet sandwiched between them (ie, a 2: 1 layer). Specifically, it is represented by the following general formula.
Xm(Y2+,Y3+)2-3Z4O10(OH)2・nH2O (式中、XはK、Na、1/2Ca、1/2Mgを、Y2+はMg2+、Fe
2+、Mn2+、Ni2+、又はZn2+を、Y3+はAl3+、Fe3+、M
n3+、又はCr3+を、ZはSi及び/又はAlを示す。なおX
は層間、Yは八面体、Zは四面体の陽イオンを表す。) スメクタイトの代表的な種類には次のものがある。X m (Y 2+ , Y 3+ ) 2-3 Z 4 O 10 (OH) 2 .nH 2 O (where X is K, Na, 1 / 2Ca, 1 / 2Mg, and Y 2+ is Mg 2+ , Fe
2+ , Mn 2+ , Ni 2+ , or Zn 2+ , Y 3+ is Al 3+ , Fe 3+ , M
n 3+ or Cr 3+ , and Z represents Si and / or Al. Note that X
Represents an interlayer, Y represents an octahedron, and Z represents a tetrahedral cation. The following are typical types of smectites.
2八面体型(八面体陽イオンが主に3価): 例えば、次式で表されるモンモリロナイト(montmori
llonite) X0.33(Al1.67Mg0.33)Si4O10(OH)2・nH2O 例えば、次式で表されるバイデライト(beidellite) X0.33(Al2)(Al0.33Si3.67)O10(OH)2・nH2O 例えば、次式で表されるノントロナイト(nontronit
e) X0.33(Fe(III)2)(Al0.33Si3.67)O10(OH)2・nH2
O 3八面体型(八面体陽イオンが主に2価): 例えば、次式で表されるサポナイト(saponite) X0.33(Mg3)(Al0.33Si3.67)O10(OH)2・nH2O 例えば、次式で表される鉄サポナイト(iron saponit
e) X0.33(Mg,Fe(II))3(Al0.33Si3.67)O10(OH)2・n
H2O 例えば、次式で表されるヘクトライト(hectorite) X0.33(Mg2.67Li0.33)Si4O10(OH)2・nH2O 例えば、次式で表されるソーコナイト(sauconite) X0.33(Mg,Zn)3(Si3.67Al0.33)O10(OH)2・nH2O 例えば、次式で表されるスチブンサイト(stevensit
e) X0.33/2(Mg2.97)Si4O10(OH)2・nH2O これらのスメクタイトのうち、モンモリロナイト、バ
イデライト、ノントロナイトは一連の系列をなし、同形
置換を生ずる。また、スチブンサイトは他のスメクタイ
トの約半分の層荷電をもち、2八面体型と3八面体型の
中間の性質を有している。Dioctahedral type (octahedral cation is mainly trivalent): For example, montmorillonite (montmori) represented by the following formula
llonite) X 0.33 (Al 1.67 Mg 0.33 ) Si 4 O 10 (OH) 2 · nH 2 O For example, beidellite X 0.33 (Al 2 ) (Al 0.33 Si 3.67 ) O 10 (OH) represented by the following formula: 2 · nH 2 O For example, nontronite (nontronit
e) X 0.33 (Fe (III) 2 ) (Al 0.33 Si 3.67 ) O 10 (OH) 2 .nH 2
O 3 octahedral type (octahedral cation is mainly divalent): For example, saponite X 0.33 (Mg 3 ) (Al 0.33 Si 3.67 ) O 10 (OH) 2 .nH 2 represented by the following formula: O For example, iron saponit expressed by the following formula
e) X 0.33 (Mg, Fe (II)) 3 (Al 0.33 Si 3.67 ) O 10 (OH) 2・ n
H 2 O For example, hectorite X 0.33 (Mg 2.67 Li 0.33 ) Si 4 O 10 (OH) 2 · nH 2 O represented by the following formula For example, sauconite X 0.33 represented by the following formula (Mg, Zn) 3 (Si 3.67 Al 0.33 ) O 10 (OH) 2 .nH 2 O For example, a stevensite represented by the following formula:
e) X 0.33 / 2 (Mg 2.97 ) Si 4 O 10 (OH) 2 .nH 2 O Among these smectites, montmorillonite, beidellite, and nontronite form a series of series and give isomorphous substitution. Also, stevensite has about half the layer charge of other smectites and has properties intermediate between the dioctahedral and trioctahedral types.
(B)バーミキュライト(ひる石、Vermiculite)は、
2:1型層状ケイ酸塩に属し、例えば、次式で表される。(B) Vermiculite (vermiculite)
It belongs to a 2: 1 type layered silicate and is represented by the following formula, for example.
(Mg,Fe(III),Al)2-3(Si4-xAlx)O10(OH)2(M+,
M2+ 1/2)x・nH2O ただし、Mは層間の交換性陽イオンであるが、粗粒な
バーミキュライトではMgが主である。nは水の量である
が、層間陽イオンがMgの場合は、広い温度範囲にわたっ
て、水は2分子層をなして入り、n=3.5〜5程度であ
る。xは層荷電であって、0.6〜0.9の範囲に入る。(Mg, Fe (III), Al) 2-3 (Si 4-x Al x ) O 10 (OH) 2 (M + ,
M 2+ 1/2 ) x · nH 2 O Note that M is an exchangeable cation between layers, but Mg is mainly used in coarse vermiculite. n is the amount of water. When the interlayer cation is Mg, water enters in two molecular layers over a wide temperature range, and n is about 3.5 to 5. x is the layer charge and falls in the range of 0.6 to 0.9.
この化学式は層荷電が全て、四面体陽イオンの置換に
よって生じているとしているが、実際には八面体シート
が負の荷電を持ち、層荷電がこれによっていることもあ
る。八面体陽イオンの数は2〜3であり、2八面体型の
バーミキュライトと3八面体型のバーミキュライトの両
方がある。黒雲母や金雲母の風化によってできた粗粒の
バーミキュライトは3八面体である。Although this formula states that all layer charges are caused by the replacement of tetrahedral cations, in practice the octahedral sheet has a negative charge, which may be attributed to layer charges. The number of octahedral cations is 2-3, and there are both dioctahedral vermiculite and trioctahedral vermiculite. The coarse-grained vermiculite formed by weathering biotite and phlogopite is trioctahedral.
(C)緑泥石(chlorite)の構造はスメクタイトとバー
ミキュライトの構造と類似しており、それらの底面間隔
は14〜15Åである。典型的な緑泥石は2:1型の含水ケイ
酸塩であり、2:1層の性質によって、3八面体型緑泥石
と2八面体型緑泥石に大別できる。3八面体型緑泥石
は、例えば、次式で表される。(C) The structure of chlorite is similar to the structure of smectite and vermiculite, and their base spacing is 14 to 15 mm. A typical chlorite is a 2: 1 type hydrated silicate, and can be roughly classified into a trioctahedral chlorite and a dioctahedral chlorite depending on the properties of the 2: 1 layer. The trioctahedral chlorite is represented, for example, by the following formula.
(R6-x 2+Rx 3+)(Si4-xAlx)O10(OH)8 ただし、R2+はMgとFe2+を主とするが、Mn2+、Ni2+等
も含まれる。R3+はAlが主で、Fe3+、Cr3+等も含まれ
る。xは0.8〜1.6の値を示す。(R 6-x 2+ R x 3+ ) (Si 4-x Al x ) O 10 (OH) 8 where R 2+ is mainly Mg and Fe 2+ , but Mn 2+ , Ni 2+ Etc. are also included. R 3+ is mainly composed of Al, and includes Fe 3+ , Cr 3+ and the like. x shows the value of 0.8-1.6.
R2+がMgを主とする緑泥石をクリノクロア〔clinochlo
re、(Mg5Al)(Si3Al)O10(OH)8〕、R2+がFe(II)
を主とする緑泥石をシャモサイト〔chamosite、(Fe5A
l)(Si3Al)O10(OH)8〕と呼んでいる。その他の3八
面体型緑泥石として、R2+がMn(II)を主成分とするペ
ナンタイト(pennantite)、R2+がNi(II)を主成分と
するニマイト(nimite)がある。R 2+ clinochlore (chlorinated chlorite)
re, (Mg 5 Al) (Si 3 Al) O 10 (OH) 8 ], R 2+ is Fe (II)
Chlorite mainly composed of chamosite [(Fe 5 A
l) (Si 3 Al) O 10 (OH) 8 ]. Other 3 octahedral chlorite, Penantaito the R 2+ is a main component Mn (II) (pennantite), R 2+ there is Nimaito (nimite) mainly composed of Ni (II).
Alを主な八面体陽イオンとする2八面体緑泥石には下記
の3種がある。There are the following three types of dioctahedral chlorite with Al as the main octahedral cation.
スドーアイト〔須藤石、Sudoite、(Mg,Al)4.6-5(Si,
Al)4O10(OH)8〕、 クッケアイト〔cookeite,(LiAl4)(Si3Al)O10(OH)
8〕、及び ドンバサイト〔donbassite,Al4-4.2R0.2(Si,Al)4O10
(OH)8〕 スメクタイトは属する粘土鉱物であるモンモリロナイ
トを主成分とし、石英、α−クリストバライト、オパー
ル、長石、雲母、沸石、方解石、ドロマイト、石膏、鉄
酸化物等を夾雑物として含むものがベントナイトと呼ば
れるものである。ベントナイトには、Naイオンに富んだ
ナトリウムベントナイトとCaイオンに富んだカルシウム
ベントナイトがあるが、ナトリウムベントナイトが膨潤
力に富むので、これが本発明における粘土鉱物に属し、
カルシウムベントナイトは膨潤力が弱いので、本発明の
範囲から除外される。Sudoite [Sudoite, Sudoite, (Mg, Al) 4.6-5 (Si,
Al) 4 O 10 (OH) 8 ], cookeite [cookeite, (LiAl 4) (Si 3 Al) O 10 (OH)
8 ], and donbasite [donbassite, Al 4-4.2 R 0.2 (Si, Al) 4 O 10
(OH) 8 ] Smectite is composed mainly of montmorillonite, a clay mineral to which it belongs, and bentonite containing quartz, α-cristobalite, opal, feldspar, mica, zeolite, calcite, dolomite, gypsum, iron oxide, etc. as impurities. It is called. Bentonite includes sodium bentonite rich in Na ions and calcium bentonite rich in Ca ions.Because sodium bentonite is rich in swelling power, it belongs to the clay mineral in the present invention,
Calcium bentonite is excluded from the scope of the present invention because of its weak swelling power.
ナトリウムベントナイトの中でも、モンモリロナイト
含量が多いほど好ましく、また、粒子径も100μm以下
が好ましく、さらに好ましくは10μm以下である。ナト
リウムベントナイトで本発明における粘土鉱物の範囲に
入るのは、粘度鉱物を乾燥物換算で水中に1重量%懸濁
した時の核磁気共鳴装置で測定した水分子の緩和時間
(T2)が900ミリ秒以下となるもの、好ましくは500ミリ
秒以下となるものである。Among sodium bentonite, the content of montmorillonite is preferably as high as possible, and the particle diameter is preferably 100 μm or less, more preferably 10 μm or less. Sodium bentonite that falls within the range of clay minerals in the present invention is that the relaxation time (T 2 ) of water molecules measured by a nuclear magnetic resonance apparatus when the viscous mineral is suspended in water at 1% by weight in terms of dry matter is 900. It is less than millisecond, preferably less than 500 millisecond.
ナトリウムベントナイトでも、産地により含有夾雑物
等が異なり、膨潤力にも差がみられるが、水篩等の操作
により、ナトリウムベントナイト中のモンモリロナイト
成分含量を高くすると、得られるナトリウムベントナイ
トの水懸濁液のT2値が小さくなり、効果をより向上させ
ることができる。Even in sodium bentonite, the content of contaminants etc. differs depending on the production area and the swelling power also differs.However, if the content of montmorillonite component in sodium bentonite is increased by operation such as a water sieve, an aqueous suspension of sodium bentonite is obtained. the T 2 value is reduced, the effect can be further improved.
以上の高分子化合物や粘土鉱物は、単独で又はこれら
を混合して用いることができる。高分子化合物や粘土鉱
物は、ノニオン界面活性剤の配合量を超えない範囲で添
加するのが好ましい。具体的には、高分子化合物や粘土
鉱物の添加量は、ノニオン界面活性剤100重量部に対し
て、好ましくは2〜40重量部、さらに好ましくは4〜20
重量部である。高分子化合物や粘土鉱物は、超重質油を
ノニオン界面活性剤を用いて水中に超重質油を乳化して
均一な混合液を調製する際に、又はその均一な混合液を
調製した後に添加しても良い。高分子化合物や粘土鉱物
を、ノニオン界面活性剤、及びアニオン界面活性剤又は
カチオン界面活性剤を含有してなる界面活性剤成分に添
加するとその高分子化合物と粘土鉱物の添加の効果が一
層顕著になる。また、高分子化合物と粘土鉱物を併用す
ることもできる。The above polymer compounds and clay minerals can be used alone or as a mixture thereof. It is preferable to add the polymer compound and the clay mineral within a range not exceeding the amount of the nonionic surfactant. Specifically, the amount of the polymer compound or clay mineral added is preferably 2 to 40 parts by weight, more preferably 4 to 20 parts by weight, based on 100 parts by weight of the nonionic surfactant.
Parts by weight. Polymer compounds and clay minerals are added when preparing a uniform mixed solution by emulsifying the super heavy oil in water using a nonionic surfactant, or after preparing the uniform mixed solution. May be. When a polymer compound or a clay mineral is added to a surfactant component containing a nonionic surfactant and an anionic surfactant or a cationic surfactant, the effect of the addition of the polymer compound and the clay mineral becomes more remarkable. Become. Further, a polymer compound and a clay mineral can be used in combination.
さらに、超重質油とノニオン界面活性剤とを乳化して
混合液を調製する際に、マグネシウム、カルシウム又は
鉄の酸化物、マグネシウム、カルシウム又は鉄の水酸化
物もしくはマグネシウム、カルシウム又は鉄の硝酸塩、
酢酸塩等の塩を添加してもよい。酸化物、水酸化物、又
は塩を添加することにより乳化安定化の効果が得られ
る。酸化物や水酸化物が添加される場合、その添加量は
超重質油100重量部に対して0.01〜0.5重量部、好ましく
は0.02〜0.08重量部である。Further, when preparing a mixed solution by emulsifying a super heavy oil and a nonionic surfactant, magnesium, calcium or iron oxide, magnesium, calcium or iron hydroxide or magnesium, calcium or iron nitrate,
A salt such as acetate may be added. By adding an oxide, a hydroxide, or a salt, an emulsion stabilizing effect can be obtained. When an oxide or hydroxide is added, the amount of addition is 0.01 to 0.5 part by weight, preferably 0.02 to 0.08 part by weight, based on 100 parts by weight of the heavy oil.
本発明の超重質油エマルション燃料の製造方法は、 (a)超重質油100重量部に対してHLB(親水性親油性バ
ランス)が13〜19のノニオン界面活性剤0.1〜0.6重量部
と水を超重質油に加え、均一な混合液を調製する工程
と、 (b)高剪断力による均一な混合液の機械的混合を行う
工程とからなる。The method for producing an ultra-heavy oil emulsion fuel according to the present invention comprises: (a) 0.1 to 0.6 parts by weight of a nonionic surfactant having an HLB (hydrophilic-lipophilic balance) of 13 to 19 and water with respect to 100 parts by weight of the ultra-heavy oil. A step of preparing a uniform mixture in addition to the heavy oil; and (b) a step of mechanically mixing the uniform mixture by high shearing force.
エマルションの粘度が高い場合は、工程(b)で得ら
れた混合物を水又はHLBが13〜19の界面活性剤等の添加
剤を含有する水により希釈する工程(c)を工程(b)
の後にさらに設けることにより、流動性の高いエマルシ
ョン燃料を調製することができる。特に、得られる混合
物の粘度(100s-1、25℃)は3000cp以下に調整すること
ができる。得られる本発明のエマルション燃料は、エマ
ルション燃料中における超重質油の濃度が76.5〜82.0重
量%、好ましくは78.0〜81.0重量%、さらに好ましくは
78.0〜81.0重量%であり、所定の好適な粒子径分布を持
つエマルションである。When the viscosity of the emulsion is high, the step (c) of diluting the mixture obtained in the step (b) with water or water containing an additive such as a surfactant having an HLB of 13 to 19 is performed in the step (b).
By further providing after, a highly fluid emulsion fuel can be prepared. In particular, the viscosity of the resulting mixture (100 s −1 , 25 ° C.) can be adjusted to 3000 cp or less. The obtained emulsion fuel of the present invention has a concentration of the super heavy oil in the emulsion fuel of 76.5 to 82.0% by weight, preferably 78.0 to 81.0% by weight, more preferably
78.0 to 81.0% by weight, which is an emulsion having a predetermined suitable particle size distribution.
本発明の製造方法により得られるエマルション燃料の
粒子径分布は、10%累積粒子径が1.5〜8μm、50%累
積粒子径が11〜30μm、好ましくは15〜20μm、90%累
積粒子径が25〜150μmであり、かつ150μm以上の粒子
径を有する粗粒は全エマルション燃料において3重量%
以下を占める。なお、粒子径は粒子の直径を意味する。
粒子径及び粗粒量は後述の実施例に記載の方法より測定
されるものと定義する。The particle size distribution of the emulsion fuel obtained by the production method of the present invention is such that the 10% cumulative particle size is 1.5 to 8 μm, the 50% cumulative particle size is 11 to 30 μm, preferably 15 to 20 μm, and the 90% cumulative particle size is 25 to Coarse particles having a particle diameter of 150 μm and having a particle diameter of 150 μm or more account for 3% by weight in all emulsion fuels
Occupies the following: In addition, a particle diameter means the diameter of a particle.
The particle diameter and the amount of coarse particles are defined as those measured by the methods described in Examples described later.
図1に後述の実施例1で得られたエマルション燃料の
粒子径分布を、図2に比較例1で得られたエマルション
燃料の粒子径分布を示す。図1と図2に示すエマルショ
ン燃料は、ノニオン界面活性剤の添加量を変更した以外
は同じ条件で製造したものである。図1中の本発明品の
粒子径分布は、10%累積粒子径が3.1μm、50%累積粒
子径が17.4μm、90%累積粒子径が58.1μmであり、15
0μm以上の粒子径を有する粗粒が全エマルション燃料
において1.0重量%を占めている。一方、図2中の比較
品の粒子径分布は10%累積粒子径が1.7μm、50%累積
粒子径が8.6μm、90%累積粒子径が30.0μmであり、1
50μm以上の粒子径を有する粗粒が全エマルション燃料
において0%を占めている。FIG. 1 shows the particle size distribution of the emulsion fuel obtained in Example 1 described later, and FIG. 2 shows the particle size distribution of the emulsion fuel obtained in Comparative Example 1. The emulsion fuels shown in FIGS. 1 and 2 were produced under the same conditions except that the amount of the nonionic surfactant added was changed. The particle size distribution of the product of the present invention in FIG. 1 is such that the 10% cumulative particle size is 3.1 μm, the 50% cumulative particle size is 17.4 μm, and the 90% cumulative particle size is 58.1 μm.
Coarse particles having a particle diameter of 0 μm or more account for 1.0% by weight of all emulsion fuels. On the other hand, the particle size distribution of the comparative product in FIG. 2 is such that the 10% cumulative particle size is 1.7 μm, the 50% cumulative particle size is 8.6 μm, and the 90% cumulative particle size is 30.0 μm.
Coarse particles having a particle diameter of 50 μm or more account for 0% of all emulsion fuels.
本発明の製造方法の特徴は、前記のようなノニオン界
面活性剤を主成分とした界面活性剤の添加量を超重質油
100重量部に対して、0.1〜0.6重量部、好ましくは0.1〜
0.5重量部に限定し、高剪断力で機械的混合を行い、上
記の範囲の粒子径分布を持つ、超重質油の濃度が76.5〜
82.0重量%、好ましくは78.0〜81.0重量%の超重質油エ
マルション燃料を製造することにある。このエマルショ
ン燃料は高い超重質油濃度で、流動性が良く、取扱いや
輸送が容易である。The feature of the production method of the present invention is that the addition amount of a surfactant containing a nonionic surfactant as a main component as described above is super heavy oil.
0.1-0.6 parts by weight, preferably 0.1-0.6 parts by weight, per 100 parts by weight
Limited to 0.5 parts by weight, mechanical mixing with high shear force, having a particle size distribution in the above range, the concentration of super heavy oil is 76.5 ~
It is to produce 82.0% by weight, preferably 78.0 to 81.0% by weight, of a super heavy oil emulsion fuel. This emulsion fuel has a high ultra-heavy oil concentration, good fluidity, and is easy to handle and transport.
本発明における予備混合に用いる攪拌機は、特に高剪
断力は必要とされず、プラペラ型の攪拌機等の一般の攪
拌機で十分である。予備混合した後の攪拌は高剪断型の
攪拌装置で行うことが好ましい。たとえば、ラインミキ
サー、矢羽根タービン翼ミキサー、プラペラ型翼ミキサ
ー、フルマージン型翼ミキサー、パドル翼ミキサー、高
剪断タービンミキサー、モホジナイザー、コロイドミル
等が使用できる。ここで、高剪断力とは1,000〜20,000s
-1の剪断力、さらに好ましくは4,000〜20,000s-1の剪断
力である。The stirrer used for the pre-mixing in the present invention does not particularly require a high shearing force, and a general stirrer such as a stirrer of a propeller type is sufficient. The stirring after the premixing is preferably performed by a high-shear type stirring device. For example, a line mixer, an arrow blade turbine blade mixer, a plateller type blade mixer, a full margin type blade mixer, a paddle blade mixer, a high shear turbine mixer, a homogenizer, a colloid mill and the like can be used. Here, high shear force is 1,000-20,000s
−1 , more preferably 4,000 to 20,000 s −1 .
超重質油の濃度が80重量%を超えると、エマルション
組成の粘度が高くなりすぎるので、前記のように高剪断
力による機械的混合の後に更に水又はHLBが13〜19の界
面活性剤の水溶液で希釈し、攪拌して、77〜79重量%の
超重質油濃度のエマルションにすると粘度も3000cp以
下、好ましくは2000cp以下、特に好ましくは300〜1000c
p(100s-1、25℃)となり、安定なエマルションを製造
することができる。If the concentration of the super heavy oil exceeds 80% by weight, the viscosity of the emulsion composition becomes too high, so that after mechanical mixing by high shear force as described above, water or an aqueous solution of a surfactant having an HLB of 13 to 19 is further added. And then stirred to form an emulsion with a super heavy oil concentration of 77 to 79% by weight, the viscosity is also 3000 cp or less, preferably 2000 cp or less, particularly preferably 300 to 1000 c
p (100 s −1 , 25 ° C.), and a stable emulsion can be produced.
以下、実施例及び比較例により本発明をさらに詳しく
説明するが、本発明の範囲をこれらに限定するものでは
ない。Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereto.
実施例1〜15及び比較例1〜4 800mlのステンレス製容器に所定量の水、アスファル
ト(コスモ石油製、JISK−2207のストレートアスファル
ト、針入度80〜100)、表1〜3に示す界面活性剤及び
/又は安定化剤を採取し、恒温水槽にて所定の温度まで
加温して、予備混合(ダブルヘリカルリボン翼の攪拌機
を用いて、回転数60rpmで5分間混合)した。その後、
得られる混合物を、T.K.ホモミキサーのM型(低粘度攪
拌翼付き、特殊機加工製)を使って混合し、乳化して、
次の条件でエマルション燃料を製造した。Examples 1 to 15 and Comparative Examples 1 to 4 In a 800 ml stainless steel container, a predetermined amount of water and asphalt (Cosmo Oil, straight asphalt of JISK-2207, penetration 80 to 100), interfaces shown in Tables 1 to 3 The activator and / or stabilizer was collected, heated to a predetermined temperature in a constant temperature water bath, and premixed (mixed at 60 rpm for 5 minutes using a double helical ribbon blade stirrer). afterwards,
The resulting mixture is mixed and emulsified using a TK homomixer M-type (with low viscosity stirrer, manufactured by special machine processing),
An emulsion fuel was manufactured under the following conditions.
製造条件は、攪拌回転数8000rpm、攪拌時間2分間、
温度80℃であり、剪断力は12000/秒である。水の比重は
0.997(25℃)、油の比重は1.026(25℃)である。粘度
の測定は25℃で二重円筒型回転粘度計RV−2型(センサ
ーMV−1、ハーケ社製)を使って、100/秒の剪断力で測
定した。The production conditions were as follows: stirring speed 8000 rpm, stirring time 2 minutes,
The temperature is 80 ° C. and the shearing force is 12000 / sec. The specific gravity of water is
0.997 (25 ° C), specific gravity of oil is 1.026 (25 ° C). The viscosity was measured at 25 ° C. using a double cylinder type rotary viscometer RV-2 (Sensor MV-1, manufactured by Haake) at a shearing force of 100 / sec.
得られたエマルション燃料の粒子径はグラニュロメー
ターHR850−B型が(シーラス社製)を用いて測定し、1
0%累積粒子径(平均の粒子直径)、50%累積粒子径
(平均の粒子直径)及び90%累積粒子径(平均の粒子直
径)を算出した。The particle size of the obtained emulsion fuel was measured using a granulometer HR850-B type (manufactured by Cirrus).
The 0% cumulative particle diameter (average particle diameter), the 50% cumulative particle diameter (average particle diameter), and the 90% cumulative particle diameter (average particle diameter) were calculated.
具体的には、粒子径は、次の方法によりなされた。0.
3重量%のノニオン界面活性剤(ポリオキシエチレン(2
0モル)ノニルフェニルエーテル)を含有する水溶液中
にエマルション燃料を数滴滴下し、得られた混合物液を
スターラーで攪拌して均一な混合液とし、これを上記の
粒度測定装置中に入れ、粒度を測定した。測定モードは
1〜600μmに設定した。Specifically, the particle size was determined by the following method. 0.
3% by weight of nonionic surfactant (polyoxyethylene (2
0 mol) Nonyl phenyl ether) is dropped into the aqueous solution containing the emulsion fuel, and the resulting mixture is stirred with a stirrer to form a uniform mixture. Was measured. The measurement mode was set to 1 to 600 μm.
粗粒量は、湿式篩にて、粒子径が150μm以上の成分
を測定した。具体的には、エマルションを20g秤量後、
篩上に注ぎ込み、水をかけて洗浄後、真空乾燥機で乾燥
した。乾燥後の篩に残った量を測定し、粗粒量を算出し
た。1日後、1週間後、1ケ月後の安定性は沈降物の量
で評価した。さらに、総合評価は、エマルション燃料の
粘度、10%累積粒子径、50%累積粒子径、90%累積粒子
径、粗粒分率、及びエマルション安定性を総合的に評価
してなされたものであり、次の基準により判定した。As for the amount of coarse particles, a component having a particle diameter of 150 μm or more was measured with a wet sieve. Specifically, after weighing 20 g of the emulsion,
The mixture was poured onto a sieve, washed with water, and dried with a vacuum drier. The amount remaining on the screen after drying was measured, and the amount of coarse particles was calculated. The stability after 1 day, 1 week and 1 month was evaluated by the amount of sediment. Furthermore, the comprehensive evaluation was made by comprehensively evaluating the emulsion fuel viscosity, 10% cumulative particle size, 50% cumulative particle size, 90% cumulative particle size, coarse particle fraction, and emulsion stability. Was determined according to the following criteria.
◎:非常に良好、 ○:良好 △:若干効果あり、並びに ×:効果なし。◎: very good, :: good Δ: slightly effective, ×: no effect.
表1〜3より明らかなように、本発明の方法により得
られたエマルション燃料は超重質油濃度が高く、かつ安
定性の優れたものであった。これに対し比較例で得られ
たエマルションは超重質油濃度が低く、高超重質油濃度
においても安定性の劣るものであった。 As is clear from Tables 1 to 3, the emulsion fuel obtained by the method of the present invention had a high concentration of super heavy oil and was excellent in stability. On the other hand, the emulsion obtained in the comparative example had a very low heavy oil concentration and was inferior in stability even at a high very heavy oil concentration.
産業上の利用可能性 本発明の製造方法によれば、超重質油濃度が高くかつ
流動性があり、取扱いが容易で、しかも安定な超重質油
エマルション燃料を簡易に製造することができる。INDUSTRIAL APPLICABILITY According to the production method of the present invention, it is possible to easily produce a stable superheavy oil emulsion fuel which has a high concentration of superheavy oil, has fluidity, is easy to handle, and is stable.
以上に述べた本発明は、明らかに同一性の範囲のもの
が多種存在する。そのような多様性は発明の意図及び範
囲から離脱したものとはみなされず、当業者に自明であ
るそのようなすべての変更は、以下の請求の範囲の技術
範囲内に含まれる。In the present invention described above, there are various types in the range of obvious identity. Such variations are not considered to be a departure from the spirit and scope of the invention, and all such changes that are obvious to those skilled in the art are included within the scope of the following claims.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 一の瀬 利光 長崎県長崎市深堀町5丁目717番1号 三菱重工業株式会社長崎研究所内 (72)発明者 坂本 康一 東京都千代田区丸の内2丁目5番1号 三菱重工業株式会社内 (58)調査した分野(Int.Cl.6,DB名) C10L 1/32 C10L 1/12 WPI/L(QUESTEL)──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Toshimitsu Ichinose 5-717-1 Fukahori-cho, Nagasaki-shi, Nagasaki Mitsubishi Heavy Industries, Ltd. Nagasaki Research Institute (72) Inventor Koichi Sakamoto 2-5-2 Marunouchi, Chiyoda-ku, Tokyo No. 1 Inside Mitsubishi Heavy Industries, Ltd. (58) Field surveyed (Int. Cl. 6 , DB name) C10L 1/32 C10L 1/12 WPI / L (QUESTEL)
Claims (8)
水性親油性バランス)が13〜19のノニオン界面活性剤0.
1〜0.6重量部と水を、超重質油に加え、均一な混合液を
調製する工程であり、必要に応じてアニオン界面活性剤
またはカチオン界面活性剤をさらに添加するが、前記ノ
ニオン界面活性剤と前記アニオン界面活性剤の合計量ま
たは前記ノニオン界面活性剤と前記カチオン界面活性剤
の合計量は、超重質油100重量部に対して0.1〜0.6重量
部であり、または前記アニオン界面活性剤または前記カ
チオン界面活性剤の量は、ノニオン界面活性剤100重量
部に対して100重量部以下である工程と、 (b)高剪断力による均一な混合液の機械的混合を行っ
て、10%累積粒子径が1.5〜8μm、50%累積粒子径が1
1〜30μm、90%累積粒子径が25〜150μmであり、かつ
150μm以上の粒子径を有する粗粒が全エマルション燃
料において3重量%以下を占める粒子径分布である、超
重質油濃度が76.5〜82.0重量%である超重質油エマルシ
ョン燃料を得る工程と、からなる超重質油エマルション
燃料の製造方法。1. A nonionic surfactant having an HLB (hydrophilic-lipophilic balance) of 13 to 19 with respect to 100 parts by weight of an ultra-heavy oil.
1 to 0.6 parts by weight and water are added to the ultra-heavy oil to prepare a uniform mixture, and if necessary, an anionic surfactant or a cationic surfactant is further added, but the nonionic surfactant is added. The total amount of the anionic surfactant or the total amount of the nonionic surfactant and the cationic surfactant is 0.1 to 0.6 parts by weight based on 100 parts by weight of the heavy oil, or the anionic surfactant or (B) performing a mechanical mixing of a uniform mixture by high shearing force, wherein the amount of the cationic surfactant is 100 parts by weight or less based on 100 parts by weight of the nonionic surfactant; Particle size is 1.5-8 μm, 50% cumulative particle size is 1
1-30 μm, 90% cumulative particle size is 25-150 μm, and
Obtaining a super-heavy oil emulsion fuel having a super-heavy oil concentration of 76.5 to 82.0% by weight, in which a coarse particle having a particle diameter of 150 μm or more accounts for 3% by weight or less in the whole emulsion fuel. A method for producing an ultra heavy oil emulsion fuel.
び合成高分子からなる群より選択された高分子化合物、
又は水膨潤性粘土鉱物をノニオン界面活性剤の配合量を
超えない範囲で添加する、請求項1記載の製造方法。2. A polymer compound selected from the group consisting of a natural polymer and a synthetic polymer in the step (a).
The method according to claim 1, wherein the water-swellable clay mineral is added within a range not exceeding the amount of the nonionic surfactant.
重量部に対してマグネシウム、カルシウム及び鉄の酸化
物、マグネシウム、カルシウム及び鉄の水酸化物並びに
マグネシウム、カルシウム及び鉄の塩からなる群より選
ばれた1種以上の化合物0.01〜0.5重量部を添加する、
請求項1又は2記載の製造方法。3. The method according to claim 1, wherein the step (a) further comprises:
0.01 to 0.5 parts by weight of one or more compounds selected from the group consisting of magnesium, calcium and iron oxides, magnesium, calcium and iron hydroxides and magnesium, calcium and iron salts are added to parts by weight. Do
The method according to claim 1.
行う、請求項1〜3いずれか記載の製造方法。4. The method according to claim 1, wherein the mechanical mixing is performed with a shearing force of 1,000 to 20,000 s −1 .
9の界面活性剤等の添加剤を含有する水により希釈し
て、得られる混合物の粘度(100s-1、25℃)を3000cp以
下に調整する工程 を有する、請求項1〜4いずれか記載の製造方法。5. After the step (b), (c) further adding water or HLB of 13 to 1 to the mixture obtained in the step (b).
The method according to any one of claims 1 to 4, further comprising a step of diluting with water containing an additive such as the surfactant of No. 9 to adjust the viscosity (100 s −1 , 25 ° C.) of the obtained mixture to 3000 cp or less. Production method.
求項1〜5いずれか記載の製造方法。6. The method according to claim 1, wherein the concentration of the super heavy oil is 78.0 to 81.0% by weight.
のアルキレンオキシド付加物である請求項1〜6のいず
れか記載の製造方法。7. The method according to claim 1, wherein the nonionic surfactant is an alkylene oxide adduct of an alkyl phenol.
塩、リグニンスルホン酸とナフタリンスルホン酸のホル
マリン縮合物、又はそれらの塩、及びナフタリンスルホ
ン酸塩のホルマリン縮合物からなる群より選ばれた1種
以上の化合物である請求項1記載の製造方法。8. An anionic surfactant selected from the group consisting of lignin sulfonic acid salt, formalin condensate of lignin sulfonic acid and naphthalene sulfonic acid, or a salt thereof, and formalin condensate of naphthalene sulfonic acid salt. The production method according to claim 1, which is the above compound.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8531325A JP2860390B2 (en) | 1995-06-01 | 1996-05-27 | Method for producing super heavy oil emulsion fuel |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7/159948 | 1995-06-01 | ||
JP7-159948 | 1995-06-01 | ||
JP7159948A JPH08325582A (en) | 1995-06-01 | 1995-06-01 | Production of superheavy oil emulsion fuel |
JP8531325A JP2860390B2 (en) | 1995-06-01 | 1996-05-27 | Method for producing super heavy oil emulsion fuel |
2000-02-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH10508898A JPH10508898A (en) | 1998-09-02 |
JP2860390B2 true JP2860390B2 (en) | 1999-02-24 |
Family
ID=26486595
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8531325A Expired - Lifetime JP2860390B2 (en) | 1995-06-01 | 1996-05-27 | Method for producing super heavy oil emulsion fuel |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2860390B2 (en) |
-
1996
- 1996-05-27 JP JP8531325A patent/JP2860390B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH10508898A (en) | 1998-09-02 |
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