US2225824A - Process for resolving petroleum emulsions - Google Patents
Process for resolving petroleum emulsions Download PDFInfo
- Publication number
- US2225824A US2225824A US247002A US24700238A US2225824A US 2225824 A US2225824 A US 2225824A US 247002 A US247002 A US 247002A US 24700238 A US24700238 A US 24700238A US 2225824 A US2225824 A US 2225824A
- Authority
- US
- United States
- Prior art keywords
- acid
- radical
- amine
- naphthalene
- employed
- 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 description 21
- 238000000034 method Methods 0.000 title description 19
- 230000008569 process Effects 0.000 title description 15
- 239000003208 petroleum Substances 0.000 title description 13
- -1 alicyclic radical Chemical class 0.000 description 63
- 150000001412 amines Chemical class 0.000 description 62
- 239000002253 acid Substances 0.000 description 51
- 125000004432 carbon atom Chemical group C* 0.000 description 32
- 150000003254 radicals Chemical class 0.000 description 26
- 239000003921 oil Substances 0.000 description 25
- 150000007513 acids Chemical class 0.000 description 20
- 235000019198 oils Nutrition 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 15
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- 235000014113 dietary fatty acids Nutrition 0.000 description 13
- 239000000194 fatty acid Substances 0.000 description 13
- 229930195729 fatty acid Natural products 0.000 description 13
- 150000002790 naphthalenes Chemical class 0.000 description 13
- 238000006386 neutralization reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000004359 castor oil Substances 0.000 description 12
- 229960001777 castor oil Drugs 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 150000004665 fatty acids Chemical class 0.000 description 12
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 12
- 235000019438 castor oil Nutrition 0.000 description 11
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229940075566 naphthalene Drugs 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 150000003460 sulfonic acids Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 125000005456 glyceride group Chemical group 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical group CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
- 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 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N alpha-naphthol Natural products C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000003974 aralkylamines Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical compound O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical class CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000011347 resin Chemical class 0.000 description 2
- 229920005989 resin Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 239000011289 tar acid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NDYMQOUYJJXCKJ-UHFFFAOYSA-N (4-fluorophenyl)-morpholin-4-ylmethanone Chemical compound C1=CC(F)=CC=C1C(=O)N1CCOCC1 NDYMQOUYJJXCKJ-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VPGSXIKVUASQIY-UHFFFAOYSA-N 1,2-dibutylnaphthalene Chemical compound C1=CC=CC2=C(CCCC)C(CCCC)=CC=C21 VPGSXIKVUASQIY-UHFFFAOYSA-N 0.000 description 1
- GIVMKUUIXYEXLH-UHFFFAOYSA-N 1,2-didecylnaphthalene Chemical compound C1=CC=CC2=C(CCCCCCCCCC)C(CCCCCCCCCC)=CC=C21 GIVMKUUIXYEXLH-UHFFFAOYSA-N 0.000 description 1
- VOMPMOXLDNRRRY-UHFFFAOYSA-N 1,2-dihexylnaphthalene Chemical compound C1=CC=CC2=C(CCCCCC)C(CCCCCC)=CC=C21 VOMPMOXLDNRRRY-UHFFFAOYSA-N 0.000 description 1
- BHWJEYCAUWCFDA-UHFFFAOYSA-N 1-aminodecan-2-ol Chemical compound CCCCCCCCC(O)CN BHWJEYCAUWCFDA-UHFFFAOYSA-N 0.000 description 1
- XRJWGFXUIIXRNM-UHFFFAOYSA-N 1-hexylnaphthalene Chemical compound C1=CC=C2C(CCCCCC)=CC=CC2=C1 XRJWGFXUIIXRNM-UHFFFAOYSA-N 0.000 description 1
- RSZXXBTXZJGELH-UHFFFAOYSA-N 2,3,4-tri(propan-2-yl)naphthalene-1-sulfonic acid Chemical class C1=CC=CC2=C(C(C)C)C(C(C)C)=C(C(C)C)C(S(O)(=O)=O)=C21 RSZXXBTXZJGELH-UHFFFAOYSA-N 0.000 description 1
- QBVUJLCYWCECLY-UHFFFAOYSA-N 2,3,4-tripropylnaphthalene-1-sulfonic acid Chemical class C1=CC=CC2=C(CCC)C(CCC)=C(CCC)C(S(O)(=O)=O)=C21 QBVUJLCYWCECLY-UHFFFAOYSA-N 0.000 description 1
- KBLAMUYRMZPYLS-UHFFFAOYSA-N 2,3-bis(2-methylpropyl)naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(O)(=O)=O)=C(CC(C)C)C(CC(C)C)=CC2=C1 KBLAMUYRMZPYLS-UHFFFAOYSA-N 0.000 description 1
- LWEAHXKXKDCSIE-UHFFFAOYSA-N 2,3-di(propan-2-yl)naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(O)(=O)=O)=C(C(C)C)C(C(C)C)=CC2=C1 LWEAHXKXKDCSIE-UHFFFAOYSA-N 0.000 description 1
- QZEDXQFZACVDJE-UHFFFAOYSA-N 2,3-dibutylnaphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(O)(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 QZEDXQFZACVDJE-UHFFFAOYSA-N 0.000 description 1
- JIAGYOWSALSPII-UHFFFAOYSA-N 2,3-dioctylnaphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(O)(=O)=O)=C(CCCCCCCC)C(CCCCCCCC)=CC2=C1 JIAGYOWSALSPII-UHFFFAOYSA-N 0.000 description 1
- XHHIVYOGJCWWCG-UHFFFAOYSA-N 2,3-dipropylnaphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(O)(=O)=O)=C(CCC)C(CCC)=CC2=C1 XHHIVYOGJCWWCG-UHFFFAOYSA-N 0.000 description 1
- YRJSLCBKZMMEPB-UHFFFAOYSA-N 2-(2-methylpropyl)naphthalene-1-sulfonic acid Chemical class C1=CC=CC2=C(S(O)(=O)=O)C(CC(C)C)=CC=C21 YRJSLCBKZMMEPB-UHFFFAOYSA-N 0.000 description 1
- LLTGNYZQUXACFO-UHFFFAOYSA-N 2-(dicyclohexylamino)ethanol Chemical compound C1CCCCC1N(CCO)C1CCCCC1 LLTGNYZQUXACFO-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- NDLNTMNRNCENRZ-UHFFFAOYSA-N 2-[2-hydroxyethyl(octadecyl)amino]ethanol Chemical compound CCCCCCCCCCCCCCCCCCN(CCO)CCO NDLNTMNRNCENRZ-UHFFFAOYSA-N 0.000 description 1
- BMRVLXHIZWDOOK-UHFFFAOYSA-N 2-butylnaphthalene-1-sulfonic acid Chemical class C1=CC=CC2=C(S(O)(=O)=O)C(CCCC)=CC=C21 BMRVLXHIZWDOOK-UHFFFAOYSA-N 0.000 description 1
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- ZTFYJIXFKGPCHV-UHFFFAOYSA-N 2-propan-2-ylnaphthalene-1-sulfonic acid Chemical class C1=CC=CC2=C(S(O)(=O)=O)C(C(C)C)=CC=C21 ZTFYJIXFKGPCHV-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 101100440696 Caenorhabditis elegans cor-1 gene Proteins 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZEMPKEQAKRGZGQ-UHFFFAOYSA-N Triricinolein Natural products CCCCCCC(O)CC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCC(O)CCCCCC)COC(=O)CCCCCCCC=CCC(O)CCCCCC ZEMPKEQAKRGZGQ-UHFFFAOYSA-N 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- OVXRPXGVKBHGQO-UHFFFAOYSA-N abietic acid methyl ester Natural products C1CC(C(C)C)=CC2=CCC3C(C(=O)OC)(C)CCCC3(C)C21 OVXRPXGVKBHGQO-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000010640 amide synthesis reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- CYGKLLHTPPFPHH-UHFFFAOYSA-N aniline;hydrate Chemical compound O.NC1=CC=CC=C1 CYGKLLHTPPFPHH-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- QVGBMEWCSSIAIC-UHFFFAOYSA-N cyclohexanol 2-(2-hydroxyethylamino)ethanol Chemical compound N(CCO)CCO.C1(CCCCC1)O QVGBMEWCSSIAIC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000011928 denatured alcohol Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- OVXRPXGVKBHGQO-UYWIDEMCSA-N methyl (1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound C1CC(C(C)C)=CC2=CC[C@H]3[C@@](C(=O)OC)(C)CCC[C@]3(C)[C@H]21 OVXRPXGVKBHGQO-UYWIDEMCSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- MDLWEBWGXACWGE-UHFFFAOYSA-N octadecane Chemical compound [CH2]CCCCCCCCCCCCCCCCC MDLWEBWGXACWGE-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229950004864 olamine Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000005254 oxyacyl group Chemical group 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TYRGSDXYMNTMML-UHFFFAOYSA-N propyl hydrogen sulfate Chemical compound CCCOS(O)(=O)=O TYRGSDXYMNTMML-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical class N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- ZEMPKEQAKRGZGQ-VBJOUPRGSA-N triricinolein Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC)COC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-VBJOUPRGSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
Definitions
- This invention relates primarily to the treatment of emulsions of mineral oil and water, such as petroleum emulsions, for the purpose of separating the oil from the water.
- One object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oll type. that are commonly re- 'ferred to as cut oil," roily oil,” “emulsified oil,”
- Another object of our invention is to provide an" economical and rapid process for separating J emulsions which have been prepared under controlled conditions frommineral oils, such as crude I vpetroleum and. relatively soft waters or weak brines. Controlled emulsiflcation and subsequent demulsification under the conditions just mentioned is'of significant value in removing impurities, particularly inorganic salts, from pipeline oil.
- the demulsi'fyingagent employed in our process is a new compound or composition of matter consisting of a certain kind of salt derived from ;a surface-active esterified amine of the kind hereinafter described and an alkylated naphthalene sulfonic acid of the kind in which. there is at least one alkyl group substituted in the naphthalene nucleus, the said alkyl group or groups in three carbon atoms and not more than ten carbon atoms.
- alkylated sulfonic acid can be described by the following formula:
- radical C2H4 which appears in the above formula, may represent any similar radical, such' as a C3Ha radical, a C4H8 radical,
- R.COO represents the oxy-acyl radical derived from a monobasic detergent-forming acid
- T represents a hydrogen atom or a nonhydroxy hydrocarbon radical, or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than eight carbon atoms
- 11. represents a small whole number, which is less than 10
- m represents the numeral 1, 2, or 3
- m' represents the numeral 0, 1, or 2
- 112.” represents the numeral 0, 1, or 2, with the proviso that m+m'+m" equals 3.
- T represents a hydrogen atom, or a nonhydroxy aliphatic hydrocarbon radical, such as a methyl radical, ethyl radical, propyl radical, amyl radical, octadecyl radical, etc.
- T may also represent a non-hydroxy alicyclic radical, such as a cyclohexyl radical or a non-hydroxy aralkyl radical, such as a benzyl radical; or T may represent the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical, or the equivalent thereof, by the acyl radical of a monobasic carboxy acid, such as acetic acid, butyricacid, heptoic acid, or the like; all of which. are characterized by having less than eight carbon atoms.
- the alkylol radical prior to acylation may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided the hydroxy radical is attached to the aliphatic residue of the aralkyl radical.
- R.COO represents the oxy-acyl or acid radical derived from the acid RCOOH.
- R.COOH represents any monobasic detergent-forming car-boxy acid, such as a typical fatty acid or abietic acid or naphthenic acid. 4
- Typical fatty acids are those which occur in naturally-occurring oils and fats, and generallyhave eight or more carbon atoms and not over 32 carbon atoms. Common examples include oleic acid, stearic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid, palmitic acid, myristic acid, etc. producesoap or soap-like materials, and are commonly referred to as being monobasic detergentforming carboxy acids.
- the alkylol radical may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided the hydroxy radical is attached to the aliphatic residue of the aralkyl radical.
- Other examples include cyclohexyloiamine, dicyclohexylolamine, cyclohexyl 'ethanolamlne, 'cyclo .hexyl propanolamine, 'benzylethanolami ne, benzylpro'panolamine, pentanclamine, hexanolamine,
- amines may serve a's'the obvious functional equivalents of the previously described aminesand which are free from an ether linkage.
- amines are not quaternary ammonium basesor salts thereof.
- the expression quaternary ammonium is properly and con octylethanolamine;octadecylethanolamine, cyclo- .
- suitable tertiary amines which may be employed include the following: triethanolamine, diethanolalkylamines, such as diethanol ethylamine, diet'hanol prop'ylamine', etc.
- Other examples include dlethanol, methylamine, tripropanoiamine, dipropanol methylamine, cyclohexanol diethanolamine, dicyclohena'nol ethanolamine, cyclol1exyl diethanol'amine, dicyclohexyl ethanolamine, dicyclohexanol ethylamine, benzyl diethanolbenzyl dipropanolamine,- tripentanolamine, trihexanolamine, hexyl" ethanoiamine,. octadecyl diethanolamine, polyethanolamine, etc.
- a st be recognized is, that these amine com-' the mmpounds used as ventionaliy applied 'to compounds in which all four hydrogen atoms of the ammonium radical NH4 have been replaced by a hydrocarbon radical or, oxy-hydrocarbon radical, as, for example, in t'rimethyl phenyl ammonium hydroxide.
- basi6-is employed .to excludetamines having little or no baslcity such as,
- benzylamlne is the primary amine, phenmethyl amine.
- a suitable non-aryl radical other than an aliphatic residue may serve as the functional equivalent; for instance, an 'alicyclic radical derived from a cyclohexyl radical, or an aralkyl radical derived from a benzyl radical.
- references to the C1121: radical as such,.or as an alkyl radical or residue is intended in the broad sense to include the alicyclic radicals or residues, or the I aralkyl" radicals or residues which are the equivalent thereof.
- an aromatic radical where there is a direct linkage between the aromatic nucleus and the amino hydrogen atom, for the reason that such products have little or no basicity and do not have the characteristic properties of the amines previously described.
- hydroxylated primary or secondary amines of the nonaryl type which may be employed to produce the amine contemplated as the demulsifying agent of the present process
- amines-of the type where a hydroxy acyl radical replaces a hydrogen atom of the hydroxyl radical of a. hydroxy primary or secondary amine are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual alkyl radical.
- ethanolamine is treated with lactic acid so as to form the lactyl derivative of the following formula;
- the manufacture of compounds from tertiary amines is relatively simple, because no precautions are necessary to prevent amidification.
- the selected detergent-forming acid, or ester as, for example, a fatty oiland the selected hydroxy tertiary amine, are mixed in' suitable proportions and heated at some point above the boiling point of water, for instance, 110 C., and at a point below the decomposition, point of the amine or the fatty oil, for instance, 180 C., for a suitable period of time, such as two to eight hours. Mild agitation is employed.
- a catalyst such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about one-half of 1%, or less.
- an ester of abietic acid or naphthenic acid might be employed, if desired.
- esterification When, however, one is employing a hydroxy secondary amine, precautions must be taken, so that one gets a substantial percentage of products derived by esterification, rather than amidification. Anysuitable ester may be employed, but it is often most convenient to employ the glyceride of a fatty acid, for instance, triricinolein.
- the selected glyceride and the selected hydroxy secondary amine are mixed in suitable proportions and heated at some point above the 'boiling point of water, for instance, 110 C., and below the decomposition point of the amine or fatty material, for instance, 180 0., for a suitable period of time, such-as 4-24 hours. Mild agitation is employed.
- A- catalyst such .as sodium oleate, sodium carbonate, caustic soda, etc., may
- fatty acids are present in ester form and not in the form of the free acid
- Example 10 B enzyl diethanolamine is substituted for ethyl diethanolamine in Example 8 above.
- Example 11 f Castor oil (triricinoleinl is employed. "Fer convenience its molecular weight is considered n as being 925.v Commercial diethanolamine and castor oil in the proportion of one'mole' of castor oil to threemolesof diethanolamine, are heated to a temperature of 120440 0., for about twelve hours. Mild agitation is employed. Loss of ,basicity is an indication of amidification. Time of. esteriiication may be extended or temperature castor oil to three.-
- naphthalene derivative such as chlor-naphthalene, alpha and beta naphthol'. etc.
- a substituted naphthalene such as chlor-naphthalene, etc.
- naphthalene is hereinafter employed to include these derivatives.
- the general process of manufacturing the particular salts used to produce the de'mulsanderr employed in our process consists in converting the naphthalene into either the alpha or beta naphthalene sulfonic acid, or a mixture of the? same,
- the alcohol employed such as propyl alcohol, a butyl alcohol, an amyl alcohol, a hexyl alcohol, a decyl alcohol, etc.
- the acid sulfate such as propyl hydrogen sulfate.
- the naphthalene sulfonic acid and the alkyl hydrogensulfate are combined in proportions so that one, two, three, or even four alkyl groups are introduced into the aromatic residue.
- This condensation reaction is generally carried out in the presence of an excess of sulfuric acid.
- the various reactions, such as sulfonation, sulfation, condensation, etc. are carried out simultaneously.
- the dialkylated and tri-alkylated material appear to yield the most desirable type of reagent.
- Thepresence of some mono-alkylated material is to yield the most desirable type of reagent. Thepresence of some mono-alkylated material,
- tetra-alkylated material is not objec- 40 tionable, and may even be desirable.
- alkylated groups introduced might be derived from olefines, such as butylene, propylene, amylene, etc., insofar that such olefines react directly with sulfuric acid, to produce the alkyl hydrogen sulfates.
- olefines such as butylene, propylene, amylene, etc.
- an alkylated group derived from ethyl or methyl alcohol or one might introduce a group derived from an aryl, aralkyl cyclic, or hydroaromatic alcohol, or the like, but regardless of whether or not one introduces suchother residues, it is necessary that at least one alkyl residue of the kind described, 1. e., having at least three carbon atoms and not more than ten carbon atoms, be introduced into the naphthalene ring.
- the composition of the desired chemical reaction is followed by a washing process which removes the excess of sul- 25 furic acid or other sulfonation, sulfation, or condensation reagent employed.
- the acidic mass thus obtained is neutralized in any convenient manner with any suitable base, such as ca'ustic soda, caustic potash, ammonium hydroxide, and 36 the like.
- the acidic mass is neutralized with the amine of the kind previously described.
- the resulting mixture consists, largely of dipropyl naphthalene sulfonic acids and tri-propyl naphthalene sulfonic acids, with possibly small amounts of mono-propyl sulfonic acids and tetra- 50 propyl sulfonic acids present Generally speak- -ing, it is easier to conduct the reaction so that thebulk of the sulfonic acid represents the beta type, although the alpha type may be produced, if desired.
- the product is neutralized with a com- 55 plex amine of the kind typified by Examples 1,2,
- the solvents which we 60 preferably employ are a'mixture of two or more of the following: Water, denatured alcohol, kerosene, or tar acid oil.
- reagents which are particularly effective are the salts formed by reaction between 65. amines of th kind exemplified by Examples 1-12,
- alkylated naphthalene sulfonic acids i. e., mono-isopropyl naphthalene sulfonic acids, di-isopropyl naphthalene sulfonic acids, tri-isopropyl naphthalene sulfonic acids, mono-normal butyl naphthalene sulfonic acids, di-normal butyl naphthalene sulfonic acids, mono-isobutyl naphthalene sulfonic acids, di-isobutyl naphthalene sulfonic acids, mono- ,amyl-napht-halene sulfonic acids, di-amyl naphthaiene sulfonic acids, tri-aniyl naphthalene sulfonic acids, monohexyl naphthalene sulionic acids, di-hexyl naphthalene suli
- more thanone'sulfonic acid radical as in'the formation oi. a disuli'onic acid, or a; trisulfonic acid, or a tetrasulfonic acid, ii desir'ed, allth'e sultonic sulfonic acids, di-isopropyl mono-amyl naphthalene sulfonicacids, mono-isopropyl mono-hexyl radicals may be neutralized wlthamines oi!
- sulionic acid radicals may be neutralized with some" other 20 suitable base, 'such as a sodium hydroxide, potassium hydroxide, ammonium hydroxide, etc., provided that at least one 'sulfonlc acid radical has been neutralized by amines or the kind previously described, f
- demulsii'ying agents employedfin the treatmentot oil fleld emulsions are used as such, or after'dilution with any suitable solvent, such; as water, petroleum hydrocarbons, such as gasoline, kerosene-stove oil, a coal tar product, such as benzene, toluene, xylene, tar acid oil,
- demulsifying agents may be used in a water-soluble form, or man oil-solubleform, or in a form exhibiting may be used in aiorm which exhibits relatively limited water solubility and relatively limited oil solubility.
- reagents are sometimes used-in a ratio of 1 to 10,000,;or 1 to 20,000,.or even-1 to 30,000, such an apparent insolubility in ,oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same factis true in regard to the material or materials employed as the demulsifyingagent of our process.
- vents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc.
- the material orimaterials employed as the demulsiiying agent of'our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsiiying agents.
- said material or materials may be used alone or inadmixture with other suitable well known classes of demuisifying agents, such as demulsiiying agents of the modi- I fled fatty acid type, complex amine type, the petroleum sulfonate type, the alkylated suli'o-aromatictype, neutralized in the conventional man:
- neutralization oi. the" alkylated sulfonic acidwith the complex amine need not necessarily take place in. stoichiometrical rela? tionship, but one may employ an excessot the sulfonic acid or or the amine.
- salts made by direct neutralization but of course can -'be producedfju'st as eflectively by some other means. For instance, a double decomposition reactionmay be, utilized, i.
- the amine hydrochloride and the sodiumor potassium salt of the sulionic acid might each-be dissolved in a hydrophobe solvent, such as an alcohol and mixed with or the kind'herein contemplated need not be has been indicated previously, in essence, We have discovered that if a suitable alkylated naphthalene sulfonic acid is neutralized with an amine of the kind described, one obtains an unusual reagent, to wit, one characterized by having both a surface-active anionand a surface-active cation;
- a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifying agent comprising a product of the kind derivable by neutralization reaction between (A) a surface-active amine of the formula type in which R.COO represents the oxy-acyl radical derived from amonobasic detergent-forming acid; T represents a hydrogen atom or a nonhydroxy hydrocarbon radical or the acylated radical obtained by replacing-a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid H having less than eight carbon atoms; n represents a small whole number which is less than 10; 112 represents the numeral 1, 2, or 3; m represents the numeral 0, 1,'or 2;.
- naphthalene nucleus contains at least -three carbon atoms and not morethan 10 carbon atoms.
- a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifying agent comprising'a product of the kind derivable by neutralization reaction between (A) a surface-active amine of the formula type in which R.COO represents the oxy-acyl radical derived from a fatty acid having at least 8 and not more than 32 carbon atoms; T represents a hydrogen atom .orv a non-hydroxy hydrocarbon radical or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an -alkylol radical by the acyl radical of a monobasic carboxy acid having less than eight carbon atoms; n represents a small whole number which is less than 10; m represents the numeral 1, 2, or 3 m represents the numeral 0, 1, or 2; and m" represents the numeral 0, 1, or 2, with the proviso that m+m'+m" equals 3; and (B) a surfaceactive
- a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifying agent comprising a product of the kind derivable-by neutralization reaction between (A) a surface-active amine of the formula type (R.o00.o,.Hz.)..
- R.COO represents the oxy-acyl radical derived from a fatty acid having at least 8 and not more than 32 carbon atoms
- '1' represents a hydrogen atom or anon-hydroxy hydrocarbon radical or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than eight carbon atoms
- n represents a small whole number which is less than 10
- m represents the numeral 1, 2, or 3
- m represents the numeral 0, 1, or 2
- m" represents the numeral 0, 1, or 2, with the proviso that m+m'+m” equals 3
- B a sur-' face-active
- R.COO represnts the boxyacyl radical derived troma fatty acid having at least 8 and not more than 32 carbon atoms
- T represents a hydrogen atom or a non-hydroxy hydrocarbon radical or the acylated radical obtained by replacinga hydrogen atom ofthe hydroxyl group of an alkylol radical by the acyl radical of a-monobasic carboxy acid having less than eight carbon atoms
- m represents the numeral 1, 2, or 3;
- naphthalene nucleus contains at least three carbon atoms and not more than 10 carbon atoms.
- demulsi1ying agent comprising a product oi the kind derivable by neutralization reaction between (A) a surfaceactive amine of the formula type (R.CO0.C1H
- R.COO represents the oxy-acyl radical derived from a Iatty'acid having at least 8 and not more than 32 carbon atoms
- m represents the numeral 1, 2, or 3
- B a surface-active alkylated naphthalene monosulfonic acid in which at least one alkyl group substituted in the naphthalene.
- nucleus contains at-leastfthree carbon atoms and' not more than carbon atoms.
- a process-for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsiiysurface-active amine of the formula type m ce 0.0m.
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Description
I Patented Dec.
i T D S TES PATENT arm: I i 4 I mocnssron nizi fiw rn'raoLnUM it i EMULSIONS Melvin ne Groote, University City, and Arthur F; Wirtei, Klrkwood, Mm, assignors, by mesne asvsignments, to Petrolite Corporation, Ltd., a cor- 1 poration of Delaware I No Drawing.v Application December 21, 1 938,
, Serial No. 247,002 7 I g I o n 7 Claims;
This invention relates primarily to the treatment of emulsions of mineral oil and water, such as petroleum emulsions, for the purpose of separating the oil from the water.
One object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oll type. that are commonly re- 'ferred to as cut oil," roily oil," "emulsified oil,"
,etc., and whichcomprise fine droplets of. natu-' rally-occurring waters or brines dispersed in a more or less permanent state throughout the oil 'which constitutes the continuous phase of the emulsion.
Another object of our invention is to provide an" economical and rapid process for separating J emulsions which have been prepared under controlled conditions frommineral oils, such as crude I vpetroleum and. relatively soft waters or weak brines. Controlled emulsiflcation and subsequent demulsification under the conditions just mentioned is'of significant value in removing impurities, particularly inorganic salts, from pipeline oil.
The demulsi'fyingagent employed in our process is a new compound or composition of matter consisting of a certain kind of salt derived from ;a surface-active esterified amine of the kind hereinafter described and an alkylated naphthalene sulfonic acid of the kind in which. there is at least one alkyl group substituted in the naphthalene nucleus, the said alkyl group or groups in three carbon atoms and not more than ten carbon atoms.
Said "alkylated sulfonic acid can be described by the following formula:
o more) v v in which n indicateSany small 'whole number,
V as 1,!2, 0r 3; but generally speaking, the
-40 monosulfonic acid would be employed, and for purposes of brevity,- the formula -D.SOaH will-}be p It is well known that certain monocarboicy organic acids containing approximately eight car- 45 bon atoms or more and not more than 32 carbon atoms; are characterized by the fact that they combine-with alkalis to produce soap or soaplike materials. 'These detergent-forming acids include fatty cids, halogenated fatty acids, resin '50 acids, hydrog nated resin acids, petroleum acids,
venience. these turn being characterized by containing 3 at least chlornaphthenic 'acids,'etc. Forjsake of conacids will be indicatedby'the v formula R.COOH. j Itis known that basic compounds may be pro duced from detergent acids, or esters thereof, and 5 monoalkylolamines, such as. monoethanolamine;
' which are characterized by the following formula:
acoaommm 1 Similarly, one can produce materials of the type 6 I indicated by the following formulas:
(acooLcmo-zNH (Rhcoocim) 3N Needless to say, in the above formulas where an amino hydrogen atom appearait may be replaced l5 1 by some suitablesubstituent; such as an alkyl- 'radical,* alicyclic radical, etc. Such amines, containing the esterified detergent-forming acid radicaL are surface active in either hydrophobe v or hydrophile solvents, 'andespeciallyafter new 20 tralization with acids such asv HCl.
Ifa surface-active amine of the kind above described is'used to neutralize an alkylated aromatic acid of the kind typified by the formula D.SO:;H,
then one obtains complex saltsicharacterized by having both a surface-active anion and a surface- =active'cation; and these salts may be'illustrated by' the following formulas:
' moooimmnnsogn v so The actual composition of the. above type of -material may be'more clearly expressed by-the following formula which is another form of the particular preceding formula, in which an esterlfied primarybasic amine'isemp'loyed for neutralization: I
. y H A g I I [RCOQCzHdfiIH sow Having indicated in a generalway the'nature cf the: vcompound or compositionof matter employed as the demulsifier in ourprocess; it is deemed desirable to indicate the method of prov One can obtain or manufacture chemical compounds who'se composition is indicated by the following formulas:
However, the radical C2H4, which appears in the above formula, may represent any similar radical, such' as a C3Ha radical, a C4H8 radical,
etc., and therefore, the above formula may be indicated as follows:
acoocmh), I
NUT)..."
oH.c,H,,
in which R.COO represents the oxy-acyl radical derived from a monobasic detergent-forming acid; T represents a hydrogen atom or a nonhydroxy hydrocarbon radical, or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than eight carbon atoms; 11. represents a small whole number, which is less than 10; m represents the numeral 1, 2, or 3; m' represents the numeral 0, 1, or 2; and 112." represents the numeral 0, 1, or 2, with the proviso that m+m'+m" equals 3.
In the above formulas it has been pointed out that T represents a hydrogen atom, or a nonhydroxy aliphatic hydrocarbon radical, such as a methyl radical, ethyl radical, propyl radical, amyl radical, octadecyl radical, etc. However, T may also represent a non-hydroxy alicyclic radical, such as a cyclohexyl radical or a non-hydroxy aralkyl radical, such as a benzyl radical; or T may represent the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical, or the equivalent thereof, by the acyl radical of a monobasic carboxy acid, such as acetic acid, butyricacid, heptoic acid, or the like; all of which. are characterized by having less than eight carbon atoms. The alkylol radical prior to acylation may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided the hydroxy radical is attached to the aliphatic residue of the aralkyl radical. v
In the above formula, as has been pointed out, R.COO represents the oxy-acyl or acid radical derived from the acid RCOOH. R.COOH represents any monobasic detergent-forming car-boxy acid, such as a typical fatty acid or abietic acid or naphthenic acid. 4
Typical fatty acids are those which occur in naturally-occurring oils and fats, and generallyhave eight or more carbon atoms and not over 32 carbon atoms. Common examples include oleic acid, stearic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid, palmitic acid, myristic acid, etc. producesoap or soap-like materials, and are commonly referred to as being monobasic detergentforming carboxy acids.
The alkylol radical, previously referred to, prior to esterification, may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided the hydroxy radical is attached to the aliphatic residue of the aralkyl radical.
As to the amines above described, which happen to be tertiary amines, it may be well to point out that these may be formed readily by a reaction involving an ester of the selected detergentforming acid, for instance, a fatty acid ester, such as the glyceride, and a corresponding amine. This may be illustrated in the following manner:
' oH.c,n.N
OH.C|H|
(I) 11.000 011mm acoomm R.COOC:H; onclrrr-N '3' '0H.C;HN+C:H;(OH)= 12.000 011cm. 011cm.
OHLCrHc omega-N OH-CIHI OELCHHA 11.000 ZZ'Z' LR'COCPCH' 011.02 acooioin R.c .7 (11) R000 omega-N -a R.COO.C:H|-N+2CiHs(OH)= R-(jOO-CIE 3:22: 3.000
OH.C:H4+N
. OH.Ca 4
ILCOO These acids combine with alkali to Reference is-made to co-pending application rcr patent Serial No. 180,993, flied December 21, 1937, by Melvin D'e Groote, Bernhard Keiser and Charles M. Blair, Jr,
If triethanolamine, employed in the above, formula; is replaced by ethyl diethanolaminep, then one would obtain one of the remaining types I aaaasaa of tertiary amines illustrated. Reference is made I t Patent No. 2,167,349, dated July 25; 1939, to
De Groote', Keiser, and Blair.
In the remaining type of material there is amino hydrogen atom present. The manufacture of such material may be illustrated by the is following reactions:
r I OHCiH I .However, if maximum yields are not necessary, one need not resort to reactions ofthe'kin'dpre viously described'to produce secondary amines, but one may employ the following type of reac- Suitable primary and secondary amines, which may be vemployed to produce materials of thekind 'J methyl ethanolamine, propanolamine, diproabove described, include the following: diethanolamine, monoethanolamine, ethyl ethanolamine,
panolamine, pro'pyl propanolamine, etc; Other examples include cyclohexyloiamine, dicyclohexylolamine, cyclohexyl 'ethanolamlne, 'cyclo .hexyl propanolamine, 'benzylethanolami ne, benzylpro'panolamine, pentanclamine, hexanolamine,
hexanolethanolamine, etc.
Itis also known thetyiie;
that one may have amines of cum canon cnno clmon' Y 0.11.00.11.01:
n-cimocimon' n-cimocimon, n-cimon cnnocnnon canon canon Canto CaH4OH 'CaHtOCrHaQH cirnocimo'rr \mmon mNclrnocmlon Such amines may serve a's'the obvious functional equivalents of the previously described aminesand which are free from an ether linkage.
All of the amines of the kind above described and characterized by the formula: 1
haveiour common characteristics. In the first s t place, these. amines are not quaternary ammonium basesor salts thereof. The expression quaternary ammonium" is properly and con octylethanolamine;octadecylethanolamine, cyclo- ,Similarly, suitable tertiary amines which may be employed include the following: triethanolamine, diethanolalkylamines, such as diethanol ethylamine, diet'hanol prop'ylamine', etc. Other examples include dlethanol, methylamine, tripropanoiamine, dipropanol methylamine, cyclohexanol diethanolamine, dicyclohena'nol ethanolamine, cyclol1exyl diethanol'amine, dicyclohexyl ethanolamine, dicyclohexanol ethylamine, benzyl diethanolbenzyl dipropanolamine,- tripentanolamine, trihexanolamine, hexyl" ethanoiamine,. octadecyl diethanolamine, polyethanolamine, etc.
a st be recognized is, that these amine com-' the mmpounds used as ventionaliy applied 'to compounds in which all four hydrogen atoms of the ammonium radical NH4 have been replaced by a hydrocarbon radical or, oxy-hydrocarbon radical, as, for example, in t'rimethyl phenyl ammonium hydroxide.
Secondly, an important characteristic which pounds are not amides. It is to be noted that an ,amide formation involves a product in which, there is a direct linkage between'the' carbox'ylic carbon atom and the nitrogen atom in the amine. This-is not the casein-the compounds employed as intermediate rawmaterials for production of dem i s agents in the present process. Y r Y In the third place, it must be recognized that these compounds are derived only. from basic amines.
The'word basi6-is employed .to excludetamines having little or no baslcity, such as,
the ordinary aromatic amines, or any amine having at "least one aryl radical directly joined to the amino nitrogen atom. For this reason, these amine prpducts which are herein-contemplated as demulsiiying agents, and which necessarily are characterized by freedom )i'rcm anyjnryl groups as such, cannot be 'derived from ar'yl amines. They are derived solely from alkyl, alicyclic, or aralkyl amines':havin'g at least onehydroxyl group present. It is truethat in the aralkyl amines there is an nryl group present, but'it is not directly attached to the nitrogen-atom, as
in the case of aryl amines, but in fact, represents nothing more or less than a substituted albiamine. For instance, we consider benzylamlne as being the primary amine, phenmethyl amine.
Finally, it must be recognized ,that these ma-, terials have not lost any basicity in the forms of the esterified' amine, and that they exhibit all the properties of a basic amine, that is," they com-,
blue with water to form a base, presumably a substitutedammonium compound, but not quaternary ammonium compound, insofar that there are always one, two, or three unsubstituted hydrogen atoms of the ammonium radical present. They combine with various acids to form salts. For example, they may be combined with acetic acid, hydrochloric acid, lactic acid, chloracetic acid, nitric acid, butyric acid, phosphoric acid, oxalic acid, or any suitable organic or inorganic acid, to form salts.
Reference is again made to the formula which summarizes the various amines used as intermediate raw materials, viz.:
in which the characteristics have their previous significance. Attention is directed to the fact that where the substituted alkyl radical OH.R.COO.CH-
appears, a suitable non-aryl radical other than an aliphatic residue may serve as the functional equivalent; for instance, an 'alicyclic radical derived from a cyclohexyl radical, or an aralkyl radical derived from a benzyl radical. In other words, in the hereto appended claims references to the C1121: radical as such,.or as an alkyl radical or residue, is intended in the broad sense to include the alicyclic radicals or residues, or the I aralkyl" radicals or residues which are the equivalent thereof. There is no intention to include an aromatic radical where there is a direct linkage between the aromatic nucleus and the amino hydrogen atom, for the reason that such products have little or no basicity and do not have the characteristic properties of the amines previously described.
amines of the non-aryl type which may be employed to produce the amine contemplated as the.
then-it is understood that such materials would not represent a hydroxy tertiary amine within the meaning orscope, as herein employed., If, on the other hand, triethanolamine were treated In indicating the various hydroxylatedtertiary with lactic acid. so as to give monolactyl triethanolamine of the following composition:
on o
cmonc-o-Cuzn .onolm-n oncln,
' then such compound would be included, due to the presence of one or more hydroxyl radicals attached to the alkyl radicals.
Similarly, in indicating the various, hydroxylated primary or secondary amines of the nonaryl type, which may be employed to produce the amine contemplated as the demulsifying agent of the present process, it is desirable to indicate that amines-of the type where a hydroxy acyl radical replaces a hydrogen atom of the hydroxyl radical of a. hydroxy primary or secondary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual alkyl radical. For instance, if ethanolamine is treated with lactic acid so as to form the lactyl derivative of the following formula;
- on o then it is understood that such materials would not represent a hydroxy primary amine within the meaning or scope, as herein employed. The same would be true if thelcorresponding product were derived from diethanolamine, provided both hydroxy radicals had been esterified with lactic acid. f
The manufacture of compounds from tertiary amines is relatively simple, because no precautions are necessary to prevent amidification. The selected detergent-forming acid, or ester, as, for example, a fatty oiland the selected hydroxy tertiary amine, are mixed in' suitable proportions and heated at some point above the boiling point of water, for instance, 110 C., and at a point below the decomposition, point of the amine or the fatty oil, for instance, 180 C., for a suitable period of time, such as two to eight hours. Mild agitation is employed. A catalyst, such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about one-half of 1%, or less. It is noted that the fatty acids'are employed in this instance, in the form of an ester, to wit, the glyceride, although, as previously pointed out, other functional equivalents can be readily employed with equal facility. It is to be noted that the reactions above described do not take place to any appreciable extent if the fatty acid has been converted into the soap or salt. Such salts are not functional equivalents. As
previously indicated, an ester of abietic acid or naphthenic acid might be employed, if desired.
When, however, one is employing a hydroxy secondary amine, precautions must be taken, so that one gets a substantial percentage of products derived by esterification, rather than amidification. Anysuitable ester may be employed, but it is often most convenient to employ the glyceride of a fatty acid, for instance, triricinolein. The selected glyceride and the selected hydroxy secondary amine are mixed in suitable proportions and heated at some point above the 'boiling point of water, for instance, 110 C., and below the decomposition point of the amine or fatty material, for instance, 180 0., for a suitable period of time, such-as 4-24 hours. Mild agitation is employed. A- catalyst, such .as sodium oleate, sodium carbonate, caustic soda, etc., may
is to be noted that the fatty acids are present in ester form and not in the form of the free acid,
and thus there is no'tendency to form the salt employedis two moles of the described.
to any marked extent; and if conducted at the lower range of reaction temperatures, there is a.
decided tendency to form the esterification' products, rather than, the amidiflcation products.
In order to illustrate suitable examples of the amines which maybe used as intermediate raw materials for neutralizing alkylated naphthalene directed tdthe following examples: I Intermediate amine 'E'x ample -1 Castor oil is employed. For the sake of convenience, its molecular weight isconsidered as being 925. Commercial triethanolamine and sulfonic acids of thekind described,- attention is castor oil in the proportion of one mole of castor -oil and three moles of triethanolamine are heated to a temperature between *150-180 C. for, two
hours. Mild agitation is employed. Intermediate amine Example? The same procedure is followed as'in Intermediate famineExample 1, except that the ratio moles of triethanolamine. 1 Intermediate amine Example 3 The same procedure is employed as in Intermediatelamine Example 1, exceptthat the ratio employed is three moles of castor oil to three moles of triethanolamine. as
Intermediate amine Eaample 4 One mole of methyl naphthenateis reacted in the mannerpreviously cule oi triethanolamine.
Intermediate amine Example 5 Diethanolamine is substituted for triethan'olamine in-Example 4. v
Intermediate amine Example .6 Methyl abietate is substituted 'for methyl rfaph- Intermediate amine Example 7 v Olive oil is substituted amples 1, 2,'and 3 above.-
Intermediate amine Example 8 Ethyl diethanoiamine' is substituted for triethanoiamine in 1 Intermediate amine Example!) preceding.
' Intermediate amine Example 10 B enzyl diethanolamine is substituted for ethyl diethanolamine in Example 8 above.
- Intermediate amine Example 11" f Castor oil (triricinoleinl is employed. "Fer convenience its molecular weight is considered n as being 925.v Commercial diethanolamine and castor oil in the proportion of one'mole' of castor oil to threemolesof diethanolamine, are heated to a temperature of 120440 0., for about twelve hours. Mild agitation is employed. Loss of ,basicity is an indication of amidification. Time of. esteriiication may be extended or temperature castor oil to three.-
described with one molefor castor oil in Ex-.
Examples 1,'and 2, previously as-suitable as another-dorm.
lowered or raised, so as to insure maximum esteriflcation, and particularly, so as to produce a product characterized by the presence of one unty by means of a conventional esteriflcation proc 1 nitrogen.
Intermediate amine Eramplelz In the previous examples wherecastor voilis employed, blown-castor-oil is substitutedtherefor. We prefer to use a'drastically oxidized castor oil having, approximately the following charv acteristics: 1 Acid number 13.2 to. 25.0 saponiflcation number 230.5 to,274.0 Iodine number 43.5 to 55.0 Acetyl number 164.0 to 192.0 'Hydroxyl value 188.0to 220.0 Percent unsaponiiiable matter .1-.1 Percent nitrogen 0.0 Percent $03..........'..... 0.0 Percent ash Trace I In employinga drastically oxidizedcastor oil, it is our preference to eliminate carboxylid'acidbess. For instance, in referring to the analyses of the blown oil above, itwill be seen that such product contains acidity equivalent to -10% of the total saponiflcation value. Such acidity can be removedby esteriflcation with an alcohol,
such as methyl alcohol, ethyl alcohol, propyl al- COhOl, etc. Qn'the other hand, insofar that glycerine is the .naturally occurring alcohol present in'most oils and fats, and alsoinsofarf erence to add suflcient glycerineto such blown that glycerine is non-volatile, it is our prefoiland keep it agitated to a temperature of approximately 125-170 C., untllcarboxylic acidity disappears. .Such neutral or completely ester- ,fled blown oil is then employed in manufacturing the intermediate amines of the kind above described.v
Reference is made to the co-pending applications' Serial No. 180,992, filed December 21,1937, 'by Melvin De Groote, Bernhard Kelserand- Charles M. Blair, Jr.;- Serial No. 202,986, filed April 19, 1938, by Melvin'De Groote, Bernhard Keiser and CharlesM. Blair, Jr.; and Serial No. 208,220, filed May 16,4938, by Melvin De Groote, Bernhard Keiser and Charles M. Blair, Jr.
7 I It has been previously pointed out thatthe. intermediate. amines are characterized'by'the fact that they combine withacids to form salts;.
for instance, they'willcombine with acetic acid,
hydrochloric acid, sulfuric acid, etc. In the present instance, of course, "they are employed to form salts, but only aparticular kind of salt,
towit, the one derived by neutralization of an alkylated naphthalene described. 'One isomeric cm of an amine is onic acid or the kind .Alkylated naphthalene sulfonicacids are pro- -duced commercially, and the salts are used for a varietyto'f purposes. They are generally produced from naphthalene, because there does not appear to be any advantage in the use of' a-'.
naphthalene derivative, such as chlor-naphthalene, alpha and beta naphthol'. etc. -Inother words, one could introduce the sulionic acid residue and the alkyl residuesinto a substituted naphthalene, such as chlor-naphthalene, etc.,
Just as readily, perhaps, as in the-case of naph-e thalene. Suchfsimple derivatives, of course, are
the chemical equivalent tat-naphthalene in the manufacture of Such .sulfonic acids as are em:
70 cohol.
ployed in the manufacture of the present reagent. It is understood that the word naphthalene is hereinafter employed to include these derivatives.
The general process of manufacturing the particular salts used to produce the de'mulsiiler employed in our process, consists in converting the naphthalene into either the alpha or beta naphthalene sulfonic acid, or a mixture of the? same,
or in some instances, into a dior even a trisulfonic acid, or a tetrasulfonic acid, or a mixture oi the various types. In most instances, there is no advantage in introducing more than one sulfonic acid residue. In many instances, it
is unnecessary to use particular care to prepare either only the alpha sulfonic acid, or either only the 'beta sulfonic acid, because "a mixture in which either one.or the other predominates, or
a mixture in which the alpha and beta sulfonic' acids are present in. approximately equal amounts, is just as satisfactory as one sulfonic .acid completely freed from the other type.
.The alcohol employed, such as propyl alcohol, a butyl alcohol, an amyl alcohol, a hexyl alcohol, a decyl alcohol, etc., is converted into the acid sulfate, such as propyl hydrogen sulfate. The naphthalene sulfonic acid and the alkyl hydrogensulfate are combined in proportions so that one, two, three, or even four alkyl groups are introduced into the aromatic residue. This condensation reaction is generally carried out in the presence of an excess of sulfuric acid. In some instances, the various reactions, such as sulfonation, sulfation, condensation, etc., are carried out simultaneously. Generally speaking, the dialkylated and tri-alkylated material appear to yield the most desirable type of reagent. Thepresence of some mono-alkylated material,
or some tetra-alkylated material is not objec- 40 tionable, and may even be desirable.
It is obvious, of course, that the alkylated groups introduced might be derived from olefines, such as butylene, propylene, amylene, etc., insofar that such olefines react directly with sulfuric acid, to produce the alkyl hydrogen sulfates. Of course, in addition to introducing such alkyl residues of the kind described, into the aromatic nucleus, one could also introduce an alkyl residue from some other alcohol, as, for
example, an alkylated group derived from ethyl or methyl alcohol, or one might introduce a group derived from an aryl, aralkyl cyclic, or hydroaromatic alcohol, or the like, but regardless of whether or not one introduces suchother residues, it is necessary that at least one alkyl residue of the kind described, 1. e., having at least three carbon atoms and not more than ten carbon atoms, be introduced into the naphthalene ring. Such compounds having some other 0 group present, such as -methyl group, might be considered as being derived from methyl naphthalene, instead of naphthalene, and thus, would fall within the class of chemical equivalents previously noted.' It is immaterial as to the particular alcohol'employed, or the particular isomeric form of the alcohol employed, although generally speaking,it is most desirable to use the one lower in cost. It is immaterial whether one uses normal propyl alcohol or isopropyl alllt is immaterial whether one uses a normal butyl or isobutyl alcohol. It is immaterial whether .the alcohol be a primary alcohol,
75 It is obvious that a large number of isomers can be produced in the manufacture of the reagent employed as the demulsifier in the present process. For instance, although the sulfonic pyl alcohol, normal butyl alcohol, isobutyl al-- 15 cohol, and amyl alcohol, it is our preference to produce our reagents from these acohols, and in some instances, it is desirable to introduce different alkyl groups, such as a propyl group and butyl group, into the'same sulfo-naphtha- 20 lene residue. I
In the actual manufacture of alkylated naphthalene sulfonic acids, the composition of the desired chemical reaction is followed by a washing process which removes the excess of sul- 25 furic acid or other sulfonation, sulfation, or condensation reagent employed. The acidic mass thus obtainedis neutralized in any convenient manner with any suitable base, such as ca'ustic soda, caustic potash, ammonium hydroxide, and 36 the like. However, in accordance with what has been said herein, the acidic mass is neutralized with the amine of the kind previously described.
moleculeof naphthalene by the customary sulfa- 45 tion, sulfonation, and condensation reactions.
The resulting mixture consists, largely of dipropyl naphthalene sulfonic acids and tri-propyl naphthalene sulfonic acids, with possibly small amounts of mono-propyl sulfonic acids and tetra- 50 propyl sulfonic acids present Generally speak- -ing, it is easier to conduct the reaction so that thebulk of the sulfonic acid represents the beta type, although the alpha type may be produced, if desired. The product is neutralized with a com- 55 plex amine of the kind typified by Examples 1,2,
3 or 12, previously described. The product so obtained is diluted with one or more solvents, so
as to reduce its viscosity to that of ordinary castor oil, or slightly greater. The solvents which we 60 preferably employ are a'mixture of two or more of the following: Water, denatured alcohol, kerosene, or tar acid oil.
Amongthe reagents which are particularly effective are the salts formed by reaction between 65. amines of th kind exemplified by Examples 1-12,
inclusive, above, and the following alkylated naphthalene sulfonic acids, i. e., mono-isopropyl naphthalene sulfonic acids, di-isopropyl naphthalene sulfonic acids, tri-isopropyl naphthalene sulfonic acids, mono-normal butyl naphthalene sulfonic acids, di-normal butyl naphthalene sulfonic acids, mono-isobutyl naphthalene sulfonic acids, di-isobutyl naphthalene sulfonic acids, mono- ,amyl-napht-halene sulfonic acids, di-amyl naphthaiene sulfonic acids, tri-aniyl naphthalene sulfonic acids, monohexyl naphthalene sulionic acids, di-hexyl naphthalene suli'onic acids, tri-' .hexylnaphthalenesulfonic acids. mono-octyl 5 naphthalene sulionic acids, di-octyl naphthalenesulfonic acids, 'mono-decyl naphthalene sultonic I acids, di-decyl naphthalene sulionic acids, monoisopropylv di-normal butyl naphthalene sultonic.
acids, di-isopropyl di-ncrmal butyl naphthalene naphthalene su'lfonic acids, etc.
- In such instances where there is present more thanone'sulfonic acid radical, as in'the formation oi. a disuli'onic acid, or a; trisulfonic acid, or a tetrasulfonic acid, ii desir'ed, allth'e sultonic sulfonic acids, di-isopropyl mono-amyl naphthalene sulfonicacids, mono-isopropyl mono-hexyl radicals may be neutralized wlthamines oi! the kind previously described, or some of the sulionic acid radicals may be neutralized with some" other 20 suitable base, 'such as a sodium hydroxide, potassium hydroxide, ammonium hydroxide, etc., provided that at least one 'sulfonlc acid radical has been neutralized by amines or the kind previously described, f
7 Conventional demulsii'ying agents employedfin the treatmentot oil fleld emulsions are used as such, or after'dilution with any suitable solvent, such; as water, petroleum hydrocarbons, such as gasoline, kerosene-stove oil, a coal tar product, such as benzene, toluene, xylene, tar acid oil,
ores o1, 'anthra'cene. oil, etc. Alcohols, particu'-; larly aliphatic alcohols, such as" methyl alcohol, ethyl alcohol, denatu'red'alcohol, propyl alcohol,
butyl alcohol, hexyl alcohol, pctyl-alcohohetc,
may be employed as diluents. Miscellaneous-sob tion, rather than the formation of a. substituted amide,- or the formation of an'imide or substiboth oil andwater solubility; 'Sometimes they tuted lmide. Such obvious departurefrom conventional nomenclaturehas been for purposes of simplicity and to show the similarity between certainreactions. I
It is well known that conventional demulsifying agents-may be used in a water-soluble form, or man oil-solubleform, or in a form exhibiting may be used in aiorm which exhibits relatively limited water solubility and relatively limited oil solubility. However, since such reagents are sometimes used-in a ratio of 1 to 10,000,;or 1 to 20,000,.or even-1 to 30,000, such an apparent insolubility in ,oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same factis true in regard to the material or materials employed as the demulsifyingagent of our process.
vents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material orimaterials employed as the demulsiiying agent of'our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsiiying agents. Moreover, said material or materials may be used alone or inadmixture with other suitable well known classes of demuisifying agents, such as demulsiiying agents of the modi- I fled fatty acid type, complex amine type, the petroleum sulfonate type, the alkylated suli'o-aromatictype, neutralized in the conventional man:
ner,'or evenun-neutralized. Incidentally, neutralization oi. the" alkylated sulfonic acidwith the complex amine need not necessarily take place in. stoichiometrical rela? tionship, but one may employ an excessot the sulfonic acid or or the amine. Incidentally, salts made by direct neutralization, but of course can -'be producedfju'st as eflectively by some other means. For instance, a double decomposition reactionmay be, utilized, i. e., the amine hydrochloride and the sodiumor potassium salt of the sulionic acid might each-be dissolved ina hydrophobe solvent, such as an alcohol and mixed with or the kind'herein contemplated need not be has been indicated previously, in essence, We have discovered that if a suitable alkylated naphthalene sulfonic acid is neutralized with an amine of the kind described, one obtains an unusual reagent, to wit, one characterized by having both a surface-active anionand a surface-active cation;
and we have .furthermore discovered that such reagent is of unusual efiectiveness for breaking oil fiel'd'emulsions. As far as demulsification is con 'cemed, there does not appear to be any suitable explanation of this unusual superiority; and similarly, there does notseen to be any basis by which one could anticipate'or foresee this unusual effectiveness. Apparently, thismarked improvement -35 is not directly related to oil or water solubility, insofar that. similar neutralization with other amines may yield .compounds .which have a greater solubility' in oily materials orin water, "and yet are not nearly as suitable and not nearly nearly as marked improvement over the correspending sodium ammonium salts, and in many cases it'might even be said that .a product is 50 1 obtained which is inferiorto the conventional sodium or ammonium salts. Apparently this in-- dicates that the increased value doesnot reside stance, aniline, toluidine, propylamine, diamyl the separation or sodium or potassium chloride.
" which could be filtered ofl! andthe alcohol evaporated, -so as to leave theamine' salt of the kind I to produce the chemical compound, Previously.
described, happened to .be neutralized with atdesired. Attention is directed-to the i'act that the word .amidiflcation has been applied to the reaction involving the-replacement oi' amine hydrogen atom byan acyl radical, without conventional" Ji m itgt ion toa reactioninvolvfing ammonia. The
replacement of the amine hydrogen atom or a v 'primaryamine or asecondary amine by an acid radical, has been considered as'being tained. In other words,.i.f the same alkylated 65 'ionic acids, such as. certainones derived i'ro m fl; t
in the additive effect in all instances or the amine residue per se. Furthermore, the .efi'ec--- tiveness of the complex amines is not enjoyed by various other amines-which at least bear some superficial analogy to the complex amines, although they are not surface-active. For inamine, triamylamine, etc.,-cannot be substituted for the amines employed for neutralization in the preceding examples, without detracting markedly from the value of the compounds obnaphthalene sulforiic' acids" which are employed least-certain other amines, such as those referred to, oneapparently-does not obtain a reagent of 7 any marked value, and especially a -reagent or any superiority or efiectiveness i'or' demulsii'y- 'ing on iieldjemulsions.v Similarly, the applicants have experimented with a number of other sulpetroleum, and found that neutralization with amines of the kind herein described does not give nearly as effective a reagent, in many instances, as conventional neutralization with caustic soda, caustic potash, ammonium hydroxide,
and the like. Based on the results of actual tests obtained in a variety of emulsified crudes occurring in a number of the major. oil fields of the United States, the conclusion one must inevitably reach is, that the result obtained by uniting the two surface-active residues, 1. e., the amineresidue of the kind described and the sulfa-aromatic residue of the kind described, in a single molecule, is an unlocked-for unique quality which could not be foreseen by the present knowledge of the art and which produces a demulsifying agent that is particularly eflective for a large number of emulsified crude oils.
It is obvious that certain functional equivalents may be employedi'for instance, hydroxyamines characterized by the presence of a cyclohexyl radical, may be replaced by those in which an alkylated cyclohexyl radical appears. Simiof the .kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various;ways or by any of the various apparatus now generally used to resolve or. break petroleum emulsions with a chemical reagent, the aboveprocedure being-used either alone or in combination with other demulsifying procedure, such as the electrical dehydration process.
Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:
1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a product of the kind derivable by neutralization reaction between (A) a surface-active amine of the formula type in which R.COO represents the oxy-acyl radical derived from amonobasic detergent-forming acid; T represents a hydrogen atom or a nonhydroxy hydrocarbon radical or the acylated radical obtained by replacing-a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid H having less than eight carbon atoms; n represents a small whole number which is less than 10; 112 represents the numeral 1, 2, or 3; m represents the numeral 0, 1,'or 2;. and m" represents thenumeral 0, 1, or 2, with the proviso that m+m'+m" equals '3; and (B) a surface-- active alkylated naphthalene sulfonic acid in which at least one alkyl'group substituted in the "naphthalene nucleus contains at least -three carbon atoms and not morethan 10 carbon atoms.
2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subiecting the emulsion to the action of a demulsifying agent comprising'a product of the kind derivable by neutralization reaction between (A) a surface-active amine of the formula type in which R.COO represents the oxy-acyl radical derived from a fatty acid having at least 8 and not more than 32 carbon atoms; T represents a hydrogen atom .orv a non-hydroxy hydrocarbon radical or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an -alkylol radical by the acyl radical of a monobasic carboxy acid having less than eight carbon atoms; n represents a small whole number which is less than 10; m represents the numeral 1, 2, or 3 m represents the numeral 0, 1, or 2; and m" represents the numeral 0, 1, or 2, with the proviso that m+m'+m" equals 3; and (B) a surfaceactive alkylated naphthalene sulfonic acid in which at leastone 'alkyl group substituted in the naphthalene nucleus contains at least three carbon atoms and not more than 10 carbon atoms.
I 3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a product of the kind derivable-by neutralization reaction between (A) a surface-active amine of the formula type (R.o00.o,.Hz.)..
v Nov) in which R.COO represents the oxy-acyl radical derived from a fatty acid having at least 8 and not more than 32 carbon atoms; '1' represents a hydrogen atom or anon-hydroxy hydrocarbon radical or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than eight carbon atoms; n represents a small whole number which is less than 10; m represents the numeral 1, 2, or 3; m represents the numeral 0, 1, or 2; and m" represents the numeral 0, 1, or 2, with the proviso that m+m'+m" equals 3; and (B) a sur-' face-active alkaylated naphthalene monosulfonic acid in which at least one alkyl group substituted in the naphthalene nucleus contains at least three 'carbon atoms and not more than 10 carbon atoms;
in which R.COO represnts the boxyacyl radical derived troma fatty acid having at least 8 and not more than 32 carbon atoms; T represents a hydrogen atom or a non-hydroxy hydrocarbon radical or the acylated radical obtained by replacinga hydrogen atom ofthe hydroxyl group of an alkylol radical by the acyl radical of a-monobasic carboxy acid having less than eight carbon atoms; m represents the numeral 1, 2, or 3; m
represents-the numeral 0,- 1, or 2; and m" represents the numeral 0, 1; or 2, with the proviso that 1n+m'+m" equals 3; and (B) .a-suriace-active alkylated naphthalene monosulfonic .acid in naphthalene nucleus contains at least three carbon atoms and not more than 10 carbon atoms.
ing the emulsion-to the action of a demulsi1ying agent comprising a product oi the kind derivable by neutralization reaction between (A) a surfaceactive amine of the formula type (R.CO0.C1H|)- v 1. (H.CzH4)-' in which R.COO represents the oxy-acyl radical derived from a Iatty'acid having at least 8 and not more than 32 carbon atoms; m represents the numeral 1, 2, or 3;and vm represents thenumere] 0, 1, or 2; with the proviso that m-i-m'=3; and (B) a surface-active alkylated naphthalene monosulfonic acid in which at least one alkyl group substituted in the naphthalene. nucleus contains at-leastfthree carbon atoms and' not more than carbon atoms.
6. A process-for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsiiysurface-active amine of the formula type m ce 0.0m.)
nhich at least one alkyl group substituted in the aderived from a fatty acid having 4? least 8 and not more than 32 carbon atoms; 1!: represents the in which R.COO represents the oxy-acyl radical numeral 1, 2, or 3; and m represents the numeral 0, 1, M2; with the proviso that m+m=3; and (B) a surface-active alkylated naphthalene mono- .sultonic acid in which at least one alkyl group substituted in the naphthalene nucleus contains at least three carbon atoms and not more than 5 carbon atoms.
7. A process for breaking petroleum emulsions of-the water-in-oil type, characterized by subjecting the emulsion tothe action of a demulsiiy ing agent comprising a product of the kind del- 'rivable by neutralization reaction between (A) a surface-active amine of the formula type (R.C00.CzH4)--\ not more than 32 carbon atoms; m represents the numeral 1 2, or 3; and m represents the numeral 0, 1, or 2; with the proviso thatm+m'=3; and
(B) a surface-active propylated naphthalene more than four propyl radicals substituted in the naphthalene nucleus.
- MELVIN DE GROOTE. ARTHUR F. WIRTEL.
"monosulfonic acid containing at least one and not
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