US2344539A - Salts of certain methylene diamines with certain petroleum sulphonic acids - Google Patents
Salts of certain methylene diamines with certain petroleum sulphonic acids Download PDFInfo
- Publication number
- US2344539A US2344539A US398494A US39849441A US2344539A US 2344539 A US2344539 A US 2344539A US 398494 A US398494 A US 398494A US 39849441 A US39849441 A US 39849441A US 2344539 A US2344539 A US 2344539A
- Authority
- US
- United States
- Prior art keywords
- acid
- acids
- radical
- certain
- oil
- 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
- 239000002253 acid Substances 0.000 title description 64
- -1 methylene diamines Chemical class 0.000 title description 52
- 150000007513 acids Chemical class 0.000 title description 42
- 239000003208 petroleum Substances 0.000 title description 27
- 150000003839 salts Chemical class 0.000 title description 11
- 150000001412 amines Chemical class 0.000 description 26
- 239000003921 oil Substances 0.000 description 21
- 229930195733 hydrocarbon Natural products 0.000 description 20
- 239000004215 Carbon black (E152) Substances 0.000 description 19
- 150000003254 radicals Chemical class 0.000 description 18
- 239000000839 emulsion Substances 0.000 description 17
- 150000004985 diamines Chemical class 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 10
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical class NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 8
- 241000158728 Meliaceae Species 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000010933 acylation Effects 0.000 description 6
- 238000005917 acylation reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000003335 secondary amines Chemical class 0.000 description 6
- 239000001117 sulphuric acid Substances 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000001447 alkali salts Chemical class 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 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 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- NIOYUNMRJMEDGI-UHFFFAOYSA-N hexadecanal Chemical compound CCCCCCCCCCCCCCCC=O NIOYUNMRJMEDGI-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KQIXMZWXFFHRAQ-UHFFFAOYSA-N 1-(2-hydroxybutylamino)butan-2-ol Chemical compound CCC(O)CNCC(O)CC KQIXMZWXFFHRAQ-UHFFFAOYSA-N 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- SAMGBMSEBPZABZ-UHFFFAOYSA-N 3-(2,3-dihydroxypropylamino)propane-1,2-diol Chemical compound OCC(O)CNCC(O)CO SAMGBMSEBPZABZ-UHFFFAOYSA-N 0.000 description 1
- CGBQPTYOFPMKAL-UHFFFAOYSA-N 3-(benzylamino)propane-1,2-diol Chemical compound OCC(O)CNCC1=CC=CC=C1 CGBQPTYOFPMKAL-UHFFFAOYSA-N 0.000 description 1
- DHWUBIRULANTFI-UHFFFAOYSA-N 3-(ethylamino)propane-1,2-diol Chemical compound CCNCC(O)CO DHWUBIRULANTFI-UHFFFAOYSA-N 0.000 description 1
- DFLPEEAGRQDYGF-UHFFFAOYSA-N 3-(propylamino)propane-1,2-diol Chemical compound CCCNCC(O)CO DFLPEEAGRQDYGF-UHFFFAOYSA-N 0.000 description 1
- WOMTYMDHLQTCHY-UHFFFAOYSA-N 3-methylamino-1,2-propanediol Chemical compound CNCC(O)CO WOMTYMDHLQTCHY-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 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
- 239000008240 homogeneous mixture Substances 0.000 description 1
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical compound O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010687 lubricating oil Substances 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
- 150000004682 monohydrates Chemical class 0.000 description 1
- HVAAHUDGWQAAOJ-UHFFFAOYSA-N n-benzylethanamine Chemical compound CCNCC1=CC=CC=C1 HVAAHUDGWQAAOJ-UHFFFAOYSA-N 0.000 description 1
- OUMBFMLKPJUWDQ-UHFFFAOYSA-N n-benzylpropan-1-amine Chemical compound CCCNCC1=CC=CC=C1 OUMBFMLKPJUWDQ-UHFFFAOYSA-N 0.000 description 1
- AGVKXDPPPSLISR-UHFFFAOYSA-N n-ethylcyclohexanamine Chemical compound CCNC1CCCCC1 AGVKXDPPPSLISR-UHFFFAOYSA-N 0.000 description 1
- SDGLZYZMEJGJDJ-UHFFFAOYSA-N n-hexylcyclohexanamine Chemical compound CCCCCCNC1CCCCC1 SDGLZYZMEJGJDJ-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- GCULWAWIZUGXTO-UHFFFAOYSA-N n-octylaniline Chemical compound CCCCCCCCNC1=CC=CC=C1 GCULWAWIZUGXTO-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UMNSMBWAESLVOC-UHFFFAOYSA-N n-pentylaniline Chemical compound CCCCCNC1=CC=CC=C1 UMNSMBWAESLVOC-UHFFFAOYSA-N 0.000 description 1
- PXKCSKRXWAZGFK-UHFFFAOYSA-N n-propylcyclohexanamine Chemical compound CCCNC1CCCCC1 PXKCSKRXWAZGFK-UHFFFAOYSA-N 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- FWWQKRXKHIRPJY-UHFFFAOYSA-N octadecyl aldehyde Natural products CCCCCCCCCCCCCCCCCC=O FWWQKRXKHIRPJY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol 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
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Chemical class 0.000 description 1
- 229920005989 resin Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- IZUPJOYPPLEPGM-UHFFFAOYSA-M sodium;hydron;phthalate Chemical compound [Na+].OC(=O)C1=CC=CC=C1C([O-])=O IZUPJOYPPLEPGM-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 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 to a new composition of matter consisting of a certain kind of amine salt derived from water-soluble petroleum sulphonic acid or acids of the kind hereinafter described.
- the main object of my invention is to provide a new material or composition of matter that is an eflicient solubilizer, particularly in instances where it is desired to make two immiscible materials mutually soluble, and which is also capable of use as a demulsifier for crude oil emulsions, either alone, or in admixture with conventional demulsifying agents, such for example, as demulsifying agents of the modified fatty acid type, or of the alkylated aromatic sulphonic' acid type.
- Petroleum sulphonic acids are produced from a wide variety of petroleum distillates or petroleum fractions, and in some instances, they are produced from the crude petroleum itself. When produced from crude petroleum itself, it is customary to use crude oil of the naphthene type, crude oil of the paramn type, crude oil of the asphaltic type and mixtures of said three different types of crude oil.
- Petroleum sulphonic acid regardless of whether derived as the principal product of reaction or as a by-product, can be divided into two general types, to wit, green acid or acids and mahogany acid or acids.
- the green acids are characterized by being water-soluble or dispersible. In other words, they form either true solutions or sols.
- the green acids as indicated by their name, frequently give an aqueous solution having a dark green or grey-green appearance. They generally appear as a component of the acid draw-off and do not remain behind dissolved in the oil fraction which has been subjected to sulphuric acid treatment.
- the green acids are not soluble in oil, even when substantially anhydrous, and certainly are not soluble in oil when they contain as much as 15% of water.
- their salts obtained by neutralization with a strong solution of caustic soda, caustic potash, or ammonia are not oil-soluble. For convenience of classification, the ammonium salt will be considered as an alkali salt.
- the oil-soluble type or the mahogany acids are characterized by being soluble in oil, especially when anhydrous, and being soluble in oil, even if they contain some dissolved water.
- Some of the mahogany acids also show limited hydrophilic properties to the extent that either some water can be dissolved in the acids, or they, in turn, may dissolved to some extent in water.
- their salts such as the sodium, ammonium, or potassium salt, will dissolve in water to give a colloidal sol.
- Green acids are hydrophile in character, as previously stated. Their hydrophile character has been increased by neutralization with materials such as triethanolamine and the like. Such green acid salts having enhanced water solubility, as compared with the ordinary alkali salts, have found application in certain arts.
- the new composition of matter which constitutes my present invention is represented by amine salts of hydrophilic non-hydrophobic green petroleum acids, as exemplified by the salt derived from such green acids by neutralization with the diamine obtained by reaction between two moles of diamylamine and one mole of formaldehyde or one mole of acetaldehyde.
- the manufacture of said composition of matter involves nothing more or less than neutralizing one mole of the selected petroleum acid with a mole of a suitable amine, or neutralizing two moles of the selected petroleum sulphonic acid with one mole of the amine, in that the amine being a diamine, is dibasic.
- a suitable indicator such as methyl orange indicator, may be employed.
- the selected petroleum sulphonic acid contain not over 15% of water. It is understood, of course, that the conventional procedure, employing double decomposition instead of direct neutralization, can be utilized in the manufacture of my new material or composition of matter.
- the sodium salt of the selected petroleum sulphonic acid can be dissolved in alcohol or other suitablesolvent, and the amine hydrochloride added so that sodium chloride will precipitate. After filtering off the precipitated sodium chloride, the alcohol can be evaporated and the amine salt recovered. If desired, a mix ture of amines instead of a single amine may be employed.
- diamines having pronounced basic properties, may be derived by various means, provided that the resultant diamine is characterized by the fact that the two amino nitrogen atoms are not attached to the same carbon atom.
- Such diamines generally referred to as alkylene diamines, are well known and may be characterized by ethylene diamine.
- Derivatives of the diamines herein contemplated are characterized by being a methylene diamine derivative, 1. e., a derivative of the hypothetical methylene diamine ondary amines are available, which may be designated by the formula type:
- B represents an alkyl, aralkyl, alicyclic, alkylol, aralkylol, hydroxy alicyclic, heterocyclic, or other equivalent radical.
- B and B jointly may represent one radical, as in piperidine.
- aldehydes particularly the aldehydes of relatively low molecular weight
- the amine so produced may be indicated by the following formula:
- T may represent a hydrogen atom derived from formaldehyde, or may represent a radical derived from acetaldhyde, propionaldehyde, butyraldehyde, heptaldehyde, lauric aldehyde, palmitic aldehyde, or stearic aldehyde.
- heterocyclic aldehydes such as furfuraldehyde, or aromatic aldehydes, such as benzaldehyde.
- Unsaturated aldehydes such as acrolein, crotonaldehyde, tiglic aldehydes, may be employed.
- B may represent an.
- aralkyl radical such as a benzyl radical, ethyl benzyl radical, dimethyl benzyl radical, an alicyclic radical, such as the cyclohexyl, methyl cyclohexyl, etc.
- B may represent a hydroxy ethyl, hydroxy propyl, hydroxy butyl, and similar radicals, such as a CeH4C2H4OH radical, or a CsHmOI-I radical;
- Other radicals include the furfural radical, or hydroxy derivatives thereof.
- Piperidine may be considered as a special adaptation in which one radical replaces two amino hydrogen atoms.
- the methylene diamine expressed by the above formula, is a tertiary diamine in the sense that neither amino nitrogen atom has attached thereto a replaceable hydrogen atom.
- the above formula may be rewritten as follows, so as to indicate such instances where there is present an alcoholic hydroxyl radical:
- B OH is obviously the monovalent hydroxy hydrocarbon radical, such as an alkylol radical or the like. Needless to say, B'OH may occur more than once, and B may occur less than three times.
- amines such as triethanolamine or the like can be acylated by reaction with fatty acids or a suitable functional derivative thereof, such as the acyl chloride or the anhydride, or even the ester. If the tertiary hydroxy methylene diamine of the kind just described is reacted with a detergent-forming monobasiccarboxy acid, the reaction may be indicated in the following manner:
- aldol In addition to aldol, other similar hydroxy aldehydes or aldehyde-alcohols may be employed. As to such aldehydes other than aldol, reference is made to Richters Organic Chemistry, volume 1, third English edition, 1934, pages 389-391.
- diethanole amine dipropanolamine, dibutanolamine, dipentanolamine, dioctanolamine, glyceryl dihexanolamine, methyl glycerylamine, ethyl glycerylamine, propyl glycerylamine, cyclohexyl glyceryltil amine, benzyl glycerylamine; dibenzylamine, ethyl benzylamine, methyl benzylamine, propyl benzylamine, cyclohexyl ethylamine, cyclohexyl propylamine, cyclohexyl hexylamine, diethylamine, dipropylamine, diamylamine, dihexylamine,
- Such amines may serve as functional equivalents of the previously described amines, which happen to be free from an ether linkage.
- one may have amines in which there is more than one ether linkage, i. e., in which the hydrocarbon radical, which replaces an amino hydrogen atom, has been interrupted more than once by an oxygen atom.
- the reaction is not limited to the two dissimilar amines, but may take place in part in such a manner as to involve two similar amines.
- the reaction is not limited to the diamine involving both A and B, but in part the diamine will be formed solely from two molecules of A, and in part solely from two molecules of B.
- oil solubility of the amine greatly increases the oil solubility of the amine; and such oil solubility is transposed, at least in part, to the final product, which is a salt of the sulphonic acid.
- oil solubility per se is the index as to effectiveness of the demuisifying agent.
- hydroxyl radicals might be reacted with an acid having less than 8 carbon atoms, for instance, acetic acid, butyric acid, heptoic acid, etc.
- More than one hydroxy hydrocarbon radical if present, may be acylated, and if two or more such radicals are reacted with acids, one need not employ the same acids, but different acids may be employed.
- a hydroxy radical attached to the aldehyde residue may be similarly acylated, as, for example, the residue from aldol.
- a compound, such as sodium hydrogen phthalate, might be used for acylation.
- My preferred reagent is manufactured in the following manner:
- the methylene diamine so obtained may be indicated by the following formula:
- the product obtained by reaction can be purified in the customary manner, so as to remove any unreacted aldehyde, and also any unreacted simple secondary amine.
- the reaction is conducted carefully, a substantial and generous yield of the desired cliamine is obtained, and it is unnecessary to resort to any purification. It has been previously pointed out that having obtained an amine of the kind desired, it is only necessary to proceed to neutralize the green acid, as previously indicated.
- one particularly desirable mixture of diamines is obtained by employing one mole of diethanolamine and one mole of diamylamine in connection with one mole of acetaldehyde.
- ant product so obtained will average two hydroxyl radicals per molecule; and one hydroxyl radical can be readily eliminated by acylation with one mole of a selected acid, particularly oleic acid or naphthenic acid. If desired, both hydroxyl radicals may be eliminated. In this instance the long carbon chain attached to an amino nitrogen atom is interrupted by an oxygen atom.
- hydrocarbon radical includes such radicals that are essentially hydrocarbon in nature, which include carbon atom chains that are interrupted at least once by an oxygen atom. This would occur, of course, in linkages such as the following:
- R is the hydrocarbon radical derived from naphthenic acid, oleic acid, acetic acid, heptoic acid, or the like.
- Acylation can be accomplished by any suitable acid compound, such as the acyl chloride, the anhydride, etc. If an amine salt is formed, such as the hydrochloride, it must be converted into a base by conventional treatment with strong caustic soda or the like.
- hydrophile non-hydrophobe petroleum sulphonic acid or acids of the green acid type vary somewhat; for instance, the molecular weight may vary within the range of 350-500 or thereabouts.
- these petroleum sulphonic acids may carry some polymerized olefins, free hydrocarbons, or the like or may even carry a bit of naphthenic acids which represent carboxylated non-sulphonated petroleum acids.
- these materials are well known commercial products, and are available in the open market, either in the form of the acid itself, or in the form of a salt.
- the amine or, more specifically, the diamine is referred to asbasic to indicate that the basicity is in the neighborhood of that of ammonia, triethanolamine, or amylamine.
- the basicity may be somewhat greater, in fact, perhaps considerably greater, and in some instances perhaps slightly less. In order to insure such basicity, it is necessar that there be no aryl or aromatic radical attached to the amino nitrogen atom from which the diamine is produced.
- the conventional method of using a chemical demulsifier to break a petroleum emulsion consists in introducing the demulsifier into the well in which the emulsion is produced; introducing the demulsifier into a conduit through which the emulsion is flowing; or introducing the demulsifier into a tank in which the emulsion is stored.
- the emulsion is allowed to stand in a quiescent state, usually in a settling tank, and usually at a temperature varying from atmospheric temperature to about 200 F., so as to permit the water or brine to separate from the oil, it being preferable to keep the temperature low enough to prevent th volatilization of valuable constituents of the oil.
- the amount of demulsifier that may be required to break the emulsion may vary from 1 part of demulsifier to 500 parts of emulsion, up to 1 part of demulsifier to 20,000 or even 30,000 parts of emulsion.
- the superiority of the reagent or demulsifying agent herein described is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but I have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.
- a new compound consisting of a waterinsoluble salt of a basic, methylene diamine of the formula type:
- T is selected from the class consisting of hydrogen atoms, hydroxy alkyl radicals and aliphatic hydrocarbon radicals
- B is selected from the class consisting of aliphatically-bound hydrocarbon radicals, alicyclic hydrocarbon radicals, aliphatic hydrocarbon radicals interrupted at least once by an oxygen atom, aliphatically-bound hydroxy hydrocarbon radicals, hydroxy alicyclic radicals, and radicals obtained by the acylation of a hydroxy hydrocarbon radical in which the acylating compound is derived from an acid containing not more than 32 carbon atoms, at least one of the radicals represented by B being such an acylated hydroxy hydrocarbon radical; said diamine salt being obtained from water-soluble, non-hydro-phobe petroleum sulphonic acid of the green acid type.
- a new compound consisting of a water-insoluble salt of a basic, methylene diamine of the formula type:
- E is selected from the class consisting of aliphatically-bound hydrocarbon radicals, alicyclic hydrocarbon radicals, aliphatic hydrocarbon radicals interrupted at least once by an oxygen atom, aliphatically-bound hydroxy hydrocarbon radicals, hydroxy alicyclic radicals, and radicals obtained by the acylation of a hydroxy hydrocarbon radical in which the acylating compound is derived from an acid containing not more than 32 carbon atoms, at least one of I the radicals represented by B being such an acylated hydroxy hydrocarbon radical; said diamine salt being obtained from water-soluble, non-hydrophobe petroleum sulphonic acid of the green acid type.
- a new compound consisting of a water-insoluble salt of a basic, methylene diamine of the formula type:
- T is a hydroxy hydrocarbon radical and B is selected from the class consisting of aliphatically-bound hydrocarbon radicals, alicyclic MELVIN DE GROOTE.
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Mar. 21, 1944 reasse- SALTS OF CERTAIN METHYLENE DIAMINES -WITH CERTAIN PETROLEUM SULPHONIC ACIDS Melvin De Groote, University City, Mo., assignor, by mesne assignments, to Petrolite Corporation, Ltd., a corporation of Delaware No Drawing. Original application May 12, 1939,
Serial No. 273,221. =Divided and this application June 1'7, 1941, Serial No. 398,494
3 Claims.
This invention relates to a new composition of matter consisting of a certain kind of amine salt derived from water-soluble petroleum sulphonic acid or acids of the kind hereinafter described.
This application is a division of my prior application Serial No. 273,221, filed May 12, 1939.
The main object of my invention is to provide a new material or composition of matter that is an eflicient solubilizer, particularly in instances where it is desired to make two immiscible materials mutually soluble, and which is also capable of use as a demulsifier for crude oil emulsions, either alone, or in admixture with conventional demulsifying agents, such for example, as demulsifying agents of the modified fatty acid type, or of the alkylated aromatic sulphonic' acid type.
Petroleum sulphonic acids are produced from a wide variety of petroleum distillates or petroleum fractions, and in some instances, they are produced from the crude petroleum itself. When produced from crude petroleum itself, it is customary to use crude oil of the naphthene type, crude oil of the paramn type, crude oil of the asphaltic type and mixtures of said three different types of crude oil.
The art of refining petroleum crude or various fractions, using sulphuric acid of various strengths, as well as monohydrate and fuming acid, is well knownprocedure. In such conventional refining procedure, petroleum sulphonic acids have been produced as icy-products. For instance, in removing the olefinic components, it has been common practice to use sulphuric acid so as to polymerize the olefines or convert them into sulphonic acids which are subsequently removed. Likewise, in the production of white oil or highly refined lubricating oils,'it has been customary to treat with fuming sulphuric acid, so as to eliminate certain undesirable components.
In recent years, certain mineral oil fractions have been treated with sulphuric acid with the primary object of producing petroleum sulphonic acids. and in such procedure the petroleum sulphonic acids represented the primary objects of reaction, rather than concomitant lay-products. Petroleum sulphonic acid, regardless of whether derived as the principal product of reaction or as a by-product, can be divided into two general types, to wit, green acid or acids and mahogany acid or acids. The green acids are characterized by being water-soluble or dispersible. In other words, they form either true solutions or sols.
referred to as water-soluble without any effort to indicate whether the solution is molecular or colloidal in nature. The green acids, as indicated by their name, frequently give an aqueous solution having a dark green or grey-green appearance. They generally appear as a component of the acid draw-off and do not remain behind dissolved in the oil fraction which has been subjected to sulphuric acid treatment. The green acids are not soluble in oil, even when substantially anhydrous, and certainly are not soluble in oil when they contain as much as 15% of water. Similarly, their salts obtained by neutralization with a strong solution of caustic soda, caustic potash, or ammonia, are not oil-soluble. For convenience of classification, the ammonium salt will be considered as an alkali salt.
In contradistinction to the hydrophile green acids, there occurs, as in the manufacture of medicinal white oil, the oil-soluble type or the mahogany acids. These mahogany acids are characterized by being soluble in oil, especially when anhydrous, and being soluble in oil, even if they contain some dissolved water. Some of the mahogany acids also show limited hydrophilic properties to the extent that either some water can be dissolved in the acids, or they, in turn, may dissolved to some extent in water. In some instances their salts, such as the sodium, ammonium, or potassium salt, will dissolve in water to give a colloidal sol. However, regardless of the presence of any hydrophilic properties whatsoever, they always have a charactertistic hydrophobe property, as indicated by the fact that the substantially anhydrous form, for instance, their alkali salts containing 5-12% water,
' will dissolve in oil. i This clearly distinguishes them from the green acids previously referred to, because the green acids in similar form containing the same amount of water, for example,
will not dissolve in oil. The green acids, as such,
For purpose of convenience, they will be herein as are essentially hydrophilic and non-hydrophobic in character.
The utility of the mahogany acids in various arts has been enhanced by increasing their water solubility; for instance, converting the mahogany acids into hydroxy alkylamine salts. On the other hand, as far as I am aware, no valuable product of commerce has resulted from decreasing the water solubility of the mahogany acids by the addition of some oil-soluble basic amine, such, for example, as triamylamine. The triamylamine salts of mahogany acids for example, are completely devoid of any solubility in water which the alkali salts may have exhibited and show, as
would be expected an increased solubility in hydrophobe solvents.
Green acids are hydrophile in character, as previously stated. Their hydrophile character has been increased by neutralization with materials such as triethanolamine and the like. Such green acid salts having enhanced water solubility, as compared with the ordinary alkali salts, have found application in certain arts.
I have found that when green acids, i. e., the oil-insoluble type, are neutralized with a diamine of the kind hereinafter described, so as to produce a water-insoluble product, that the resulting material, even though it does not exhibit any marked oil solubility, especially when it contains 5-10% of water, still has pronounced valueas a demulsifier for oil field emulsions, either when used alone, or in conjunction with other known demulsifying agents. I employ diamines of the kind derivable most readily by reactions involving an aldehyde and a secondary amine, all of which is hereinafter described in detail. I have also found that sometimes such amine salt of green acids will mix in with a hydrophobe material and a hydrophile material, so as to produce a homogeneous mixture. The effectiveness of the above described material or composition of matter as a demulsifying agent for oil field emulsions appears to be related to some factor other than its solubility characteristics.
The new composition of matter which constitutes my present invention is represented by amine salts of hydrophilic non-hydrophobic green petroleum acids, as exemplified by the salt derived from such green acids by neutralization with the diamine obtained by reaction between two moles of diamylamine and one mole of formaldehyde or one mole of acetaldehyde. The manufacture of said composition of matter involves nothing more or less than neutralizing one mole of the selected petroleum acid with a mole of a suitable amine, or neutralizing two moles of the selected petroleum sulphonic acid with one mole of the amine, in that the amine being a diamine, is dibasic. In the latter case, a suitable indicator, such as methyl orange indicator, may be employed. For purposes of convenience, I prefer that the selected petroleum sulphonic acid contain not over 15% of water. It is understood, of course, that the conventional procedure, employing double decomposition instead of direct neutralization, can be utilized in the manufacture of my new material or composition of matter. For instance, the sodium salt of the selected petroleum sulphonic acid can be dissolved in alcohol or other suitablesolvent, and the amine hydrochloride added so that sodium chloride will precipitate. After filtering off the precipitated sodium chloride, the alcohol can be evaporated and the amine salt recovered. If desired, a mix ture of amines instead of a single amine may be employed.
It is well known that certain monocarboxy organic acids, containing approximately eight carbon atoms or more, and not more than thirtytwo carbon atoms, are characterized by the fact that they combine with alkalies to produce soap or soap-like materials. These detergent-forming acids include fatty acids, resin acids, petroleum acids, etc. For the sake of convenience, these acids will be indicated by the formula R.COOH.
It is also well known that diamines, having pronounced basic properties, may be derived by various means, provided that the resultant diamine is characterized by the fact that the two amino nitrogen atoms are not attached to the same carbon atom. Such diamines, generally referred to as alkylene diamines, are well known and may be characterized by ethylene diamine. Derivatives of the diamines herein contemplated are characterized by being a methylene diamine derivative, 1. e., a derivative of the hypothetical methylene diamine ondary amines are available, which may be designated by the formula type:
in which B represents an alkyl, aralkyl, alicyclic, alkylol, aralkylol, hydroxy alicyclic, heterocyclic, or other equivalent radical. B and B jointly may represent one radical, as in piperidine.
It is well known that aldehydes, particularly the aldehydes of relatively low molecular weight,
such as formaldehyde, acetaldehyde, aldol, furfural, benzaldehyde, hexahydro-benzaldehyde, phenyl-acetaldehyde, etc., can combine with two moles of a secondary amine, so as to yield a methylene diamine, characterized by the fact that the two amino nitrogen atoms are attached to the same carbon radical. Such reaction may be indicated in the following manner:
The amine so produced may be indicated by the following formula:
in which, as has been previously pointed out, T may represent a hydrogen atom derived from formaldehyde, or may represent a radical derived from acetaldhyde, propionaldehyde, butyraldehyde, heptaldehyde, lauric aldehyde, palmitic aldehyde, or stearic aldehyde.
Similarly, instead of aliphatic aldehydes, one may employ heterocyclic aldehydes, such as furfuraldehyde, or aromatic aldehydes, such as benzaldehyde. Unsaturated aldehydes, such as acrolein, crotonaldehyde, tiglic aldehydes, may be employed. As previously indicated, Brepresents a radical, such as the methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, hexadecyl, octadecyl, or a similar radical. Similarly, B may represent an. aralkyl radical, such as a benzyl radical, ethyl benzyl radical, dimethyl benzyl radical, an alicyclic radical, such as the cyclohexyl, methyl cyclohexyl, etc.; likewise, B may represent a hydroxy ethyl, hydroxy propyl, hydroxy butyl, and similar radicals, such as a CeH4C2H4OH radical, or a CsHmOI-I radical; Other radicals include the furfural radical, or hydroxy derivatives thereof. Piperidine may be considered as a special adaptation in which one radical replaces two amino hydrogen atoms.
It is to be noted that the methylene diamine, expressed by the above formula, is a tertiary diamine in the sense that neither amino nitrogen atom has attached thereto a replaceable hydrogen atom. For convenience, the above formula may be rewritten as follows, so as to indicate such instances where there is present an alcoholic hydroxyl radical:
in which B OH is obviously the monovalent hydroxy hydrocarbon radical, such as an alkylol radical or the like. Needless to say, B'OH may occur more than once, and B may occur less than three times. It is well known that amines such as triethanolamine or the like can be acylated by reaction with fatty acids or a suitable functional derivative thereof, such as the acyl chloride or the anhydride, or even the ester. If the tertiary hydroxy methylene diamine of the kind just described is reacted with a detergent-forming monobasiccarboxy acid, the reaction may be indicated in the following manner:
with the formation of an intermediate ester which may be indicated in the following manner:
In addition to aldol, other similar hydroxy aldehydes or aldehyde-alcohols may be employed. As to such aldehydes other than aldol, reference is made to Richters Organic Chemistry, volume 1, third English edition, 1934, pages 389-391.
In view of what has been said previously, it does not appear necessary to enumerate various suitable amines which may be employed, but it may be well to indicate that among those which may be employed are the following: diethanole amine, dipropanolamine, dibutanolamine, dipentanolamine, dioctanolamine, glyceryl dihexanolamine, methyl glycerylamine, ethyl glycerylamine, propyl glycerylamine, cyclohexyl glyceryltil amine, benzyl glycerylamine; dibenzylamine, ethyl benzylamine, methyl benzylamine, propyl benzylamine, cyclohexyl ethylamine, cyclohexyl propylamine, cyclohexyl hexylamine, diethylamine, dipropylamine, diamylamine, dihexylamine, dioctylamine, diglycerylamine, etc. In all the previous examples, each radical indicates a substituent for an amino hydrogen atom. Similarly, amines can be obtained from polyglycerols or polyglycols, as for instance, the secondary amines, indicated by the following formulas:
Such amines may serve as functional equivalents of the previously described amines, which happen to be free from an ether linkage. Likewise, one may have amines in which there is more than one ether linkage, i. e., in which the hydrocarbon radical, which replaces an amino hydrogen atom, has been interrupted more than once by an oxygen atom.
In examining the previous formulas, it becomes evident that if two different amines are employed the reaction is not limited to the two dissimilar amines, but may take place in part in such a manner as to involve two similar amines. In other Words, if the two different amines be indicated as A and B, the reaction is not limited to the diamine involving both A and B, but in part the diamine will be formed solely from two molecules of A, and in part solely from two molecules of B. For practical purposes, then, it is most expedient, in the majority of instances, to manufacture or produce a methylene diamine from a single kind of secondary amine; and in such event, everything else being equal, it is most desirable to use the cheapest secondary amine available that will produce at least a fairly waterinsoluble product, and the cheapest aldehyde available. I particularly prefer to use diethanolamine and to completely or at least partially esterify the diethanolamine with a long chain carbon atom acid, particularly a detergent-forming acid, having at least 8 carbon atoms and not more than 32 carbon atoms, such as oleic acid, naphthenic acid, or abietic acid. Naturally the introduction of one or more of such long chain carbon compounds greatly increases the oil solubility of the amine; and such oil solubility is transposed, at least in part, to the final product, which is a salt of the sulphonic acid. As previously pointed out, it is not believed that oil solubility per se is the index as to effectiveness of the demuisifying agent. One may, of course, employ the hydroxylated diamine Without acylation, but in such event, my experience has been that it is more preferable perhaps to employ diamylamine. Similarly, attention is again directed to the fact that wherever hydroxyl radicals exist, then such hydroxyl radical might be reacted with an acid having less than 8 carbon atoms, for instance, acetic acid, butyric acid, heptoic acid, etc. More than one hydroxy hydrocarbon radical, if present, may be acylated, and if two or more such radicals are reacted with acids, one need not employ the same acids, but different acids may be employed. A hydroxy radical attached to the aldehyde residue may be similarly acylated, as, for example, the residue from aldol. A compound, such as sodium hydrogen phthalate, might be used for acylation.
My preferred reagent is manufactured in the following manner:
Two moles of diamylamine are cautiously reacted with a solution of formaldehyde, or preferably, with acetaldehyde, with cooling during the early stages to prevent the reaction from taking place too rapidly, and with a slight application of heat during the latter stages, so as to obtain complete reaction,
The methylene diamine so obtained may be indicated by the following formula:
C511 CH3.C
If desired, of course, the product obtained by reaction can be purified in the customary manner, so as to remove any unreacted aldehyde, and also any unreacted simple secondary amine. However, if the reaction is conducted carefully, a substantial and generous yield of the desired cliamine is obtained, and it is unnecessary to resort to any purification. It has been previously pointed out that having obtained an amine of the kind desired, it is only necessary to proceed to neutralize the green acid, as previously indicated.
Incidentally, it may be well to point out that one particularly desirable mixture of diamines is obtained by employing one mole of diethanolamine and one mole of diamylamine in connection with one mole of acetaldehyde. ant product so obtained will average two hydroxyl radicals per molecule; and one hydroxyl radical can be readily eliminated by acylation with one mole of a selected acid, particularly oleic acid or naphthenic acid. If desired, both hydroxyl radicals may be eliminated. In this instance the long carbon chain attached to an amino nitrogen atom is interrupted by an oxygen atom. It is understood in the hereto appended claims that reference to a hydrocarbon radical includes such radicals that are essentially hydrocarbon in nature, which include carbon atom chains that are interrupted at least once by an oxygen atom. This would occur, of course, in linkages such as the following:
Ncinioon where R is the hydrocarbon radical derived from naphthenic acid, oleic acid, acetic acid, heptoic acid, or the like. Acylation can be accomplished by any suitable acid compound, such as the acyl chloride, the anhydride, etc. If an amine salt is formed, such as the hydrochloride, it must be converted into a base by conventional treatment with strong caustic soda or the like.
Returning momentarily to the preparation of the preferred reagent, no additional information is required. However, it may be well to point out that I prefer to use a green acid selected so The resultthat it is relatively free from inorganic acid, such as sulphurous acid and sulphuric acid, and containing not over 15% water, and preferably, as little unsulphonated hydrocarbon material as possible. A convenient amount of such material, for instance, a thousand pounds, is neutralized with a diamyl diamine previously described, so that the resultant compound indicates neutral or slightly basic to methyl orange, or some other acceptable indicator.
It may be well to point out that hydrophile non-hydrophobe petroleum sulphonic acid or acids of the green acid type vary somewhat; for instance, the molecular weight may vary within the range of 350-500 or thereabouts. Naturally, these petroleum sulphonic acids may carry some polymerized olefins, free hydrocarbons, or the like or may even carry a bit of naphthenic acids which represent carboxylated non-sulphonated petroleum acids. As previousl stated, these materials are well known commercial products, and are available in the open market, either in the form of the acid itself, or in the form of a salt.
In the claims the amine or, more specifically, the diamine, is referred to asbasic to indicate that the basicity is in the neighborhood of that of ammonia, triethanolamine, or amylamine. In some instances the basicity may be somewhat greater, in fact, perhaps considerably greater, and in some instances perhaps slightly less. In order to insure such basicity, it is necessar that there be no aryl or aromatic radical attached to the amino nitrogen atom from which the diamine is produced. In other words, such material as phenyl amylamine, diphenylamine, phenyl octylamine, etc., are not satisfactory, due to the presence of the aromatic phenyl radical or an aryl radical, such as the naphthyl radical attached directly to the amino nitrogen atom. In the event that such aryl radical is attached to the amino nitrogen atom, the basicity of the amine is reduced to that of the aniline, or the like. Such amines of low basicity do not form stable salts with the petroleum acids of the kind described. For this reason the expression basic is employed to clearly characterize the amine. The term sulphonic acid used in the claims is intended to refer to a substance consisting either of a single acid or a mixture of acids.
In my divisional application Serial No. 300,843, filed October 23, 1939, I have described a novel process for resolving or breaking petroleum emulsions of the water-in-oil type. Said process involves subjecting the emulsion to the action of a demulsifier consisting of the above described new material or composition of matter. Said material is used either alone or in admixture with another or with other conventional demulsifying agents, and its method of use is the same as that generally employed in resolving or breaking petroleum emulsions of the water-in-oil type with a chemical demulsifier. Briefly stated, the conventional method of using a chemical demulsifier to break a petroleum emulsion consists in introducing the demulsifier into the well in which the emulsion is produced; introducing the demulsifier into a conduit through which the emulsion is flowing; or introducing the demulsifier into a tank in which the emulsion is stored. After treatment the emulsion is allowed to stand in a quiescent state, usually in a settling tank, and usually at a temperature varying from atmospheric temperature to about 200 F., so as to permit the water or brine to separate from the oil, it being preferable to keep the temperature low enough to prevent th volatilization of valuable constituents of the oil. The amount of demulsifier that may be required to break the emulsion may vary from 1 part of demulsifier to 500 parts of emulsion, up to 1 part of demulsifier to 20,000 or even 30,000 parts of emulsion.
I desire to point out that the superiority of the reagent or demulsifying agent herein described is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but I have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.
I claim:
1. A new compound consisting of a waterinsoluble salt of a basic, methylene diamine of the formula type:
in which T is selected from the class consisting of hydrogen atoms, hydroxy alkyl radicals and aliphatic hydrocarbon radicals and B is selected from the class consisting of aliphatically-bound hydrocarbon radicals, alicyclic hydrocarbon radicals, aliphatic hydrocarbon radicals interrupted at least once by an oxygen atom, aliphatically-bound hydroxy hydrocarbon radicals, hydroxy alicyclic radicals, and radicals obtained by the acylation of a hydroxy hydrocarbon radical in which the acylating compound is derived from an acid containing not more than 32 carbon atoms, at least one of the radicals represented by B being such an acylated hydroxy hydrocarbon radical; said diamine salt being obtained from water-soluble, non-hydro-phobe petroleum sulphonic acid of the green acid type.
2. A new compound consisting of a water-insoluble salt of a basic, methylene diamine of the formula type:
in which E is selected from the class consisting of aliphatically-bound hydrocarbon radicals, alicyclic hydrocarbon radicals, aliphatic hydrocarbon radicals interrupted at least once by an oxygen atom, aliphatically-bound hydroxy hydrocarbon radicals, hydroxy alicyclic radicals, and radicals obtained by the acylation of a hydroxy hydrocarbon radical in which the acylating compound is derived from an acid containing not more than 32 carbon atoms, at least one of I the radicals represented by B being such an acylated hydroxy hydrocarbon radical; said diamine salt being obtained from water-soluble, non-hydrophobe petroleum sulphonic acid of the green acid type.
3. A new compound consisting of a water-insoluble salt of a basic, methylene diamine of the formula type:
H/ \NB in which T is a hydroxy hydrocarbon radical and B is selected from the class consisting of aliphatically-bound hydrocarbon radicals, alicyclic MELVIN DE GROOTE.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US398494A US2344539A (en) | 1939-05-12 | 1941-06-17 | Salts of certain methylene diamines with certain petroleum sulphonic acids |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US273221A US2270681A (en) | 1939-05-12 | 1939-05-12 | Salts of certain methylene diamines with certain petroleum suphonic acids |
US398494A US2344539A (en) | 1939-05-12 | 1941-06-17 | Salts of certain methylene diamines with certain petroleum sulphonic acids |
Publications (1)
Publication Number | Publication Date |
---|---|
US2344539A true US2344539A (en) | 1944-03-21 |
Family
ID=26956022
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US398494A Expired - Lifetime US2344539A (en) | 1939-05-12 | 1941-06-17 | Salts of certain methylene diamines with certain petroleum sulphonic acids |
Country Status (1)
Country | Link |
---|---|
US (1) | US2344539A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2898267A (en) * | 1955-09-07 | 1959-08-04 | Witco Chemical Corp | Emulsifiable toxicant compositions and emulsifying agents therefor |
US3234270A (en) * | 1957-08-28 | 1966-02-08 | Sinclair Research Inc | Mixed sulfonic-carboxylic acid salts of fatty diamines |
US3268576A (en) * | 1962-01-23 | 1966-08-23 | American Cyanamid Co | Di-alkanoic acid esters of 2, 2'-(ethylenedhino)-di-1-butanols |
-
1941
- 1941-06-17 US US398494A patent/US2344539A/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2898267A (en) * | 1955-09-07 | 1959-08-04 | Witco Chemical Corp | Emulsifiable toxicant compositions and emulsifying agents therefor |
US3234270A (en) * | 1957-08-28 | 1966-02-08 | Sinclair Research Inc | Mixed sulfonic-carboxylic acid salts of fatty diamines |
US3268576A (en) * | 1962-01-23 | 1966-08-23 | American Cyanamid Co | Di-alkanoic acid esters of 2, 2'-(ethylenedhino)-di-1-butanols |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2243329A (en) | Process for breaking petroleum emulsions | |
US2270681A (en) | Salts of certain methylene diamines with certain petroleum suphonic acids | |
US2468180A (en) | Process for breaking petroleum emulsions | |
US2344539A (en) | Salts of certain methylene diamines with certain petroleum sulphonic acids | |
US2353694A (en) | Process for breaking petroleum emulsions | |
US2278163A (en) | Aldimine salts of petroleum sulphonic acids | |
US2226121A (en) | Process for resolving petroleum emulsions | |
US2375899A (en) | Salts of certain substituted aldimines, etc. | |
US2372257A (en) | Process for breaking petroleum emulsions | |
US2226122A (en) | Process for resolving petroleum emulsions | |
US2167349A (en) | Process for breaking petroleum emulsions | |
US2363504A (en) | Process for breaking petroleum emulsions | |
US2231753A (en) | Process for resolving petroleum emulsions | |
US2246856A (en) | Process for resolving petroleum emulsions | |
US2385969A (en) | Process for breaking petroleum emulsions | |
US2250407A (en) | Process for breaking petroleum emulsions | |
US2335262A (en) | Process for breaking petroleum emulsions | |
US2363505A (en) | Process for breaking petroleum emulsions | |
US2226120A (en) | Process for resolving petroleum emulsions | |
US2153744A (en) | Process for resolving petroleum emulsions | |
US2083225A (en) | Process for breaking petroleum emulsions | |
US2344978A (en) | Process for breaking petroleum emulsions | |
US2278164A (en) | Process for breaking petroleum emulsions | |
US2405737A (en) | Certain sulphosuccinates and method of making same | |
US2300554A (en) | Process for breaking petroleum emulsions |