US2980518A - Inhibiting gel formation in fuel oils - Google Patents
Inhibiting gel formation in fuel oils Download PDFInfo
- Publication number
- US2980518A US2980518A US606186A US60618656A US2980518A US 2980518 A US2980518 A US 2980518A US 606186 A US606186 A US 606186A US 60618656 A US60618656 A US 60618656A US 2980518 A US2980518 A US 2980518A
- Authority
- US
- United States
- Prior art keywords
- copper
- carbon atoms
- gel
- fuel oil
- amino groups
- 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
- 239000000295 fuel oil Substances 0.000 title claims description 55
- 230000015572 biosynthetic process Effects 0.000 title claims description 29
- 230000002401 inhibitory effect Effects 0.000 title description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 48
- 150000002430 hydrocarbons Chemical class 0.000 claims description 48
- 239000004215 Carbon black (E152) Substances 0.000 claims description 46
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 25
- 229910052717 sulfur Inorganic materials 0.000 claims description 25
- 239000011593 sulfur Substances 0.000 claims description 25
- 150000004985 diamines Chemical class 0.000 claims description 24
- 239000010771 distillate fuel oil Substances 0.000 claims description 24
- -1 AMINO GROUPS Chemical group 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000005749 Copper compound Substances 0.000 claims description 15
- 150000001880 copper compounds Chemical class 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 7
- 239000000499 gel Substances 0.000 description 95
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 85
- 239000010949 copper Substances 0.000 description 85
- 229940108928 copper Drugs 0.000 description 85
- 229910052802 copper Inorganic materials 0.000 description 85
- 125000004432 carbon atom Chemical group C* 0.000 description 60
- 150000003839 salts Chemical class 0.000 description 30
- 239000000203 mixture Substances 0.000 description 26
- 125000003277 amino group Chemical group 0.000 description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 21
- 229910001369 Brass Inorganic materials 0.000 description 17
- 239000010951 brass Substances 0.000 description 17
- 229920000768 polyamine Polymers 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 125000005608 naphthenic acid group Chemical group 0.000 description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012937 correction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229940095050 propylene Drugs 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000008096 xylene Substances 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229940120693 copper naphthenate Drugs 0.000 description 2
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229940065278 sulfur compound Drugs 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- 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
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 1
- NDKJATAIMQKTPM-UHFFFAOYSA-N 2,3-dimethylbenzenethiol Chemical compound CC1=CC=CC(S)=C1C NDKJATAIMQKTPM-UHFFFAOYSA-N 0.000 description 1
- IYFLSGCPMZKERB-UHFFFAOYSA-N 2,4-dimethylpentane-2,4-diamine Chemical compound CC(C)(N)CC(C)(C)N IYFLSGCPMZKERB-UHFFFAOYSA-N 0.000 description 1
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical class CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 1
- XGJHPGPVESLKKD-UHFFFAOYSA-N 2-ethylbutane-1,4-diamine Chemical compound CCC(CN)CCN XGJHPGPVESLKKD-UHFFFAOYSA-N 0.000 description 1
- MIKNSPXOIZYKIT-UHFFFAOYSA-N 2-methylbutane-2,3-diamine Chemical compound CC(N)C(C)(C)N MIKNSPXOIZYKIT-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WHLFXPIYRPOHGB-UHFFFAOYSA-N 4-methylpentane-1,4-diamine Chemical compound CC(C)(N)CCCN WHLFXPIYRPOHGB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000256844 Apis mellifera Species 0.000 description 1
- WTXLVGDAKGTUEK-UHFFFAOYSA-N C(CCCCCCCC=C/CCCCCCCC)(=O)O.C=C.C=C Chemical group C(CCCCCCCC=C/CCCCCCCC)(=O)O.C=C.C=C WTXLVGDAKGTUEK-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 241000289669 Erinaceus europaeus Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 241000692885 Nymphalis antiopa Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 235000014987 copper Nutrition 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- PXFOUACPROHHPK-KVVVOXFISA-N ethene;(z)-octadec-9-enoic acid Chemical group C=C.CCCCCCCC\C=C/CCCCCCCC(O)=O PXFOUACPROHHPK-KVVVOXFISA-N 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000010742 number 1 fuel oil Substances 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
- 229960002446 octanoic acid Drugs 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 150000002931 p-cresols Chemical class 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
Definitions
- This invention relates to inhibiting the formation of copper mercaptide gels in hydrocarbon distillate fuel oils and to liquefying preformed copper mercaptide gels.
- Another object is to provide concentrated solutions of such inhibitors for ready and economical transportation and use thereof, including particularly for use in liquefying preformed copper mercaptide gel.
- a further object is to provide a process for liquefying' copper mercaptide gel and, particularly, for removing deposits of such gel from equipment.
- Other objects are to provide new compo sitions of matter and to advance the art. Still o her objects will appear hereinafter. 3
- a hydrocarbon distillate fuel oil which contains at least one mercaptan which normally tends to form a copper mercaptide gel and to which fuel oil th'ere has been added a small proportion, sufficient to inhibit such gel formation, of at least one polyamino compound of the group consisting of alkylene primary dia mines of2 to 10 carbon atoms in which the primary amino groupsare separated by 2 to 6 carbon atoms, dialkylenetriamines of 4 to '10 carbon atoms in which the amino groups 'are'separated by 2 to 4 carbon atoms and two of the amino groups are primary amino groups, and mono-acid salts of said diamines and said triamines in which the acids are selected from the group consisting ofmonocarboxylic fatty acids of 8 to about 22 carbon atoms,monohydric mononuclear phenols, and monocarboxylic petroleum naphth enic acids of about 8 to about 29
- Sulfur-compounds generally occur as impurities in all petroleum hydrocarbon products, the type and quantity of the sulfur compounds being'determined by the source 1 r and previous processing history of the petroleum product.
- Mercaptans in particular, have hithertobeen objection- "able to the industry for various reasons (odor, corrosiveness, .etc.) and many processes have been devised. for
- polyamino compounds of this invention when added 'in a small. proportion 'to a hydrocarbon distillate fuel oil that contains at least one mercaptan which normally tends to form' a copper merecaptide gel when the fuel oil is brough into contact with copper or brass, are very effective *to'inhibit such gel formation and the depositionof 'such' gelmon surfaces with which the fuel oil may bebrought into'co'n'tact.
- the alkylene primary diamines and" the dialkylene .triamines together may be represented by the formulaz .urated aliphatic hydrocarbon radical C H and the nitrogen atoms are bonded to different carbon, atoms.
- m is equal to 0
- n representsran integer of V2 to 10, preferably 2 6
- an'd the- .twoNHg groups are separated by 2 m6 carbon-atoms, preferably 2m. 4 carbon atoms.
- Inthedialkylene tri amines,.'m is equalto 1, n in each alkylene grouprepresents an integer-of 2 to'8, preferably 2- to'-4, and the.
- Thef'amino 'groups may lac attached to primary, secondary ortertiar-y carbon atoms; the term;.primary.gin;falkylenepringary qdiarnine referring, toithe primary amino groups (*NHQ.
- the alkylene units may be the same or difierent.
- alkylene diamines are: ethylene diamine; 1,2-propylene diamine; 1,3-propylene diamine; l,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane; the 1,2-, 1,3-, 1,4-,and 2,3-butylene diamines and carbon-alkylated derivatives such as 2,3-diamino-2- methylbutane and 1,4-diamino-2-ethylbutane; pentylene diamines typified by 1,2-, 2,4-, and 1,5-diaminopentane, including carbon alkylated compounds such as 1,4-diamino-4-methylpentane and 2,4-diamino-2,4-dimethylpentane; hexylene diamines represented by 1,6-hexylene diamine (hexamethylene diamine) and 2,4-hexylene diamine, and including higher homologs such
- Typical dialkylene'triamines of this invention are: 1,2- diethylene triamine; 1,2- and 1,3-dipropylene triamine; and the corresponding dibutylene triamines in which each pair of nitrogen atomsin the chainis separated by at least 2 carbon atoms.
- Fuel oil soluble mono-acid salts of the hereinbefore defined alkylene primary diamines and dialkylene triamines. are also effective for the purposes of this invention.
- Such mono-acid salts contain one mole of the acid. for each mole of the polyamine and are prepared by methods well known and conventional in the art, such as by mixing the polyamine with the organic acid in equimolecular proportions at atmospheric temperature, the reaction being substantially instantaneous.
- Suitable organic acids are monocarboxylic fatty acids of 8 to about 22 carbon atoms, monohydric mononuclear phe- 11015, and monocarboxylic petroleum naphthenic acids of about 8 to about 29 carbon atoms.
- These mono-acid salts offer the advantageof increased .fuel oil solubility over the corresponding polyamine, especially with the "lower members of the series, e.g., ethylene diamine and diethylene triamine. They are particularly desirable for the preparation of concentrated solutions in normally liquid hydrocarbons.
- Representative monocarboxylic fatty acids of this in .vention are ole'ic acid, caprylic acid, pelargonic (nonanoic) acid, undecylic acid, lauric acid, stearic acid, linoleic acid, linolinic acid, behenic'acid, and the like. Oleic 'acid is preferred.
- monohydric mononuclear phenols are phenol, thecresols, the ethyl phenols, the xylenols, and the like. Particularly desirable are the commercially available mixturese known as cresylic acids (a mixture of o-, mand p-cresols) and xylenols. Such mixtures result in mixtures of the mono-acid polyamine salts of -cyclopentane, its homologs and bicyclic derivatives.
- carboxyl group is usually attached to a' parafi'inic side refined commercial naphthenic acids, and hence are mixtures of the mon-acid salts of the several napthenic acids.
- hydrocarbon distillate fuel oils to which the polyamino compounds of this invention are to be added, are the hydrocarbon distillates which areheavier than gasoline and which are known to the art as furnace oil, burner oil, heating oil, range oil, diesel fuel, jet fuel, and fuel oil. In general, these. oils have a boiling range of frornabout 300 F. to about 750 F.
- the hydrocarbon distillate fuel oils contain active mercaptans.
- Active mercaptans are those which, when fuel oil containing them is brought into contact with copper, copper compounds. or brass, will react therewith to form copper mercaptides that form copper mercaptide gels.
- the most active mercaptans are. the aliphatic mercaptans, the activity thereof decreasing from the primary to the secondary to the tertiary mercaptans.
- aromatic mercaptans alone do notform solid copper mercaptide gels but, in the presence of an aliphatic primary mercaptan, they and the aliphatic secondary and tertiary mercaptans appear to contribute to the formation of such gels.
- the quantity of polyamine compound of this invention which will be added'to a hydrocarbon distillate fuel oil is from 0.1 to. about 5 parts byweight for each part of active'rnercaptan sulfur present in the fuel oil, preferably from about 0.5 to about 3 parts by weight.
- this will be from 0.0001% toabout 0.15% by weight based on the fuel oil, preferably from about 0.0005% to chain of the ring, but may be directly attached to a ring carbon atom'.
- naphthenic acids of frorn*7'.or 8 to about '29 carbon atoms usually not more than 20 carbon'fatoms and av eraging about 12 to 14 carbon atoms, sometimes also containing minor proportions of fatty acids and carboxylic acids derived from cyclohexane and its homologs.
- Refined comniercialnaphthenic acids generally have an apparent molecularweight of 'abputi200-250which cerrespondstoanaverage of 1 2 to 14 carbon atoms in the molecule.
- the naphthenic acid .morio ,salts" or mono- 'naphthenates of the examples were prepared from such about 0.1%. Larger a mounts of polyamine compound may be used, but generally. will be wasteful unless the fuel oil contains unusually large amounts of active mercaptan sulfur or it is to be used in equipment whichuis already fouled with copper mercapticle gel.
- 'Afpolyamino compound of this invention or a mixture of any two or more thereof may be added as such to the hydrocarbon distillate fuel oil at atmospheric temperature or, if desired, at moderately elevatedterhperature and stirring until solution is complete.
- the polyamin'o compound or mixture of compounds will be'add'ed in the form of a concentrated solution in a normally liquid hydrocarbon, such as benzene,
- the polyamino compounds will be in a Concentration of from about to about 70% by weight, preferably from about 30% to about 50% by weight.
- These concentrated solutions represent the commercial form in which the polyamino compound will be shipped to the refiner for addition to the fuel oil to be treated. Such solutions are more convenient to transport, to handle (e.g. pour) and to measure.
- the maximum concentration obtainable will depend upon the solubility of the polyamino compound in the liquid hydrocarbon and, for this purpose, it will be most desirable to employ those compounds of high solubility, preferably the mono-acid salts of the polyamines.
- the concentration of the solution increases with increase in concentration of polyamino compound therein, the concentration generally will be limited by the maximum viscosity which can be efiiciently poured and measured, usually a concentration of not more than about 50% by weight being optimum for this purpose.
- the concentrated solutions are suitable for this purpose, preferably those in which the polyamino compounds are in a concentration of from about 15% to about 30% by weight, particularly in kerosene. As little as 1 part of polyamino compound is elfective to liquefy up to 100 parts .by weight of gel. Larger amounts may be used, but large excesses are wasteful.
- feed lines can be disconnected from the fuel oil storage '6 it is was used or'handled in a concentrated solution-,the concentration thereof, and whether it isto'be; usedto break up preformed gel. While any of the polyamino compounds of this invention may be used very effectively to inhibit copper mercaptide gel formation in fuel oil,
- the polyamino compounds vary in effectiveness, hexamethyle'ne diamine being much less effective for this purpose than those diamines in which the amino groups'are separated by fewer carbon atoms, the effectiveness increasing with decrease in the numberof carbon atoms-separating the amino groups.
- alkylene diamines in which the two amino groups are separated by 2 to 4 carbon atoms
- Higher polyalkylene polyamines i.e., the trialkylene tetramines and the tetraalkylene pentamines, have little orno effect to inhibit the formation of copper merca'p- I tide gel in fuel oil or to break up preformed gel.- For example, it has been found that tetraethylene pentamine neither inhibits nor breaks up copper mercaptide gel.
- polyamino compounds of this invention may be employed in hydrocarbon distillate, fuel oils along .with other additives which are conventionally employed to impart other desirable characteristics to the, base oil,
- Example I J A 'five" portion of catalytically cracked pf ilel oil containing a) a total of 0.4.weight percent mercaptan sulfer present as added dodecyl' mercaptan and" (b) 0.1
- Example2 h A solid copper mercaptide gel was prepared by mixing (a) an equal volume of catalytically cracked fuel oil containing 0.4 weight percent mercaptan sulfur, present :as added dodecyl mercaptan, with (b) anequal volume of fuel oil containing 0.4% copper, present as added copper naphthenate. To samples of this 'solid gel (9 parts each) was added from 0.15 to 0.25 part of diethylene triamine and themixture was shaken. .In a few moments, the gel broke up (completely liquefied), in each case, the original straw color changing to the bluishgreen color of the copper-polyamine complex.
- Solid copper mercaptide gel (containing 0.2 weight percent copper) was prepared by mixing equal volumes of catalytically cracked fuel oil containing, respectively, 0.4 weight percent mercaptan sulfur ,as a 1:1 mixture of dodecyl. and xylylmercaptans and 0.4% copper as the naphetenate.
- One part samples of the gel were brokenup by adding 0.1 part of oleic acid mono salt ofethylene diamine (prepared by mixing 1 mole. of oleic acid and 1 mole of ethylene diamine).
- Cresylic acid mono salt of ethylene'diamine 0.2 part
- Naphthenic acid mono salt of ethylene diamine 0.2
- Example 4 c accelerated test, simulating field conditions, was devised todetermine the sensitivity of fuel oils to copper mercaptide gel formation and to evaluate the eifectiveness of various materials as inhibitors of gel formation.
- the test comprises passing or circulating (i.e. any number of passes) a sample of fuel oil over a specially prepared ,(corroded).
- the copper strips maybe stored in a tightly capped bottle forlO -IS days.
- f 150 ml. of henacne and 30 mlgof concentrated aqueous ammonium hydroxid are mixed and shakeri' vigorously for- 2 to 3 1 minutes to saturate the benzene with ammonia! -Ihe mix- "ture is allowed to' separate for to minutes and the aqueous layer is drawn off and' discarded.
- *Two or three polished copper strips, prepared as described above, are i immersed in the ammonia-saturated benzene for 24 hours.
- the active mercaptan content of fuel oil samples were standardized by incorporating in them known quantities of active mercaptans such as dodecyl mercaptan or 1:1 mixture of dodecyl mercaptan and xylyl mercaptan.
- this invention providesnovel means and methods for inhibitcentrated solutions useful for preparing such fuel oil compositions and for breaking up preformed gels and clean ing equipment containing them.
- this invention solvesserious problems of the art and constitutes a valuable improvement in and contribution to the art.
- a hydrocarbon distillate fuel oil which is in contact with a member of, the group consisting of copper, copper compounds and'brass, and which contains at least one mercaptan which normally tends to form a copper mercap tide gel, and a small proportion sufficieritto inhibit such to, 10 carbon atoms" in which the amino groups are sepselectedfrom the group consistingof monocarboxylicfatty nuclear phenols; and.
- a hydrocarbon distillate fuel oil which is in contact with a member of the group' consisting'of copper, copper compounds and brass, and which contains at least one mercaptan which normally tends to form a copper mer- ,captide gel, and from about 0.5 to about 3 parts-byw weight for eaclipartvof active mercaptan sulfur present in the fuel oil'of at least one polyamino compound of the group consistingtofalkyleneprirnary diamines of 2 to 10' carbon altomsin whichthe primary amino groups are separated by 2'to 6 carbon atoms, dialkylene triamines of 4 to 10 carbon atomsinwhich the amino groups are separated by Zto 4'carbon'atoms and two of the amino groups are primary amino groups, and mono-acid salts of said diamines ltindsaid'triamines in which the acids are selected from the group"consisting of monoca'rboxylic fatty acids of 8,to about 22" carbon atoms, monohydric mononucle
- hydrocarbon distillate fuel oil which is in contact with a men'iberof the group consisting of copper, copper compounds and brass, and which contains at least one mercaptan which normally tends to form a copper flarept-ide gel, "and a small" proportion suflici'ent' to iilhibit gel format ion-of at least one alkyleneprimary di- -amine:of-'2 to 6 carbon' atoms in which the primary amino groups are separated byz'to 3 carbon atoms,'saiddiamine "Being in a'proportion' of 1' toabout pa'rfts thereof for each part of active mercaptan: sulfur in the fuel oil a 5.
- a hydrocarbon distillate fuel oil which is in contact with a member of the group consisting of copper, copper compounds and brass, and which contains at least one mercaptan which normally tends to form a copper mercaptide gel, and a small proportion sufficient to inhibit such gel formation of at least one propylene primary diamine in which the primary amino groups are separated by 2 to 3 carbon atoms, said diamine being in a proportion of 0.1 to about 5 parts thereof for each part of activev mercaptan sulfur in the fuel oil.
- a hydrocarbon distillate fuel oil which is in contact with a member of the group consisting of copper, copper compounds and'bra'ss, and which contains at least one mercaptan which normally tends to form a copper mercaptide gel, and a small proportion sufficient to inhibit such gel formation of at least one dialkylene triamine of 4 to carbon atoms in which the amino groups are separated by 2 to 4 carbon atoms and two of the amino groups are primary amino groups, said triamine being in a proportion of 0.1 to about Sparts thereof for each part of active mercaptan sulfur in thefuel oil.
- a hydrocarbon distillate fuel oil which is in contact with avme'mber of the group consisting of copper, copper V compounds and brass, and which contains at least one mercaptan which normally tends to form a copper rrlercaptide gel, and a small proportion sufficint to inhibit such gel formation of at least one dialkylene triamine of 4m 8 asserts carbon atoms in which the amino groups arefseparated r with-a member of the group consisting of copper; copper compounds and brass, and which contains at least one mercaptan which normally-tends to form a copper mercaptide gel, and a small proportion sufficient to inhibit such gel formation of diethylene triamine, said triamine being in a proportion of 0.1 to about 5 parts thereof for each part of active mercaptan sulfur in the fuel oil.
- a hydrocarbon distillate fuel oil which is in contact with a memberof the group consisting of copper, copper compounds and brass, and which contains at least one mercaptan which normally tends to form a'copper mercaptide gel, and a small proportion suflicient to inhibit such gel formation of at least one mono-acid salt of an alkylene primary diamine of 2 to 10 carbon atoms in which the prmiary amino groups are separated by 2 to 6 carbon atoms, the acid component of said salt being a monocarboxylic fatty acid of 8 to about 22 carbon atoms, said salt being in a proportion equivalent to 0.1 to about 5 parts of diamine for each part of active mercaptan sulfur in the fuel oil.
- a hydrocarbon distillate fuel oil which is in contact with a member of the groupconsisting of copper,copper compounds and'brass, and which contains at least one mercaptan which normally tends to form a copper mercaptide gel, and a small proportion sutficient to inhibit such gel formation of at least one monooleate of an alkylene primary diamine of 2 to 6 carbon atoms in which the 7 primary amino groups are separated by 2 to 3 carbon atoms,,said monooleate being in a proportion equivalent to 0.1 to about 5 parts of diamine for each part of active mercaptan sulfur in the fuel oil.
- a hydrocarbon distillate fuel oil which is in contact with a member. of the group consistingof copper, copper acid component of said salt being a monocarboxylic fatty acid of 8 to about 22 carbon atoms, said salt being in a proportion equivalent to 0.1 to about 5 parts of triamine for eachhpart of active mercaptan sulfur in the fuel oil.
- a hydrocarbon distillate fuel oil which is in contact with amember of the group consisting of copper', copper compounds and brass, and which contains at least one mercaptan which normally tends to form a copper mercaptide gel, and a small proportion sufiicient to inhibit such gel formation of at least one monooleate of a dialkylene triamine of 4 to 8 carbon atoms .in which the amino groups are separated by2 to 3 carbon atoms and two of the amino groups are primary amino groups, said monooleate being in a proportion equivalentto 0.1 to about 5 parts of triamine for each'part of activemercaptan sulfur in the fuel oil.
- A'hydrocarbon distillate fuel oil which is in contact with a member of the group consisting of copper, copper compounds and brass, and which contains at least one mercaptan which normally tends to form a copper mercaptide gel, and a small proportion suificient to inhibit such gel formation of diethylene triamine monooleate, said monooleate beingin a proportion equivalent to' 0.1 to
- a composition for liquefying' a gel, formed by the action of a copper mercaptide on a normally liquid hydrocarbon .which composition consists essentially of a normallyliquid hydrocarbon having dissolved therein, in a concentration of from about 15% to about 70% by weight, .at least one polyamino compound ofithe group consisting of alkylene primary diamines of 2 to carbon atoms inwhich the primary ,amino groups are separated by 2 to 6 carbon atoms, dialkyl ene triamines of 4 to 10 carbon atoms in which the amino groups are separated by 2 to 4 carbon atoms and two of the amino groups are primary amino groups, and mono-acid salts of said diamines and said triamines in which the acids are selected from the group consisting of monocarboxylic fatty acids of 8 to about 22 carbon atoms, monohydric mononuclear phenols, and monocarboxylic petroleum naphthenic acids of about 8
- a composition for liquefying a gel, formed by the action of a copp r mercaptide on a normally liquid hydro carbon which composition consists essentially of a nor mally liquid hydrocarbon having dissolved therein, in a concentration of from about to about,50% by weight,
- a 19 The process for lique'fyinga gel,,formed by the action of a copper mercaptide ona normally liquid hydrocarbon, which comprises adding to said gel at least 1% by weight of at least one alkylene primary diamine of 2 to 4 carbon atoms in which the primary amino, groups are'separated by 2 to 3 carbon atoms.
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)
- Solid Fuels And Fuel-Associated Substances (AREA)
Description
U t Sta s ate INHIBITING GEL FORMATION 1N FUEL OILS Philip L. Bartlett, Wilmington, Del., assignor to E. L dn Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Aug. 27,1956, Ser. No. 606,186
20 Claims. (Cl. 44 66) This invention relates to inhibiting the formation of copper mercaptide gels in hydrocarbon distillate fuel oils and to liquefying preformed copper mercaptide gels.
It is known that a gel frequently is formed in hydrocarbon distillate fuel oils under storage andservice conditions, such as in domestic oil burner installations, diesel service and the like, and forms gelatinous deposits in the equipment which plug lines, orifices, filter screens, and the like. The gel is formed in the presence of copper or brass equipment, such as brass filters, floats and needle valves, and copper tubing and contains copper mercaptides which act as the gelling agents. This gel' is con- I mately 0.1 to" 1.0%), the copper being in the cuprous' form, and .of major proportions of hydrocarbon components (at least 95% and sometimes over 99%); also small quantities of oxygenated material and water are 2,980,518 n ed Arr- .18, 19
sition of such gels on surfaces'in contact therewith. All? other object is to provide concentrated solutions of such inhibitors for ready and economical transportation and use thereof, including particularly for use in liquefying preformed copper mercaptide gel. A further object is to provide a process for liquefying' copper mercaptide gel and, particularly, for removing deposits of such gel from equipment. Other objects are to provide new compo sitions of matter and to advance the art. Still o her objects will appear hereinafter. 3
The above and other objects may beaceomplished in accord with this invention which comprises (1) a hydrocarbon distillate fuel oil which contains at least one mercaptan which normally tends to form a copper mercaptide gel and to which fuel oil th'ere has been added a small proportion, sufficient to inhibit such gel formation, of at least one polyamino compound of the group consisting of alkylene primary dia mines of2 to 10 carbon atoms in which the primary amino groupsare separated by 2 to 6 carbon atoms, dialkylenetriamines of 4 to '10 carbon atoms in which the amino groups 'are'separated by 2 to 4 carbon atoms and two of the amino groups are primary amino groups, and mono-acid salts of said diamines and said triamines in which the acids are selected from the group consisting ofmonocarboxylic fatty acids of 8 to about 22 carbon atoms,monohydric mononuclear phenols, and monocarboxylic petroleum naphth enic acids of about 8 to about 29 carbon atoms; (2) the process .of liquefying a gel, formed by the action of a copper mercaptide on a normally liquid hydrocarbomby adding'to said gel at least '1% by weight'of at least oneof said polyamino compounds, as such or as a concentrated sohrtion in a normally liquid hydrocarbon; and (3) concertoften present. The usual fuel oil sludge inhibitors are ineffective in preventing formation of such gel andin breaking-up existing gel.
Sulfur-compounds generally occur as impurities in all petroleum hydrocarbon products, the type and quantity of the sulfur compounds being'determined by the source 1 r and previous processing history of the petroleum product. Mercaptans, in particular, have hithertobeen objection- "able to the industry for various reasons (odor, corrosiveness, .etc.) and many processes have been devised. for
ing them" more or less completely from petroleum products. "How ever, likev all refining processes, these are costly,and some are ratherinefiicient. in destroying or removing mercaptans. .As a result, many hydrocarbon distillate fuels are often marketed unrefined or only partially refined, with mercaptans. still present in various amounts, depending ontheirflultimate -use,1,part i'cularly* 'fuel oils. designatedas'burner, heating, orfurnace oil. The mercaptansjulfur"content. of such fuel oils mayrange from as low *as:0.00 1 weight percentfto :as high as about Where careful; refining of1all: gradesv of hydrocarbon equipment.
' Iris an object of'this invention to v provide hydro carbon distillate fuel oils containingcompounds which inhibit the formation .otcopper mercapti'de gel; therein and the: depoconverting them into innocuous materials or for eliminati where m is is equal to 0 or 1 aIk-ylene is a divalent sattrated solutions of at least one ofsaid polyamino conr pounds in a normally liquid hydrocarbon.
It has been found that the polyamino compounds of this invention, when added 'in a small. proportion 'to a hydrocarbon distillate fuel oil that contains at least one mercaptan which normally tends to form' a copper merecaptide gel when the fuel oil is brough into contact with copper or brass, are very effective *to'inhibit such gel formation and the depositionof 'such' gelmon surfaces with which the fuel oil may bebrought into'co'n'tact. It has been found further that when smallproportion's of said polyamino compounds, as such or as'concentrated solutions in normally liquid hydrocarbons, are'addedfto copper mercaptide gels, the gels are broken up (liquefied) and can be readily removed from equipmentby washing with'a normally liquidhydrocarbon, whereby such equipment can be unplugged and cleaned of'such'gelswithout stripping down or dismantling the equipment.
. The alkylene primary diamines and" the dialkylene .triamines together may be represented by the formulaz .urated aliphatic hydrocarbon radical C H and the nitrogen atoms are bonded to different carbon, atoms. In the alkylene primary diamines, m is equal to 0, n representsran integer of V2 to 10, preferably 2 6,"an'd the- .twoNHg groups are separated by 2 m6 carbon-atoms, preferably 2m. 4 carbon atoms. Inthedialkylene tri amines,.'m is equalto 1, n in each alkylene grouprepresents an integer-of 2 to'8, preferably 2- to'-4, and the.
5 groups may :be straight or branched chain. Thef'amino 'groupsmay lac attached to primary, secondary ortertiar-y carbon atoms; the term;.primary.gin;falkylenepringary qdiarnine referring, toithe primary amino groups (*NHQ.
s In the dialkylene triamines, the alkylene units may be the same or difierent. Homologous alkylene primary diamines and dialkylene triamines containing more than 'carbon atoms, while operable, are generallyless desirable for reasons of cost and economy.
j Representative alkylene diamines are: ethylene diamine; 1,2-propylene diamine; 1,3-propylene diamine; l,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane; the 1,2-, 1,3-, 1,4-,and 2,3-butylene diamines and carbon-alkylated derivatives such as 2,3-diamino-2- methylbutane and 1,4-diamino-2-ethylbutane; pentylene diamines typified by 1,2-, 2,4-, and 1,5-diaminopentane, including carbon alkylated compounds such as 1,4-diamino-4-methylpentane and 2,4-diamino-2,4-dimethylpentane; hexylene diamines represented by 1,6-hexylene diamine (hexamethylene diamine) and 2,4-hexylene diamine, and including higher homologs such as 2,5-diamino-2,S-dimethylhexane.
Typical dialkylene'triamines of this invention are: 1,2- diethylene triamine; 1,2- and 1,3-dipropylene triamine; and the corresponding dibutylene triamines in which each pair of nitrogen atomsin the chainis separated by at least 2 carbon atoms.
Fuel oil soluble mono-acid salts of the hereinbefore defined alkylene primary diamines and dialkylene triamines. are also effective for the purposes of this invention. Such mono-acid salts contain one mole of the acid. for each mole of the polyamine and are prepared by methods well known and conventional in the art, such as by mixing the polyamine with the organic acid in equimolecular proportions at atmospheric temperature, the reaction being substantially instantaneous. Suitable organic acids are monocarboxylic fatty acids of 8 to about 22 carbon atoms, monohydric mononuclear phe- 11015, and monocarboxylic petroleum naphthenic acids of about 8 to about 29 carbon atoms. These mono-acid salts offer the advantageof increased .fuel oil solubility over the corresponding polyamine, especially with the "lower members of the series, e.g., ethylene diamine and diethylene triamine. They are particularly desirable for the preparation of concentrated solutions in normally liquid hydrocarbons.
Representative monocarboxylic fatty acids of this in .vention are ole'ic acid, caprylic acid, pelargonic (nonanoic) acid, undecylic acid, lauric acid, stearic acid, linoleic acid, linolinic acid, behenic'acid, and the like. Oleic 'acid is preferred.
Representative monohydric mononuclear phenols 'are phenol, thecresols, the ethyl phenols, the xylenols, and the like. Particularly desirable are the commercially available mixturese known as cresylic acids (a mixture of o-, mand p-cresols) and xylenols. Such mixtures result in mixtures of the mono-acid polyamine salts of -cyclopentane, its homologs and bicyclic derivatives. The
carboxyl group is usually attached to a' parafi'inic side refined commercial naphthenic acids, and hence are mixtures of the mon-acid salts of the several napthenic acids.
Representative mono-acid salts of this invention which have been found to be particularly satisfactory for the purposes of this invention are:
Ethylene diamine monooleate 1,2-propylene diamine monooleate 2,3-butylene diamine monooleate Diethylene triamine monooleate Ethylene diamine mononaphthenate Diethylene triamine mononaphthenate Ethylene diamine monocresylate Diethylene triamine monocresylate The hydrocarbon distillate fuel oils, to which the polyamino compounds of this invention are to be added, are the hydrocarbon distillates which areheavier than gasoline and which are known to the art as furnace oil, burner oil, heating oil, range oil, diesel fuel, jet fuel, and fuel oil. In general, these. oils have a boiling range of frornabout 300 F. to about 750 F. Also, the hydrocarbon distillate fuel oils contain active mercaptans. Active mercaptans are those which, when fuel oil containing them is brought into contact with copper, copper compounds. or brass, will react therewith to form copper mercaptides that form copper mercaptide gels. The most active mercaptans are. the aliphatic mercaptans, the activity thereof decreasing from the primary to the secondary to the tertiary mercaptans. Usually, aromatic mercaptans alone do notform solid copper mercaptide gels but, in the presence of an aliphatic primary mercaptan, they and the aliphatic secondary and tertiary mercaptans appear to contribute to the formation of such gels. I i i The occurrence of mercaptans of all types in distillate hydrocarbon fuel oils is well known. Commercial hydrocarbon distillate fuel oils offered today for "heating use, contain, when fresh from as low as 0.001% to as high as 0.03% by weight of mercaptan sulfur. This mercaptan sulfur content varies, depending on the source of the fuel oil, its processing history, and its age- For example, the mercaptan; sulfur content of catalytic cracked fuel oil tends to diminish on aging, which may be attributed to the reaction of mercaptans with olefin groups under :conditions of storage. Thus, while the tendency of some fuel oils to form sludge, increases on aging, the tendencyto .form copper mercaptide gel may actually decrease during this same period. Even quite minute quantities of active mercaptan sulfur in a fuel oil tends to result in objectionable.troublesome fouling of equipment, that is, small quantities of active mercaptan sulfur cause the deposition of rather large volumes of fuel oil as an insoluble gelatinous precipitate.
Generally, the quantity of polyamine compound of this invention which will be added'to a hydrocarbon distillate fuel oil is from 0.1 to. about 5 parts byweight for each part of active'rnercaptan sulfur present in the fuel oil, preferably from about 0.5 to about 3 parts by weight. For most hydrocarbon distillate fuel oils, this will be from 0.0001% toabout 0.15% by weight based on the fuel oil, preferably from about 0.0005% to chain of the ring, but may be directly attached to a ring carbon atom'. The commercially available'products, ob-
tainedfrom various petroleum sources aire mixtures or "naphthenic acids of frorn*7'.or 8 to about '29 carbon atoms, usually not more than 20 carbon'fatoms and av eraging about 12 to 14 carbon atoms, sometimes also containing minor proportions of fatty acids and carboxylic acids derived from cyclohexane and its homologs. Refined comniercialnaphthenic acids generally have an apparent molecularweight of 'abputi200-250which cerrespondstoanaverage of 1 2 to 14 carbon atoms in the molecule. "The naphthenic acid .morio ,salts" or mono- 'naphthenates of the examples were prepared from such about 0.1%. Larger a mounts of polyamine compound may be used, but generally. will be wasteful unless the fuel oil contains unusually large amounts of active mercaptan sulfur or it is to be used in equipment whichuis already fouled with copper mercapticle gel.
'Afpolyamino compound of this invention or a mixture of any two or more thereofmay be added as such to the hydrocarbon distillate fuel oil at atmospheric temperature or, if desired, at moderately elevatedterhperature and stirring until solution is complete. Preferablly the polyamin'o compound or mixture of compounds will be'add'ed in the form of a concentrated solution in a normally liquid hydrocarbon, such as benzene,
toluene, xylene, gasoline, kerosene, fuel oils, and tlre Iike. Generally, the polyamino compounds will be in a Concentration of from about to about 70% by weight, preferably from about 30% to about 50% by weight. These concentrated solutions represent the commercial form in which the polyamino compound will be shipped to the refiner for addition to the fuel oil to be treated. Such solutions are more convenient to transport, to handle (e.g. pour) and to measure. The maximum concentration obtainable will depend upon the solubility of the polyamino compound in the liquid hydrocarbon and, for this purpose, it will be most desirable to employ those compounds of high solubility, preferably the mono-acid salts of the polyamines. Also, since the viscosity of the solution increases with increase in concentration of polyamino compound therein, the concentration generally will be limited by the maximum viscosity which can be efiiciently poured and measured, usually a concentration of not more than about 50% by weight being optimum for this purpose. f
For the purpose of breaking up and removing gel which has been formed in a system, an excess of polyamino compound may be incorporated in the fuel oil supply itself. However, this procedure will be fairly slow in removing the gel due to the low concentrations of the polyamino compound once it has finally diffused through the oil into the gel. On the other hand, rapid and effective breaking up of the gel has beenobtained by adding the polyamino compound, as such, directly to the gel. However, it is preferred to employ concentrated solutions of the polyamino compound or of a mixture thereof in a normally liquid hydrocarbon. The concentrated solutions, described in the next precedingparagraph, are suitable for this purpose, preferably those in which the polyamino compounds are in a concentration of from about 15% to about 30% by weight, particularly in kerosene. As little as 1 part of polyamino compound is elfective to liquefy up to 100 parts .by weight of gel. Larger amounts may be used, but large excesses are wasteful.
In breaking up and removing gel from equipment which has become coated or fouled with the gel, it is' desirable to bring the polyamino compounds rapidly into compound. If'a domestic oil burner becomes plugged with gel: during operatiouwith an untreated fuel oil, thepolyamino compound can be addedto the system at any 7 point'which leads to the affected parts. For? example, the
feed lines can be disconnected from the fuel oil storage '6 it is was used or'handled in a concentrated solution-,the concentration thereof, and whether it isto'be; usedto break up preformed gel. While any of the polyamino compounds of this invention may be used very effectively to inhibit copper mercaptide gel formation in fuel oil,
it will be preferred to employ any one or more of ethylene diamine, diethylene trimine, the propylene diamines, the dipropylene triamines, and the monoleates and mononaphthenates of those polyamines. In breaking up or liquefying preformed copper mercaptide gel, the polyamino compounds vary in effectiveness, hexamethyle'ne diamine being much less effective for this purpose than those diamines in which the amino groups'are separated by fewer carbon atoms, the effectiveness increasing with decrease in the numberof carbon atoms-separating the amino groups. Thus, in breaking up preformed gel, it is preferred to employ alkylene diamines in which the two amino groups are separated by 2 to 4 carbon atoms,
' especially 2 to 3 carbon atoms, and dialkylene triamine's in which each amino group is separated from the nearest other amino group by 2 to 3 carbon atoms.
Higher polyalkylene polyamines, i.e., the trialkylene tetramines and the tetraalkylene pentamines, have little orno effect to inhibit the formation of copper merca'p- I tide gel in fuel oil or to break up preformed gel.- For example, it has been found that tetraethylene pentamine neither inhibits nor breaks up copper mercaptide gel. Similarly, when the polyamines of this invention are alkylated to convert one orboth of the primary amino groups to a secondary or a tertiary amino group, such as the N-alkyl-, N-N-dialkyl-, or N,N'-dialkyl-substituted compounds, their effectiveness for the purposes of this invention is greatly decreased or destroyed.v V
' The polyamino compounds of this invention may be employed in hydrocarbon distillate, fuel oils along .with other additives which are conventionally employed to impart other desirable characteristics to the, base oil,
such as resistance to discoloration and the formationof tank, and the-fuelremaining therein drained or blown: out I i and replaced by a concentrated solution of the polyamino compound.. The system isthen tested for normal flow. The cleaning operation c an be repeated as may be necessary, using fresh solution:or'recirculating the old solution through the contaminated'parts, e.g., nozzle, filter screen, or feed line. Finally, theequipmentshould be rinsed'with -a normally liquid hydrocarbon; which does not contain polyamino compound, as before. ..Since concentrated solutions of the polyamino compounds are I flr ather corrosive to coppe'nin the presenceofroxygen 1 'and/orgmoisturqit is desirableto washsuchsblutions" fromcopper-surfaces assoon as possibleafter the' poly amino compounds have broken up the gels, i.e., to. rinse them as set forth above.
; ;Theparticularpolyarnino compound or mixture there-5 {employed will-depend upon the manner aridlform in played in-Exa'mple 'l instead of 0.;1we'ight' percent of the above polyamines of this invention. Solid gel formed: I
sludge and to improve the combustion of the oil'.
In orderto more clearly illustratezthis invention, suitable modes of carrying it into effect, and the advantageousresults to be obtained thereby, the following examples are given in which the polyamino compounds employed are technical grade products and the, salts were prepared by mixing one .mole of. theorg'anic acid, carboxylic acid or phenol, with one mole of the polyamino at .room temperature: v
. Example I J A 'five" portion of catalytically cracked pf ilel oil containing a) a total of 0.4.weight percent mercaptan sulfer present as added dodecyl' mercaptan and" (b) 0.1
copper present as added copper naphthenate. No insoluble gel formed; the mixture remaining mobile and free-of gelindefinitely (for at least several weeks).
Ina control experiment, under identical conditions "except that no ethylene diarnine' was present, imme diate gelation of the fuel: took place.-
When ethylene diamine was replaced in the above example by an'equal weight of any of the following polyamines, complete inhibition of solid Igel' formation was observed-:- 1 2-propylene diamine, 1,3-propy-lene diamine, l,? -,butylenej ;diamine hexamethylene. diamine,
diethylene'triamine, di-(l,3-propylene), triarniriek' The Y i mixture, in each case, remained-free of gel. indefinitely.
In contrast, solid gel" was .formedimmediately-when 0.2 weightpercent of-tetraethylene -pentamine waseminlO minutes when as much fa gawei'lghtripercentvof ''3-diethylaminopropylaniine" was similarly ftes'te'd as an 'lwhi ch'it isto be usediandthe results desired,.i.'e., whether" inhibitor;. likewise; witha2' weightvpercenfi of: 3-i'sopro-Q pylaminopropylamine present the mixture solidified to gel in 3 minutes. r Example2 h A solid copper mercaptide gel was prepared by mixing (a) an equal volume of catalytically cracked fuel oil containing 0.4 weight percent mercaptan sulfur, present :as added dodecyl mercaptan, with (b) anequal volume of fuel oil containing 0.4% copper, present as added copper naphthenate. To samples of this 'solid gel (9 parts each) was added from 0.15 to 0.25 part of diethylene triamine and themixture was shaken. .In a few moments, the gel broke up (completely liquefied), in each case, the original straw color changing to the bluishgreen color of the copper-polyamine complex.
Example. 3
Solid copper mercaptide gel (containing 0.2 weight percent copper) was prepared by mixing equal volumes of catalytically cracked fuel oil containing, respectively, 0.4 weight percent mercaptan sulfur ,as a 1:1 mixture of dodecyl. and xylylmercaptans and 0.4% copper as the naphetenate. One part samples of the gel were brokenup by adding 0.1 part of oleic acid mono salt ofethylene diamine (prepared by mixing 1 mole. of oleic acid and 1 mole of ethylene diamine).
' Substantially the same results, i.e. complete break up of the gel, are obtained on replacing the above ethylene diamine monooleic acid salt with any of the following polyamino compounds of this invention:
Cresylic acid mono salt of ethylene'diamine (0.2 part) Naphthenic acid mono salt of ethylene diamine (0.2
part) i Naphthenic mono salt of :diethylene triamine (0.4
-part) Oleic acid mono salt of diethylene triamine (0.6 part of a 33% weight percent solution in xylene i.e. 0.2 part active ingredient) Oleic acid mono salt of 1,2-propylene diamine (0.6 part of a 50 weight percent solution in xylene containing 0.3 part activeingre dient) oleic acid mono salt of 2,3-butylene diamine (0.4 part) Example 4 c accelerated test, simulating field conditions, was devised todetermine the sensitivity of fuel oils to copper mercaptide gel formation and to evaluate the eifectiveness of various materials as inhibitors of gel formation. The test comprises passing or circulating (i.e. any number of passes) a sample of fuel oil over a specially prepared ,(corroded). ,copper. strip, at a specified temperature and rate of flow, and'then determining the increase in weight of the copper strip as a measure of the quantity of gel produced in c a given 'time- The corroded copper strips are specially prepared to ,speed up gel formation and to provide uniform conditions for the test. Preparation of corroded copper for the copper mercaptide gel testisas follows: I
,Copper strips, approximately 0.25 inch x 2.5 inches,
areroughly polished with,00 emery cloth, steel wool-polished until uniformly bright, then washed with light naphtha, and dried in air. The copper strips maybe stored in a tightly capped bottle forlO -IS days. f 150 ml. of henacne and 30 mlgof concentrated aqueous ammonium hydroxid are mixed and shakeri' vigorously for- 2 to 3 1 minutes to saturate the benzene with ammonia! -Ihe mix- "ture is allowed to' separate for to minutes and the aqueous layer is drawn off and' discarded. *Two or three polished copper strips, prepared as described above, are i immersed in the ammonia-saturated benzene for 24 hours. 1 The resulting corroded. copper strips are dried by allow- .ing the benzene to evaporate in air and then stored in a V tightly capped bottleuntil neededri. t H c When fuel oil whichis normally subjectto copper mer- -.;captide gel formation irizthe .jfield, i.e. contains naturally occurring active mercaptans, is allowed to flow over a corroded copper strip (prepared as above described) at a rate of one liter per 24 hours at 37 F., a characteristic yellowish gelatinous deposit is present on the copper strip after 24 hours. Fuel oils giving a negative test, i.e. no .gelappears and the copper strip shows no gain in weight, are considered free of active mercaptans, i.e. those forming insoluble copper mercaptide gel.
In order ot determine under controlled conditions the effectiveness of various materials in preventing insoluble gel, the active mercaptan content of fuel oil samples were standardized by incorporating in them known quantities of active mercaptans such as dodecyl mercaptan or 1:1 mixture of dodecyl mercaptan and xylyl mercaptan.
" In the following test, catalytically cracked fuel oil, containing (a) a total of 0.005 weight percent of active mercaptan sulfur (approximately004 g. S/liter), which was added to the fuel oil as 1:1 dodecyl and xylyl mercaptans, and (b) 0.0006 weight percent of diethylene triamine monooleate, was passed over a preweighed corroded copper strip (prepared as described above) at a rate of l liter/24 hours at 37 F. At the end of 24 hours, the cop per strip was washed with cyclohexane, air-dried and weighed. There was no increase in the weight of the copper strip. c j c 1 t In a control experiment under identical conditions and using the same base fuel containing the above mercaptans ;but withno added inhibitor present, the increase in weight the polyamines of this invention may be employed to intion.
"gel formation of at. least one polyamino' compound of the f group consisting of alkylene'primary diamines of 2 to 10 carbon atoms inwhich thejprimary amino groups are sep- 7 7 arated by 2; to 6 carbonatoms, dialkylene triamines of 4 arated by 2 to 4 carbon' atoms .and twoof the amino groups are primary amino groups, and mqno acid salts of said diamines'and'saidtriamines in which the acids are acids of 8 to about 22 carbon; atoms, l tnonohydric monoof the copper strip was 0.1462 g.
Following the above-described test procedure, any of hibit the formation of gelatinous deposit on copper; the
copper strip remains clean and shows essentially no inlimited to the specific embodiments disclosed therein.
While only certain polyamino compounds and compositions have beenemployed in the examples, mixtures of any two or more thereof may be similarly employed. Also,
other polyamino compounds and compositions, within the general disclosure, may be substituted therefor. Furthermore, the proportions, conditions, procedures, etc. may be varied widely as pointed out in the general description, without departing from the spirit and scope of thisinven- From the preceding disclosure, it isapparent that this invention providesnovel means and methods for inhibitcentrated solutions useful for preparing such fuel oil compositions and for breaking up preformed gels and clean ing equipment containing them. Thus, this invention solvesserious problems of the art and constitutes a valuable improvement in and contribution to the art.
The embodiments of the invention in which an exclusix e property or privilege is claimed are defined as follows: 1. A hydrocarbon distillate fuel oil which is in contact with a member of, the group consisting of copper, copper compounds and'brass, and which contains at least one mercaptan which normally tends to form a copper mercap tide gel, and a small proportion sufficieritto inhibit such to, 10 carbon atoms" in which the amino groups are sepselectedfrom the group consistingof monocarboxylicfatty nuclear phenols; and. mono'carbo'xylic petroleu'mhaph} thenic acids' of" about 8 to about 29'carbon atoms, s'aid polyamino compound being in a proportion equivalent toofrtoabout 5 parts of polyamino for each part of active mercaptan sulfur ill-the fuel oil. r g V 3 2. A hydrocarbon distillate fuel oil which is in contact with a member of the group' consisting'of copper, copper compounds and brass, and which contains at least one mercaptan which normally tends to form a copper mer- ,captide gel, and from about 0.5 to about 3 parts-byw weight for eaclipartvof active mercaptan sulfur present in the fuel oil'of at least one polyamino compound of the group consistingtofalkyleneprirnary diamines of 2 to 10' carbon altomsin whichthe primary amino groups are separated by 2'to 6 carbon atoms, dialkylene triamines of 4 to 10 carbon atomsinwhich the amino groups are separated by Zto 4'carbon'atoms and two of the amino groups are primary amino groups, and mono-acid salts of said diamines ltindsaid'triamines in which the acids are selected from the group"consisting of monoca'rboxylic fatty acids of 8,to about 22" carbon atoms, monohydric mononuclear phenols, and nionocar'boxylic petroleum naphthenic acids of about Stof about 29 carbon atoms.
3: A hydrocarbon distillate fuel on which is'in contact with a member of the group consisting of copper, copper compounds and brass, and which contains, at least one mercaptan whichrnormallytends to form a copper mercaptide gel, and a small proportion sufficient to inhibit 'sueh gel formation of attleasttone'alkylene primary dieminent 2 to? lolcarbonatoms in which the primary' amino groups'are'separatedfiby 2.to ,6 carbon atoms, said ,di-'
"stains being in aproportion of 0.1 'to about 5 parts thereof fiwf' ea'ch 'parttof active mercaptan sulfur in the fuel oil.
114. hydrocarbon distillate fuel oil which is in contact with a men'iberof the group consisting of copper, copper compounds and brass, and which contains at least one mercaptan which normally tends to form a copper mercipt-ide gel, "and a small" proportion suflici'ent' to iilhibit gel format ion-of at least one alkyleneprimary di- -amine:of-'2 to 6 carbon' atoms in which the primary amino groups are separated byz'to 3 carbon atoms,'saiddiamine "Being in a'proportion' of 1' toabout pa'rfts thereof for each part of active mercaptan: sulfur in the fuel oil a 5. A hydrocarbon distillate fuel oil which is in contact with a member of the group consisting of copper, copper compounds and brass, and which contains at least one mercaptan which normally tends to form a copper mercaptide gel, and a small proportion sufficient to inhibit such gel formation of at least one propylene primary diamine in which the primary amino groups are separated by 2 to 3 carbon atoms, said diamine being in a proportion of 0.1 to about 5 parts thereof for each part of activev mercaptan sulfur in the fuel oil. p 6. A hydrocarbon distillate fuel oil which is in contact with a member of the group consisting of copper, copper compounds and'bra'ss, and which contains at least one mercaptan which normally tends to form a copper mercaptide gel, and a small proportion sufficient to inhibit such gel formation of at least one dialkylene triamine of 4 to carbon atoms in which the amino groups are separated by 2 to 4 carbon atoms and two of the amino groups are primary amino groups, said triamine being in a proportion of 0.1 to about Sparts thereof for each part of active mercaptan sulfur in thefuel oil.
7. A hydrocarbon distillate fuel oil which is in contact with avme'mber of the group consisting of copper, copper V compounds and brass, and which contains at least one mercaptan which normally tends to form a copper rrlercaptide gel, and a small proportion sufficint to inhibit such gel formation of at least one dialkylene triamine of 4m 8 asserts carbon atoms in which the amino groups arefseparated r with-a member of the group consisting of copper; copper compounds and brass, and which contains at least one mercaptan which normally-tends to form a copper mercaptide gel, and a small proportion sufficient to inhibit such gel formation of diethylene triamine, said triamine being in a proportion of 0.1 to about 5 parts thereof for each part of active mercaptan sulfur in the fuel oil.
'v 9. A hydrocarbon distillate fuel oil which is in contact with a memberof the group consisting of copper, copper compounds and brass, and which contains at least one mercaptan which normally tends to form a'copper mercaptide gel, and a small proportion suflicient to inhibit such gel formation of at least one mono-acid salt of an alkylene primary diamine of 2 to 10 carbon atoms in which the prmiary amino groups are separated by 2 to 6 carbon atoms, the acid component of said salt being a monocarboxylic fatty acid of 8 to about 22 carbon atoms, said salt being in a proportion equivalent to 0.1 to about 5 parts of diamine for each part of active mercaptan sulfur in the fuel oil.
0. A hydrocarbon distillate fuel oil which is in contact with a member of the groupconsisting of copper,copper compounds and'brass, and which contains at least one mercaptan which normally tends to form a copper mercaptide gel, and a small proportion sutficient to inhibit such gel formation of at least one monooleate of an alkylene primary diamine of 2 to 6 carbon atoms in which the 7 primary amino groups are separated by 2 to 3 carbon atoms,,said monooleate being in a proportion equivalent to 0.1 to about 5 parts of diamine for each part of active mercaptan sulfur in the fuel oil.
11. A hydrocarbon distillate fuel oil which is in contact.
witharnember of the groupconsisting of copper, copper compounds and brass, and which contains at least one mercaptan which normally tends to form a copper mercaptide' gel, and a small proportion sufiicient to inhibit such gel formation of ethylene diamine monooleate, said 'monooleate being in a proportion equivalent to 0.1 to I active about 5 parts of ethylene diamine for each part' of mercaptan sulfur in the fuel oil. V
12'. A hydrocarbon distillate fuel oil which is in contact with a member. of the group consistingof copper, copper acid component of said salt being a monocarboxylic fatty acid of 8 to about 22 carbon atoms, said salt being in a proportion equivalent to 0.1 to about 5 parts of triamine for eachhpart of active mercaptan sulfur in the fuel oil.
13. A hydrocarbon distillate fuel oil which is in contact with amember of the group consisting of copper', copper compounds and brass, and which contains at least one mercaptan which normally tends to form a copper mercaptide gel, and a small proportion sufiicient to inhibit such gel formation of at least one monooleate of a dialkylene triamine of 4 to 8 carbon atoms .in which the amino groups are separated by2 to 3 carbon atoms and two of the amino groups are primary amino groups, said monooleate being in a proportion equivalentto 0.1 to about 5 parts of triamine for each'part of activemercaptan sulfur in the fuel oil.
14. A'hydrocarbon distillate fuel oil which is in contact with a member of the group consisting of copper, copper compounds and brass, and which contains at least one mercaptan which normally tends to form a copper mercaptide gel, and a small proportion suificient to inhibit such gel formation of diethylene triamine monooleate, said monooleate beingin a proportion equivalent to' 0.1 to
tive mercaptan sulfur in the fuel oil;
about 5 parts of diethylene triamine for each part of ac- I 15. A composition for liquefying' a gel, formed by the action of a copper mercaptide on a normally liquid hydrocarbon, .which composition consists essentially of a normallyliquid hydrocarbon having dissolved therein, in a concentration of from about 15% to about 70% by weight, .at least one polyamino compound ofithe group consisting of alkylene primary diamines of 2 to carbon atoms inwhich the primary ,amino groups are separated by 2 to 6 carbon atoms, dialkyl ene triamines of 4 to 10 carbon atoms in which the amino groups are separated by 2 to 4 carbon atoms and two of the amino groups are primary amino groups, and mono-acid salts of said diamines and said triamines in which the acids are selected from the group consisting of monocarboxylic fatty acids of 8 to about 22 carbon atoms, monohydric mononuclear phenols, and monocarboxylic petroleum naphthenic acids of about 8 to about 29 carbon atoms. I
16. A composition for liquefying a gel, formed by the action of a copp r mercaptide on a normally liquid hydro carbon, which composition consists essentially of a nor mally liquid hydrocarbon having dissolved therein, in a concentration of from about to about,50% by weight,
at least one mono-acid salt of analkylene primary diamine of 2 to 10 carbon atoms in which the primary amino groups are separated by 2 to-6 carbon atoms, the acid component of said salt being a monocarboxylic fatty acid of 8 to about 22 carbon atoms.
17. A compositionfor liquefying a gel, formed bythe action of a copper mercaptide on a normally liquid hydrocarbon, which'composition consists essentially of a normally liquid: hydrocarbon having dissolved therein, in a concentration of from about 15% to about 50% by weight, t
at least one mono-acid saltof a dialkylene triamine of 4 to 10 carbon atoms in whcih the amino'groups are separated by 2 to 4 carbon atoms and two of the amino groups are primary amino groups, the acid component of said salt being a monocarboxylic fatty acid of 8 to about 22 carbon atoms.
18. The process for liquefying agel, formed by the action of a copper mercaptide on a normally liquid hydrocarbon atomsin which the primary amino groups are sep arated by 2 to 6 carbon atoms, dialkylene triamines of 4 to 10 carbon atoms in which the amino groups, are sep arated by 2 to 4 carbon atoms and two of the amino groups are primary amino groups, and mono-acid salts of said diamines and said triamines in which the acids are selected from the group consisting of monocarboxylic fatty acids,
of .8 to a'bdut 22 carbon atoms, monohydric mononuclear phenols, and monocarboxylic petroleum naphthenic acids of about 8 to. about 29 carbon atoms. 1
a 19. The process for lique'fyinga gel,,formed by the action of a copper mercaptide ona normally liquid hydrocarbon, which comprises adding to said gel at least 1% by weight of at least one alkylene primary diamine of 2 to 4 carbon atoms in which the primary amino, groups are'separated by 2 to 3 carbon atoms. 1
20. .A hydrocarbon distillate fuel oilwhich is in, contact with a member of the group consisting of copper, copper compounds and brass, andwhich contains at least one mercaptan which normally tends to form a copper mercaptide gel, and a small proportion sufiicient to inhibit such gel formation of 1,2-propylene diamine monooleate, said monooleate being in aproportion equivalentto 0.1 to about 5 parts of-the diamine for each part of active mercaptan sulfur in the fuel oil. i i t i V References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES 1 Organic Nitrogen Compounds," Carbide and Carbon Chem.:Corp., recd March27, 1950, page 4. i
Industrial Solvents, by Mellan, Second Ed, 1950, Reinhold'Pub. Corp.. N.Y.,,page 424. i
How's Your Fuel-0il Quality? Osterhuut et al., Petraleum Processing, January 6, pages 67-71.
I (SEAL) UNITED STATES EATENTf OFFICE CERTIFICATE DF CORRECTION Patent No. 2,980.518 April 18, 1961 v I Philip L. Bartlett It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as "correctd below.
olumn 2, line 4L0 for lorough" read brought column 3, line 51, for "mixturese" read mixtures column 4 line 2, for "mOn acid" read mono-acid column 6 line 7 for 'Ytrimine" read triamine line 8, for "monoleates" read monooleates column 9, line 4, for "polyamino" read 'polyamine column 10, line 16, for "prmiary" read primary column 11 line 34, for "whcih" read which Signed and sealed this 10th day of October 1961 Attest:
ERNEST W. SWIDER DAVID L. LADD Attesting Officer I Commissioner of Patents USCOMM-DC UNITED STATE S PATENT f OFFICE CERTIFICATE OF CORRECTION Patent NO 2,980,518 April 18, 1961 Philip L. Bartlett It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent. should read as "corrected below.
Column 2, line 40, for hrouo h" read brought column 3, line 51, for "mixturese" read mixtures column 4, line 2, for "mon acid" read mono-acid column 6, line 7, for "trimine" read triamine line 8, for "monoleates" read monooleates column 9, line 4, for "polyamino" read polyamine column 10, line 16, for "prmiary" read primary column ll, line 34, for "whcih" read which Signed and sealed this 10th day of October 1961.
(SEAL) Attest:
ERNEST W. SWIDER 1 DAVID L. LADD I Commissioner of Patents Attesting Officer USCOM M-DC"
Claims (1)
1. A HYDROCARBON DISTILLATE FUEL OIL WHICH IS IN CONTACT WITH A MEMBER OF THE GROUP CONSISTING OF COPPER, COPPER COMPOUNDS AND BRASS, AND WHICH CONTAINS AT LEAST ONE MERCAPTAN WHICH NORMALLY TENDS TO FORM A COPPER MERCAPTIDE GEL, AND A SMALL PROPORTION SUFFICIENT TO INHIBIT SUCH GEL FORMATION OF AT LEAST ONE POLYAMINO COMPOUND OF THE GROUP CONSISTING OF ALKYLENE PRIMARY DIAMINES OF 2 TO 10 CARBON ATOMS IN WHICH THE PRIMARY AMINO GROUPS ARE SEPARATED BY 2 TO 6 CARBON ATOMS, DIALKYLENE TRIAMINES OF 4 TO 10 CARBON ATOMS IN WHICH THE AMINO GROUPS ARE SEPARATED BY 2 TO 4 CARBON ATOMS AND TWO OF THE AMINO GROUPS ARE PRIMARY AMINO GROUPS, AND MONO-ACID SALTS OF SAID DIAMINES AND SAID TRIAMINES IN WHICH THE ACIDS ARE SELECTED FROM THE GROUP CONSISTING OF MONOCARBOXYDRIC FATTY ACIDS OF 8 TO ABOUT 22 CARBON ATOMS, MONOHYDRIC MONONUCLEAR PHENOLS, AND MONOCARBOXYLIC PETROLEUM NAPHTHENIC ACIDS OF ABOUT 8 TO ABOUT 29 CARBON ATOMS, SAID POLYAMINO COMPOUND BEING IN A PROPORTION EQUIVALENT TO 0.1 TO ABOUT 5 PARTS OF POLYAMINO FOR EACH PART OF ACTIVE MERCAPTAN SULFUR IN THE FUEL OIL.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US606186A US2980518A (en) | 1956-08-27 | 1956-08-27 | Inhibiting gel formation in fuel oils |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US606186A US2980518A (en) | 1956-08-27 | 1956-08-27 | Inhibiting gel formation in fuel oils |
Publications (1)
Publication Number | Publication Date |
---|---|
US2980518A true US2980518A (en) | 1961-04-18 |
Family
ID=24426925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US606186A Expired - Lifetime US2980518A (en) | 1956-08-27 | 1956-08-27 | Inhibiting gel formation in fuel oils |
Country Status (1)
Country | Link |
---|---|
US (1) | US2980518A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0240255A2 (en) * | 1986-03-27 | 1987-10-07 | Exxon Research And Engineering Company | Anti-fouling fuel composition |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2204234A (en) * | 1938-11-09 | 1940-06-11 | Phillips Petroleum Co | Treatment of hydrocarbon oils |
US2329251A (en) * | 1941-01-21 | 1943-09-14 | Universal Oil Prod Co | Treatment of gasoline |
US2369490A (en) * | 1941-06-16 | 1945-02-13 | Standard Oil Co | Stabilizers for oils |
US2503627A (en) * | 1949-04-27 | 1950-04-11 | Phillips Petroleum Co | Removal of mercaptans from gasoline |
US2559574A (en) * | 1948-06-03 | 1951-07-03 | Irving J Rifkin | Composition and method for removing oil sludge |
US2759875A (en) * | 1951-11-28 | 1956-08-21 | Sun Oil Co | Refining mineral oil to remove copper therefrom by treating with a metal acetate |
US2851344A (en) * | 1955-02-02 | 1958-09-09 | Armour & Co | Fuel oil compositions |
-
1956
- 1956-08-27 US US606186A patent/US2980518A/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2204234A (en) * | 1938-11-09 | 1940-06-11 | Phillips Petroleum Co | Treatment of hydrocarbon oils |
US2329251A (en) * | 1941-01-21 | 1943-09-14 | Universal Oil Prod Co | Treatment of gasoline |
US2369490A (en) * | 1941-06-16 | 1945-02-13 | Standard Oil Co | Stabilizers for oils |
US2559574A (en) * | 1948-06-03 | 1951-07-03 | Irving J Rifkin | Composition and method for removing oil sludge |
US2503627A (en) * | 1949-04-27 | 1950-04-11 | Phillips Petroleum Co | Removal of mercaptans from gasoline |
US2759875A (en) * | 1951-11-28 | 1956-08-21 | Sun Oil Co | Refining mineral oil to remove copper therefrom by treating with a metal acetate |
US2851344A (en) * | 1955-02-02 | 1958-09-09 | Armour & Co | Fuel oil compositions |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0240255A2 (en) * | 1986-03-27 | 1987-10-07 | Exxon Research And Engineering Company | Anti-fouling fuel composition |
EP0240255A3 (en) * | 1986-03-27 | 1988-01-07 | Exxon Research And Engineering Company | Anti-fouling fuel composition |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3031282A (en) | Stabilized distillate fuel oil | |
US2736641A (en) | Fuel oil additive | |
US2553183A (en) | Fuel oil composition | |
US3035907A (en) | Hydrocarbon composition containing an itaconic acid-amine reaction product | |
US2907646A (en) | Rust inhibitor for fuel fractions of mineral oil | |
US3060007A (en) | Hydrocarbon oils containing reaction products of imidazolines and alkylene iminodiacetic acids | |
US3873278A (en) | Gasoline | |
US2632694A (en) | Petroleum distillates containing ammonium mahogany sulfonates and oil soluble carboxylic acids to prevent corrosion | |
US2980518A (en) | Inhibiting gel formation in fuel oils | |
US3092475A (en) | Fuel composition | |
US2851344A (en) | Fuel oil compositions | |
CA1113503A (en) | Ether diamine salts of n-acylsarcosines and their use as corrosion inhibitors | |
US4166725A (en) | Oil-soluble biocide combination for distillate fuels | |
DE1235062B (en) | Stabilizing distillate fuels | |
US3701641A (en) | Stabilized distillate hydrocarbon fuel oil compositions and additives therefor | |
US2081130A (en) | Distribution of fuel gases | |
US2959915A (en) | Fuel for and method of operating a jet engine | |
US3905781A (en) | Carburetor detergent and corrosion inhibiting motor fuel compositions | |
US3025239A (en) | Petroleum oil composition | |
US3084034A (en) | Stable petroleum distillate fuels | |
US3393058A (en) | Microbiological control of hydrocarbon fluids | |
US3240574A (en) | Stabilization of organic compounds | |
US3640692A (en) | Stabilized distillate hydrocarbon fuel oil compositions and additives therefor | |
US2768884A (en) | Corrosion prevention | |
US3279901A (en) | Distillate fuels |