US3694175A - Overbased barium additive and fuel oil composition - Google Patents
Overbased barium additive and fuel oil composition Download PDFInfo
- Publication number
- US3694175A US3694175A US762369A US3694175DA US3694175A US 3694175 A US3694175 A US 3694175A US 762369 A US762369 A US 762369A US 3694175D A US3694175D A US 3694175DA US 3694175 A US3694175 A US 3694175A
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- US
- United States
- Prior art keywords
- barium
- product
- sulfonic acid
- mixture
- diesel fuel
- 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
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- 229910052788 barium Inorganic materials 0.000 title abstract description 26
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title abstract description 23
- 239000000203 mixture Substances 0.000 title description 62
- 239000000654 additive Substances 0.000 title description 3
- 230000000996 additive effect Effects 0.000 title description 2
- 239000000295 fuel oil Substances 0.000 title description 2
- 238000000034 method Methods 0.000 abstract description 55
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 abstract description 38
- 239000002283 diesel fuel Substances 0.000 abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 abstract description 28
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 25
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 50
- 150000001336 alkenes Chemical class 0.000 description 45
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000003921 oil Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- -1 barium sulfonates Chemical class 0.000 description 14
- 239000000779 smoke Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000446 fuel Substances 0.000 description 10
- 150000008053 sultones Chemical class 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 150000003460 sulfonic acids Chemical class 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 238000007127 saponification reaction Methods 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 7
- 150000004996 alkyl benzenes Chemical class 0.000 description 7
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 7
- 241000565357 Fraxinus nigra Species 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 150000005673 monoalkenes Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 241000158728 Meliaceae Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- YMDQBEDUPBAOHY-UHFFFAOYSA-N 2-heptadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O YMDQBEDUPBAOHY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000005674 acyclic monoalkenes Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 239000011874 heated mixture Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- CTIFKKWVNGEOBU-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O CTIFKKWVNGEOBU-UHFFFAOYSA-N 0.000 description 1
- UDTHXSLCACXSKA-UHFFFAOYSA-N 3-tetradecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCC1=CC=CC(S(O)(=O)=O)=C1 UDTHXSLCACXSKA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 238000003547 Friedel-Crafts alkylation reaction Methods 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006280 diesel fuel additive Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 238000002360 preparation method Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012360 testing method Methods 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- 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
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
- C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
Definitions
- This invention is directed to a method of preparing overbased barium sulfonates and their use in distillate fuels.
- overbased indicates that the resultant product from these various processes contains an amount of alkaline earth metal greater than the stoichiometric amount of metal which would be present if the particular sulfonic acid were fully neutralized.
- the theory of this overbased complex formation is not fully understood.
- One suggestion has been that the oil soluble sulfonates act as protective colloids or dispersants thus keeping an alkaline earth compound suspended in a fiuid carrier.
- a general method of preparing these complexes features the in situ formation of a finely divided alkaline earth compound such as CaCO in the presence of a petroleum sulfonate in a hydrocarbon medium. This is accomplished by introducing an acidic gas such as carbon dioxide into an alkaline earth containing, petroleum sulfonate dispersion in a hydrocarbon medium. Recent improvements in this process feature the use of promoters such as low molecular Weight alcohols, phenols, amines, and the like.
- the present invention provides a method of preparing overbased barium sulfonates featuring the use of barium sulfide as the barium source.
- the products are elfective smoke suppressors in diesel fuels.
- the molar ratio of barium sulfide to said sulfonic acid material is from about 1:1 to about 10:1, (3) introducing carbon dioxide gas into the heated mixture of Step (2) until substantially no hydrogen sulfide is evolved from said mixture, and (4) distilling said alkanol and water from said mixture.
- Another preferred embodiment of this process features the use of sulfonated olefin derivatives prepared by sulfonating a C olefin Whose specific composition is given below.
- Dodecyl benzene sulfonic acid is used in a most preferred embodiment.
- Barium sulfide in the crude form known as black ash is a most preferred form of BaS.
- Sulfonic acid materials of various types may be used in the present process. These include alkenyl sulfonic acids, alkyl sulfonic acids, hydroxy alkyl sulfonic acids, sultones, mixtures thereof, as Well as alkyl benzene sulfonic acid. Hydrocarbon soluble petroleum sulfonic acids, the socalled mahogany" sulfonic acids, are also useful in this process. These mahogany sulfonic acids are mixtures of sulfonic acids obtained during sulfuric acid treatment of petroleum refinery streams.
- Sulfonic acid containing products obtained on sulfonating olefins are another type of useful sulfonic acid material. These products are referred to herein as sulfonated olefin derivatives.
- olefins I mean hydrocarbon olefins.
- the products obtained on sulfonating acyclic monoolefins having from about 14 to about 30 carbon atoms are particularly useful.
- Especially useful olefin starting materials are the mixtures of acyclic olefins obtained from synthetic manufacturing processes such as dehydrogenation of parafiins or polymerization of low molecular weight olefins such as ethylene and propylene.
- Synthetically prepared monoolefins having the following olefin makeup and configurations (double bond position) are most preferred; the olefins are predominantly alpha. These mixed olefins are identified herein as C olefins.
- Olefin chain length Percent by weight 1 C and lower 0-3 C 0.5-17 C 33-52 C 19-37 C 9-15 C 2-7 25+ 08 1 Vapor phase chromatography analysis.
- Olefin configurations Percent distribution Vinyl 32-54 Internal 12-31 Vinylidene 32-47 Nuclear magnetic resonance analysis.
- any suitable sulfonation procedure may be utilized. Suitable procedures are described in the following patents: US. 3,259,645; U.S. 3,337,437; British 1,072,601; French 1,403,407 and French 1,399,570.
- the sulfonation of olefins comprises treating olefins with a sulfonating agent such as S0 to produce a sulfonated derivative.
- the mixtures of useful ole-fins contain varying ratios and combinations of olefins having from about 14 to about 30 carbon atoms. These mixtures may contain linear olefins, branched olefins, and mixtures thereof.
- monoolefin mixtures from which preferred sulfonated olefin derivatives are prepared are presented in the following table; the mixtures contain more than about 60 percent a-olefins.
- Blends of these mixtures are also useful.
- a blend of seven volumes of mixture A and eleven volumes of mixture B is a particularly useful blend.
- the products obtained may be mixtures containing alkenyl sulfonic acids, hydroxyalkyl (or -alkenyl) sulfonic acids, and 5 and 6 membered ring inner esters called sultones.
- sultones may comprise as high as 50 percent of the sulfonated olefin product when using a falling film reactor system.
- the sultones are readily saponified by treatment with a strong base.
- the hydrocarbon sulfonic acid material in the present process it is desirable to saponify this product so that the full sulfonic acid value of the material is realized in the process.
- the saponification can be carried out prior to the overbasing step in the process.
- overbasing step is meant the point at which carbon dioxide is introduced into the reaction mixture to form barium carbonate in situ.
- This saponification can be carried out by treating the sulfonated olefin product with a strong base such as sodium hydroxide or potassium hydroxide and heating to an elevated temperature for a few minutes. This saponification would yield the sodium or potassium salt of all the sulfonic acids present. It would be better then to convert this salt to the corresponding barium salt for use in the present process.
- a more preferred procedure is to saponify the sultone containing sulfonated olefin derivative with barium oxide or barium sulfide/water as the first step in the process and then to continue with the overbasing step.
- a most preferred Way of saponifying the sultone is to charge the sulfonated olefin derivative, the hydrocarbon medium, and the barium sulfide-water-alcohol ingredients into the reactor and then heat this mixture to effect the saponification while bubbling the carbon dioxide through the mixture.
- This saponification step is an important feature of the process when sulfonated olefin derivatives which may contain sultones are used as a starting material.
- Alkylbenzene sulfonic acids wherein the alkyl group has 12 to 17 carbon atoms are also useful. Laurylbenzene sulfonic acid, heptadecylbenzene sulfonic acid, hexadecylbenzene sulfonic acid, tetradecylbenzene sulfonic acid and the like are examples of useful sulfonic acids.
- Mixed alkylbenzene sulfonic acids prepared for example from the hydrocarbon product of the Friedel Crafts alkylation of benzene with an olefin containing principally tetrapropylene, are another example of a useful sulfonic acid.
- the useful alkyl benzene sulfonic acids are also characterized by having a molecular weight of less than about 400.
- Dodecylbenzene sulfonic acid is an especially preferred alkylbenzene sulfonic acid.
- Barium sulfide is the reactant utilized in the present process to supply the barium values for the overbased.
- a preferred form of barium sulfide is a crude product obtained in the commercial preparation of barium sulfide by reducing a barium sulfate 1 with carbon. This crude product is commonly called black ash; it contains up to about percent barium sulfide.
- the reaction of the present process is carried out in a suitable hydrocarbon medium.
- the medium is characterized by being (1) inert during the process of the reaction and (2) a solvent for the sulfonic acid starting material. It is also preferred that this medium be a solvent for the overbased product which is obtained in the process; and this hydrocarbon medium should be compatible with diesel fuel. Any hydrocarbon which meets these criteria may be used.
- Aromatic hydrocarbons, parafiinic hydrocarbons, olefinic hydrocarbons, mixtures thereof, light distillate hydrocarbon oils, distillate fuels, kerosene, straight run naphtha, petroleum refinery streams such as catalytic reformate, thermally or catalytically cracked streams, alkylated refinery streams, catalytically cracked naphtha and the like, are useful hydrocarbon media.
- Benzene, C -C alkylbenzenes such as toluene, xylene, actylbenzene, pentylbenzene and the like, (I -C paraflins such as hexane, heptane, dodecane and the like, aviation alkylate, light processing oils such as No. 9 oil and the like, catalytic reformate containing over about 70 percent aromatic hydrocarbons and the like, and mixtures thereof are some examples of useful media.
- the amount of hydrocarbon medium used in the process is not critical. An amount of inert hydrocarbon ranging from about 0.5 to about 10 times the Weight of the sulfonic acid material can be used.
- Alkanols having from about 1 to about 5 carbon atoms are used in the present process. The exact function of the alkanol used in the process is not understood; however, the alkanol is required in order for the reaction of the present process to be carried out. Examples of useful alkanols are ethanol, isopropanol, pentanol-3, amyl alcohol, butyl alcohol, and mixtures of these alcohols. Methanol is a most preferred alkanol.
- the amount of alkanol used may be varied. Generally the barium sulfide reactant is dispersed in the alkanol as an initial step. The amount of alkanol used is based on the amount of barium sulfide used. Thus, amounts of alkanol ranging from about to about 400 parts by weight per mole (167 parts by weight) of barium sulfide are generally used.
- Water is also required in the present process. At least an equimolar amount of water based on the barium sulfide used is necessary. A larger amount of water, for example up to 2 times the necessary amount, can also be used. The water (and alkanol) has to be distilled off as a final step in the process. As a practical matter then, too large an excess of water is not used.
- the amount of barium sulfide used in the present process must be more than the stoichiometric amount required to neutralize the sulfonic acid supplied by the sulfonic acid material.
- One mole of barium sulfide will neutralize two moles of a sulfonic acid.
- the stoichiometric relationship in moles of sulfonic acid to moles of barium 1 A Bills od ore is used.
- sulfide is 2:1. Since the product obtained in the present process is overbased, that is, contains more than the stoichiometric amount of barium, a. greater than stoichiometric amount of barium sulfide must be used in carrying out this process. Molar ratios of sulfonic acid to barium sulfide of from 1:1 up to about 1:10 can be used. Ratios of from about 1:2 to about 1:5 are preferred.
- reaction temperatures ranging from about 50 C. up to the reflux temperature of the reaction mixture are used.
- the reflux temperature will be dependent upon the particular hydrocarbon medium used, its amount, and the amount of alkanol and water in the reaction mixture.
- An upper temperature limit would be about 150 C.
- This reaction temperature is the temperature at which the carbon dioxide is passed into the solution to effect formation of the overbased complex.
- the mixture containing the sulfonic acid material in hydrocarbon medium, BaS, H 0, and alkanol is subjected to treatment with carbon dioxide gas; this is the overbasing step.
- the CO is simply bubbled through the mixture at the aforesaid reaction temperatures until substantially no H 8 gas is evolved from the mixture. At this point the reaction is considered complete. Any means of detecting the presence of H 8 in the efli-uent gas coming from the mixture can be used to determine this point; a convenient method is to test the efiluent gas with wet lead acetate paper.
- the treatment with CO effectively complexes the stiochiometric excess of barium sulfide (converted to barium carbonate) with the neutralized sulfonic acid, thus forming an overbased barium sulfonate.
- the process of this invention is ordinarily carried out at atmospheric pressures. However, it can also be carried out at pressure above atmospheric.
- the use of pressures above atmospheric can be used to advantage to minimize solvent loss while carrying out the reaction; higher pressures might also be desirable when a reaction temperature higher than the reflux temperature is used to carry out the reaction.
- the following examples illustrate the process of the present invention; all parts are by weight unless otherwise indicated.
- EXAMPLE 1 A vessel fitted with stirrer, thermometer, water collector, and condenser is charged with 100 parts (0.5 mole) of 85 percent assay barium sulfide and 300 parts methanol. This slurry is stirred and about 9 parts (0.5 mole) of water was added; the mixture was heated to 55-60 C. and kept at this temperature for 50 minutes. A solution of 59.8 parts (0.2 mole) of dodecyl benzene sulfonic acid in about 220 parts of xylene was added and the mixture was refluxed for 30 minutes (hydrogen sulfide was evolved). A stream of carbon dioxide gas was then bubbled through the mixture until evolution of hydrogen sulfide had essentially stopped hours).
- the methanol and water were then distilled from the mixture (about 44 parts of xylene containing about .8 part of dimethyl formamide was added during the distillation).
- the mixture was cooled and then diluted further with about 310 parts of benzene containing about .8 part of dimethyl formamide.
- the solution was then filtered twice and the benzene and a portion of the xylene were distilled off under vacuum.
- the product at this point gelled on cooling.
- the product was diluted again with benzene (about 180 parts) and dimethyl formamide (about 2.5 parts).
- the solution was stirred and then the benzene was distilled off under vacuum. 229 parts of a slightly viscous, clear product were obtained.
- About 0.8 part of dimethyl formamide was added to the product to reduce its viscosity.
- Example 1 is repeated substituting 0.05 mole of heptadecylbenzene sulfonic acid for the dodecylbenzene sulfonrc 6 acid, 50 parts of isopropanol for the method and toluene for the xylene; the reaction mixture is heated to about 5 0 C. while the carbon dioxide is bubbled into it.
- EXAMPLE 3 A vessel fitted with a stirrer, thermometer, water collector, and condenser was charged with 100 parts (0.5 mole) percent assay barium sulfide and 300 parts of methanol. This suspension was stirred and about 9 parts (0.5 mole) of water were added, followed by a solution of 59.8 parts (0.2 mole) dodecylbenzene sulfonic acid in 75 parts pale oil (Sun Circo )Q(X Lt) and 170 parts naphtha (aviation alkylate). This mixture was refluxed for 30 minutes and then carbon dioxide was passed through the mixture for 5.5 hours. The methanol and water were then distilled off; about 80 parts naphtha were added during this distillation period. The mixture was cooled and it was further diluted with about 270 parts of hexane. The solution was then filtered; the filtrate was stripped of solvents under vacuum. 224.3 parts of a very dark, slightly hazy viscous liquid product were obtained.
- Example 2 Similar results are obtained when mahogany sulfonic acid is used in place of the dodecyl benzene sulfonic acid. Using black ash to provide an equivalent amount of barium sulfide also produces an analogous product.
- the reaction of Example 2 is carried out with similar results when ethanol, isopropanol or amyl alcohol is used in place of the methanol. Similar results are obtained when the reaction in Example 3 is carried out in benzene, kerosene, hexane, toluene, and a mixture of No. 9 oil and xylene.
- EXAMPLE 4 A vessel fitted with a stirrer, thermometer, water collector and condenser is charged with parts (0.5 mole BaS) of black ash (84.5 percent barium sulfide) about 400 parts methanol. About 9 parts (0.5 mole) of water is added to the stirred slurry and the mixture is heated to about 60 for about one hour. To this suspension is added a solution of 97.4 parts (0.08 mole) of a sulfonated C olefin derivative in about 450 parts of xylene; this mixture is then refluxed for about 30 minutes. Carbon dioxide gas is then bubbled through the mixture until substantially no hydrogen sulfide is evolved from the reaction mixture (detectible by lead acetate paper). The methanol and water are distilled olf. The mixture is then diluted with about 400 parts of benzene. This solution is filtered. The product obtained is an overbased barium sulfonate.
- BaS black ash (84.5 percent barium sulf
- the sulfonated C olefin derivative used in Example 4 is a product obtained on sulfonating an olefin mixture having the general composition disclosed above.
- its acid number and its saponification number are determined.
- the difference between the saponification number and the acid number represents the amount of sultone present in the sulfonated derivative. If a substantial portion of the product is sultone then a saponification step using barium oxide or barium sulfide and water as herein described may be used in carrying out the process of Example 4 more efiiciently.
- the products of the process of this invention as illustrated by the examples above, are especially useful as smoke reducing additives in diesel fuel.
- Another embodiment of this invention is a diesel fuel containing a smoke reducing quantity of a product made by the process of the present invention.
- the amount of such product added to a diesel fuel ranges from about 0.05 percent by weight to about 3 percent by weight of the fuel.
- the products obtained by the process of the present invention as illustrated in the above examples are especial- 1y useful as smoke suppressors in distillate hydrocarbon fuels used in diesel engines, and can be added to any commercial diesel fuel. In general these fuels are characterized as having a boiling range of 350 F. to 700 F. So-called residual oils having higher boiling points than this are sometimes blended with a lower boiling diesel fuel. Suitable diesel fuel oils are Federal Specification VV-F800 Grades DF-A, DF-l, DF-2 and DF-4, as well as ASTM Classes 1, 2, 3, and 4. Marine diesel fuel oils are also useful. A tabulation and discussion of suitable diesel fuel oils is presented in Fuels and Lubricants, Milosh Popovich and Carl Hering, pages 134; 146-151, John Wiley and Sons, Inc., New York (1959).
- EXAMPLE 5 A diesel fuel composition is prepared by adding 0.05 percent by weight of the product of Example 2 to a Class 1 diesel fuel oil.
- EXAMPLE 6 A diesel fuel composition is prepared by adding 3 percent by weight of the product of Example 1 to Grade DF-3 diesel fuel oil.
- EXAMPLE 7 A diesel fuel composition is prepared by adding 1.5 percent of the product of Example 3 to a Class 2 diesel fuel oli.
- EXAMPLE 8 A diesel fuel composition is prepared by adding 0.2 percent by weight of the product of Example 4 to Grade DF-2 diesel fuel oil.
- EXAMPLE 9 A diesel fuel composition is prepared by adding 0.6 percent by weight of the product of Example 2 to a marine grade diesel fuel oil.
- the fuel compositions of the present invention produce less exhaust smoke than the same base fuel containing none of the overbased barium sulfonate products of the present invention.
- noticeably less smoke is emitted from a diesel engine when it is operating on the fuel composition of Example 6 than when it is operating on Grade DF-3 diesel fuel containing no overbased barium product.
- the tendency of a diesel engine to produce exhaust smoke is substantially reduced when a diesel fuel containing the overbased product prepared by the process herein described is used as a fuel.
- a process for preparing an overbased barium sulfonate which comprises:
- sulfonated olefin derivatives prepared by sulfonating mixtures of cyclic, monoolefins having from about 14 to about 30 carbon atoms, such that the molar ratio of barium sulfide to said sulfonic acid material is from about 1:1 to about 10: 1,
- Step (3) introducing carbon dioxide gas into the heated mixture of Step (2) until substantially no hydrogen sulfide is evolved from said mixture, and
- said sulfonic acid material is a sulfonated olefin derivative prepared by sulfonating a mixture of acyclic monoolefins comprising by weight 0-3% C and lower olefins 05-17% C olefins, 33-52% C olefins, 19-37% C olefins, 9-115 C olefins, 2-7% C olefins and 0-8% C and higher olefins and wherein the distribution of olefin configurations in said mixture is 12-31% internal, 32-54% vinyl and 32- 47% vinylidene, and wherein said ratio of barium sulfide to said sulfonated olefin derivative is from 1:1 to about 5:1.
- said sulfonic acid is dodecyl benzene sulfonic acid
- said hydrocarbon medium is selected from xylene, light hydrocarbon oils, naphtha, aviation alkylate, and hexane
- said alkanol is methanol and wherein the molar ratio of barium sulfide to dodecyl benzene sulfonic acid is about 2.5: 1.
- a diesel fuel containing a smoke reducing quantity of the product prepared by the process of claim 1.
- a diesel fuel containing a smoke reducing quantity of the product prepared by the process of claim 4.
- a diesel fuel containing a smoke reducing quantity of the product prepared by the process of claim 5.
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Abstract
A PROCESS FOR PREPARING OVERBASED BARIUM HYDROCARBON SULFONATE FEATURING THE USE OF BARIUM SULFIDE AS THE BARIUM SOURCE. THE PRODUCT OBTAINED FROM THIS PROCESS AND DIESEL FUEL CONTAINING A SMOKE REDUCING QUANTITY OF THIS PRODUCT ARE DESCRIBED.
Description
United States Patent Office Patented Sept. 26, 1972 3,694,175 OVERBASED BARIUM ADDITIVE AND FUEL OIL COMPOSITION Charles E. Marble, Troy, Mich., assignor to Ethyl Corporation, New York, N.Y. No Drawing. Filed Sept. 16,1968, Ser. No. 762,369 Int. Cl. C101 1/32; C10m 1/40 US. Cl. 44-51 10 Claims ABSTRACT OF THE DISCLOSURE A process for preparing overbased barium hydrocarbon sulfonate featuring the use of barium sulfide as the barium source. The product obtained from this process and diesel fuel containing a smoke reducing quantity of this product are described.
BACKGROUND OF THE INVENTION This invention is directed to a method of preparing overbased barium sulfonates and their use in distillate fuels.
Processes for preparing overbased alkaline earth oil soluble sulfonates are available in the art (see e.g. US. 2,617,049, US. 2,956,018, US. 3,027,325, and US. 3,- 312,618). The principal products disclosed in the art appear to be those prepared from petroleum derived sulfonic acids. These petroleum derived sulfonic acids are in general alkaryl sulfonates obtained as side products from the sulfuric acid treatment of petroleum hydrocarbons in refining operations.
The term overbased indicates that the resultant product from these various processes contains an amount of alkaline earth metal greater than the stoichiometric amount of metal which would be present if the particular sulfonic acid were fully neutralized. The theory of this overbased complex formation is not fully understood. One suggestion has been that the oil soluble sulfonates act as protective colloids or dispersants thus keeping an alkaline earth compound suspended in a fiuid carrier.
A general method of preparing these complexes features the in situ formation of a finely divided alkaline earth compound such as CaCO in the presence of a petroleum sulfonate in a hydrocarbon medium. This is accomplished by introducing an acidic gas such as carbon dioxide into an alkaline earth containing, petroleum sulfonate dispersion in a hydrocarbon medium. Recent improvements in this process feature the use of promoters such as low molecular Weight alcohols, phenols, amines, and the like.
The present invention provides a method of preparing overbased barium sulfonates featuring the use of barium sulfide as the barium source. The products are elfective smoke suppressors in diesel fuels.
SUMMARY OF THE INVENTION A process for preparing overbased barium sulfonates from a sulfonic acid material, barium sulfide, and carbon dioxide in the presence of C -C alkanol and water in a hydrocarbon medium; the product obtained by this process and its use as a smoke reducing diesel fuel additive.
DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of this invention is a process for preparing an overbased barium sulfonate which comprises:
(1) preparing a slurry of barium sulfide in from about 100 to about 800 parts by weight of C -C alkanol per mole of barium sulfide, adding at least an equimolar amount of water based on barium sulfide, and heating said mixture to a temperature from about 50 C. to the reflux temperature,
(2) adding thereto a mixture of an inert hydrocarbon medium and a sulfonic acid material selected from:
(a) G -C alkyl benzene sulfonic acids, and
(b) sulfonated olefin derivatives prepared by sulfonating mixtures of acyclic, monoolefins having from about 14 to about 30 carbon atoms,
such that the molar ratio of barium sulfide to said sulfonic acid material is from about 1:1 to about 10:1, (3) introducing carbon dioxide gas into the heated mixture of Step (2) until substantially no hydrogen sulfide is evolved from said mixture, and (4) distilling said alkanol and water from said mixture.
Another preferred embodiment of this process features the use of sulfonated olefin derivatives prepared by sulfonating a C olefin Whose specific composition is given below. Dodecyl benzene sulfonic acid is used in a most preferred embodiment. Barium sulfide in the crude form known as black ash is a most preferred form of BaS.
Sulfonic acid materials of various types may be used in the present process. These include alkenyl sulfonic acids, alkyl sulfonic acids, hydroxy alkyl sulfonic acids, sultones, mixtures thereof, as Well as alkyl benzene sulfonic acid. Hydrocarbon soluble petroleum sulfonic acids, the socalled mahogany" sulfonic acids, are also useful in this process. These mahogany sulfonic acids are mixtures of sulfonic acids obtained during sulfuric acid treatment of petroleum refinery streams.
Sulfonic acid containing products obtained on sulfonating olefins are another type of useful sulfonic acid material. These products are referred to herein as sulfonated olefin derivatives. By olefins I mean hydrocarbon olefins. The products obtained on sulfonating acyclic monoolefins having from about 14 to about 30 carbon atoms are particularly useful. Especially useful olefin starting materials are the mixtures of acyclic olefins obtained from synthetic manufacturing processes such as dehydrogenation of parafiins or polymerization of low molecular weight olefins such as ethylene and propylene. Synthetically prepared monoolefins having the following olefin makeup and configurations (double bond position) are most preferred; the olefins are predominantly alpha. These mixed olefins are identified herein as C olefins.
Olefin chain length: Percent by weight 1 C and lower 0-3 C 0.5-17 C 33-52 C 19-37 C 9-15 C 2-7 25+ 08 1 Vapor phase chromatography analysis.
Olefin configurations Percent distribution Vinyl 32-54 Internal 12-31 Vinylidene 32-47 Nuclear magnetic resonance analysis.
In sulfonating olefins,, any suitable sulfonation procedure may be utilized. Suitable procedures are described in the following patents: US. 3,259,645; U.S. 3,337,437; British 1,072,601; French 1,403,407 and French 1,399,570. In general, the sulfonation of olefins comprises treating olefins with a sulfonating agent such as S0 to produce a sulfonated derivative.
The mixtures of useful ole-fins contain varying ratios and combinations of olefins having from about 14 to about 30 carbon atoms. These mixtures may contain linear olefins, branched olefins, and mixtures thereof.
Representative examples of monoolefin mixtures from which preferred sulfonated olefin derivatives are prepared are presented in the following table; the mixtures contain more than about 60 percent a-olefins.
Blends of these mixtures are also useful. A blend of seven volumes of mixture A and eleven volumes of mixture B is a particularly useful blend.
Especially useful olefin sulfonation processes and the mechanisms involved are described in the journal Hydrocarbon Processing, vol. 47, No. 3, pages 109-114, March 1968. The material therein described is incorporated by reference. When sulfonating olefins, the products obtained may be mixtures containing alkenyl sulfonic acids, hydroxyalkyl (or -alkenyl) sulfonic acids, and 5 and 6 membered ring inner esters called sultones. These sultones may comprise as high as 50 percent of the sulfonated olefin product when using a falling film reactor system. The sultones are readily saponified by treatment with a strong base. Thus, when sulfonated ole-fin products are used as the hydrocarbon sulfonic acid material in the present process, it is desirable to saponify this product so that the full sulfonic acid value of the material is realized in the process. The saponification can be carried out prior to the overbasing step in the process. By overbasing step is meant the point at which carbon dioxide is introduced into the reaction mixture to form barium carbonate in situ. This saponification can be carried out by treating the sulfonated olefin product with a strong base such as sodium hydroxide or potassium hydroxide and heating to an elevated temperature for a few minutes. This saponification would yield the sodium or potassium salt of all the sulfonic acids present. It would be better then to convert this salt to the corresponding barium salt for use in the present process.
A more preferred procedure is to saponify the sultone containing sulfonated olefin derivative with barium oxide or barium sulfide/water as the first step in the process and then to continue with the overbasing step.
A most preferred Way of saponifying the sultone is to charge the sulfonated olefin derivative, the hydrocarbon medium, and the barium sulfide-water-alcohol ingredients into the reactor and then heat this mixture to effect the saponification while bubbling the carbon dioxide through the mixture. This saponification step is an important feature of the process when sulfonated olefin derivatives which may contain sultones are used as a starting material.
Alkylbenzene sulfonic acids wherein the alkyl group has 12 to 17 carbon atoms are also useful. Laurylbenzene sulfonic acid, heptadecylbenzene sulfonic acid, hexadecylbenzene sulfonic acid, tetradecylbenzene sulfonic acid and the like are examples of useful sulfonic acids. Mixed alkylbenzene sulfonic acids prepared for example from the hydrocarbon product of the Friedel Crafts alkylation of benzene with an olefin containing principally tetrapropylene, are another example of a useful sulfonic acid. The useful alkyl benzene sulfonic acids are also characterized by having a molecular weight of less than about 400.
Dodecylbenzene sulfonic acid is an especially preferred alkylbenzene sulfonic acid.
Barium sulfide is the reactant utilized in the present process to supply the barium values for the overbased.
product. A preferred form of barium sulfide is a crude product obtained in the commercial preparation of barium sulfide by reducing a barium sulfate 1 with carbon. This crude product is commonly called black ash; it contains up to about percent barium sulfide.
Typical analysis of commercial black ash is as follows; all percentages are by weight.
Black ash typical analysis Percent Assay BaS 71.2-88.0 Insoluble material 19.2-10.4 Calcium and strontium (as oxides) 0.5 Silica 0.4 Aluminum and iron (as oxides) 1.5 Carbon 3.7 Magnesium (as oxide) 0.2 2.8
Thio and other reducible sulfur compounds The reaction of the present process is carried out in a suitable hydrocarbon medium. The medium is characterized by being (1) inert during the process of the reaction and (2) a solvent for the sulfonic acid starting material. It is also preferred that this medium be a solvent for the overbased product which is obtained in the process; and this hydrocarbon medium should be compatible with diesel fuel. Any hydrocarbon which meets these criteria may be used. Aromatic hydrocarbons, parafiinic hydrocarbons, olefinic hydrocarbons, mixtures thereof, light distillate hydrocarbon oils, distillate fuels, kerosene, straight run naphtha, petroleum refinery streams such as catalytic reformate, thermally or catalytically cracked streams, alkylated refinery streams, catalytically cracked naphtha and the like, are useful hydrocarbon media. Benzene, C -C alkylbenzenes such as toluene, xylene, actylbenzene, pentylbenzene and the like, (I -C paraflins such as hexane, heptane, dodecane and the like, aviation alkylate, light processing oils such as No. 9 oil and the like, catalytic reformate containing over about 70 percent aromatic hydrocarbons and the like, and mixtures thereof are some examples of useful media.
The amount of hydrocarbon medium used in the process is not critical. An amount of inert hydrocarbon ranging from about 0.5 to about 10 times the Weight of the sulfonic acid material can be used.
Alkanols having from about 1 to about 5 carbon atoms are used in the present process. The exact function of the alkanol used in the process is not understood; however, the alkanol is required in order for the reaction of the present process to be carried out. Examples of useful alkanols are ethanol, isopropanol, pentanol-3, amyl alcohol, butyl alcohol, and mixtures of these alcohols. Methanol is a most preferred alkanol.
The amount of alkanol used may be varied. Generally the barium sulfide reactant is dispersed in the alkanol as an initial step. The amount of alkanol used is based on the amount of barium sulfide used. Thus, amounts of alkanol ranging from about to about 400 parts by weight per mole (167 parts by weight) of barium sulfide are generally used.
Water is also required in the present process. At least an equimolar amount of water based on the barium sulfide used is necessary. A larger amount of water, for example up to 2 times the necessary amount, can also be used. The water (and alkanol) has to be distilled off as a final step in the process. As a practical matter then, too large an excess of water is not used.
The amount of barium sulfide used in the present process must be more than the stoichiometric amount required to neutralize the sulfonic acid supplied by the sulfonic acid material. One mole of barium sulfide will neutralize two moles of a sulfonic acid. Thus, the stoichiometric relationship in moles of sulfonic acid to moles of barium 1 A Bills od ore is used.
sulfide is 2:1. Since the product obtained in the present process is overbased, that is, contains more than the stoichiometric amount of barium, a. greater than stoichiometric amount of barium sulfide must be used in carrying out this process. Molar ratios of sulfonic acid to barium sulfide of from 1:1 up to about 1:10 can be used. Ratios of from about 1:2 to about 1:5 are preferred.
The process is carried out at elevated temperatures. Reaction temperatures ranging from about 50 C. up to the reflux temperature of the reaction mixture are used. The reflux temperature, of course, will be dependent upon the particular hydrocarbon medium used, its amount, and the amount of alkanol and water in the reaction mixture. An upper temperature limit would be about 150 C. This reaction temperature is the temperature at which the carbon dioxide is passed into the solution to effect formation of the overbased complex.
The mixture containing the sulfonic acid material in hydrocarbon medium, BaS, H 0, and alkanol is subjected to treatment with carbon dioxide gas; this is the overbasing step. The CO is simply bubbled through the mixture at the aforesaid reaction temperatures until substantially no H 8 gas is evolved from the mixture. At this point the reaction is considered complete. Any means of detecting the presence of H 8 in the efli-uent gas coming from the mixture can be used to determine this point; a convenient method is to test the efiluent gas with wet lead acetate paper. The treatment with CO effectively complexes the stiochiometric excess of barium sulfide (converted to barium carbonate) with the neutralized sulfonic acid, thus forming an overbased barium sulfonate.
The process of this invention is ordinarily carried out at atmospheric pressures. However, it can also be carried out at pressure above atmospheric. The use of pressures above atmospheric can be used to advantage to minimize solvent loss while carrying out the reaction; higher pressures might also be desirable when a reaction temperature higher than the reflux temperature is used to carry out the reaction. The following examples illustrate the process of the present invention; all parts are by weight unless otherwise indicated.
EXAMPLE 1 A vessel fitted with stirrer, thermometer, water collector, and condenser is charged with 100 parts (0.5 mole) of 85 percent assay barium sulfide and 300 parts methanol. This slurry is stirred and about 9 parts (0.5 mole) of water was added; the mixture was heated to 55-60 C. and kept at this temperature for 50 minutes. A solution of 59.8 parts (0.2 mole) of dodecyl benzene sulfonic acid in about 220 parts of xylene was added and the mixture was refluxed for 30 minutes (hydrogen sulfide was evolved). A stream of carbon dioxide gas was then bubbled through the mixture until evolution of hydrogen sulfide had essentially stopped hours). The methanol and water were then distilled from the mixture (about 44 parts of xylene containing about .8 part of dimethyl formamide was added during the distillation). The mixture was cooled and then diluted further with about 310 parts of benzene containing about .8 part of dimethyl formamide. The solution was then filtered twice and the benzene and a portion of the xylene were distilled off under vacuum. The product at this point gelled on cooling. The product was diluted again with benzene (about 180 parts) and dimethyl formamide (about 2.5 parts). The solution was stirred and then the benzene was distilled off under vacuum. 229 parts of a slightly viscous, clear product were obtained. About 0.8 part of dimethyl formamide was added to the product to reduce its viscosity.
Analysis of the overbased barium sulfonate product showed that it contained 23.6 percent barium and 2.4 percent sulfur.
EXAMPLE 2 Example 1 is repeated substituting 0.05 mole of heptadecylbenzene sulfonic acid for the dodecylbenzene sulfonrc 6 acid, 50 parts of isopropanol for the method and toluene for the xylene; the reaction mixture is heated to about 5 0 C. while the carbon dioxide is bubbled into it.
An overbased barium sulfonate product is obtained.
EXAMPLE 3 A vessel fitted with a stirrer, thermometer, water collector, and condenser was charged with 100 parts (0.5 mole) percent assay barium sulfide and 300 parts of methanol. This suspension was stirred and about 9 parts (0.5 mole) of water were added, followed by a solution of 59.8 parts (0.2 mole) dodecylbenzene sulfonic acid in 75 parts pale oil (Sun Circo )Q(X Lt) and 170 parts naphtha (aviation alkylate). This mixture was refluxed for 30 minutes and then carbon dioxide was passed through the mixture for 5.5 hours. The methanol and water were then distilled off; about 80 parts naphtha were added during this distillation period. The mixture was cooled and it was further diluted with about 270 parts of hexane. The solution was then filtered; the filtrate was stripped of solvents under vacuum. 224.3 parts of a very dark, slightly hazy viscous liquid product were obtained.
Analysis of this product showed it to contain 28.1 percent barium, 3.1 percent sulfur.
Similar results are obtained when mahogany sulfonic acid is used in place of the dodecyl benzene sulfonic acid. Using black ash to provide an equivalent amount of barium sulfide also produces an analogous product. The reaction of Example 2 is carried out with similar results when ethanol, isopropanol or amyl alcohol is used in place of the methanol. Similar results are obtained when the reaction in Example 3 is carried out in benzene, kerosene, hexane, toluene, and a mixture of No. 9 oil and xylene.
EXAMPLE 4 A vessel fitted with a stirrer, thermometer, water collector and condenser is charged with parts (0.5 mole BaS) of black ash (84.5 percent barium sulfide) about 400 parts methanol. About 9 parts (0.5 mole) of water is added to the stirred slurry and the mixture is heated to about 60 for about one hour. To this suspension is added a solution of 97.4 parts (0.08 mole) of a sulfonated C olefin derivative in about 450 parts of xylene; this mixture is then refluxed for about 30 minutes. Carbon dioxide gas is then bubbled through the mixture until substantially no hydrogen sulfide is evolved from the reaction mixture (detectible by lead acetate paper). The methanol and water are distilled olf. The mixture is then diluted with about 400 parts of benzene. This solution is filtered. The product obtained is an overbased barium sulfonate.
An analogous product is obtained when the process of Example 4 is carried out under pressure at a temperature of C.
The sulfonated C olefin derivative used in Example 4 is a product obtained on sulfonating an olefin mixture having the general composition disclosed above. In order to determine the sulfonic acid content and the sultone content of this derivative, its acid number and its saponification number are determined. The difference between the saponification number and the acid number represents the amount of sultone present in the sulfonated derivative. If a substantial portion of the product is sultone then a saponification step using barium oxide or barium sulfide and water as herein described may be used in carrying out the process of Example 4 more efiiciently.
The products of the process of this invention as illustrated by the examples above, are especially useful as smoke reducing additives in diesel fuel. Another embodiment of this invention is a diesel fuel containing a smoke reducing quantity of a product made by the process of the present invention. The amount of such product added to a diesel fuel ranges from about 0.05 percent by weight to about 3 percent by weight of the fuel.
The products obtained by the process of the present invention as illustrated in the above examples are especial- 1y useful as smoke suppressors in distillate hydrocarbon fuels used in diesel engines, and can be added to any commercial diesel fuel. In general these fuels are characterized as having a boiling range of 350 F. to 700 F. So-called residual oils having higher boiling points than this are sometimes blended with a lower boiling diesel fuel. Suitable diesel fuel oils are Federal Specification VV-F800 Grades DF-A, DF-l, DF-2 and DF-4, as well as ASTM Classes 1, 2, 3, and 4. Marine diesel fuel oils are also useful. A tabulation and discussion of suitable diesel fuel oils is presented in Fuels and Lubricants, Milosh Popovich and Carl Hering, pages 134; 146-151, John Wiley and Sons, Inc., New York (1959).
Following are examples of diesel fuel compositions of this invention.
EXAMPLE 5 A diesel fuel composition is prepared by adding 0.05 percent by weight of the product of Example 2 to a Class 1 diesel fuel oil.
EXAMPLE 6 A diesel fuel composition is prepared by adding 3 percent by weight of the product of Example 1 to Grade DF-3 diesel fuel oil.
EXAMPLE 7 A diesel fuel composition is prepared by adding 1.5 percent of the product of Example 3 to a Class 2 diesel fuel oli.
EXAMPLE 8 A diesel fuel composition is prepared by adding 0.2 percent by weight of the product of Example 4 to Grade DF-2 diesel fuel oil.
EXAMPLE 9 A diesel fuel composition is prepared by adding 0.6 percent by weight of the product of Example 2 to a marine grade diesel fuel oil.
The fuel compositions of the present invention produce less exhaust smoke than the same base fuel containing none of the overbased barium sulfonate products of the present invention. For example, noticeably less smoke is emitted from a diesel engine when it is operating on the fuel composition of Example 6 than when it is operating on Grade DF-3 diesel fuel containing no overbased barium product. Thus, the tendency of a diesel engine to produce exhaust smoke is substantially reduced when a diesel fuel containing the overbased product prepared by the process herein described is used as a fuel.
The present invention therefore is encompassed in three embodiments,
(1) a process for preparing overbased barium sulfonate products, (2) the overbased barium sulfonate product, and
,(3) diesel fuel containing a smoke reducing quantity of this product.
All three embodiments have been described in the foregoing disclosure; it is desired to limit this invention only within the spirit and scope of the following claims.
I claim:
1. A process for preparing an overbased barium sulfonate which comprises:
(1) preparing a slurry of barium sulfide in from about 100 to about 800 parts by weight of C -C alkanol per mole of barium sulfide, adding at least an equimolar amount of water based on barium sulfide, and heating said mixture to a temperature from about 50 C. to the reflux temperature, 2. The process of claim 1 wherein said barium sulfide medium and a sulfonic acid material selected from: '(a) C12-C17 alkyl benzene sulfonic acids, and
(b) sulfonated olefin derivatives prepared by sulfonating mixtures of cyclic, monoolefins having from about 14 to about 30 carbon atoms, such that the molar ratio of barium sulfide to said sulfonic acid material is from about 1:1 to about 10: 1,
(3) introducing carbon dioxide gas into the heated mixture of Step (2) until substantially no hydrogen sulfide is evolved from said mixture, and
(4) distilling said alkanol and water from said mixture.
2. The process of claim 1 wherein said barium sulfide is a crude barium sulfide.
3. The process of claim 1 wherein said sulfonic acid material is said alkylbenzene sulfonic acid and wherein the said molar ratio of barium sulfide to sulfonic acid is from 1:1 to about 5: 1.
4. The process of claim 1 wherein said sulfonic acid material is a sulfonated olefin derivative prepared by sulfonating a mixture of acyclic monoolefins comprising by weight 0-3% C and lower olefins 05-17% C olefins, 33-52% C olefins, 19-37% C olefins, 9-115 C olefins, 2-7% C olefins and 0-8% C and higher olefins and wherein the distribution of olefin configurations in said mixture is 12-31% internal, 32-54% vinyl and 32- 47% vinylidene, and wherein said ratio of barium sulfide to said sulfonated olefin derivative is from 1:1 to about 5:1.
5. The process of claim 3 wherein said sulfonic acid is dodecyl benzene sulfonic acid, said hydrocarbon medium is selected from xylene, light hydrocarbon oils, naphtha, aviation alkylate, and hexane, said alkanol is methanol and wherein the molar ratio of barium sulfide to dodecyl benzene sulfonic acid is about 2.5: 1.
6. The product prepared by the process of claim 1.
7. The product prepared by the process of claim 2.
8. A diesel fuel containing a smoke reducing quantity of the product prepared by the process of claim 1.
9. A diesel fuel containing a smoke reducing quantity of the product prepared by the process of claim 4.
10. A diesel fuel containing a smoke reducing quantity of the product prepared by the process of claim 5.
References Cited UNITED STATES PATENTS 2,695,910 11/1954 Asself et al 25233 X 2,956,018 10/1960 Carlyle et al. 25218 3,021,280 2/ 1962 Carlyle 25233 3,282,835 11/1966 Asseff 25233 X 3,312,618 4/1967 Le Suer et al. 25233 3,437,465 4/ 1969 Le Suer 4451 FOREIGN PATENTS 661,907 2/1965 Belgium 44-76 DANIEL E. WYMAN, Primary Examiner W. .T. SHINE, Assistant Examiner U.S. Cl. X.R. 44-76; 25233 *;g;;g V UNITED STATES PATENT OFFICE CERTIFICATE OF CQRRECITION' Patent No. 3,694,175 a I Dated September 26, 1 972 Infintoz-(I) Charles E. Marble Iris certifiedthat error appears in thoabove-ide'ntificd patent h and that said Letters Patent are hereby corrected as shown below f l,- Column 8, line 5 the correct phrase should read (2) adding thereto a mixture of an inert hydrocarbon j instead of as shown in the patent.
Claim 1, Column 8, line 9 "cyclic" should read e -acyclic .jClaim 4, Column 8, line 27 v' thecorreot ratio should read 9 15/o C instead of as shown in the patent.
Signed and sealed this 6th day of February 1973.
(SEAL) A-ttest:
EDWARD M.FL1:;TCHER,JR ROBERT GOT'ISCHALK Attestlng Officer Commissioner of Patents
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US76236968A | 1968-09-16 | 1968-09-16 |
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US762369A Expired - Lifetime US3694175A (en) | 1968-09-16 | 1968-09-16 | Overbased barium additive and fuel oil composition |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4670022A (en) * | 1984-11-05 | 1987-06-02 | Honda Giken Kogyo Kabushiki Kaisha | Fuel composition for spark-ignition engine |
-
1968
- 1968-09-16 US US762369A patent/US3694175A/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4670022A (en) * | 1984-11-05 | 1987-06-02 | Honda Giken Kogyo Kabushiki Kaisha | Fuel composition for spark-ignition engine |
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