US2725396A - Process for the oxidation of white mineral oils to dicarboxylic naphthenic acids - Google Patents
Process for the oxidation of white mineral oils to dicarboxylic naphthenic acids Download PDFInfo
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- US2725396A US2725396A US419900A US41990054A US2725396A US 2725396 A US2725396 A US 2725396A US 419900 A US419900 A US 419900A US 41990054 A US41990054 A US 41990054A US 2725396 A US2725396 A US 2725396A
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- oxidation
- acids
- dicarboxylic
- naphthenic
- oxidized
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- 238000007254 oxidation reaction Methods 0.000 title claims description 51
- 230000003647 oxidation Effects 0.000 title claims description 49
- 239000002480 mineral oil Substances 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 17
- 125000005608 naphthenic acid group Chemical group 0.000 title description 26
- 239000003921 oil Substances 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000000194 fatty acid Substances 0.000 claims description 13
- -1 PEROXIDE SALT 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
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 150000007513 acids Chemical class 0.000 claims description 9
- 238000007127 saponification reaction Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 239000000047 product Substances 0.000 description 29
- 235000010446 mineral oil Nutrition 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- 150000002763 monocarboxylic acids Chemical class 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 238000001256 steam distillation Methods 0.000 description 4
- 239000004160 Ammonium persulphate Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 235000019395 ammonium persulphate Nutrition 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229960002163 hydrogen peroxide Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229920000728 polyester Polymers 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 2
- 235000019809 paraffin wax Nutrition 0.000 description 2
- 235000019271 petrolatum Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- NKWCGTOZTHZDHB-UHFFFAOYSA-N 1h-imidazol-1-ium-4-carboxylate Chemical compound OC(=O)C1=CNC=N1 NKWCGTOZTHZDHB-UHFFFAOYSA-N 0.000 description 1
- 235000009355 Dianthus caryophyllus Nutrition 0.000 description 1
- 240000006497 Dianthus caryophyllus Species 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003330 sebacic acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C405/00—Compounds containing a five-membered ring having two side-chains in ortho position to each other, and having oxygen atoms directly attached to the ring in ortho position to one of the side-chains, one side-chain containing, not directly attached to the ring, a carbon atom having three bonds to hetero atoms with at the most one bond to halogen, and the other side-chain having oxygen atoms attached in gamma-position to the ring, e.g. prostaglandins ; Analogues or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/126—Acids containing more than four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/14—Adipic acid
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation
Definitions
- White mineral oils are considered intermolecular mixtures of naphthene rings with paraffin side chains. They are practically free of aromatic and naphthene parafiin side chain compounds and solid paraffin waxes. White mineral oils are compounds which have the following basic structure:
- n is in the range of 5 to 40.
- the mineral oil distillate produced from crude oil, must be properly purified. This purification is done normally by ex haustive treatment with sulphuric acid monohydrate and later with large amounts, in two to washes, with oleum, containing 20% and more of free S03. In order to remove from the sour oil the sulphonated products, this oil is again treated in the last wash with sulphuric acid monohydrate. In the final treatment, the sour white mineral oil is deacidified with alcoholic solutions of caustic soda and absorbent clay in order to obtain an entirely acid-free, water-free white mineral oil.
- white mineral oils can be oxidized with air, with or without catalysts, under atmospheric pressure or at pressures up to 50 atmospheres; at temperatures ranging from 100 to 200 C., to monocarboxylic acid products. These products, however, are dark colored and malodorous and their sodium salts cannot be separated by salting out. Lighter monocarboxylic acid products are obtained by partial oxidation of white mineral oils, when only a part of the oil is converted by oxidation to corresponding monocarboxylic acids having the following basic structure:
- om writ M00011 The unchanged, non oxidized main part of the white oil, after separation from the produced acids (11), by conventional methods of selective extraction, is returned back to the oxidation process.
- the produced monocarboxylic acids are utilized for the production of industrial soaps, soap based greases, etc.
- the air oxidation of white mineral oils to monoearboxylic acids was used industrially only during World War II, in Ger many, and later abandoned when fatty acids again became abundant.
- the object of this invention is to provide a process for the manufacturing of dicarboxylic naphthenic acids from white mineral oils by a new two-step liquid phase oxidation, which comprises:
- Step N0 Exhaustive air oxidation Exhaustive oxidation of white mineral oils with air under pressure at temperatures of from 100 to 200 C., in the presence of a catalyst.
- m is in the range of 0 to 25.
- This mixture of homologous dicarboxylic naphthenic acids contains, besides small amounts of unchanged white oil (I), one to 5% of volatile, low molecular fatty acids, produced during the first step of the oxidation process, due to the splitting of the long aliphatic chain by the oxygen of the air; -(C2)nCH3, attached to the cyclopentane ring in position 3-, into two separate monocarboxylic acids. Nevertheless, this finely oxidized material has a much gentler odor of fatty acids, its viscosity is much lower, its color is straw-yellow, and its specific gravity is much higher.
- An additional steam distillation removes the low molecular fatty acids leaving analmost odorless product, which contains more than 80% of dicarboxylic naphthenic acids.
- an extraction with an alcohol-water mixture removes the acids, leaving insoluble the unsaponifiable matter.
- a subsequent distillation of the water-alcohol solution of the dicarboxylic naphthenic acids removes the solvent mixture, and the mixture of the dicarboxylic naphthenic acids can be finally fractionated under vacuum into narrow cuts of the individual homologs of the dicarboxylic naphthenic acids, which are believed to have formula as shown in (VIII) above.
- EXAMPLE 1 As the starting commercial oil, a semi-refined white oil, called AI-1C Process Oil, made by Socony Vacuum Co., was selected. Its physical-chemical properties were as follows:
- Hot-acid testb1ack n 1.4.808; di -0.886; dist. range C./10 mm. of to 95%173 to 223; flash point-15.85 C.; viscosity in centistokes/ZO C.3l; aniline pointplus 811 C.
- This oil was exhaustively refined with a 20% oleum to a white oil, which had the following physico-chemical properties:
- This oxidation was mrn.5%/131 C., 75%/256 C.; carbonyl No. 98; unsaponf'. matter20%; naphthenic and hydroxynaphthenic acids5l%; carbonyl-naphthenic acids37%; volatile fatty acids--2%.
- the 101 pounds of the product are saponified and further oxidized with about 120 pounds of a 35% aqueous solution of potassium permanganate. This amount was calculated from the quantitative analysis by using an excess of one mole of the IMn04 for the carbonyl group in each mole of the carbonyl-naphthenic acids; in excess of two moles of KMnOi for the methoxy-group in each mole of the hydroxy-naphthenic acids, and in excess of three moles of KMnOa for the methyl group in each mole of the naphthenic acids.
- the 101 pounds of the air oxidized oil were heated to a temperature of about 70 C. At this temperature, while thoroughly stirring, at atmospheric pressure, the calculated amount of the above mentioned KMnO4- aqueous solution was slowly added and during the addition, the temperature was maintained at about 70 C. by the use of a cooling bath. After the exothermic reaction was completed the mixture was allowed to cool to room temperature, at which temperature it was maintained while continuously stirring for about 24 hours. Every hour a sample of the oxidized product was withdrawn and its saponification number was determined. The reaction was considered as finished when in an hour interval no significant increase in the saponification number Occurred. Afterwards, the mixture was separated into two layers.
- the lower, aqueous layer was used for the regeneration of the KM1'104, and the upper, light colored oily layer, was washed thoroughly with hot water, and by steam distillation freed from the volatile low molecular fatty acids. The remaining oil was dried at 100 C., under vacuum and finally filtered. The obtained amount of the final product, which is believed to be predominantly a mixture of homologs of dicarboxylic naphthenic acids (VIII), was analysed and had the following physicochemical properties:
- This mixture of homologs of dicarboxylic naphthenic acids can be easily esterified with polyalcohols, as for example with glycerine, yielding resinous polyesters.
- polyalcohols as for example with glycerine
- the unsaponifiable matter must be removed.
- the most economic way to do it is by theextraction of the dicarboxylic naphthenic acids with an aqueous solution of ethyl alcohol, in which the unsaponifiable matter is insoluble.
- the unsaponifiable matter which consists, mainly of unreacted white oil and some naphthenic alcohols, is returned into the air oxidation process.
- EXAMPLE 2 As the starting commercial white mineral oil, a product called Carnation White Oil, and made by L. Sonneborn and Sons Inc., was selected. Its physico-chemical properties were as follows:
- Hot-acid test-water white n 1.4587; d4 0.839; dist. range C./10' mm. of 5% to was 210 to 225; flash point-185 C.; viscosity in centistokes/20 C.-25; molecular weight-325; pour point-plus 28 C.; anili'ne point-plus 105 C.; percent aliphatic side chains- 23; percent naphthenic rings7-2.
- the calculated amount of 100 pounds of the 50% hydrogen peroxide solution was slowly added, and throughout the addition, the temperature was maintained at about plus 50 C. by the use of a cooling bath. After the exothermic reaction was completed, the mixture was allowed to cool off to room temperature, at which temperature it was maintained, while stirring thoroughly for about 20 hours. The oxidation reaction was considered as completed when after one more hour the saponification number of the oxidized product remained almost unchanged. Afterwards, the mixture was separated into two layers. The aqueous layer was discharged and the resulting light colored oily layer was washed with small amounts of warm water and the light volatile low molecular fatty acids removed by a steam distillation. The remaining oil was dried at 100 C.- under vacuum and finally filtered.
- the oil is reacted with an aqueous solution of caustic soda, and the unsaponifiable matter is extracted from the resulting sodium salts of the dicarboxylic acids with benzene.
- the unsaponifiable matter is extracted from the resulting sodium salts of the dicarboxylic acids with benzene.
- acidification with an inorganic acid the pure dicarboxylic naphthenic acids are obtained.
- vacuum distillation pure individual acids result.
- EXAMPLE 3 As the starting commercial white mineral oil, a product called Superla No. 10a made by Standard Oil Co. of Indiana was selected. Its physico-chemical properties were as follows:
- Hot acid testwater white n l.464l; d4 0.85l; distil. range C./10 mm. of 5% to 95%-2l6 to 299; flash point184 C.; viscosity in centistokes/ZO" C.- 41; molecular weight345; pour point-plus 25 C.; aniline point-plus 106 C.; percent aliphatic side chains-44; percent naphthenic rings56.
- Example 2 For the recovered 101 pounds of the air oxidized product, about 250 pounds of the 45% aqueous ammonium persulphate solution was used. This amount was calculated in the same way as indicated in Example 1. First the 101 pounds of the air oxidized white oil was heated to a temperature of about 60 C. At this temperature, while stirring thoroughly, under atmospheric pressure, the calculated amount of 250 pounds of the 45 ammonium persulphate solution was slowly added and through the addition the temperature was maintained at about 55-60 C. by the use of a cooling bath. After the exothermic reaction was completed, the mixture was allowed to cool off to room temperature, at which temperature it was held while stirring thoroughly for about 26 hours. The oxidation reaction was considered as completed, when after one hour more, the saponification number of the oxidized product remained practically unchanged.
- the mixture was separated from the aqueous layer, which was discharged.
- the strawyellow colored oily upper layer was washed with small amounts of a warm saturated aqueous solution of sodium chloride and subsequently freed from the volatile, low molecular fatty acids by a short distillation with superheated steam.
- the two-step oxidation process under the present invention can be applied to any commercial white mineral oil, or any mineral oil, from which previously through exhaustive refining all aromatic and unsaturated compounds have been removed. Also it is important that the white mineral oil does not contain parafiin waxes. Parafiin waxes when oxidized with air, yield fattyand hydroxy-fatty acids, which by further oxidation with aqueous peroxide solutions do not give the desired dicarboxylic naphthenic acids, as required under this invention, but give dark resinous and useless products. Therefore the success of this invention depends upon the proper selection of the white mineral oil, free from paraffin waxes and unsaturated and aromatic hydrocarbons.
- the process of this invention is such that the desired dicarboxylic naphthenic acids can be produced economically, safely and efficiently, thus opening for the first time a new abundant source of this industrially im portant class of dicarboxylic acids.
- a two-step oxidation process for the manufacture of predominantly dicarboxylic naphthenic acids from white. mineral oils which comprises, as the first: step, oxidizing said oils with airat temperatures. from 100 tov 200 C., under'pressure. not higher than 10 atmospheres, in the presence of a catalyst belonging to the class of polyvalent heavy metal salts of fatty acids, whereby the oxidation isv conducted until no appreciable increase in the; carbonyl number of the oxidized. oil occurs; said oxidation product being subjected to a second oxidation step, which comprises further oxidation with an aqueous solution of at peroxide salt, this final oxidation being conducted. until noappreciable increase in. the saponification number of the oxidized product occurs.
- 2,,A twostep oxidation process for the manufacture of. predominantly dicarboxylic naphthenic acids from white mineral oils which comprises, as the first step, oxidizing said oils with air at temperatures from 100 to 209" C.,. under, pressure not higher than 10 atmospheres, inthe presence of a catalyst belonging tothe class of polyvalent heavy metal salts of fatty acids, whereby the oxidation is conducted. until no appreciable increase in the carbonylnumber of. the oxidized oil occurs; said oxidation product. being subjected to.
- a second oxidation step which comprises further oxidation with an aqueous solution of aperoxide-salt, at a temperature not higher than 100 C., said peroxide salt being, present in a ratio of at least one mole for the carbonyl group in each mole of the carbonylnaphthenic acids, at least two moles for the methoxygroup in each mole of the hydroxy-naphthenic acids, and at least. three moles for one methyl group in the pentane ring of; each; mole of. the naphthenic acids, said final oxidation being conducted until no appreciable increase in the saponification number of the oxidized product occurs.
- a two-step oxidation process for the manufacture of predominantly dicarboxylic naphthenic acids from white mineral oils which comprises, as the first step, oxidizing said oils with air at temperatures from 100 to 20.0: C., under pressure, not higher than 1Qv atmospheres, in the. presence of a catalyst belonging to the class. of polyvalent heavy metal salts of fatty acids, whereby the. oxidation. is conducted until. no. appreciable increasein the carbonyl number of the. oxidized oil, occurs; said oxidation product. being subjected to a second oxidation step, which comprises further oxidation with an aqueous. solution of a peroxide salt, at temperatures. not higher than 1.00" C.,, said. peroxide salt.
Description
2,725,396 Patented Nov. 29, 1955 PROCESS FQR THE OXIDATION OF WHITE MIN- ERALS OILS TO DICARBOXYLIC NAPHTHENIC ACID Joseph Winkler, Queens, N. Y., assignor to American Collo Corporation, New York, N. Y.
N Drawing. Application March 30, 1954, Serial No. 419,900
3 Claims. (Cl. 260514) White mineral oils are considered intermolecular mixtures of naphthene rings with paraffin side chains. They are practically free of aromatic and naphthene parafiin side chain compounds and solid paraffin waxes. White mineral oils are compounds which have the following basic structure:
I CH1 CHa Depending on its molecular weight, n is in the range of 5 to 40. In orderto make a white mineral oil, the mineral oil distillate, produced from crude oil, must be properly purified. This purification is done normally by ex haustive treatment with sulphuric acid monohydrate and later with large amounts, in two to washes, with oleum, containing 20% and more of free S03. In order to remove from the sour oil the sulphonated products, this oil is again treated in the last wash with sulphuric acid monohydrate. In the final treatment, the sour white mineral oil is deacidified with alcoholic solutions of caustic soda and absorbent clay in order to obtain an entirely acid-free, water-free white mineral oil.
It is known that white mineral oils can be oxidized with air, with or without catalysts, under atmospheric pressure or at pressures up to 50 atmospheres; at temperatures ranging from 100 to 200 C., to monocarboxylic acid products. These products, however, are dark colored and malodorous and their sodium salts cannot be separated by salting out. Lighter monocarboxylic acid products are obtained by partial oxidation of white mineral oils, when only a part of the oil is converted by oxidation to corresponding monocarboxylic acids having the following basic structure:
II CH: CH:
om writ M00011 The unchanged, non oxidized main part of the white oil, after separation from the produced acids (11), by conventional methods of selective extraction, is returned back to the oxidation process. The produced monocarboxylic acids are utilized for the production of industrial soaps, soap based greases, etc. However, because of the low quality of these acids (dark color, sharp odor), the air oxidation of white mineral oils to monoearboxylic acids was used industrially only during World War II, in Ger many, and later abandoned when fatty acids again became abundant.
, The object of this invention, is to provide a process for the manufacturing of dicarboxylic naphthenic acids from white mineral oils by a new two-step liquid phase oxidation, which comprises:
Step N0. 1.Exhaustive air oxidation Exhaustive oxidation of white mineral oils with air under pressure at temperatures of from 100 to 200 C., in the presence of a catalyst. As an intermediate product there is obtained a mixture of a small amount of unchanged white mineral oil (I) with more than of the following monocarboxylic acids: (II) naphthenic acids; (III) hydroxy-naphthenic acids; (IV) carbonyl-naphthenic acids; and their innerand hetero-esters (V, VI, and VII). 7
III CH3 CHzOH CHa ICHE/MCOOH IV CH: COH
CHa- -'/CH:IMCOOH V CH3 CHzO f3 CH3 --/CH2/mCO VI CH1 CHzO-OC/CHz/m CH;
CH; /C.Hz/,,COOH CH3 CH3 VII 7 CH: CHzOOC/CHz/m CH;
CEQICHZIMCOOH Cfia COH Step No. 2.-Exhaustive oxidation with an aqueous solution of a peroxide salt The product from the exhaustive air oxidationas described above, is a two-phase, malodorous, dark brown, highly viscous oil. This intermediate material, is according to the present invention further exhaustively oxidized with an aqueous concentrated solution of a peroxide salt, at temperatures not higher than C. I have found that any peroxide salt which is soluble in water performs in the same manner and gives the same desired result; i. e.
the formation of dicarboxylic naphthenic acids. Such cheap VIII 0H3 COOH on, 4 om .,.oooH
Depending in its molecular weight, m is in the range of 0 to 25. This mixture of homologous dicarboxylic naphthenic acids contains, besides small amounts of unchanged white oil (I), one to 5% of volatile, low molecular fatty acids, produced during the first step of the oxidation process, due to the splitting of the long aliphatic chain by the oxygen of the air; -(C2)nCH3, attached to the cyclopentane ring in position 3-, into two separate monocarboxylic acids. Nevertheless, this finely oxidized material has a much gentler odor of fatty acids, its viscosity is much lower, its color is straw-yellow, and its specific gravity is much higher. An additional steam distillation removes the low molecular fatty acids leaving analmost odorless product, which contains more than 80% of dicarboxylic naphthenic acids. In order to free them from. the non-saponifiable matter, an extraction with an alcohol-water mixture removes the acids, leaving insoluble the unsaponifiable matter. A subsequent distillation of the water-alcohol solution of the dicarboxylic naphthenic acids removes the solvent mixture, and the mixture of the dicarboxylic naphthenic acids can be finally fractionated under vacuum into narrow cuts of the individual homologs of the dicarboxylic naphthenic acids, which are believed to have formula as shown in (VIII) above. These acids are very valuable starting materials for purposes of further syntheses, in which aliphatic and aromatic dicarboxylic acids were previously being used, suchas for example, maleic, sebacic, succinic and adipic acids in the aliphatic series, and phthalic, and terephthalic acids in the aromatic series. Consequently, for the first time through my new two-step oxidation process a new class of dicarboxylic naphthenic acids is created, which lends itself to the manufacture of industrially valuable esters, salts, polyesters, polyamides, polyurethanes etc.,. from which different synthetic fibers, plastics, and elastomers can be cheaply produced.
The following examples are illustrative of this invention:
EXAMPLE 1 As the starting commercial oil, a semi-refined white oil, called AI-1C Process Oil, made by Socony Vacuum Co., was selected. Its physical-chemical properties were as follows:
Hot-acid testb1ack; n 1.4.808; di -0.886; dist. range C./10 mm. of to 95%173 to 223; flash point-15.85 C.; viscosity in centistokes/ZO C.3l; aniline pointplus 811 C. This oil, was exhaustively refined with a 20% oleum to a white oil, which had the following physico-chemical properties:
I-Iot-acid test-water-white; 11 1.407; d4 -0.869; dist. range C./'1O mm. of 5 to 95'%-l76 to 246; flash point-448 Cl; viscosity in centistokes/20 C.24.4; aniline pointplus 91? Cl; molecular weight292; Pour point-less than minus 50 C.; percent aliphatic side chains49; percent naphthenic rings-51.
100 pounds of above. white mineral oil were exhaustively oxidized at a temperature below 160 C., in the presence of a catalyst belonging to the class of fatty'acid salts of polyvalent heavy metals. conducted in a stainless steel autoclave, equipped with a turbomixer, and having a total capacity of 60 gallons. The pressure. during the air oxidation was kept below atmospheres. Every hour a. sample of the oxidized oil was withdrawn from the autoclave and analysed for the carbonyl number by the method of Bertram, described in the Journal Inst. of Petr. Techn, 34, 930 (1948-): The air oxidation was considered as finished as .soon, as in an hour interval the. carbonyl number did not" increase by more than one unit. Further oxidation. would be useless, because instead of increasing the content of the carbonyl-naphthenic acids, a considerable resinification would take place. The oxidation was considered as finished after a total oxidation time of hours. From 100 pounds of the starting white oil, 101 pounds of the oxidized product were obtained. Analysis of this product;
Colorr dark brown; appearancertwo separate. layers; odQra- -sharp-stingy of burned oil; d,4?-0.99.5.;. n 1.4.7.893, visc; in centistokes/ C.-8961; dist. range/ 1-0.
This oxidation was mrn.5%/131 C., 75%/256 C.; carbonyl No. 98; unsaponf'. matter20%; naphthenic and hydroxynaphthenic acids5l%; carbonyl-naphthenic acids37%; volatile fatty acids--2%.
This two-phase mixture without separating is subsequently oxidized in the same autoclave with a 35% aqueous solution of potassium permanganate as follows:
The 101 pounds of the product are saponified and further oxidized with about 120 pounds of a 35% aqueous solution of potassium permanganate. This amount was calculated from the quantitative analysis by using an excess of one mole of the IMn04 for the carbonyl group in each mole of the carbonyl-naphthenic acids; in excess of two moles of KMnOi for the methoxy-group in each mole of the hydroxy-naphthenic acids, and in excess of three moles of KMnOa for the methyl group in each mole of the naphthenic acids.
First the 101 pounds of the air oxidized oil were heated to a temperature of about 70 C. At this temperature, while thoroughly stirring, at atmospheric pressure, the calculated amount of the above mentioned KMnO4- aqueous solution was slowly added and during the addition, the temperature was maintained at about 70 C. by the use of a cooling bath. After the exothermic reaction was completed the mixture was allowed to cool to room temperature, at which temperature it was maintained while continuously stirring for about 24 hours. Every hour a sample of the oxidized product was withdrawn and its saponification number was determined. The reaction was considered as finished when in an hour interval no significant increase in the saponification number Occurred. Afterwards, the mixture was separated into two layers. The lower, aqueous layer was used for the regeneration of the KM1'104, and the upper, light colored oily layer, was washed thoroughly with hot water, and by steam distillation freed from the volatile low molecular fatty acids. The remaining oil was dried at 100 C., under vacuum and finally filtered. The obtained amount of the final product, which is believed to be predominantly a mixture of homologs of dicarboxylic naphthenic acids (VIII), was analysed and had the following physicochemical properties:
Color-straw yellow; odoracidic; viscosity in centistokes/20 C.-l; unsaponifiable matter23%; saponifiable matter77%; acid No. 386; saponif No. 391. The product gives typical reaction of dicarboxylic acids.
This mixture of homologs of dicarboxylic naphthenic acids can be easily esterified with polyalcohols, as for example with glycerine, yielding resinous polyesters. However, in some cases, where a more pure polyester is desired, the unsaponifiable matter must be removed. The most economic way to do it is by theextraction of the dicarboxylic naphthenic acids with an aqueous solution of ethyl alcohol, in which the unsaponifiable matter is insoluble. The unsaponifiable matter, which consists, mainly of unreacted white oil and some naphthenic alcohols, is returned into the air oxidation process.
EXAMPLE 2 As the starting commercial white mineral oil, a product called Carnation White Oil, and made by L. Sonneborn and Sons Inc., was selected. Its physico-chemical properties were as follows:
Hot-acid test-water white; n 1.4587; d4 0.839; dist. range C./10' mm. of 5% to was 210 to 225; flash point-185 C.; viscosity in centistokes/20 C.-25; molecular weight-325; pour point-plus 28 C.; anili'ne point-plus 105 C.; percent aliphatic side chains- 23; percent naphthenic rings7-2.
pounds of this white mineral oil were oxidized with air under the same conditions as described in Example. l. After 14 hours of oxidizing, a product was obtained with the following physico-chemical properties:
Color-dark brown; appearance-two-separate layers;-
5 7 1.4917; viscosity in centistokes/20 C.-l200; dist. range/20 mm.-5%/6 2 C., 50%/225 C.; 75%/280 C.; aniline pointplus 60 C.; acid No. 172; saponif. N0. 265; carbonyl No. 128; naphthenic and hydroxynaphthenic acids-31%; carbonyl-naphthenic acids-51%; volatile fatty acids5%; unsaponif. matter-13%; recovery-l07 This dark colored, malodorous viscous liquid was oxidized in the same autoclave with a strong 50% aqueous solution of hydrogen peroxide as follows:
For 107 pounds of the air oxidized product about 100 pounds of the 50% hydrogen peroxide solution was used. This amount was calculated in the same way as indicated in Example 1. First the 107 pounds of the air oxidized white oil was heated to a temperature of about plus 50 C. At this temperature, while stirring,
. at atmospheric pressure, the calculated amount of 100 pounds of the 50% hydrogen peroxide solution was slowly added, and throughout the addition, the temperature was maintained at about plus 50 C. by the use of a cooling bath. After the exothermic reaction was completed, the mixture was allowed to cool off to room temperature, at which temperature it was maintained, while stirring thoroughly for about 20 hours. The oxidation reaction was considered as completed when after one more hour the saponification number of the oxidized product remained almost unchanged. Afterwards, the mixture was separated into two layers. The aqueous layer was discharged and the resulting light colored oily layer was washed with small amounts of warm water and the light volatile low molecular fatty acids removed by a steam distillation. The remaining oil was dried at 100 C.- under vacuum and finally filtered.
Analysis of this product: Recovery--115 pounds, 100 lbs. white oil.
Colorstraw yellow; odor--acidic; viscosity in centistokes/20 C.180; unsaponifiable matter--15%; saponifiable matter85%; carbonyl No. acid No. 370; saponif. No. 372. Gives typical reactions of dicarboxylic acids.
In order to remove the unsaponifiable matter, the oil is reacted with an aqueous solution of caustic soda, and the unsaponifiable matter is extracted from the resulting sodium salts of the dicarboxylic acids with benzene. By acidification with an inorganic acid the pure dicarboxylic naphthenic acids are obtained. By a subsequent vacuum distillation pure individual acids result.
EXAMPLE 3 As the starting commercial white mineral oil, a product called Superla No. 10a made by Standard Oil Co. of Indiana was selected. Its physico-chemical properties were as follows:
Hot acid testwater white; n l.464l; d4 0.85l; distil. range C./10 mm. of 5% to 95%-2l6 to 299; flash point184 C.; viscosity in centistokes/ZO" C.- 41; molecular weight345; pour point-plus 25 C.; aniline point-plus 106 C.; percent aliphatic side chains-44; percent naphthenic rings56.
100 pounds of this white mineral oil was oxidized with air under the same conditions as described in Example 1. After 13 hours of oxidizing, a product was obtained with the following physico-chemical properties:
Color-dark brown; appearancetwo separate layers; odorsharp and stingy as of burned oil; d4 1.004; n 1.485; viscosity in centistokes/20 C.l200; distil. range/l0 mm.--5%/l45 C., 50%/238 C., 75%/292 C.; aniline pointplus 59 C.; acid No. 137; saponif. No. 256; carbonyl No. 138; unsaponif. matterl8%; naphthenic and hydroxy-naphthenic acids-39%; carbonyl-naphthenic acids-46%; volatile low molecular acids5%; recoveryl0l pounds.
This dark colored, malodorous, viscous liquid was oxidized in the same autoclave with a 45% aqueous solution of ammonium persulphate as follows.
For the recovered 101 pounds of the air oxidized product, about 250 pounds of the 45% aqueous ammonium persulphate solution was used. This amount was calculated in the same way as indicated in Example 1. First the 101 pounds of the air oxidized white oil was heated to a temperature of about 60 C. At this temperature, while stirring thoroughly, under atmospheric pressure, the calculated amount of 250 pounds of the 45 ammonium persulphate solution was slowly added and through the addition the temperature was maintained at about 55-60 C. by the use of a cooling bath. After the exothermic reaction was completed, the mixture was allowed to cool off to room temperature, at which temperature it was held while stirring thoroughly for about 26 hours. The oxidation reaction was considered as completed, when after one hour more, the saponification number of the oxidized product remained practically unchanged. Afterwards, the mixture was separated from the aqueous layer, which was discharged. The strawyellow colored oily upper layer, was washed with small amounts of a warm saturated aqueous solution of sodium chloride and subsequently freed from the volatile, low molecular fatty acids by a short distillation with superheated steam.
Further purification of the obtained dicarboxylic naphthenic acids, if necessary, is performed as described in Example 1 or 2.
Essentially, the two-step oxidation process under the present invention can be applied to any commercial white mineral oil, or any mineral oil, from which previously through exhaustive refining all aromatic and unsaturated compounds have been removed. Also it is important that the white mineral oil does not contain parafiin waxes. Parafiin waxes when oxidized with air, yield fattyand hydroxy-fatty acids, which by further oxidation with aqueous peroxide solutions do not give the desired dicarboxylic naphthenic acids, as required under this invention, but give dark resinous and useless products. Therefore the success of this invention depends upon the proper selection of the white mineral oil, free from paraffin waxes and unsaturated and aromatic hydrocarbons. It is also proper to mention in this place, that by air oxidation alone from white mineral oils, dicarboxylic naphthenic acids cannot be obtained under any circumstances. I have found in my experiments that as soon as the maximum amount of the unsaponifiable matter is oxidized to monocarboxylic acids and their esters, as exemplified by Formulas II to VII, further air oxidation produces only resin-like dark useless products and not the desired light colored dicarboxylic naphthenic acids. Therefore the only way to arrive at such dicarboxylic naphthenic acids, is to interrupt the air oxidation process at the moment when no further conversion of unsaponifiable matter into carbonyl-naphthenic takes place and proceed with the oxidation using an aqueous solution of peroxide salts, which alone have the property to oxidize the carbonyl-, the methoxy-, and one of the methyl group into a second carboxyl group.
As is also evidenced in the specification and examples, the process of this invention is such that the desired dicarboxylic naphthenic acids can be produced economically, safely and efficiently, thus opening for the first time a new abundant source of this industrially im portant class of dicarboxylic acids.
It should be furthermore understood that the present invention is not based upon or dependent upon the theories which I have expressed, nor is the invention to be regarded as limited to the express procedure or material set forth, these details being given only by way of illustration and to aid in clarification of this invention.
Finally it shall be understood that I do not claim the process of air oxidation of white mineral oils into monocarboxylic acids as such.
What I claim is:
l. A two-step oxidation process for the manufacture of predominantly dicarboxylic naphthenic acids from white. mineral oils, which comprises, as the first: step, oxidizing said oils with airat temperatures. from 100 tov 200 C., under'pressure. not higher than 10 atmospheres, in the presence of a catalyst belonging to the class of polyvalent heavy metal salts of fatty acids, whereby the oxidation isv conducted until no appreciable increase in the; carbonyl number of the oxidized. oil occurs; said oxidation product being subjected to a second oxidation step, which comprises further oxidation with an aqueous solution of at peroxide salt, this final oxidation being conducted. until noappreciable increase in. the saponification number of the oxidized product occurs.
2,,A twostep oxidation process for the manufacture of. predominantly dicarboxylic naphthenic acids from white mineral oils, which comprises, as the first step, oxidizing said oils with air at temperatures from 100 to 209" C.,. under, pressure not higher than 10 atmospheres, inthe presence of a catalyst belonging tothe class of polyvalent heavy metal salts of fatty acids, whereby the oxidation is conducted. until no appreciable increase in the carbonylnumber of. the oxidized oil occurs; said oxidation product. being subjected to. a second oxidation step, which comprises further oxidation with an aqueous solution of aperoxide-salt, at a temperature not higher than 100 C., said peroxide salt being, present in a ratio of at least one mole for the carbonyl group in each mole of the carbonylnaphthenic acids, at least two moles for the methoxygroup in each mole of the hydroxy-naphthenic acids, and at least. three moles for one methyl group in the pentane ring of; each; mole of. the naphthenic acids, said final oxidation being conducted until no appreciable increase in the saponification number of the oxidized product occurs.
3;. A two-step oxidation process for the manufacture of predominantly dicarboxylic naphthenic acids from white mineral oils, which comprises, as the first step, oxidizing said oils with air at temperatures from 100 to 20.0: C., under pressure, not higher than 1Qv atmospheres, in the. presence of a catalyst belonging to the class. of polyvalent heavy metal salts of fatty acids, whereby the. oxidation. is conducted until. no. appreciable increasein the carbonyl number of the. oxidized oil, occurs; said oxidation product. being subjected to a second oxidation step, which comprises further oxidation with an aqueous. solution of a peroxide salt, at temperatures. not higher than 1.00" C.,, said. peroxide salt. being hydrogenperoxide, said hydrogen peroxide being present in a ratio of at least one mole for the carbonyl group in each mole of the carbonylnaphthenic acids, atv least two moles for the. methoxygroup in each moleof the hydroxy-naphthenic acids, at least three moles for one methyl group in the cyclopentane ring of each mole of the naphthenic acids, saidoxidation being conducted. until no appreciable increase in the saponification number of. the oxidized product occurs; said oxidized product being free from the low molecular volatile fatty acids by steam distillation and. after. Wash.
. ing and drying being further purified. from unsaponifiable matter by selective extraction of the saponifiable matter. with an aqueous solution of ethyl alcohol, and finally by fractionating vacuum distillation being divided into narrow fractions, each containing predominantly an individual dicarboxylic naphthenic acid.
References Cited in the file of'this patent UNITED. STATES. PATENTS James July 23, 1929 Denton Aug. 15, 1950 OTHER REFERENCES.
3 87 and 102.
Beilstein, vol- IX, page. 768. Beilstein, vol. IX, 2nd Supplement, p. 534.
Claims (1)
1. A TWO-STEP OXIDATION PROCESS FOR THE MANUFACTURE OF PREDOMINANTLY DICARBOXYLIC NAPHTHENIC ACIDS FROM WHITE MINERAL OILS, WHICH COMPRISES, AS THE FIRST STEP, OXIDIZING SAID OILS WITH AIR AT TEMPERATURES FROM 100* TO 200* C., UNDER PRESSURE NOT HIGHER THAN 10 ATMOSPHERES, IN THE PRESENCE OF A CATALYST BELONGING TO THE CLASS OF POLYVALENT HEAVY METAL SALTS OF FATTY ACIDS, WHEREBY THE OXIDATION IS CONDUCTED UNTIL NO APPRECIABLE INCREASE IN THE CABONYL NUMBER OF THE OXIDIZED OIL OCCURS; SAID OXIDATION PRODUCT BEING SUBJECTED TO A SECOND OXIDATION STEP, WHICH COMPRISES FURTHER OXIDATION WITH AN AQUEOUS SOLUTION OF A PEROXIDE SALT, THIS FINAL OXIDATION BEING CONDUCTED UNTIL NO APPRECIABLE INCREASE IN THE SAPONIFICATION NUMBER OF THE OXIDIZED PRODUCT OCCURS.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2890247A (en) * | 1955-09-15 | 1959-06-09 | Gulf Research Development Co | Oxidation of naphthenic acids to polybasic acids |
US2955123A (en) * | 1956-07-13 | 1960-10-04 | Exxon Research Engineering Co | Selective ozone oxidation of hydrocarbons |
US3069461A (en) * | 1958-06-05 | 1962-12-18 | Heyden Newport Chemical Corp | Peroxide oxidation of polyhalobenzaldehydes |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US1721959A (en) * | 1923-05-18 | 1929-07-23 | James Joseph Hidy | Treating partial-oxidation products |
US2519309A (en) * | 1948-06-29 | 1950-08-15 | Socony Vacuum Oil Co Inc | Preparation of oxygenated naphthenes |
-
1954
- 1954-03-30 US US419900A patent/US2725396A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1721959A (en) * | 1923-05-18 | 1929-07-23 | James Joseph Hidy | Treating partial-oxidation products |
US2519309A (en) * | 1948-06-29 | 1950-08-15 | Socony Vacuum Oil Co Inc | Preparation of oxygenated naphthenes |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2890247A (en) * | 1955-09-15 | 1959-06-09 | Gulf Research Development Co | Oxidation of naphthenic acids to polybasic acids |
US2955123A (en) * | 1956-07-13 | 1960-10-04 | Exxon Research Engineering Co | Selective ozone oxidation of hydrocarbons |
US3069461A (en) * | 1958-06-05 | 1962-12-18 | Heyden Newport Chemical Corp | Peroxide oxidation of polyhalobenzaldehydes |
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