Title of Invention

NEW ANTIOXIDANT COMPOSITION FOR MOTOR GASOLINE

Abstract A process of Manufacturing Metal Reinforced Polyethylene / Polypropylene Pipes comprising the following steps : 1) Producing a Reinforced inner Metal Shell Section ; 2) Producing a inner layer of extruded Polyethylene / Polypropylene Material wrapped around the collapsable Mandrel ; or by layering inside the metal shell or by wrapping and welding Polyethylene / Polypropylene sheets inside metal shell section ; 3) Inserting the inner Polyethylene / Polypropylene sleeve into the Reinforced Metal Shell section ; 4) Applying bonding agent over reinforced inner Metal Shell section and outer surface ; 5) Producing a outside Polyethylene/Polypropylene layer on to the Metal Shell which has been coated with bonding agent ; 6) Finishing / Joining end connection and Trimming. To, The Controller of Patents, The Patent Office, Mumbai.
Full Text THE PATENTS ACT, 1970 COMPLETE SPECIFICATION
Section 10
New Antioxidant Composition For Motor Gasoline.
Indian Oil Corporation Limited, an Indian company, of G-9, Ali Yavar Jung Marg) Batidra (East)^ Mumbai-400 051, Maharashtra^ India.
The following specification particularly describes and ascertains the nature of this invention and the manner in which it is to be performed:
FORM

NEW ANTIOXIDANT COMPOSITION FOR MOTOR GASOLINE
This invention relates to the development of new antioxidant composition for use in motor gasoline fuel.
Motor gasoline fuel when stored for prolonged period of time eventually deteriorates due to oxidation and polymerization. Cracked streams, increasingly being used in gasoline fuel, are worsening the problem. The deterioration of fuel is evidenced by the formation of gums and darkening of color. The gum formation in the fuel system further leads to filter blockage resulting in reduction in fuel flow in engine systems.
In general, the process of fuel degradation is very complex in view of a variety of complex hydrocarbons involved in it. It involves free radical reactions, which are characterized by three distinct stages, viz. initiation, propagation and termination. These reactions are very complex and have implications on the quality of fuel.
Unsaturated compounds such as olefins &dienes contribute to instability by auto-oxidation and/or polymerization reactions in presence of oxygen. Higher levels of unsaturated compounds in the fuels are due to increased severity of secondary refining operations in Fluid Catalytic Cracking (FCQ as well as renewed blending of streams from thermal processes such as Viscosity Breaker (VB) and Coker. These products are used for blending gasoline fuel in order to meet the growing market demand.
Furthermore, only olefins & dienes are not responsible for instability of fuels. In deeply hydrotreated or reformed fuels, most of the natural antioxidants get removed during the process leading to poor stability of the product. If even trace amount of copper is present in the fuel, it shall accelerate the rapid formation of peroxides. The peroxides thus formed shall attack the copper parts of fuel system with the result copper dissolution takes place leading to even more peroxide formation resulting into accelerated oxidation of fuel. Frequent source of copper contamination are copper-containing alloys in refinery equipment, product distribution systems, chemicals used in the refining and the fuel system of vehicles. The catalytic effect of copper is so strong that even the most effective antioxidants/stabilizers cannot provide adequate stability thus causing deterioration of the product.
The options available with the refiners for improving gasoline fuel quality are limited. Following four main routes are usually practiced at the refineries the world over for improving gasoline fuel quality:
• Selective blending of refinery streams,
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• Use of chemical additives,
• Adopting appropriate processing route, which include, aromatic extraction, hydrogenation and hydro-cracking,
• Use of chemical additives in combination with processing
Aromatic extraction and hydro-cracking options result in significant changes in product yield whereas hydrogenation has only marginal impact on product balances. The problem of gasoline stability can effectively be solved by the incorporation of carefully selected chemical additives in proper concentrations. These chemical additives primarily retard the natural degradation of gasoline fuel during long-term storage.
BACKGROUND OF THE INVENTION
Alkyl or aryl substituted hindered phenols are commonly used for stabilisation of gasoline fuel. The stearic hindrance in the hindered phenols is provided by bulky substituents in ortho position to hydroxyl group in the ring of the phenolic antioxidant. These bulky subsituents influence the specificity of the phenols by blocking phenoxyl radicals from abstracting hydrogen atoms from organic substrates. 2,6-Di-t-butylphenol(DTBP) is most widely used functional group in commercial hindered phenolic antioxidants. This group is effective and easily made at moderate cost by the ortho alkylation of phenol by olefins using ortho selective catalyst. Preparation of nitroalkane based hindered phenols and their antioxidant properties are reported in British Patent No. 1,561,311.
European Patent No. EP 106,799 assigned to M/s Sanodz GmbH reported a
mixture of sterically hindered phenols having recrystalisation temperature deg.G These types of compounds are reported to be useful antioxidants for liquid
fuels, especially the gasoline. Canadian Patent CA 1,216,308 assigned to M/s Ethyl
Corporation reported p-alkylenes hindered phenols as useful antioxidants for
gasoline, lubricating oils, plastics, rubbers etc. US Patent 4,981,495 reported that
the oxidation stability of gasoline mixture is improved by adding to the gasoline
1-10,000 ppm of an alkyl-1,2-dihydoquinoline compounds, dimer, trimer or
polymers. Optionally a hindered phenol may be jointly used with the quinoline
compounds. Halon and Vincent have reported in European Patent EP 427,456
that liquid mixture of alkyl phenols composed of 2-t-butylphenol and 2,6-di-t-
butylpheno are suitable for use as stabilisers for middle distillate fuels, fuel oils etc.
European Patent EP 410,577 discusses polymeric reaction products of an ortho
substituted phenol as antioxidant for liquid hydrocarbon such as kerosene and
gasoline. German Patent No. 2,917,927 describes that alkylated dihydroxybiphenyl
are useful as antioxidants and can help in the improvement in induction period.
Japanese Patent No. 81,92,235 reported that malkyl-tris(3,5-dialkyl-4-
hydroxyberrzyl) benzene and 1,2,4- trimethyi- 3,5,6- tris (3,5- diisopropyl)- 4-
2


hydroxybenzyl)benzene as stabiliser for rubbers, gasoline etc. However, the disadvantage associated with using phenolic antioxidant alone includes high treat levels, inability to effectively control peroxides formed during the oxidation process and their inability to check colour degradation of fuels.
Aromatic amines are well known as antioxidants for a long time but the mechanism of their action is not well established compared to the phenolic antioxidants. Basically some of the aromatic amines are of quite complex compositions and a number of oxidation products are obtained from the reaction of aromatic amines and fuel degradation products. Aromatic amines commonly being used are phenylenediamines and diarylamines. However, several synergistic combinations are also documented in literature.
US Patent No. 4,279,621 reported that heavy polyamines distillation residues can be used as antioxidants for gasolines at a treat level of 0.05 wt%. Japanese patent Jpn Kokai Tokkyo Koho JP 58,76,492 assigned to M/s Sumitomo Chemical Co. Ltd. reported mixture of a 2-tert-butyl alkyl phenol, bis(nonyl phenol) amine and ditridecylthiodipropionate as antioxidants for gasoline, kerosene, light oils and heavy oils. US Patent No. 4,456,541 assigned to Ethyl Corporation reports that the addition of 3,5-diethyltolune-2,4-diamine or 3,5-diethykolune-2,6-diamine or their mixture in appropriate concentration provides antioxidant properties to polymers, gasoline, lube oils and other organic compounds.
US Patent No. 4,871,374 assigned to Weers of Petrolite Corp. reported that a fuel oil can be stabilized with an inline-enamine condensate. Additive is claimed to be effective in improving the colour stability, sedimentation of distillate oils. US Patent No. 4,647,290 reports that the colour deterioration of a distillate fuel oil is inhibited by adding a mixture of N-(2 - aminoethyl) piperazine and HONEt2. A straight -run gasoline fuel containing 200 ppm of N-(2 - aminoethyl) piperazine and 300 ppm of HONEt2 was placed in an oven at 140 deg.F for 14 days, cooled, and filtered; the ASTM colour of the filtrate was 2.5 (ASTM D-1500), compared with 5.0 for the gasoline fuel containing only N-(2 - aminoethyl) piperazine. US Patent No. 5,197,996 reports that boron based additive helps in the colour stabilisation of distillate fuel oil. US Patent No. 5,035,719 describes that storage stability of middle distillate fuels is improved by adding an acrylate polymer containing moieties derived from 4-vinylpyridine or the enamine ester of morpholine etc. and propionaldehyde as additive. US Patent No. 4,978,366 reported that distillate fuel especially which has a high acid number initially or which develops a high acid number as result of fuel degradation, is stabilized with a diaminomethane. Henry and West have reported in US Patent No. 5,011,504 that block copolymers of acrylic and acrylic amines can be used as additives for fuel oils to diminish sediment and colour formulation. A suitable additive as reported by them is 2-emylhexylmethacrylate-dimethylaminoethyl methacrylate copolymer. US Patent No. 5,057,123 describes that diesel fuel at high temperature
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can be stabilized with an amine-containing copolymer selected from aminopropyl morpholine ethylene- propylene- hexadiene copolymer N- phenylenediamine ethylene- propylene-hexadiene copolymer and N-aminopropyl- N phenylenediamine ethylene- propylene- hexadiene copolymer. Though amine based antioxidants are excellent oxidation inhibitors for gasoline and other middle distillate fuels, but they are cosdy and their use in fuels adversely affects the economics of oil refineries.
Cashew Nut Shell Liquid (popularly known as CNSL) is obtained after the hydrogenation of naturally occurring, biodegradable, vegetable based Cashew Nut Shell Liquid. CNSL occurs as a reddish brown viscous liquid in the soft honeycomb structure of the shell of cashewnut. CNSL, extracted with low boiling petroleum ether, contains about 90% anacardic acid and about 10% cardol. CNSL, on distillation, gives the pale yellow phenolic derivatives, which are a mixture of biodegradable unsaturated m-alkylphenols, including cardanol. Catalytic hydrogenation of these phenols gives a white waxy material, predominantly rich in tetrahydroanacardol, which is also known as hydrogenated CNSL. CNSL and its derivatives have been known for producing high temperature phenolic resins and friction elements, as exemplified in U.S. Pat. Nos. 4,395,498 and 5,218,038. Friction lining production from CNSL is also reported in U.S. Pat. No. 5,433,774. Likewise, it is also known to form different types of friction materials, mainly for use in brake lining system of automobiles and coating resins from CNSL.
Mannich condensation products are rarely reported as antioxidants for gasoline. However, they are known to act as dispersants and detergents in various types of hydrocarbon stocks. Use in lighter hydrocarbon stocks, such as gasolines, has been disclosed in US. Pat. Nos. 3,269,810 and 3,649,229. U.S. Pat. No. 3,235,484 (Now U.S. Pat. No. Re. 26,330) which describes the addition of certain disclosed compositions to refinery hydrocarbon fuel stocks for the purpose of inhibiting the accumulation of carbonaceous deposits in refinery cracking units.
Several distinct disadvantages are associated with using phenolic antioxidants alone. Such disadvantages include high treat levels, inability to effectively control peroxides formed during the oxidation process and their inability to check colour degradation of fuels.
The disadvantage associated with using amine based antioxidants alone is the considerable costs of such compounds that affects the refinery economics and their tendency to impart colour to gasoline, as some of the amine based antioxidants are pretty dark in colour.
The disadvantage associated with using only Mannich bases is their poor antioxidant efficacy for gasoline fuel, when used singularly.
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Therefore, an object of this invention is to propose a new gasoline antioxidant composition, which obviates the above referred disadvantages.
Another object of this invention is to propose a new gasoline antioxidant composition, which can effectively control the gum formation during storage and use.
A further object of this invention is to propose a new gasoline antioxidant composition, which can effectively control the colour degradation of gasoline.
A still further object of this invention is to propose a new gasoline antioxidant composition with improved antioxidant characteristics.
Another object of this invention is to propose a new gasoline antioxidant composition, which when used in gasoline can reduce copper corrosion and pitting tendency up to the desired level.
Yet further object of this invention is to propose a new gasoline antioxidant composition, which when used in fuels can help in controlling water emulsification up to the desired extent.
Another object of this invention is to propose a new gasoline antioxidant composition, which does not require use of costly metal deactivator in wide variety of gasoline fuel.
SUMMARY OF THE INVENTION
It has now been established through this invention that when Mannich base is incorporated in combination with an amine based antioxidant into the gasoline fuel containing cracked components obtained from various secondary processing units (viz. FCC, VB and Coker, etc.), the oxidation of fuel, sediment formation, corrosion inhibition and water uptake tendencies are improved appreciably in comparison to when any of the aforesaid components is added singularly to the fuel.
For example, if amine based antioxidant was used alone then potential gum level was reduced from base value of 132 g/m3 - 258 g/m3 to around 32 g/m3 - 38 g/m3 in gasoline fuel at 20 mg/lit to 50mg/lit as per ASTM D- 873 / IP: 138 (Modified). While at the same dosages level and at higher levels of Mannich Base alone, the potential gum level could not be brought down to the desired level of less than 50 g/m3. However, in the case of a combination of Mannich base and an amine- based antioxidant, the potential gum level in the gasoline fuel was reduced to around 28 g/m3 as compared to 258 g/m3 potential gum value of the base gasoline fuel.
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A successful attempt has been made to develop an antioxidant formulation using synergistic combination of amine based antioxidant and Mannich bases derived from commercially available p-substituted phenols and from Cashew Nut Shell Liquid (CSNL).
The amine based antioxidant of the present invention belong to N,N-Alkyl-butyl-paraphenylenediamine chemistry.
The alkyl phenols used in the process of preparation of Mannich bases are para-nonyl phenol or para-dodecyl phenol or hydrogenated and distilled Cashew Nut Shell Liquid (popularly known as CNSL). CNSL, on distillation, gives the pale yellow phenolic derivatives, which are a mixture of biodegradable unsaturated m-alkylphenols, including cardanol. Catalytic hydrogenation of these phenols gives a white waxy material, predominantly rich in tetrahydroanacardol, which is also known as hydrogenated CNSL. Mannich condensation products were prepared by the reaction of para-nonyl phenol or para-dodecyl phenol or the hydrogenated CNSL( hydrogenation of cashew nut shell liquid was carried out in an autoclave using conventional method of catalytic hydrogenation), an amine having at least one reactive hydrogen atom, and an aldehyde in the molar ratio of I:0.1tol0:0.1tol0 at a temperature ranging from 70 °C - 175 °C for 6 to 12 hours in presence of a protic organic solvent.
The Mannich base present in the Antioxidant compositions varies from 50.0 to 95% by weight, whereas the amine based component is in the range of 50% to 5% by weight. The overall nitrogen content of the synergistic compositions used in the present invention may varyfrom 3.5 wt% to 8.5 wt%.
The composition of the present invention has a synergistic effect. Further object and advantages of this invention will be more apparent from the ensuing examples. It is being understood that such examples are not intended to limit the scope of the present invention.
DETAILED DESCRITION OF THE INVENTION
Evaluation Methodology
A correlation programme was done to compare various test methods used for assessing antioxidant performance of gasoline antioxidants. In view that Potential Gum was found to be quite stringent test for assessing the antioxidant performance of gasoline, the Potential Gum Test as per ASTM D- 873 / IP: 138 (Modified) was selected as the test for evaluating the performance of the various individual components and in formulated packages used in this invention. Selected short listed, final compositions were additionally evaluated for Existent Gum as per ASTM D-381
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/ IP: 131, Induction Period test as per ASTM D- 525 / IP: 40 and Ambient Aging test for three months. The details of various test used for assessing the antioxidant characteristics in the present invention are given below:
1. POTENTIAL GUM: A measured quantity of fuel (50 ml) is oxidized under prescribed condition in a Bomb for 4 hrs at 100 deg. C after pressurizing it with 100 psi oxygen pressure. The aged product is subjected to Residue on Evaporation test. The adhered gums are included after washing the sample container with gum solvent and residue is washed with heptane also . Results are reported as gm/m3- The maximum allowable limit for gums by this method is 50 gm/m3.
2. EXISTENT GUM: A measured quantity of fuel (50 ml) is evaporated under controlled conditions of temperature and flow of air. The resulting residue is weighed and reported as gm/m3. For motor gasoline, the residue is weighed before and after washining with n-heptane and the result reported as gm/m3. The maximum allowable limit for gums by this method is 40 gm/m3.
3. INDUCTION PERIOD: A measured quantity of fuel (50 ml) is oxidized under prescribed condition in a Bomb Initially filled at 15 to 25 deg. C with oxygen pressure at 100 psi and heated at a temperature between 98 to 102 deg. G The pressure is read at stated intervals or recorded continuously until the brake point is reached. The time required for the sample to reach this point is observed and reported as induction period. The maximum allowable limit by this method is 360 minutes.
4. AMBIENT AGING FOR THREE MONTHS: 400 ml of
antioxidant doped gasoline sample is kept in 500 ml capacity borosilicate glass botdes for three months at ambient temperatures in triplicate. After completion of the first, second and third months one set is subjected to Existent Gum Test as per ASTM D-381 and the result reported as gm/m3. Colour of the fuel is also noted after completion of each month.
The short listed composition was additionally tested for following characteristics:
1. WATER REACTION OF FUELS: This test is designed to measure water tolerance characteristics of gasoline. It is a quick way to measure the ability of a fuel to separate rapidly from water after mixing under low shear conditions. Briefly the procedure involves hand shaking of 80
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ml of fuel with 20 ml of phosphate buffer solution for two minutes. After a 5 minutes settling period, the fuel water interface and water layer are rated for emulsion, the fuel phase and clarity.
2. DYNAMIC CORROSION TEST: This test is carried out to evaluate the ability of fuels to prevent rusting of ferrous parts when fuel comes in contact with water. Corrosion can lead to severe problems in storage tanks, pipelines tankers and automobile fuel tanks. The particles of rust can also clog fuel lines, filters carburetor orifices or jets. This evaluation procedure is based upon ASTM D-665-95 standard test method for mineral oils with modification so that the test is run at ambient temperature for fuels. 300 ml of the fuel is stirred at lOOOi 50 rpm with 30 ml of distilled water for 24 hrs using polished steel spindle conforming to grade 1018 of ASTM A-108 specifications.
Experimental Details
In order to evaluate the performance of the various components, e.g. phenolic antioxidants, amine based antioxidants or Mannich base, a comprehensive evaluation program was prepared. The evaluation program includes three important variables such as selection of components, optimization of their treat rate and the selection of base gasoline composition. Composition of the base gasoline was kept constant during the evaluation of the selected component for the development of optimized formulation. In order to verify the results, few selected components were also evaluated in different gasoline compositions. The final antioxidant compositions were evaluated in different gasoline compositions being produced by the Indian refineries. The components were initially evaluated at low treat rate and depending on the response, evaluation was done at higher or lower treat rates. The final composition was up-scaled in a chemical pilot plant and tested on a large scale in one of the Indian refineries. The gasoline compositions used for the study are given as follows:

Gasoline Composition - 1
Streams % Volume
FCC Gasoline 50
Reformate Stream 40
Vis-breaker Naphtna 10
Gasoline Composition - 2
Streams % Volume
FCC Gasoline 55
Reformate Stream 35
K7TOP Stream 10

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Example 1 to 7:
Phenolic antioxidant, 2,6-ditertiary-butyl-para-cresol (DBPQ 99 % purity), was dissolved in Gasoline Composition - 1 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

s.
NO GASOLINE FUEL POTENTIAL GUM,
gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-1 132
2. GASOLINE FUEL + 5 mg/lit of DBPC 66
3. GASOLINE FUEL + 10 mg/lit of DBPC 48
4. GASOLINE FUEL + 15 mg/lit of DBPC 44
5. GASOLINE FUEL + 20 mg/lit of DBPC 40
6. GASOLINE FUEL + 30 mg/lit of DBPC 20
7. GASOLINE FUEL + 50 mg/lit of DBPC 20
Example 8 to 13
Another liquid hindered phenolic antioxidant,(LHPA), was dissolved in Gasoline Composition - 1 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

S.
NO GASOLINE FUEL POTENTIAL
GUM, gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-1 132
2. GASOLINE FUEL + 5 mg/lit of LHPA 76
3. GASOLINE FUEL + 10 mg/lit of LHPA 64
4. GASOLINE FUEL + 15 mg/lit of LHPA 60
5. GASOLINE FUEL + 20 mg/lit of LHPA 52
6. GASOLINE FUEL + 30 mg/lit of LHPA 42
7. GASOLINE FUEL + 50 mg/lit of LHPA 36
Example 14 to 17
The above liquid hindered phenolic antioxidant,(LHPA), was dissolved in Gasoline Composition - 2 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

s. GASOLINE FUEL POTENTIAL
NO GUM,
■ gm / m3
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1. GASOLINE FUEL AS PER GASOLINE COMPOSITIONS 258
2. GASOLINE FUEL + 10 mg/lit of LHPA 158
3. GASOLINE FUEL + 20 mg/lit of LHPA 84
4. GASOLINE FUEL + 40 mg/lit of LHPA 36
Example 18 to 23
Amine antioxidant, N,N-Disecondary-butyl-paraphenylenediamine (PDA, 99% purity), was dissolved in Gasoline Composition - 1 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

s.
NO GASOLINE FUEL POTENTIAL GUM,
gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-1 132
2. GASOLINE FUEL + 5 mg/lit of PDA 46
3. GASOLINE FUEL + 10 mg/lit of PDA 42
4. GASOLINE FUEL + 15 mg/lit of PDA 40
5. GASOLINE FUEL + 20 mg/lit of PDA 40
6. GASOLINE FUEL + 30 mg/lit of PDA 40
7. GASOLINE FUEL + 50 mg/lit of PDA 38
Example 24 to 25
The above amine antioxidant,(PDA, 99% purity), received from two different sources was dissolved in Gasoline Composition - 2 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

S. NO GASOLINE FUEL POTENTIAL GUM,
gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITIONS 258
2. GASOLINE FUEL + 20 mg/lit of PDA -Source - A 28
3. GASOLINE FUEL + 20 mg/lit of PDA -Source - B 32


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"Example 26 to 37
Various Mannich bases were dissolved in Gasoline Composition - 1 at the ambient temperature. The details of their concentrations in gasoline fuel and the results obtained are as given below:

s.
NO GASOLINE FUEL POTENTIAL
GUM,
gm / m3
1 GASOLINE FUEL AS PER GASOLINE COMPOSITION-1 132
2 GASOLINE FUEL + 20 mg/lit of Mannich Base using CSNL & C4 Amine 108
3 GASOLINE FUEL + 50 mg/lit of Mannich Base using CSNL & C4 Amine 95
4 GASOLINE FUEL + 100 mg/lit of Mannich Base using CSNL & Q Amine 80
5 GASOLINE FUEL + 150 mg/lit of Mannich Base using CSNL & Q Amine 60
6 GASOLINE FUEL + 20 mg/lit of Mannich Base using para-nonyl phenol & Q Amine 122
7 GASOLINE FUEL + 50 mg/lit of Mannich Base using para-nonyl phenol & Q Amine 98
8 GASOLINE FUEL + 100 mg/lit of Mannich Base using para-nonyl phenol & Q Amine 90
9 GASOLINE FUEL + 150 mg/lit of Mannich Base using para-nonyl phenol & C4 Amine 80
10 GASOLINE FUEL + 20 mg/lit of Mannich Base using para-dodecyl phenol & C4 Amine 128
11 GASOLINE FUEL + 50 mg/lit of Mannich Base using para-dodecyl phenol & C4 Amine 118
12 GASOLINE FUEL + 100 mg/lit of Mannich Base using para-dodecyl phenol & C4 Amine 100
13 GASOLINE FUEL + 150 mg/lit of Mannich Base using para-dodecyl phenol & C4 Amine 92
Example: 38 to 43
A combination of phenolic antioxidant, 2,6-ditertiary-butyl-para-cresol(DBPC 99 % purity level) and N;N-Disecondary-butyl-paraphenylenediamine (99% purity) in 1:1 weight ratio (AO Combination - 1) was dissolved in Gasoline Composition - 1 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:


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s.
NO GASOLINE FUEL POTENTIAL
GUM, gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-1 132
2. GASOLINE FUEL + 5 mg/lit of AO Combination - 1 42
3. GASOLINE FUEL + 10 mg/lit of AO Combination - 1 42
4. GASOLINE FUEL + 15 mg/lit of AO Combination - 1 40
5. GASOLINE FUEL + 20 mg/lit of AO Combination - 1 40
6. GASOLINE FUEL + 30 mg/lit of AO Combination - 1 28
7. GASOLINE FUEL + 50 mg/lit of AO Combination - 1 28
Example: 44 to 49
Another combination containing liquid hindered phenolic antioxidant(LHPA) and N,N-Disecondary-butyl-paraphenylenediamine (98% purity) in 1:1 weight ratio (AO Combination - 2) was dissolved in Gasoline Composition - 1 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

s.
NO GASOLINE FUEL POTENTIAL GUM,
e:m / rrr
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-1 132
2. GASOLINE FUEL + 5 mg/lit of AO Combination - 2 50
3. GASOLINE FUEL + 10 mg/lit of AO Combination - 2 46
4. GASOLINE FUEL + 15 mg/lit of AO Combination - 2 36
5. GASOLINE FUEL + 20 mg/lit of AO Combination - 2 36
6. GASOLINE FUEL + 30 mg/lit of AO Combination - 2 32
7. GASOLINE FUEL + 50 mg/lit of AO Combination - 2 32


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Example: 50 to 55
A combination of phenolic antioxidant, 2,6-cUtertiary-butyl-para-cresol(DBPC, 99 % purity level) and Mannich base (prepared by reacting paranonyl phenol, Q -alkyl amine and an aldehyde) in 1:1 weight ratio (AO Combination - 3) was dissolved in Gasoline Composition - 1 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below.

s.
NO GASOLINE FUEL POTENTIAL GUM,
gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-1 132
2. GASOLINE FUEL + 5 mg/lit of AO Combination - 3 84
3, GASOLINE FUEL + 10 mg/lit of AO Combination - 3 64
4. GASOLINE FUEL + 15 mg/lit of AO Combination - 3 58
5. GASOLINE FUEL + 20 mg/lit of AO Combination - 3 38
6. GASOLINE FUEL + 30 mg/lit of AO Combination - 3 28
7. GASOLINE FUEL + 50 mg/lit of AO Combination - 3 28
Example: 56 to 61
A combination containing liquid hindered phenolic antioxidant(LHPA) and Mannich base (prepared by reacting paranonyl phenol, C4 - alkyl amine and an aldehyde) in 1:1 weight ratio (AO Combination - 4) was dissolved in Gasoline Composition - 1 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:



s.
NO GASOLINE FUEL POTENTIAL GUM,
gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-1 132
2. GASOLINE FUEL + 5 mg/lit of AO Combination - 4 78
3. GASOLINE FUEL + 10 mg/lit of AO Combination - 4 60
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4. GASOLINE FUEL + 15 mg/lit of AO Combination - 4 54
5. GASOLINE FUEL + 20 mg/lit of AO Combination - 4 40
6. GASOLINE FUEL + 30 mg/lit of AO Combination - 4 34
7. GASOLINE FUEL + 50 nig/lit of AO Combination - 4 32
Example: 62 to 66
A combination containing liquid hindered phenolic antioxidant (LHPA) and Mannich base (prepared by reacting paranonyl phenol, C4 - alkyi amine and an aldehyde) in 1:1 weight ratio (AO Combination - 4) was dissolved in Gasoline Composition - 2 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

s.
NO GASOLINE FUEL POTENTIAL GUM,
gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITIONS 258
2. GASOLINE FUEL + 10 mg/lit of AO Combination - 4 200
3. GASOLINE FUEL + 15 mg/lit of AO Combination - 4 138
4. GASOLINE FUEL + 20 mg/lit of AO Combination - 4 138
5. GASOLINE FUEL + 30 mg/lit of AO Combination - 4 90
6. GASOLINE FUEL + 50 mg/lit of AO Combination - 4 48
Example: 67 to 72
A combination containing N,N-Disecondaty-butyl-paraphenylenedkrriine (99% purity) and Mannich base (prepared by reacting paranonyl phenol, C4 - alkyi amine and an aldehyde) m 1:1 weight ratio (AO Combination - 5) was dissolved in Gasoline Composition - 1 at the ambient temperature. The details of its concentrations in gaso]lne fuel and the result obtained are as given below:

s. GASOLINE FUEL POTENTIAL
NO GUM,
. gm / m3
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1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-1 132
2. GASOLINE FUEL + 5 mg/lit of AO Combination - 5 44
3. GASOLINE FUEL + 10 mg/lit of AO Combination - 5 40
4. GASOLINE FUEL + 15 mg/lit of AO Combination - 5 38
5. GASOLINE FUEL + 20 mg/lit of AO Combination - 5 38
6. GASOLINE FUEL + 30 mg/lit of AO Combination - 5 34
7. GASOLINE FUEL + 50 mg/lit of AO Combination - 5 34
Example: 73 to 78
A combination containing N,^-Disecondary-butyl-paraphenylenedianiine (98% purity) and Mannich base (prepared by reacting paranonyl phenol, C4 - alkyl amine and an aldehyde) in 1:2 weight ratio (AO Combination - 6) was dissolved in Gasoline Composition - 1 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

s.
NO GASOLINE FUEL POTENTIAL
GUM,
gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-1 132
2. GASOLINE FUEL + 5 mg/lit of AO Combination - 6 44
3. GASOLINE FUEL + 10 mg/lit of AO Combination - 6 42
4. GASOLINE FUEL + 15 mg/lit of AO Combination - 6 40
5. GASOLINE FUEL + 20 mg/lit of AO Combination - 6 40
6. GASOLINE FUEL + 30 mg/lit of AO Combination - 6 36
7. GASOLINE FUEL + 50 mg/lit of AO Combination - 6 34


6269(P-12)
Example: 79 to 84
A combination containing N,N'-Disecondary-butyl-paraphenylenediamine (98% purity) and Mannich base (prepared by reacting paranonyl phenol, C - alhyl amine and an aldehyde) in 1:3 weight ratio (AO Combination - 7) was dissolved in Gasoline Composition - 1 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

s.
NO GASOLINE FUEL POTENTIAL GUM,
gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-1 132
2. GASOLINE FUEL + 5 mg/lit of AO Combination - 7 50
3. GASOLINE FUEL + 10 mg/lit of AO Combination - 7 40
4. GASOLINE FUEL + 15 mg/lit of AO Combination - 7 38
5. GASOLINE FUEL + 20 mg/lit of AO Combination - 7 34
6. GASOLINE FUEL + 30 mg/lit of AO Combination - 7 34
7. GASOLINE FUEL + 50 mg/lit of AO Combination - 7 34
Example: 85 to 89
A combination containing N,N-Disecondary-butyl-paraphenylenediamine (98% purity) and Mannich base (prepared by reacting paranonyl phenol, C4 - alkyl amine and an aldehyde) in 1:3 weight ratio (AO Combination - 7) was dissolved in Gasoline Composition - 2 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

s.
NO GASOLINE FUEL POTENTIAL GUM,
gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-2 258
2. GASOLINE FUEL + 5 mg/lit of AO Combination - 7 104
3. GASOLINE FUEL + 10 mg/lit of AO Combination - 7 72




1 4. GASOLINE FUEL + 15 mg/lit of AO Combination - 7 42
5. GASOLINE FUEL + 20 mg/lit of AO Combination - 7 36
6. GASOLINE FUEL + 30 mg/lit of AO Combination - 7 30
Example: 90 to 94
A combination containing N,N,-Disecondary-butyl-paraphenylenecdarnine (98% purity) and Mannich base (prepared by reacting paranonyl phenol, C4 - alkyl amine and an aldehyde) in 1:9 weight ratio (AO Combination - 8) was dissolved in Gasoline Composition - 2 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

s.
NO GASOLINE FUEL POTENTIAL GUM,
gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-2 258
2. GASOLINE FUEL + 5 mg/lit of AO Combination - 8 118
3. GASOLINE FUEL + 10 mg/lit of AO Combination - 8 72
4. GASOLINE FUEL + 15 mg/lit of AO Combination - 8 44
5. GASOLINE FUEL + 20 mg/lit of AO Combination - 8 40
6. GASOLINE FUEL + 30 mg/lit of AO Combination - 8 36
Example: 95 to 99
A combination containing NN'-Disecondary-butyl-paraphenylenecUamine (98% purity) and Mannich base (prepared by reacting CNSL, C4 - alkyl amine and an aldehyde) in 1:3 weight ratio (AO Combination - 9) was dissolved in Gasoline Composition - 2 at the ambient temperature. The details of its concentrations in gasoline fuel and the result obtained are as given below:

s.
NO GASOLINE FUEL POTENTIAL GUM,
gm / m3
1. GASOLINE FUEL AS PER GASOLINE COMPOSITION-2 258


6269(P-12)

2. GASOLINE FUEL + 5 mg/lit of AO Combination - 9 96
3. GASOLINE FUEL + 10 mg/lit of AO Combination - 9 60
4. GASOLINE FUEL + 15 mg/lit of AO Combination - 9 42
5. GASOLINE FUEL + 20 mg/lit of AO Combination - 9 36
6. GASOLINE FUEL + 30 mg/lit of AO Combination - 9 32
In order to establish the efficacy of Antioxidant Combination - 7, the same combination was also evaluated in various gasoline fuel compositions with a variety of cracked components and severity. The gasoline samples included in the study were obtained from refineries having Coker / Fluidized Catalytic Cracking(FCQ and the hydrocraker units. It has been observed that the Antioxidant Composition - 7 gives the maximum synergism and the composition is able to control potential gum in the gasoline fuel to desirable level.
In order to confirm the potential antioxidant performance of Antioxidant Composition - 7, the composition was tested in different gasoline compositions using additional tests such as Existent Gum test as per ASTM D-381 / IP: 131, Induction Period test as per ASTM D- 525 / IP: 40 and Ambient Aging test as per IP 378/87 (Modified) for three months. The fuel composition details and result of antioxidant characteristics of Antioxidant Composition - 7 are given as follows:
Gasoline Composition - 1
Streams % Volume
FCC Gasoline 50
Reformate Stream 40
Vis-breaker Naphtna 10
Gasoline Composition - 2

Streams % Volume
FCC Gasoline 55
Reformate Stream 35
K7TOP Stream 10
Gasoline Composition - 3

Streams % Volume
FCC Gasoline 45


'. 6269(P-12)

Reformate Stream 35
Straight Run Naphtha 10
Vis-breaker Naphtna 10
Gasoline Composition - 4

Streams % Volume
FCC Gasoline 55
Reformate Stream 35
Vis-breaker Naphtna 10
Gasoline Composition - 5

Streams % Volume
FCC Gasoline 40
CRU Stream 60
With Gasoline Composition - 1

S.No. GASOLINE FUEL GUM, &m / m3 Induction Time
(Min)


Potential Existent Existent after
Ambient
Aging Test

1 Base Fuel 132 10 55 257
2 Base Fuel + 5 mg/lit of AO Combination -
7 50 10 38 400
3 Base Fuel + 10 mg/lit of AO Combination -
7 40 10 38 435
With Gasoline Composition - 2

GUM, gm / m3


Existent after

Potential Existent Ambient Induction
S.No. GASOLINE FUEL Aging Test Time
(Min)
19

With Gasoline Composition - 3

S.No. GASOLINE FUEL GUM, gm / m3 Induction Time
(Min)


Potential Existent Existent after
Ambient
Aging Test

1 Base Fuel 118 8 52 300
2 Base Fuel + 5 mg/lit of AO
Combination -7 40 8 34 430
3 Base Fuel + 10 mg/lit of AO
Combination -7 38 8 32 540
With Gasoline Composition - 4

S.No. GASOLINE
FUEL GUM, gm / m3 Induction Time
(Min)


Potential Existent Existent after
Ambient
Aging Test

1 Base Fuel 289 14 70 189
2 Base Fuel + 5 mg/lit of AO
Combination -7 42 14 36 430
3 Base Fuel + 10 mg/lit of AO Combination -
7 40 14 34 510
With Gasoline Composition - 5

GUM, gm / m3 Induction


Potential Existent Existent after Ambient



6269(P-12)

S.No. GASOLINE FUEL Aging Test Time (Min)
1 Base Fuel 232 12 72 200
2 Base Fuel + 5 mg/lit of AO
Combination -7 40 12 38 410
3 Base Fuel + 10 mg/lit of AO Combination -
7 36 12 34 540
WATER REACTION OF FUELS
Gasoline with Antioxidant Composition - 7 was evaluated and the results are given as follows:

Sr. No Product Test Results
1 GASOLINE COMPOSITION -1+20 mg/lit of AO Combination - 7 Pass
2 GASOLINE COMPOSITION -2+20 mg/lit of AO Combination - 7 Pass
3 GASOLINE COMPOSITION -3+20 mg/lit of AO Combination - 7 Pass
4 GASOLINE COMPOSITION -4+20 mg/lit of AO Combination - 7 Pass
5 GASOLINE COMPOSITION -5+20 mg/lit of AO Combination - 7 Pass
Addition of AO Combination - 7 does not deteriorate the gasoline quality. DYNAMIC CORROSION TEST
The test results are as follows:

Sr.
No Product Test Results
1 GASOLINE COMPOSITION -1+20 mg/lit of AO Combination - 7 Pass
22



12 GASOLINE COMPOSITION -2+20 mg/lit of AO Combination - 7 Pass
3 GASOLINE COMPOSITION -3+20 mg/lit of AO Combination - 7 Pass
4 GASOLINE COMPOSITION -4+20 mg/lit of AO Combination - 7 Pass
5 GASOLINE COMPOSITION -5+20 mg/lit of AO Combination - 7 Pass
The gasoline quality is not deteriorated on addition of AO Combination - 7 in terms of corrosion.
Large Scale Trail of Antioxidant Composition - 7
The Antioxidant Composition - 7 was tested at large scale in one of the Indian Oil Refineries. Antioxidant Composition - 7 was prepared in bulk and transported to the refinery in HDPE drums. Initially the composition was tested in the refinery laboratory. Laboratory blend of gasoline containing FCC stream was prepared in consultation with Technical Department with the refinery. The composition of gasoline used for evaluation work is as follows:

Streams % Volume
FCC Gasoline of Refinery- A 55
Reformate Stream of Refinery- A 35
K7TOP Stream of Refinery- A 10
The Antioxidant Composition - 7 along with the Commercial Antioxidant (N,N'-Disecondry-butyl-paraphenylenediamine) already in use at the refinery7 were tested for Potential Gum Test as per ASTM D- 873 / IP: 138 (Modified). The laboratory evaluation data revealed that Antioxidant Composition - 7 is quite effective even at 10 mg/lit treat level compared to the Commercial Antioxidant (N,N'-Disecondry-butyl-paraphenylenediamine). Results are summarised as follows:

Antioxidant Treat Rate, mg/Lit Potential Gum,
- - 158
Commercial Amine AO 10 44
Commercial Amine AO 20 38
Antioxidant Composition - 7 10 26
Antioxidant Composition - 7 20 20
As a sequel to laboratory testing, the Antioxidant Composition - 7 was added in two tanks (about 7300KL) at a treat rate of lOmg/lit, which is 50% lower than the
23

*269(F-12)


^dlar treat rate of commercial AO being used at the test refinery. Results are summarised as follows:

Tank No. Potential Gum, g/m3
Intermediate Sample from Gasoline tank No. 61 22
Final sample from Gasoline tank No. 61 20
Intermediate Sample from Gasoline tank No. 76 18
Final sample from Gasoline tank No. 76 20
Further, the detailed costing of the Antioxidant Composition - 7 indicates that it is quite cheap compared to the commercial AO.


6269(P-12)

We claim
1. A gasoline anti-oxidant composition comprising at least one Mannich base and an amine for stabilization of cracked components for the secondary processing units and the finished gasoline in the following ratio 50-95 % : 5- 50% by weight of the composition
2. A composition as claimed in claim 1 wherein the concentration of the nitrogen is in the range of 3.5 to 8.5 wt%.
3. A composition as claimed in claim 1, wherein the Mannich base is derived from p-substituted phenols
4. A composition as claimed in claim 1, wherein the Mannich base is derived from Cashew Nut Shell liquid.
5. A composition as claimed in claim 1, wherein the amine is selected from substituted p-phenylenediamines.
6. A composition as claimed in claim 5, wherein the amine is NT- N-di-alkyl-p-phenylenediamine.
7. A composition as claimed in claim 6, wherein the NT- N-di-alkyl-p-phenylenediamine is NT- N-alkyl butyl para phenylenediamine.
8. A gasoline anti-oxidant composition substantially as herein described with reference to the foregoing examples

Dated this 29th day of October 2003 s
Of Anand An^^aM^vaciteT Attorneyforme Applicant
25

Documents:

1150-mum-2003 abstract.pdf

1150-mum-2003 claims.pdf

1150-mum-2003 complete spacification cancelled.pdf

1150-mum-2003 corresondence.pdf

1150-mum-2003 correspondence(ipo).pdf

1150-mum-2003 description(granted).pdf

1150-mum-2003 form 1.pdf

1150-mum-2003 form 19.pdf

1150-mum-2003 form 2(granted).pdf

1150-mum-2003 form 2(title page).pdf

1150-mum-2003 form 3.pdf

1150-mum-2003 power of attorney.pdf

1150-mum-2003-abstract.doc

1150-mum-2003-cancelled pages(31-10-2003).pdf

1150-mum-2003-claims(granted)(31-10-2003).pdf

1150-mum-2003-claims(granted)-(31-10-2003).doc

1150-mum-2003-claims.doc

1150-mum-2003-correspondence(27-01-2005).pdf

1150-MUM-2003-CORRESPONDENCE(30-1-2012).pdf

1150-mum-2003-correspondence(ipo)-(09-12-2004).pdf

1150-mum-2003-description(granted).doc

1150-mum-2003-form 1(17-12-2003).pdf

1150-mum-2003-form 1(31-10-2003).pdf

1150-MUM-2003-FORM 15(30-1-2012).pdf

1150-mum-2003-form 19(28-11-2003).pdf

1150-mum-2003-form 2(granted)-(31-10-2003).doc

1150-mum-2003-form 2(granted)-(31-10-2003).pdf

1150-mum-2003-form 2(granted).doc

1150-mum-2003-form 3(16-09-2004).pdf

1150-mum-2003-form 3(31-10-2003).pdf

1150-mum-2003-other documents(17-12-2003).pdf


Patent Number 207061
Indian Patent Application Number 1150/MUM/2003
PG Journal Number 30/2008
Publication Date 25-Jul-2008
Grant Date 21-May-2007
Date of Filing 31-Oct-2003
Name of Patentee INDIAN OIL CORPORATION LIMITED
Applicant Address G-9, ALI YAVAR JUNG MARG, BANDRA (EAST), MUMBAI - 400 051, MAHARASHTRA
Inventors:
# Inventor's Name Inventor's Address
1 GUPTA ANURAG ATEET C/O INDIAN OIL CORPORATION LIMITED., G-9, ALI YAVAR JUNG MARG, BANDRA (EAST), MUMBAI - 400 051, MAHARASHTRA
PCT International Classification Number C10L 01/22
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA