Title of Invention	AN IMPROVED PROCESS FOR THE PREPARATION OF SULPHURISED DERIVATIVES OF NON-TRADITIONAL VEGETABLE OILS
Abstract	The present invention relates to a process for the synthesis of sulfurised derivatives of non traditional vegetable oils such as Mohwa oil, Neem oil, Karanja oil etc., useful as extreme pressure antiwear additive and components comprising degumming of the non traditional vegetable, sulfurising the degummed oil by reacting with sulfur powder, dissolving the reaction material in a hydrocarbon solvent, filtering to remove undissolved material, distilling the filtrate to remove the solvent and redissolving the resultant product in hydrocarbon solvent. The purpose of the present invention is to convert the non traditional vegetable oil into value added environment friendly products.

Title of Invention

AN IMPROVED PROCESS FOR THE PREPARATION OF SULPHURISED DERIVATIVES OF NON-TRADITIONAL VEGETABLE OILS

Abstract

The present invention relates to a process for the synthesis of sulfurised derivatives of non traditional vegetable oils such as Mohwa oil, Neem oil, Karanja oil etc., useful as extreme pressure antiwear additive and components comprising degumming of the non traditional vegetable, sulfurising the degummed oil by reacting with sulfur powder, dissolving the reaction material in a hydrocarbon solvent, filtering to remove undissolved material, distilling the filtrate to remove the solvent and redissolving the resultant product in hydrocarbon solvent. The purpose of the present invention is to convert the non traditional vegetable oil into value added environment friendly products.

Full Text	The present invention relates to an improved process for the preparation of sulfurised derivatives of non traditional vegetable oils useful as extreme pressure and antiwear additives. The present invention particularly relates to the preparation of sulfurised derivatives of non traditional vegetable oils such as Mohwa oil, Neem oil, Karanja oil useful as extreme pressure antiwear additive and components. Organic sulfides, sulfurised fatty oils, sulfurised olefines and alkyl aryl phosphorothioates as a class of compounds whether alone or in admixtures with each other are being extensively employed as extreme pressure (e.p.), antiwear and antifriction additives. Extensive published information (papers & patents) is available on the mode and mechanism of action of these additives and formulations for various types of gear oils and metal working oils over the past thirty years. Most of the sulfurised olefines and phospho sulfurised alkyl phenols used in not def extreme presenr formulations have high toxicity and low biodegradability. These products usually have high corrosivity towards copper which is suppressed by use of metal deactivators which depress their performance characteristics too. The present invention describes the development of an improved process for the synthesis of sulfurised derivatives of vegetable oils useful as extreme pressure, antiwear additives. Reference may be made to U.S. US4, 485, 04427 which relates to esterification of linoleic acid oleic acid trimer and sulfurisation of the ester with sulfur for 2 hrs. giving a product containing 2.2% by weight of sulfur. The process required esterification of acids which are obtained from vegetable oils using several additional steps such as hydrolysis and polymerisation and esterification with a monohydric alcohols while the present invention uses the vegetable oils as such. The sulfur content of the product is six times less than the that obtained in the present invention thus requiring very large concentration of the product to reduce the wear and friction at comparable levels with that of sulfurised vegetable oils developed by the process herein described. With reference to another patent IN 155, 144 where in sulfurisation of jojoba oil has been done at 250° with sulfur for 2.5 - 3 hours to obtain 20% sulfur. Jojoba oils is a mono ester of an unsaturated alcohol and an unsaturated acid which is several times costlier than the vegetable oils used in the present invention without contributing any additional advantages compared to these oils such as thermoxidative stability, biodegradability or performance characteristics. Excess sulfur on other hand leads to corrosivity problems towards copper and this leads to addition of metal passivators which lower the performance. Similarly in patent Japan Kokai Tokkyo JP 8265794 mono esters of olelyl alcohol prepared with lanolin fatty acids have been used which are obtained from animal fat and are mono esters instead of vegetable oils used in present invention which are glycerides the process is substantially different from the present invention. The main object of the present invention is to provide an improved process for the preparation of sulfurised derivatives of non traditional vegetable oils useful as extreme pressure, antiwear additives which obviate the drawbacks of the hitherto known processes. Another object is to provide an improved process which leads to value addition to uses of non traditional vegetable oils. Yet another objective is to provide a process for preparation of additive components having low toxicity and high biodegradability as compared to petroleum based products. Still another object is to provide an improved process which utilises renewable resources such as vegetable oils of forest and waste land origin. Accordingly the pre ent invention provides an improved process for the preparation of sulfurised derivatives of non traditional vegetable oils useful as extreme pressures antiwear and antifriction additives, which comprises degumming of the non traditional vegetable oils by solvent extraction methods, sulfurising the degummed oil by reacting with sulfur powder at a temperature 100-160°C over a period of 3 to 8 hours, dissolving the reaction material in a hydrocarbon solvent, filtering to remove undissolved material, distilling the filtrate to remove the solvent followed by passing of nitrogen through residue at the rate of 5-100ml/sec at a temperature 100-180°C for a period of atleast 2 hours, redissoliving the resultant product in hydrocarbon solvent followed by filtration and distillation to remove solvent from the filtrate and obtaining the product by drying under vacuum the residual product left after distillation. In an embodiment of the present invention the degumming of the non traditional vegetable oil may be effected by known methods such as extraction with hexane. In another embodiment of present invention the ratio of sulfur to non traditional vegetable oil may be in the range of 5-30% by weight. In yet another embodiment the hydrocarbon solvent,may be such as heptane, benzene and/ or toluene. In still another embodiment the volume of hydrocarbon solvent used may be 2 to 10 times of reacted material. In yet another embodiment the nitrogen may be passed through the residue till evolution of hydrogen sulfide ceases. The process of the present invention is illustrated by following examples, however, these should not be construed to limit the scope of the invention. Example 1 Sulfurised Neem Oil: 1000 gm. of neem oil of iodine value 75 was dissolved in 10 litres of hexane and alllowed to cool for 6 hrs. at 10 ± 5°C. The hexane solution is decanted and filtered. Hexane is removed by distillation to give 921 gm. of refined neem oil which is free from hexane insoluble residue. Refined neem oil 900 gm. was treated with 100 gm. of sulfur powder over a period of six hours in 10 gm. portion at 100°C fresh portion of sulfur powder is added each time the evolution of hydrogen sulfide is reduced to minimal quantity as a result of reaction of the earlier portion with vegetable oil. The temperature is raised to 130°C and heating continued till hydrogen sulfide evolution ceases. Nitrogen was blown through this product and the temperature is raised to 160°C. Blowing of nitrogen is discontinued when no more hydrogen sulfide is evolved. The product is dissolved in a paraffinic solvent allowed to stand for 3 to 4 hours and filtered. The solvent is removed and the product has been analysed for sulfur, copper corrosion at 120°C for 3 hours, welding load, wear scar diameter at 20 kg. and 1800 rpm on four ball friction wear and e.p. tester. The sulfur content was 10.6%. A 5% solution in SAE 90 lubricant base stocks gave welding load 280 kg., wear scar dia 0.35 mm, co-efficient of friction 0.085, the value of copper corrosion at 120°C for 3 hrs. was Ib. Example 2 Refined karanja oil 900 gm of iodine value 80 is treated with 135 gm of sulfur powder over a period of 5 hours at 130°C in portions of 15 gm each. Fresh portions of sulfur powder is added each time evolution of hydrogen sulfide becomes negligible due to reaction of the portion of sulfur powder added prior to the fresh one. The temperature is raised to 150°C and heating continued till evolution of hydrogen sulfide ceases. 10 gm of copper powder is added and temperature raised to 160°C till evolution of hydrogen sulfide ceases. The reaction mixture is cooled and diluted with a paraffinic solvent such as hexane, heptane or petroleum naphtha-80 - 100°C and allowed to stand for 4 hours and filtered. The solvent is removed the product obtained has a sulfur content 14% by weight. A 5% solution in SAE-90 lubircant base stock gave welding load 350 kg., wear scar dia 0.35 mm and co-efficient of friction 0.089. The copper corrosion at 120°C for 3 hours is between Ib and 2a. The value is reduced between la and Ib when 100 ppm of a hetrocyclic nitrogen compound such as an alkyl triazole is added. Example 3 Refined Mohvva oil 900 gm. of Iodine value 60 is treated with 120 gm of sulfur powder over a period of 8 hours at 140°C in portions of 5 gm each. Fresh portions of sulfur powder is added each time evolution of hydrogen sulfide becomes negligible due to reaction of the portion of sulfur powder added to fresh one. The temperature is raised to 155°C and heating continued till hydrogen sulfide evolution ceases. Nitrogen was blown through this product at 165°C for 5 hours. The product is dissolved in a paraffinic solvent boiling range 100-110°C and allowed to stand for 6 hours and filtered. The solvent is recovered by distillation. The product obtained had sulfur content of 11% by weight. A 5% solution in SAE-90 lubricant base stock gave welding load 250Kg., wear scar dia 0.31 mm and co-efficient of friction 0.09. The copper corrosion at 120°C for 3 hours is Ib. The main advantages of the process of the present invention are the non traditional vegetable oils may be converted into value added environment friendly not del and antiwear additives for industrial gear oils. The non traditional vegetable oils may be made more effective as starting materials for preparing additives by refining them with hexane and removing the insoluble gummy and unstable impurities. The vegetable oils may be sulfurised in a manner such that the sulfurised vegetable oils formed give lower corrosion rating and better load carrying and antiwear properties. The sulfurised vegetable oils may be prepared with copper corrosion ratings as low as Ib at 120°C for 3 hours without using copper passivators and thermal stability improved by blowing nitrogen through the sulfurised oils. We claim; 1. An improved process for the preparation of sulfurised derivatives of non traditional vegetable oils useful as extreme pressures antiwear and antifriction additives, which comprises degumming of the non traditional vegetable oils by solvent extraction methods, sulfurising the degummed oil by reacting with sulfur powder at a temperature 100-160°C over a period of 3 to 8 hours, dissolving the reaction material in a hydrocarbon solvent, filtering to remove undissolved material, distilling the filtrate to remove the solvent followed by passing of nitrogen through residue at the rate of 5-100ml/sec at a temperature 100-180°C for a period of atleast 2 hours, redissoliving the resultant product in hydrocarbon solvent followed by filtration and distillation to remove solvent from the filtrate and obtaining the product by drying under vacuum the residual product left after distillation. 2. An improved process as claimed in claiml, wherein the ratio of sulfur to non- traditional vegetable oil in the range of 5-30% by weight. 3. An improved process as claimed in claim 1, wherein the hydrocarbon solvent used is such as heptane, benzene and/or toluene. 4. An improved process as claimed in claiml, wherein the volume of hydrocarbon solvent used is 2 to 10 times of reacted material. 5. An improved process as claimed in claqiml, wherein the nitrogen is passed through the residue till evolution of hydrogen sulfide ceases. 6. An improved process as for the preparation of sulfurised derivatives of non- traditional vegetable oils useful as extreme pressure, antiwear additives substantially as herein described with reference to the examples.

Full Text

The present invention relates to an improved process for the preparation of sulfurised derivatives of non traditional vegetable oils useful as extreme pressure and antiwear additives.
The present invention particularly relates to the preparation of sulfurised derivatives of non traditional vegetable oils such as Mohwa oil, Neem oil, Karanja oil useful as extreme pressure antiwear additive and components.
Organic sulfides, sulfurised fatty oils, sulfurised olefines and alkyl aryl phosphorothioates as a class of compounds whether alone or in admixtures with each other are being extensively employed as extreme pressure (e.p.), antiwear and antifriction additives. Extensive published information (papers & patents) is available on the mode and mechanism of action of these additives and formulations for various types of gear oils and metal working oils over the past thirty years. Most of the sulfurised olefines and phospho sulfurised alkyl phenols used in not def extreme presenr
formulations have high toxicity and low biodegradability. These products usually have high corrosivity towards copper which is suppressed by use of metal deactivators which depress their performance characteristics too. The present invention describes the development of an improved process for the
synthesis of sulfurised derivatives of vegetable oils useful as extreme pressure, antiwear
additives. Reference may be made to U.S. US4, 485, 04427 which relates to
esterification of linoleic acid oleic acid trimer and sulfurisation of the ester with sulfur for 2 hrs. giving a product containing 2.2% by weight of sulfur. The process required esterification of acids which are obtained from vegetable oils using several additional steps such as hydrolysis and polymerisation and esterification with a monohydric
alcohols while the present invention uses the vegetable oils as such. The sulfur content of the product is six times less than the that obtained in the present invention thus requiring very large concentration of the product to reduce the wear and friction at comparable levels with that of sulfurised vegetable oils developed by the process herein described.
With reference to another patent IN 155, 144 where in sulfurisation of jojoba oil has been
done at 250° with sulfur for 2.5 - 3 hours to obtain 20% sulfur. Jojoba oils is a mono
ester of an unsaturated alcohol and an unsaturated acid which is several times costlier
than the vegetable oils used in the present invention without contributing any additional
advantages compared to these oils such as thermoxidative stability, biodegradability or
performance characteristics. Excess sulfur on other hand leads to corrosivity problems
towards copper and this leads to addition of metal passivators which lower the
performance.
Similarly in patent Japan Kokai Tokkyo JP 8265794 mono esters of olelyl alcohol
prepared with lanolin fatty acids have been used which are obtained from animal fat and
are mono esters instead of vegetable oils used in present invention which are glycerides
the process is substantially different from the present invention.
The main object of the present invention is to provide an improved process for the
preparation of sulfurised derivatives of non traditional vegetable oils useful as extreme
pressure, antiwear additives which obviate the drawbacks of the hitherto known
processes.
Another object is to provide an improved process which leads to value addition to uses of
non traditional vegetable oils.
Yet another objective is to provide a process for preparation of additive components having low toxicity and high biodegradability as compared to petroleum based products. Still another object is to provide an improved process which utilises renewable resources such as vegetable oils of forest and waste land origin.
Accordingly the pre ent invention provides an improved process for the preparation of sulfurised derivatives of non traditional vegetable oils useful as extreme pressures antiwear and antifriction additives, which comprises degumming of the non traditional vegetable oils by solvent extraction methods, sulfurising the degummed oil by reacting with sulfur powder at a temperature 100-160°C over a period of 3 to 8 hours, dissolving the reaction material in a hydrocarbon solvent, filtering to remove undissolved material, distilling the filtrate to remove the solvent followed by passing of nitrogen through residue at the rate of 5-100ml/sec at a temperature 100-180°C for a period of atleast 2 hours, redissoliving the resultant product in hydrocarbon solvent followed by filtration and distillation to remove solvent from the filtrate and obtaining the product by drying under vacuum the residual product left after distillation.
In an embodiment of the present invention the degumming of the non traditional
vegetable oil may be effected by known methods such as extraction with hexane.
In another embodiment of present invention the ratio of sulfur to non traditional vegetable
oil may be in the range of 5-30% by weight.
In yet another embodiment the hydrocarbon solvent,may be such as heptane, benzene
and/ or toluene.
In still another embodiment the volume of hydrocarbon solvent used may be 2 to 10 times
of reacted material.
In yet another embodiment the nitrogen may be passed through the residue till evolution of hydrogen sulfide ceases.
The process of the present invention is illustrated by following examples, however, these should not be construed to limit the scope of the invention.
Example 1 Sulfurised Neem Oil:
1000 gm. of neem oil of iodine value 75 was dissolved in 10 litres of hexane and alllowed to cool for 6 hrs. at 10 ± 5°C. The hexane solution is decanted and filtered. Hexane is removed by distillation to give 921 gm. of refined neem oil which is free from hexane insoluble residue.
Refined neem oil 900 gm. was treated with 100 gm. of sulfur powder over a period of six hours in 10 gm. portion at 100°C fresh portion of sulfur powder is added each time the evolution of hydrogen sulfide is reduced to minimal quantity as a result of reaction of the earlier portion with vegetable oil. The temperature is raised to 130°C and heating continued till hydrogen sulfide evolution ceases. Nitrogen was blown through this product and the temperature is raised to 160°C. Blowing of nitrogen is discontinued when no more hydrogen sulfide is evolved. The product is dissolved in a paraffinic solvent allowed to stand for 3 to 4 hours and filtered. The solvent is removed and the product has been analysed for sulfur, copper corrosion at 120°C for 3 hours, welding load, wear scar diameter at 20 kg. and 1800 rpm on four ball friction wear and e.p. tester. The sulfur content was 10.6%. A 5% solution in SAE 90 lubricant base stocks gave welding load 280 kg., wear scar dia 0.35 mm, co-efficient of friction 0.085, the value of copper corrosion at 120°C for 3 hrs. was Ib.
Example 2
Refined karanja oil 900 gm of iodine value 80 is treated with 135 gm of sulfur powder over a period of 5 hours at 130°C in portions of 15 gm each. Fresh portions of sulfur powder is added each time evolution of hydrogen sulfide becomes negligible due to reaction of the portion of sulfur powder added prior to the fresh one. The temperature is raised to 150°C and heating continued till evolution of hydrogen sulfide ceases. 10 gm of copper powder is added and temperature raised to 160°C till evolution of hydrogen sulfide ceases. The reaction mixture is cooled and diluted with a paraffinic solvent such as hexane, heptane or petroleum naphtha-80 - 100°C and allowed to stand for 4 hours and filtered. The solvent is removed the product obtained has a sulfur content 14% by weight. A 5% solution in SAE-90 lubircant base stock gave welding load 350 kg., wear scar dia 0.35 mm and co-efficient of friction 0.089. The copper corrosion at 120°C for 3 hours is between Ib and 2a. The value is reduced between la and Ib when 100 ppm of a hetrocyclic nitrogen compound such as an alkyl triazole is added.
Example 3
Refined Mohvva oil 900 gm. of Iodine value 60 is treated with 120 gm of sulfur powder over a period of 8 hours at 140°C in portions of 5 gm each. Fresh portions of sulfur powder is added each time evolution of hydrogen sulfide becomes negligible due to reaction of the portion of sulfur powder added to fresh one. The temperature is raised to 155°C and heating continued till hydrogen sulfide evolution ceases. Nitrogen was blown through this product at 165°C for 5 hours. The product is dissolved in a paraffinic solvent boiling range 100-110°C and allowed to stand for 6 hours and filtered. The solvent is recovered by distillation. The product obtained had sulfur content of 11% by
weight. A 5% solution in SAE-90 lubricant base stock gave welding load 250Kg., wear scar dia 0.31 mm and co-efficient of friction 0.09. The copper corrosion at 120°C for 3 hours is Ib.
The main advantages of the process of the present invention are the non traditional
vegetable oils may be converted into value added environment friendly not del and antiwear
additives for industrial gear oils.
The non traditional vegetable oils may be made more effective as starting materials for
preparing additives by refining them with hexane and removing the insoluble gummy and
unstable impurities.
The vegetable oils may be sulfurised in a manner such that the sulfurised vegetable oils
formed give lower corrosion rating and better load carrying and antiwear properties.
The sulfurised vegetable oils may be prepared with copper corrosion ratings as low as Ib
at 120°C for 3 hours without using copper passivators and thermal stability improved by
blowing nitrogen through the sulfurised oils.

We claim;
1. An improved process for the preparation of sulfurised derivatives of non
traditional vegetable oils useful as extreme pressures antiwear and antifriction
additives, which comprises degumming of the non traditional vegetable oils by
solvent extraction methods, sulfurising the degummed oil by reacting with sulfur
powder at a temperature 100-160°C over a period of 3 to 8 hours, dissolving the
reaction material in a hydrocarbon solvent, filtering to remove undissolved
material, distilling the filtrate to remove the solvent followed by passing of
nitrogen through residue at the rate of 5-100ml/sec at a temperature 100-180°C
for a period of atleast 2 hours, redissoliving the resultant product in hydrocarbon
solvent followed by filtration and distillation to remove solvent from the filtrate
and obtaining the product by drying under vacuum the residual product left after
distillation.
2. An improved process as claimed in claiml, wherein the ratio of sulfur to non-
traditional vegetable oil in the range of 5-30% by weight.
3. An improved process as claimed in claim 1, wherein the hydrocarbon solvent
used is such as heptane, benzene and/or toluene.
4. An improved process as claimed in claiml, wherein the volume of hydrocarbon
solvent used is 2 to 10 times of reacted material.
5. An improved process as claimed in claqiml, wherein the nitrogen is passed
through the residue till evolution of hydrogen sulfide ceases.
6. An improved process as for the preparation of sulfurised derivatives of non-
traditional vegetable oils useful as extreme pressure, antiwear additives
substantially as herein described with reference to the examples.

Documents:

2523-del-1998-abstract.pdf

2523-del-1998-claims.pdf

2523-del-1998-correspondence-others.pdf

2523-del-1998-correspondence-po.pdf

2523-del-1998-description (complete).pdf

2523-del-1998-form-1.pdf

2523-del-1998-form-19.pdf

2523-del-1998-form-2.pdf

« Previous Patent

Next Patent »

Patent Number

216128

Indian Patent Application Number

2523/DEL/1998

PG Journal Number

12/2008

Publication Date

21-Mar-2008

Grant Date

10-Mar-2008

Date of Filing

26-Aug-1998

Name of Patentee

COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH

Applicant Address

RAFI MARG, NEW DELHI-110001.

Inventors:

#	Inventor's Name	Inventor's Address
1	ASHOK KUMAR GUPTA	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
2	ONKAR NATH ANAND	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INIDA.
3	VIJAY KUMAR CHHIBBER	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
4	KALYAN DUTT NEEMLA	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
5	NAVAL KISHORE PANDEY	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
6	RAJ PAL SINGH BISHT	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.

PCT International Classification Number

C01M 141/08

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA