NZ243075A

NZ243075A - Degreasing composition containing emulsifier and oil which is paraffinic monounsaturated wax ester; transesterification of fish oil and transesterified product

Info

Publication number: NZ243075A
Application number: NZ24307592A
Authority: NZ
Inventors: Bernd Kutzner
Original assignee: Beku Environmental Products Lt
Priority date: 1991-06-11
Filing date: 1992-06-09
Publication date: 1995-07-26
Also published as: WO1992022631A1

Description

New Zealand Paient Spedficaiion for Paient Number £43075 243075 .fori [■ > llik.lf?.!.; .^OPV*«t* Spcciiiccticn ... i CQlC.}ffft^CCi • 2 S JU1 1995-- No: XxJ ■ U W kri M> m W NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION A COMPOSITION AND A PROCESS We, BEKU ENVIRONMENTAL PRODUCTS LTD, an Australian company, of 8 Stewart Crescent, Taroona 7053, Tasmania, Australia hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particjlarly described in and by the following statement:- (followed by page - la -) MM *ZA*nWT(*FIC€ < -9JI/W992 PEglV"> | - !«.- The present invention relates to a de-greaser composition and to a process for producing a component of the de-greaser composition from a fish oil.

De-greaser compositions are used widely in industry in applications such as, special cleaners for the maritime industry, cleaners for food processing equipment, and general and all purpose cleaners, and usually comprise an emulsifier/detergent and a hydrophobic solvent which carries the emulsifier into the grease.

There is an increasing recognition that, in addition to grease-removal and corrosion inhibition properties, de-greaser compositions should have other properties such as biodegradability, non-toxicity and non-flammability.

An object of the present invention is to provide a de-greaser composition which exhibits the combination of properties described in the preceding paragraph.

Another object of the present invention is to provide a process for producing a component of the de-greaser composition from fish oil.

According to the present invention there is provided a de-greaser composition comprising: (a) an oil comprising a substantially paraffinic monounsaturated wax ester; and (b) an emulsifier or an emulsifier blend.

It is preferred that the oil contains no or at most a low concentration of polyunsaturated fatty alcohols or acids as these are potential sites for the development of rancidity. It is particularly preferred that the oil contains less than 10% of polyunsaturated fatty alcohols or acids. It is more particularly preferred that the oil contains less than 5% of polyunsaturated fatty alcohols or acids. Throughout the specification and claimst the percentages referred to are on a weight basis.

It is preferred that the oil comprises fish oil extracted from marine, more preferably deep,sea marine, species. Typically, the fish oil is extracted from Orange Rouphy (Hoplostethus alanticus) and Dory. It is preferred that the fish oil is chemically modified by transesterification to lower the pour point of the fi oil.

ZH £ U / 0 It is preferred that the emulsifier or the emulsifier blend has a hydrophilic/lipophilic balance of between 5 and 9.

It is preferred that the emulsifier or the emulsifier blend is biodegradable as determined by AS 1792-1976.

It is preferred that the emulsifier or the emulsifier blend is non-toxic.

The emulsifier or the emulsifier blend may be formed in situ, eg, by reaction of polyethylene glycol and the oil to form polyethylene glycol esters or neutralization with an alkali of any free fatty acids to form soaps.

Typically, the emulsifier or emulsifier blend comprises one or more of polyethylene glycol 200 mono oleate, polyethylene glycol 400 dioleate, and laurylpolyethylene glycol ether 3 mole.

It is preferred that the de-greaser composition comprises 3% to 25%, more preferably 8% to 20%, of the emulsifier or emulsifier blend.

It has been found that at concentrations of less than 3% the emulsifier or emulsifier blend level is insufficient to impart rinsability and de-greasing strength to the oil and that at concentrations of more than 25% the product has insufficient "break" to leave a film which is necessary to impart anticorrosive properties. 24 3075 According to the present invention there is also provided a process for producing an oil comprising a substantially paraffinic monounsaturated wax ester by transesterification of a fish oil, the process 5 comprising: (a) mixing the fish oil, an alcohol and an acid catalyst; and (b) heating the mixture of the fish oil, the alcohol and the catalyst at a temperature between 40 and 150°C for a prescribed time.

By appropriate selection of the temperature, time, and relative amounts of the fish oil, alcohol, and catalyst, the above process produces a product which comprises a mixture of wax acid esters of the added 15 alcohol, wax alcohols and residual wax esters and which has a lower pour point than the fish oil.

It is preferred that in step (a) the amount of the alcohol is between 0.2 and 20 times the amount of the fish oil on a molar basis. jo It is preferred that the alcohol comprises one or more of methanol, ethanol, n-propanol, iso-propanol, ethylene glycol, propylene glycol, and isomers of butanol.

It is preferred that in step (a) the amount of the 25 catalyst is between 0.2 and 5.0% of the total mass of the fish oil, the alcohol and the catalyst.

It is particularly preferred that the acid cata is an alkyl or arylalkylsulphonate.

Z43U/0 The present invention is described further in the following examples.

Example 1 - Production of Transesterlfled Fish Oil 600 kg of Orange Roughy oil, 450 1 of ethanol and 10 5 kg of dodecylbenzenesulphonic acid were heated to 70°C and stirred at that temperature for 8 hours at which point equilibration was achieved. Upon cooling and evaporation of unconsumed ethanol, the resultant product was found to comprise 50% fatty acid ethyl esters, 40% 10 free fatty alcohols and 10% unmodified wax esters and had a pour point of -6°C.

A complete analysis of the product is set out in Table 1 below.

Table 1 Saturated Ethyl Ester % Alcohol t Wax t C 14 C 16 0.9 1.0 2.1 5.1 C 18 Tr 6.0 Unsaturated C 14-15 Tr 4.1 Tr 3.2 Tr 14.0 7.0 .6 C-16:1 C-17 Tr 26.0 8.1 3.1 C-18:1 C-20:1 C-22:1 243U7D C-24:1 Tr 1.9 C-32 Tr C-33 2.1 C-36 3.2 C-38 4.3 C-40 3.7 C-42 1.2 C-42 Tr Example 2 - Production of Transesterified Fish Oil 300 kg of Orange Roughy oil, 440 1 of isopropyl alcohol and 5 kg of toluenesulphonic acid were heated to 85°C within 1 hour, maintained at that temperature for 10 hours, and then cooled. After unreacted isopropyl alcohol was removed the resultant product was found to 15 comprise 48% fatty acid isopropyl esters, 37% free fatty alcohols and 15% wax esters.

Example 3 - Production of Transesterified Fish Oil 1,000 kg of Dory oil, 110 1 of methanol and 20 kg of laurylsulphonic acid were heated to the reflux 20 temperature of the mixture (78°C) over 2 hours and maintained at that temperature fcr 5 hours. After evaporative removal of residual methanol, the resultant product comprised 39% fatty acid methyl esters, 28% fatty alcohols, and 28% unmodified wax esters and had a 2 5 pour point of 1°C. 242075 7 Example 4 - Performance Characteristics of De-oreaser Composition A series of experiments was carried out to evaluate the biodegradability, toxicity, flammability, grease removal and corrosion inhibition properties of preferred de-greaser compositions of the present invention. The formulations of the de-greaser compositions tested in the experimental work are set out in Table 2 below.

Table 2 Formulation Oil No. 1 • Orange Roughy 2. Orange Roughy Orange Roughy 4. Orange Roughy transesterified as per Example 1 . Dory oil 6. Orange Roughy Emulsifier Comment Polyethyleneglycol Polyethyleneglycol 200 monooleate Product formulated with 3% emulsifier, ie at the lower limit of the scope of the present invention Product formulated with 10% emulsifier, ie within the scope of the present invention Polyethyleneglycol 200 monooleate Polyethyleneglycol 400 dioleate Polyethyleneglycol 200 monooleate Polyethyleneglycol 200 monooleate Product formulated with 15% emulsifier, ie within the scope of the present invention Product formulated with 15% emulsifier, ie within the scope of the present invention Product formulated with 80% emulsifier, ie at the upper limit of the present invention Product formulated with 25% emulsifier, ie outside the scope of the present invention 7 . 8.

Kerosine 92% Coconutdiethanolamide 4% Laurylpolyethyleneglycol ether 4 mole 4% Methylene Chloride 65% Butyl Icinol Nonolyphenolethoxa1ate 5 mole 8 % C 17 polyethyleneglycol ether 3 mole 7% Known kerosine based de-greaser Known chlorinated solvent de-greaser 24 & 0 7 5 As is evident from Table 2, formulations 2, 3, 4 and 5 comprise fish oil and emulsifier in proportions within the scope of the present invention; formulations 1 and 6 comprise fish oil and emulsifier in proportions at the 5 limits of the scope of the present invention; and formulations 7 and 8 comprise commercially available preparations.

A brief discussion of the experimental work carried out on the formulations and the results is set out below. (a) Biodegradability The formulations were tested to ISO 7827 using the following standards: Soft Anionic - dodecylbenzene sulphonate; Soft Nonionic - nonylphenol ethoxalate. It was found that formulations 1 to 6 completely degraded 15 within 10 days. (b) Toxicity Formulations 1 to 6 were non-toxic and formulations 7 and 8 were toxic. (c) Flammability Formulations 1 to 6 had a high flash point and were relatively non-flammable compared with formulation 7. Formulation 8 was non-flammable. (d) Grease Removal and Corrosion Inhibition A uniform coating of 2 mm grease was applied to 10 25 by 15 cm plates of mild steel, and the plates were subsequently treated as follows: 24 30 7 5 (1) the plates were sprayed with unit volumes of the formulations, (2) the formulations were allowed to penetrate for 30 min, (3) the plates were rinsed with cold water, (4) after a visual assessment of complete degreasing the plates were immersed in 5% hydrochloric acid to accelerate corrosion, and (5) an assessment was made of the degree of corrosion after 2 hours.

The results are summarised in Table 3.

Table 3 Formulation Degreasing Corrosion (1) (2) (3) (4 ) (5) (6) (7) (8) Ineffective Effective Effective Effective Effective Effective Effective Effective Not tested Not evident Not evident Not evident Not evident Slight Severe Severe The results indicate that formulation 1 was an ineffective de-greaser, formulations 2 to 8 were 248075 effective de-greasers, formulations 2 to 5 imparted significant corrosion inhibition, and formulation 4 imparted reasonable corrosion inhibition.

In summary, the experimental work established that formulations 2 to 6 in accordance with the present invention have a superior combination of biodegradability, non-toxicity, non-flammability, grease removal and corrosion resistance properties than the other formulations including formulations 7 and 8 of commercially available de-greaser compositions. 243075 13 -

Claims

WHAT WE CLAIM IS;

1. A de-greaser composition comprising: (a) an oil comprising a substantially paraffinic monounsaturated wax ester; and (b) an emulsifier or an emulsifier blend.

2. The composition defined in claim 1, wherein the oil contains substantially no polyunsaturated fatty alcohols or acids.

3. The composition defined in claim 2, wherein the oil contains less than 10% of polyunsaturated fatty alcohols or acids.

4. The composition defined in claim 3, wherein the oil contains less than 5% of polyunsaturated fatty alcohols or acids.

5. The composition defined in any one of the preceding claims, wherein the oil comprises fish oil extracted from marine species.

6. The composition defined in claim 5, wherein the fish oil is extracted from Orange Roughy (Hoplostethus alanticus) or Dory.

7. The composition defined in claim 5 or claim 6, wherein the fish oil is chemically modified by CfOU / D 14 transesterification to lower the pour point of the fish oil.

8. The composition defined in any one of the preceding claims, wherein the emulsifier or the emulsifier blend has a hydrophilic/lipophilic balance of between 5 and 9.

9. The composition defined in claim 8, wherein the emulsifier or the emulsifier blend is biodegradable as determined by Australian Standard (AS) 1792-1976.

10. The composition defined in any one of the preceding claims, wherein the emulsifier or the emulsifier blend is non-toxic.

11. The composition defined in any one of the preceding claims, wherein the emulsifier or the emulsifier blend is formed in situ.

12. The composition defined in any one of the preceding claims, wherein the emulsifier or emulsifier blend comprises one or more of polyethylene glycol 200 mono oleate, polyethylene glycol 400 dioleate, and laurylpolyethylene glycol ether 3 mole, wherein the molecular ratio of lauric acid to polyethylene glycol is 3.

13. The composition defined in any one of the preceding claims, comprising 3% to 25% of the emulsifier or emulsifier blend.

14. The composition defined in claim 13, comprising 8 to 20% of the emulsifier or emulsifier blend. 2i3075 15 -

15. A process for producing an oil comprising a substantially paraffinic monounsaturated wax ester by transesterification of a fish oil, the process comprising: (a) mixing the fish oil, an alcohol and an acid catalyst; and (b) heating the mixture of the fish oil, the alcohol and the catalyst at a temperature between 40 and 150°C.

16. The process defined in claim 15, wherein the amount of the alcohol is between 0.2 and 20 times the amount of the fish oil on a molar basis.

17. The process defined in claim 15 or claim 16, wherein the alcohol comprises one or more of methanol, ethanol, n-propanol, iso-propanol, ethylene glycol, propylene glycol, and isomers of butanol.

18. The process defined in any one of claims 15 to 17, wherein the amount of the catalyst is between 0.2 and 5.0% of the total mass of the fish oil, the alcohol and the catalyst.

19. The process defined in any one of claims 15 to 18, wherein the acid catalyst is an alkyl or arylalkylsulphonate. 243075 16 -

20. A transesterifled fish oil produced by the process of any one of claims 15 to 19.

21. A de-greaser composition as defined in claim 1 substantially as herein described with reference to any example thereof.

22. A process for producing an oil as defined in claim 15 when performed substantially as herein described with reference to any example thereof. By the authorised agents A. J. PARK & SON