WO1992022631A1

WO1992022631A1 - Degreaser composition comprising monounsaturated wax ester

Info

Publication number: WO1992022631A1
Application number: PCT/AU1992/000262
Authority: WO
Inventors: Bernd Kutzner
Original assignee: Beku Environmental Products Ltd.
Priority date: 1991-06-11
Filing date: 1992-06-05
Publication date: 1992-12-23
Also published as: NZ243075A

Abstract

A degreaser composition comprises an oil comprising a substantially paraffinic monounsaturated wax ester and an emulsifier or an emulsifier blend. The preferred oil is a fish oil extracted from Orange Roughy and Dory that has been treated in a transesterification process. The transesterification process comprises mixing the fish oil, an alcohol and an acid catalyst, and heating the mixture at a temperature between 40 and 150 °C for a prescribed time.

Description

DEGREASER COMPOSITION COMPRISING MONOUNSATURATED WAX ESTER

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.

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 fish oil.

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. 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

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 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 012 and 20 times the amount of the fish oil on a molar basis. It is preferred that the alcohol comprises one or more of methanol, ethanol, n-propanol, iso-propanol, ethylene glycol, propylene glycol, and isomers or

butanol.

It is preferred that in step (a) 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.

It is particularly preferred that the acid catalyst s an alkyl or arylalkylsulphonate. The present invention is described further in the following examples.

Example 1 - Production of Transesterified Fish Oil

600 kg of Orange Rouphy oil, 450 l of ethanol and 10 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% 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 % Wax %

C 14 1.0 2.1

C 16 0.9 5.1

C 18 Tr 6.0

Unsaturated

C 14-15 Tr Tr

C-16:l 4.1 3.2

C-17 Tr Tr

C-18:l 26.0 14.0

C-20:l 8.1 7.0

C-22:l 3.1 5.6 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 Rouphy 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 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

temperature of the mixture (78°C) over 2 hours and maintained at that temperature for 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 pour point of 1ºC. Example 4 - Performance Characteristics of De-greaser 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.

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 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 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 by 15 cm plates of mild steel, and the plates were

subsequently treated as follows: (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) Ineffective Not tested

(2) Effective Not evident

(3) Effective Not evident

(4) Effective Not evident

(5) Effective Not evident

(6) Effective Slight

(7) Effective Severe

(8) Effective Severe

The results indicate that formulation 1 was an ineffective de-greaser, formulations 2 to 8 were 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.

Claims

THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 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 no or at most a low concentration of 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 coil 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 Rouphy (Hoplostethus alanticus) and Dory.

7. The composition defined in claim 5 or claim 6, wherein the fish oil is chemically modified by 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 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.

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.

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

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 or 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.

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