US20060183649A1

US20060183649A1 - Natural and synthetic sodium sulfonate emulsifier blends

Info

Publication number: US20060183649A1
Application number: US11/326,210
Authority: US
Inventors: Michael Costello; Igor Riff; Joseph Weaver; Rebecca Seibert
Original assignee: Chemtura Corp
Current assignee: Lanxess Solutions US Inc
Priority date: 2005-02-15
Filing date: 2006-01-04
Publication date: 2006-08-17
Also published as: WO2006089310A1; KR20070110282A; JP2008529776A; EP1848525A1

Abstract

An emulsifier composition includes at least one natural alkali metal petroleum sulfonate and at least one synthetic alkali metal sulfonate. The emulsifier composition can be combined with a lubricant oil to provide a water-miscible lubricating oil concentrate which forms a stable aqueous emulsion upon the addition thereto of an aqueous medium.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims priority to U.S. provisional application Ser. No. 60/653,685 filed Feb. 15, 2005 to which priority is claimed and which is herein incorporated by reference.

BACKGROUND

1. Field of the Invention
The present invention relates to an emulsifier composition including a blend of natural and synthetic sodium sulfonates.
2. Background of the Art
Sodium petroleum sulfonates are widely used as the primary emulsifier in formulating emulsifiable lubricating compositions used for cutting fluid, hydraulic fluids, metalworking lubricants, and so forth.
Sodium petroleum sulfonates are typically produced as a by-product of refining processes in which certain highly refined petroleum products such as white lubricating oils, medicinal oils, and certain grades of transformer oils, are produced. The highly refined petroleum products are produced by treating a refined petroleum distillate or raffinate with fuming sulfuric acid which reacts with certain components of the oil to produce sulfonic acids, some of which are oil-soluble and some of which are water-soluble, thus forming a two-phase system. The two phases separate into two layers one of which is the oil layer containing the oil-soluble reddish-brown or mahogany sulfonic acids, and one of which is the water-soluble layer commonly referred to as an acid sludge layer that contains resinous materials, unreacted sulfuric acid, and water-soluble or green sulfonic acids. The layers are then separated and the oil-soluble sulfonic acids are recovered from the oil layer, usually in the form of their sodium salts.
The mahogany sulfonic acids being preferentially oil-soluble have found wide use in the preparation of emulsifiable petroleum products, such as in soluble cutting oils, hydraulic fluids, metalworking lubricating fluids for forming of metals, and so forth. The acid oil layer is neutralized to make a sodium salt and extracted with a polar solvent, typically alcohol, to separate most of the oil phase, and to increase the activity of the sodium sulfonate. This type of process is discussed generally in U.S. Pat. No. 1,930,488. The manufacture of white oils by the above process has become increasingly uneconomical and as a result, the production of sulfonates as by-products of white oil refining is substantially declining. This has left a significant shortage of sodium petroleum sulfonates.
Another major disadvantage with the natural petroleum sulfonates is their inconsistency in quality, and hence a variance in their emulsifying properties. In order to improve emulsification properties, secondary surface active agents of different types are often added, for instance, fatty acid salts. The amount of the secondary surface active agent used is varied depending on the quality of the sulfonate being employed. U.S. Pat. No. 4,140,642 describes an improved emulsifier composition in which salts of alkylaryl sulfonic acids are employed with an organic or mineral base, and in which the equivalent weights of the acids are distributed according to a function of C=f(M) where C denotes the concentration and M denotes the equivalent weight of individual acids, which function has two distinct equivalent weight maximum M₁and M₂, with M₁<M₂. Surprisingly, the present inventors have found a blend of sulfonates that provides an emulsifier composition that has consistent emulsification properties, and that is economical as well. This blend comprises at least one natural alkali metal petroleum sulfonate that is not prepared as a by-product of an oil refining process and may be non-extracted, and a blend of other high active synthetic sulfonates or sulfonic acids selected so as to produce an emulsification system that has 60% or greater active content, and selected so as to balance the oil solubility and emulsification performance thus providing an excellent surfactant system.

SUMMARY

An emulsifier composition is provided herein which includes a blend of at least one natural alkali metal petroleum sulfonate, and at least one synthetic alkali metal sulfonate. Preferably, the blend includes at least about 30% by weight of a synthetic alkali metal sulfonate including at least about 30% by weight of alkali metal branched dodecylxylene sulfonate having an equivalent weight of from about 500 to about 550.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENT(S)

The present invention relates to a blend of natural and synthetic alkali metal sulfonates, preferably sodium sulfonates. Natural sodium sulfonates are produced by the sulfonation of petroleum fractions derived from naturally occurring crude oil. Synthetic sodium sulfonates are produced by the sulfonation of selected hydrocarbon compounds such as linear or branched alkyl or alkylaromatic compounds.
The following list of sulfonates in Table 1 is illustrative of the various sulfonates which can be blended to make a product that has emulsion performance equal to, or better than, that of Shell Reg (465). The sulfonates are commercially available and are provided with designations herein for purposes of identifying the sulfonates corresponding to the test results in the Examples below.

Table 1

Sulfonate Description

- Sulfonate A sodium salt of a straight chained mono- and dialkylbenzene sulfonate with an equivalent weight of about 510 to about 530, preferably about 520
- Sulfonate B sodium salt of a straight chained mono- and dialkylbenzene sulfonate with an equivalent weight of about 420 to about 440, preferably about 430
- Sulfonate C sodium salt of a straight chained mono- and dialkylbenzene sulfonate with an equivalent weight of about 450 to 470, preferably about 460
- Sulfonate D sodium salt of synthetic sulfonate with an equivalent weight of about 480 to 500, preferably about 490
- Sulfonate E sodium salt of the blend of sulfonates from a 600 SUS mineral oil, C₁₂-C₁₄dialkylbenzene sulfonate and a C₂₀-C₂₄mono alkylbenzene sulfonate with an equivalent weight of about 510 to about 530, preferably about 520
- Sulfonate F sodium salt of a linear C₁₂-C₁₄alkylxylene sulfonate with an equivalent weight of about 370 to about 390, preferably about 380
- Sulfonate G sodium salt of a linear benzene sulfonate with an equivalent weight of about 450 to about 470, preferably about 460
- Sulfonate H sodium salt of a blend of sulfonates from a 600 SUS mineral oil, C₁₂-C₁₄dialkylbenzene sulfonate and a C₂₀-C₂₄mono alkylbenzene sulfonate with an equivalent weight of about 510 to about 530, preferably about 520
- Sulfonate I sodium salt of the sulfonate from a mineral oil yielding an equivalent weight of about 540 to about 560, preferably about 550
- Sulfonate J sodium salt of a synthetic sulfonate
- Sulfonate K sodium salt of a synthetic sulfonate
- Sulfonate L sodium salt of a sulfonate
- Sulfonate M sodium salt of a sulfonate from mineral oil with an equivalent weight of about 440 to about 460, preferably about 450
- Sulfonate N sodium salt of the sulfonate from mineral oil with an equivalent weight of about 490 to about 510, preferably about 500
- Sulfonate O sodium salt of tridecylbenzene sulfonate with an equivalent weight of about 330 to about 350, preferably about 340
- Sulfonate P sodium salt of dinonylnaphthalene sulfonate with an equivalent weight of about 460 to about 480, preferably about 470
- Sulfonate Q sodium salt of a sulfonate from a mineral oil yielding an equivalent weight of about 450 to about 470, preferably about 460
- Sulfonate R sodium salt of a sulfonate from a mineral oil yielding an equivalent weight of about 450 to about 470, preferably about 460
- Sulfonate S sodium salt of a sulfonate from a mineral oil yielding an equivalent weight of about 410 to about 430, preferably about 420
- Sulfonate T sodium salt of the sulfonate from the co-sulfonation of a 600 SUS mineral oil and straight chain dialkyl (C₁₂-C₁₄)benzene sulfonate with an equivalent weight of about 515 to about 535, preferably about 527
- Sulfonate U sodium salt of the co-sulfonation of mineral oil and linear dodecylxylene blended with sodium dodecylbenzene sulfonate and straight chained mono- and dialkylbenzene sulfonate with a equivalent weight of about 420 to about 440, preferably about 430
- Sulfonate V sodium salt of a sulfonate from a mineral oil yielding an equivalent weight of about 580 to about 600, preferably about 590
- Sulfonate W sodium salt of a sulfonate from a mineral oil yielding an equivalent weight of about 450 to about 460, preferably about 455
- Sulfonate X sodium salt of a blend of sulfonates from a 600 SUS mineral oil, C₁₂-C₁₄dialkylbenzene sulfonate and a C₂₀-C₂₄mono alkylbenzene sulfonate with an equivalent weight of about 510 to about 530, preferably about 520
- Sulfonate Y sodium salt of a sulfonate from a mineral oil yielding an equivalent weight of about 560 to about 570, preferably about 565
- Sulfonate Z sodium salt of a sulfonate from a mineral oil yielding an equivalent weight of about 450 to about 470, preferably about 460
- Sulfonate AA sodium salt of an alkylaromatic sulfonate with an equivalent weight of about 510 to about 530, preferably about 520
- Sulfonate AB sodium salt of a branched dodecylortho-xylene sulfonate with an equivalent weight of about 380 to about 400, preferably about 390

Synthetic sodium sulfonates suitable for use in such blends include Sulfonate AA, a sodium salt of an alkyl aromatic sulfonate having an equivalent weight (“EW”) of about 520, and/or Sulfonate AB, a sodium salt of a branched dodecyl orthoxylene sulfonate having an equivalent weight of about 390. A preferred blend includes at least about 30% by weight of a sodium salt of Sulfonate AA, preferably from about 40% to 90%, and yet more preferably from about 50% to 80%.
Suitable examples of natural sodium sulfonates can include, for example, Sulfonate S, a low molecular weight (420 EW) sodium petroleum sulfonate, and Sulfonate R, a medium molecular weight (460 EW) sodium petroleum sulfonate. Also suitable as a source of natural sodium sulfonate is Sulfonate T, the product of the sulfonation of a blend of 600 SUS petroleum oil (56-59 wt %) and a straight chain C₁₂-C₁₄dialkylbenzene alkylate.
The proportions of natural and synthetic sulfonates present in the emulsifier blends can vary widely. In general, the emulsifier blend prepared in accordance with this invention can contain from about 10 to about 70, preferably from about 20 to about 60, and more preferably from about 30 to about 50, weight percent natural petroleum sulfonate emulsifier(s), the remainder of the emulsifier blend being made up of the synthetic emulsifier(s).
To prepare a water-miscible lubricating oil concentrate, a sufficient amount of emulsifier blend as described above is substantially uniformly admixed with a quantity of lubricating oil (“base oil”) such that upon addition of an aqueous medium thereto a stable oil-in-water emulsion will result.
Preferred lubricating oils have a kinematic viscosity in the range of from 1 to about 1,000 cSt at a temperature of 40° C. Suitable lubricating oils include mineral oils and synthetic oils. Examples of mineral oils include a distilled oil which can be obtained by distilling a paraffinic crude oil, an intermediate crude oil or a naphthenic crude oil under atmospheric pressure, or by distilling, under reduced pressure, a residual oil at the time of distillation under atmospheric pressure, and a refined oil obtained by refining this distilled oil. Examples of the refined oil include a solvent-refined oil, a hydrogenation-refined oil, a dewaxed oil and a clay-treated oil. Examples of synthetic oils include a low-molecular weight polybutene, a low-molecular weight polypropylene, oligomers of a-olefins having 8 to 14 carbon atoms and hydrides thereof, alkylbenzenes, and alkylnaphthalenes. These mineral oils and synthetic oils can be used singly or in a combination of two or more thereof.
It is preferred that the lubricating oil contain from about 20 percent to about 60 percent by weight of a highly refined base oil having a kinematic viscosity of from about 30 to about 800 cSt at a temperature of 40° C., for example, a mineral oil having a sulfur content of about 500 ppm or less, preferably about 100 ppm or less, treated by a hydrogenation-refining process and/or a (co)polymer of an olefin, because the employment of the highly refined base oil tends to inhibit the generation of stains and rust on worked articles.
The amount of emulsifier blend to be added to a given weight of lubricating oil will, of course, depend on the nature of the emulsifier blend, the nature of the lubricating oil and other factors as those skilled in the art will readily appreciate. Optimum amounts of a particular emulsifier blend and a particular lubricating oil can be determined employing routine testing methods. In general, a lubricating oil concentrate in accordance with this invention can contain from 1 to about 50, preferably from 2 to about 30, and more preferably from about 5 to about 20, weight percent of emulsifier blend herein. The lubricating oil, in addition to the emulsifier blend, can contain up to about 10 weight percent fatty acid soap(s), up to about 10 weight percent extreme pressure lubricating agent(s), up to about 5 weight percent anti-corrosion agent(s) and up to 3 weight percent of one or more biostatic and/or biocidal agents. Such additives are well known to those with skill in the art and are commonly available.
The water-miscible lubricating oil concentrate herein upon addition to an aqueous medium, usually water, forms a stable aqueous emulsion suitable for a variety of applications, metalworking principally amongst them. Aqueous emulsions of the oil-in-water and water-in-oil type can be formed with the addition of from about 1 to about 50, preferably from about 2 to about 30 and more preferably from about 3 to about 20 weight parts of lubricating oil concentrate herein per 100 weight parts of water.
The following experimental results illustrate various aspects of the invention including blends which performed successfully and blends which did not form satisfactory emulsions. Evaluation of the emulsion performance of various blends was performed in accordance with the following method.

Samples were diluted in white mineral oil at a 6% sulfonate level. The sulfonates in white oil were tested alone (100%) and in blends of sulfonates at 10 wt % intervals from 10 to 90% for emulsion performance. The emulsion test method used 10 mls of the test blend emulsified in 90 mls deionized water by shaking a stoppered graduated cylinder. The emulsions were rated after 24 hours. The rating system employed was zero to 5 with zero representing an emulsion that had no distinct separation between any cream and the emulsion layer. The rating of 5 indicated a nearly complete separation or oil and water with little or no haziness in the water layer. The following numerical rating scale was used.

TABLE 2


Emulsion Rating Scale

Rating	Description

0	Superior - completely white emulsion with little or
	no separation
0.5
1	Excellent - white cream with white milky emulsion layer
1.5
2	Good - trace oil, with white milky emulsion layer.
2.5
3	Fair - small oil layer, weak milky emulsion layer
3.5
4	Poor - oil layer, skim milky emulsion layer
4.5
5	Negative - oil layer, possible small white cream
	layer, watery emulsion layer

The emulsion results and equivalent weights for the unblended sulfonates are given in Table 2. Of the unblended 22 sulfonates tested, only Sulfonate AA and Sulfonate U gave emulsions. Sulfonate AA was unexpectedly good considering its high molecular weight (520) and was similar to petroleum derived products like Sulfonate S or Sulfonate Q.

TABLE 3


Emulsion Results for Sulfonates

		Equivalent
Sulfonate	Rating	Weight	Type of Sulfonate

Sulfonate AA	0.5	520	Branched
			dodecylxylene
Sulfonate U	2.5	420	Blend
Sulfonate AB	4.5	390	Alkylaromatic
Sulfonate F	5	390	Linear dodecylxylene
Sulfonate B	5	390	Alkylaromatic
Sulfonate C	5	395	Alkylaromatic
Sulfonate J	5	Low	Alkylaromatic
Sulfonate M	5	445	Petroleum
Sulfonate K	5	Medium	Alkylaromatic
Sulfonate W	5	458	Petroleum
Sulfonate G	5	460	Alkylaromatic
Sulfonate L	5	461
Sulfonate P	5	485	Dialkylnaphthalene
Sulfonate D	5	490	Synthetic
Sulfonate N	5	500	Petroleum
Sulfonate E	5	510	Blend
Sulfonate H	5	510	Blend
Sulfonate X	5	510	Blend
Sulfonate I	5	540	Petroleum
Sulfonate Y	5	540	Petroleum
Sulfonate V	5	600	Petroleum
Sulfonate A	49 mls emulsion &	520	Alkylaromatic
	51 mls water

Various binary blends were tested for emulsion performance. Table 4 illustrates the best performing blends of those tested, and is a compilation of Tables 3 and 5 through 14.

TABLE 4


Best Binary Blends

		% of	% of
Sulfonate 1	Sulfonate 2	Sulfonate 1	Sulfonate 2	Rating

Sulfonate AA	—	100		0.5
″	Sulfonate B	50	50	0
″	Sulfonate E	90	10	0
″	Sulfonate I	80	20	0
″	Sulfonate F	80	20	1-1.5
″	Sulfonate J	80	20	0
″	Sulfonate K	60	40	2-2.5
″	Sulfonate L	80	20	0.5
″	Sulfonate M	40-80	60-20	1-1.5
″	Sulfonate N	40-80	60-20	1-1.5
″	Sulfonate P	80	20	0
″	Sulfonate V	90	10	1-1.5
″	Sulfonate W	80	20	2-2.5
″	Sulfonate X	90	10	0
″	Sulfonate Y	90	10	0
″	Sulfonate E	80	20	2-2.5
″	Sulfonate I	45	55	1-1.5
″	Sulfonate V	40	60	0
″	Sulfonate U	90	10	2-2.5
″	Sulfonate X	75	25	1-1.5
″	Sulfonate Y	70	30	2-2.5

Of the above listed sulfonates, Sulfonate I, Sulfonate M, Sulfonate N, Sulfonate V, Sulfonate W and Sulfonate Y were natural sodium petroleum sulfonates.
Table 5 illustrates the emulsion test results of the combinations of Sulfonate AB with the various sulfonates listed above. As can be seen, Sulfonate AB produced stable emulsions when blended in certain proportions with Sulfonate AA, Sulfonate I, Sulfonate E, Sulfonate U, Sulfonate Y, Sulfonate X and Sulfonate V.
Table 6 illustrates the emulsion test results of the combinations of Sulfonate AA with the various sulfonates listed above. Sulfonate AA produced stable emulsions when blended in certain proportions with Sulfonate B, Sulfonate I, Sulfonate P, Sulfonate E, Sulfonate F, Sulfonate Y, Sulfonate L, Sulfonate X, Sulfonate V, Sulfonate W, Sulfonate J, Sulfonate K, Sulfonate M and Sulfonate N.
Tables 7 to 15 illustrate the emulsion test results for sulfonate combinations with respectively Sulfonate F, Sulfonate Y, Sulfonate A, Sulfonate J, Sulfonate X, Sulfonate K, Sulfonate M, Sulfonate V and Sulfonate G. As can be seen, none of these sulfonate blends provided satisfactory emulsifier compositions.

Referring now to Table 16 below, binary blends with Sulfonate R were best when the Sulfonate R was combined with Sulfonate AA, although Sulfonate AB also provided satisfactory emulsion test results as well as Sulfonate F, Sulfonate J, Sulfonate M and Sulfonate N.

TABLE 5


Emulsions on Blends with Sulfonate AB

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
AB	AB	AA	B	C	A	D	G	I	P	E	F

10	—	1.5	5	5	5	5	5	5	5	5	5
20	—	2	5	5	5	5	5	5	5	5	5
30	—	2.5	5	5	5	5	5	5	5	5	5
40	—	4	5	5	5	5	5	1	5	5	5
50	—	4	5	5	5	5	5	1.5	5	4	5
60	—	4.5	5	5	5	5	5	1.5	5	4.5	5
70	—	4.5	5	5	5	5	5	3	5	4.5	5
80	—	4.5	5	5	5	5	5	3.5	5	2.5	5
90	—	4.5	5	5	5	5	5	4	5	2.5	5

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
AB	U	Y	L	X	V	W	J	K	H	M	N

10	2.5	5	5	5	5	5	5	5	5	5	5
20	2.5	5	5	5	5	5	5	5	5	5	5
30	2.5	5	5	5	5	5	5	5	5	5	5
40	3	5	5	5	5	5	5	5	5	5	5
50	3	5	5	5	5	5	5	5	4	5	5
60	3	5	5	5	0	5	5	5	4	5	5
70	3	2.5	5	1	0.5	5	5	5	4.5	5	5
80	5	2.5	5	1	0.5	5	5	5	4.5	5	5
90	5	3	5	2.5	2.5	5	5	5	5	5	5

(—) Same sulfonate
(x) Results on another table

TABLE 6


Emulsions on Blends with Sulfonate AA

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
AA	AB	AA	B	C	A	D	G	I	P	E	F

10	x	—	5	4	5	5	5	5	5	5	4.5
20	x	—	5	4	5	5	5	5	5	5	4
30	x	—	4	4	5	5	5	5	5	5	2.5
40	x	—	0.5	4	5	5	5	5	5	5	2.5
50	x	—	0	4	5	5	4	5	5	5	2
60	x	—	0.5	5	4	5	4	2.5	5	5	2
70	x	—	4	5	4	5	4	0	2.5	5	1
80	x	—	5	5	4	5	4	0	1	5	1
90	x	—	5	5	4	3	4	0	2.5	0	1

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
AA	U	Y	L	X	V	W	J	K	H	M	N

10	x	5	5	5	5	5	5	5	5	5	5
20	x	5	5	5	5	5	5	5	5	5	5
30	x	5	5	5	5	5	2.5	5	5	2.5	5
40	x	5	5	5	5	5	2.5	5	5	1	1
50	x	5	5	5	5	5	2.5	5	5	1	1
60	x	5	3	5	5	5	2	2.5	5	1	1
70	x	5	2.5	5	5	5	1.5	2.5	5	1	1
80	x	1.5	0.5	2	2	2.5	1.5	2.5	5	1	1
90	x	0	1	0	1	2.5	2.5	2.5	5	2.5	2.5

(—) Same sulfonate
(x) Results on another table

TABLE 7


Emulsions on Blends with Sulfonate F

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
F	AB	AA	B	C	A	D	G	I	P	E	F

10	x	x	5	5	5	4.5	5	5	5	5	—
20	x	x	5	5	5	4.5	5	5	5	5	—
30	x	x	5	5	5	4.5	5	5	5	5	—
40	x	x	5	5	5	5	5	5	5	5	—
50	x	x	5	5	5	5	5	5	5	5	—
60	x	x	5	5	5	5	5	4.5	5	5	—
70	x	x	5	5	5	5	5	4	5	5	—
80	x	x	5	5	5	5	5	4	5	4.5	—
90	x	x	5	5	5	5	5	4.5	5	4	—

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
F	U	Y	L	X	V	W	J	K	H	M	N

10
20
30
40
50
60
70
80
90

(—) Same sulfonate
(x) Results on another table

TABLE 8


Emulsions on Blends with Sulfonate Y

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
Y	AB	AA	B	C	A	D	G	I	P	E	F

10	x	x					5				x
20	x	x					5				x
30	x	x					5				x
40	x	x					5				x
50	x	x					5				x
60	x	x					5				x
70	x	x					5				x
80	x	x					5				x
90	x	x					5				x

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
Y	U	Y	L	X	V	W	J	K	H	M	N

10		—	5	5	5		5	5		5
20		—	5	5	5		5	5		5
30		—	5	5	5		5	5		5
40		—	5	5	5		5	5		5
50		—	5	5	5		5	5		5
60		—	5	5	5		5	5		5
70		—	5	5	5		5	5		5
80		—	5	5	5		5	5		5
90		—	5	5	5		5	5		5

(—) Same sulfonate
(x) Results on another table

TABLE 9


Emulsions of blends with Sulfonate A

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
A	AB	AA	B	C	A	D	G	I	P	E	F

10	x	x			—						x
20	x	x			—						x
30	x	x			—						x
40	x	x			—						x
50	x	x			—						x
60	x	x			—						x
70	x	x			—						x
80	x	x			—						x
90	x	x			—						x

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
A	U	Y	L	X	V	W	J	K	H	M	N

10		x					5	5
20		x					5	5
30		x					5	4
40		x					5	4
50		x					5	4
60		x					5	4
70		x					5	4
80		x					4	4
90		x					4	4

(—) Same sulfonate
(x) Results on another table

TABLE 10


Emulsions on Blends with Sulfonate J

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
J	AB	AA	B	C	A	D	G	I	P	E	F

10	x	x			x		5		5
20	x	x			x		5		5
30	x	x			x		5		5
40	x	x			x		5		5
50	x	x			x		5		5
60	x	x			x		5		5
70	x	x			x		5		5
80	x	x			x		5		5
90	x	x			x		5		5

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
J	U	Y	L	X	V	W	J	K	H	M	W

10		x	5	5	5	5	—	5		5	5
20		x	5	5	5	5	—	5		5	5
30		x	5	5	5	5	—	5		5	5
40		x	5	5	5	5	—	5		5	5
50		x	5	5	5	5	—	5		5	5
60		x	5	5	5	5	—	5		5	5
70		x	5	5	5	5	—	5		5	5
80		x	5	5	5	5	—	5		5	5
90		x	5	5	5	5	—	5		5	5

(—) Same sulfonate
(x) Results on another table

TABLE 11


Emulsions on Blends with Sulfonate X

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
X	AB	AA	B	C	A	D	G	I	P	E	F

10	x	x	5				5
20	x	x	5				5
30	x	x	5				5
40	x	x	5				5
50	x	x	5				5
60	x	x	5				5
70	x	x	5				5
80	x	x	5				5
90	x	x	5				5

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
X	U	Y	L	X	V	W	J	K	H	M	N

10		x	x	—	5		x	5		5
20		x	x	—	5		x	5		5
30		x	x	—	5		x	5		5
40		x	x	—	5		x	5		5
50		x	x	—	5		x	5		5
60		x	x	—	5		x	5		5
70		x	x	—	5		x	5		5
80		x	x	—	5		x	5		5
90		x	x	—	5		x	5		5

(—) Same sulfonate
(x) Results on another table

TABLE 12


Emulsions on Blends with Sulfonate K

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
K	AB	AA	B	C	A	D	G	I	P	E	F

10	x	x			x		5		5
20	x	x			x		5		5
30	x	x			x		5		5
40	x	x			x		5		5
50	x	x			x		5		5
60	x	x			x		5		5
70	x	x			x		5		5
80	x	x			x		5		5
90	x	x			x		5		5

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
K	U	Y	L	X	V	W	J	K	H	M	N

10		x	5	x	5		x	—		5	5
20		x	5	x	5		x	—		5	5
30		x	5	x	5		x	—		5	5
40		x	5	x	5		x	—		5	5
50		x	5	x	5		x	—		5	5
60		x	5	x	5		x	—		5	5
70		x	5	x	5		x	—		5	5
80		x	5	x	5		x	—		5	5
90		x	5	x	5		x	—		5	5

(—) Same sulfonate
(x) Results on another table

TABLE 13


Emulsions on Blends with Sulfonate M

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
M	AB	AA	B	C	A	D	G	I	P	E	F

10	x	x			5		5		5
20	x	x			5		5		5
30	x	x			5		5		5
40	x	x			5		5		5
50	x	x			5		5		5
60	x	x			5		5		5
70	x	x			5		5		5
80	x	x			5		5		5
90	x	x			5		5		5

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
M	U	Y	L	X	V	W	J	K	H	M	N

10		x		x			x	x		—
20		x		x			x	x		—
30		x		x			x	x		—
40		x		x			x	x		—
50		x		x			x	x		—
60		x		x			x	x		—
70		x		x			x	x		—
80		x		x			x	x		—
90		x		x			x	x		—

(—) Same sulfonate
(x) Results on another table

TABLE 14


Emulsions on Blends with Sulfonate V

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
V	AB	AA	B	C	A	D	G	I	P	E	F

10	x	x					5
20	x	x					5
30	x	x					5
40	x	x					5
50	x	x					5
60	x	x					5
70	x	x					5
80	x	x					5
90	x	x					5

% Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-	Sulfo-
nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate	nate
V	U	Y	L	X	V	W	J	K	H	M	N

10		x	5	x	—		x	x
20		x	5	x	—		x	x
30		x	5	x	—		x	x
40		x	5	x	—		x	x
50		x	5	x	—		x	x
60		x	5	x	—		x	x
70		x	5	x	—		x	x
80		x	5	x	—		x	x
90		x	5	x	—		x	x

(—) Same sulfonate
(x) Results on another table

TABLE 15


Emulsions on Blends with Sulfonate G

% Sulfonate G	Sulfonate AB	Sulfonate AA	Sulfonate B	Sulfonate C	Sulfonate A	Sulfonate D	Sulfonate G	Sulfonate I

10	x	x					—
20	x	x					—
30	x	x					—
40	x	x					—
50	x	x					—
60	x	x					—
70	x	x					—
80	x	x					—
90	x	x					—

% Sulfonate G	Sulfonate P	Sulfonate E	Sulfonate F	Sulfonate U	Sulfonate Y	Sulfonate L	Sulfonate X	Sulfonate V

10			x		x	5	x	x
20			x		x	5	x	x
30			x		x	5	x	x
40			x		x	5	x	x
50			x		x	5	x	x
60			x		x	5	x	x
70			x		x	5	x	x
80			x		x	5	x	x
90			x		x	5	x	x

% Sulfonate G	Sulfonate W	Sulfonate J	Sulfonate K	Sulfonate H	Sulfonate M	Sulfonate N

10		x	x		x
20		x	x		x
30		x	x		x
40		x	x		x
50		x	x		x
60		x	x		x
70		x	x		x
80		x	x		x
90		x	x		x

(—) Same sulfonate
(x) Results on another table

TABLE 16


Emulsions on Binary Blends with Sulfonate R

% Sulfonate R	Sulfonate AB	Sulfonate AA	Sulfonate B	Sulfonate C	Sulfonate A	Sulfonate D	Sulfonate G	Sulfonate I

0	4.5	0.5	5	?	5	5	5	5
10		1.5
20	2.5	0
30	2.5	0
40	2.5	1.5
50	2.5	2.5
60	1.5	2.5						5
70	2.5	2.5						1.5
80	2.5	2.5	5	5	5	5	5	2
90
100	2.5	2.5	2.5	2.5	2.5	2.5	2.5	2.5

% Sulfonate R	Sulfonate P	Sulfonate E	Sulfonate F	Sulfonate U	Sulfonate Y	Sulfonate L	Sulfonate X	Sulfonate V

0	5	5	2.5	5	5	5	5	5
10
20			4
30
40			4
50			3
60			2.5
70			2.5
80	5	5	1.5	5	5	5	5	5
90			1.5
100	2.5	2.5	2.5	2.5	2.5	2.5	2.5	2.5

% Sulfonate R	Sulfonate W	Sulfonate J	Sulfonate K	Sulfonate H	Sulfonate M	Sulfonate N

0	5	5	5		5	5
10
20		5
30		2.5
40		1.5	5		5
50		1.5			3.5	5
60		1.5	5		2.5	3.5
70		2.5	5		1	3.5
80	5	2	2	5	2	2
90			1		1	1
100	2.5	2.5	2.5	2.5	2.5	2.5

0
0.5
1-1.5 Petronate L and HL-I
2-2.5 Equal Equilon HL
5 No emulsion

The natural alkali metal petroleum sulfonate can also be combined with more than one synthetic alkali metal sulfonate in ternary mixtures. For example, Table 17 below sets forth emulsion test results for various combinations of Sulfonate R (natural sodium petroleum sulfonate) with Sulfonate X and Sulfonate O. The designation “B&C” refers to quality of blending and clarity. “Hazy/Sep” indicates a hazy condition with separation of the emulsion. The emulsion ratings are as indicated above.

TABLE 17


Ternary Blend to Sulfonate R

			Oil Blend
Sulfonate R	Sulfonate X	Sulfonate O	Clarity	Emulsion

100	0	0	B&C	2.5
90	0	10	B&C	2
85	0	15	B&C	2
80	0	20	Hazy/Sep	4.5
80	5	15	B&C	2
80	10	10	B&C	3
80	20	0	B&C	4.5
75	5	20	B&C	2.5
70	5	25	Hazy	2.5
70	10	20	B&C	2
70	20	10	B&C	5
65	10	25	B&C	2.5
60	10	30	Hazy	5
60	15	25	B&C	3.5
60	20	20	B&C	4.5
55	20	25	B&C	3.5
50	15	35	Hazy/Sep	2.5
50	20	30	Hazy/Sep	2.5
50	25	25	B&C	3.5
50	30	20	B&C	4.5
50	35	15	B&C	5
50	40	10	B&C	5
50	50	0	B&C	5

As can be seen, the best ternary mixtures were those in which the natural petroleum Sulfonate R comprised at least about 50% of the mixture and the amount of Sulfonate O exceeded the amount of Sulfonate X.
While the above description contains many specifics, these specifics should not be construed as limitations of the invention, but merely as exemplifications of preferred embodiments thereof.

Claims

1. An emulsifier composition comprising a blend of:

a) at least one natural alkali metal petroleum sulfonate; and

b) at least one synthetic alkali metal sulfonate.

2. The emulsifier composition of claim 1 wherein the alkali metal is sodium.

3. The emulsifier composition of claim 1 wherein the synthetic alkali metal sulfonate is produced by the sulfonation of linear or branched alkyl or alkylaromatic compounds.

4. The emulsifier composition of claim 1 comprising at least 30% by weight of the synthetic alkali metal sulfonate.

5. The emulsifier composition of claim 1 wherein the synthetic alkali metal sulfonate comprises a synthetic sodium branched dodecylxylene sulfonate having an equivalent weight of from about 500 to about 550.

6. The emulsifier composition of claim 1 comprises at least about 40% by weight of at least one synthetic sodium alkyl aromatic sulfonate having an equivalent weight of from about 350 to about 400 and wherein the natural alkali metal sulfonate comprises at least one natural sodium petroleum sulfonate.

7. The emulsifier composition of claim 1 further comprising:

c) an alkali metal salt of a mixed natural and synthetic sulfonate blend.

8. The emulsifier composition of claim 7 wherein the natural alkali metal sulfonate constitutes at least 50% by weight of the emulsifier composition and comprises the sodium salt of a sulfonate from a mineral oil yielding an equivalent weight of from about 450 to about 470.

9. The composition of claim 8 wherein the alkali metal salt of the mixed natural and synthetic sulfonate blend comprises the sodium salt of a blend of sulfonates from a mineral oil, a C₁₂-C₁₄dialkylbenzene sulfonate and a C₂₀-C₂₄monoalkylbenzene sulfonate with an equivalent weight of about 510 to about 530.

10. The composition of claim 9 wherein the synthetic alkali metal sulfonate comprises a sodium salt of tridecylbenzene sulfonate having an equivalent weight of from about 330 to about 350.

11. The composition of claim 10 wherein the quantity of the of synthetic sodium salt of the tridecylbenzene sulfonate exceeds the quantity of the sodium salt of the mixed natural and synthetic sulfonate blend.

12. A water-miscible lubricating oil concentrate which comprises:

a) at least one oil of lubricating viscosity, and

b) a blend of emulsifiers in admixture with the oil in an amount sufficient to provide a stable aqueous emulsion upon the addition of an aqueous medium thereto, the blend of emulsifiers comprising:

(i) at least one natural alkali metal petroleum sulfonate; and,

(ii) at least one synthetic alkali metal sulfonate.

13. The water-miscible lubricating oil concentrate of claim 12 wherein the oil of lubricating viscosity comprises a mineral and/or synthetic lubricating oil selected from the group consisting of oils obtained by the distillation of paraffinic crude oil, intermediate crude oil, naphthenic crude oil, petroleum residue, solvent refined oils, hydrogenation refined oils, dewaxed oils, clay treated oils, low molecular weigh polybutene, low molecular weight polypropylene, oligomers of alpha-olefins having from about 8 to about 14 carbon atoms, alkylbenzenes, alkylnaphthalenes and combinations thereof.

14. The water-miscible lubricating oil concentrate of claim 13 wherein the blend of emulsifiers constitutes from about 1% to about 50% by weight of the concentrate.

15. The water-miscible lubricating oil concentrate of claim 13 further comprising one or more additives selected from the group consisting of fatty acid soap, extreme pressure additive, anticorrosion agents, biostatic agents and biocidal agents.

16. The water-miscible lubricating oil concentrate of claim 13 wherein the synthetic alkali metal sulfonate comprises one or more of a sodium branched dodecylxylene sulfonate, sodium dinonylnaphthalene sulfonate, sodium tridecylbenzene sulfonate, sodium dodecylbenzene sulfonate or sodium dialkylbenzene sulfonate.

17. An aqueous lubricant oil-containing emulsion containing:

a) water; and

b) a water-miscible lubricating oil concentrate which comprises:

i) at least one oil of lubricating viscosity, and

ii) a blend of emulsifiers in admixture with the oil in an amount sufficient to provide a stable aqueous emulsion upon the addition of an aqueous medium thereto, the blend of emulsifiers including at least one natural alkali metal petroleum sulfonate, and at least one synthetic alkali metal sulfonate.

18. The aqueous lubricant oil-containing emulsion of claim 16 wherein the blend of emulsifiers further includes an alkali metal salt of a mixed natural and synthetic sulfonate blend.

19. The aqueous lubricant oil containing emulsion of claim 16, wherein said emulsion is a metalworking lubricant.