US3751373A - Petroleum sulfonic acid foam control composition and its use - Google Patents

Abstract

THE PRESENT INVENTION IS DIRECTED TO A COMPOSITION AND ITS USE FOR THE CONTROL OF FOAM IN AQUEOUS SYSTEMS AND IN PARTICULAR PULP AND PAPER MAKING SYSTEMS. THE METHOD GENERALLY COMPRISES ADDING TO THE AQUEOUS SYSTEM A COMPOSITION COMPRISING A WATER-INSOLUBLE ORGANIC LIQUID, AN ESTER OF POLYETHYLENE GLYCOL, A PETROLEUM SULFONIC ACID AND A TALLOW FATTY ACID AND/OR TALLOW FATTY ALCOHOL.

Description

United States Patent 3,751,373 PETROLEUM SULFONIC ACID FOAM CONTROL COMPOSITION AND ITS USE Hillel Lieberman, Andalusia, and Anthony J. Gralfeo, Willow Grove, Pa., assignors to Betz Laboratories, Inc., Trevose, Pa.

No Drawing. Filed Dec. 29, 1970, Ser. No. 102,553 Int. Cl. B01d 17/00 US. Cl. 252--321 13 Claims ABSTRACT OF THE DISCLOSURE The present invention is directed to a composition and its use for the control of foam in aqueous systems and in particular pulp and paper making systems. The method generally comprises adding to the aqueous system a composition comprising a water-insoluble organic liquid, an ester of polyethylene glycol, a petroleum sulfonic acid and a tallow fatty acid and/or tallow fatty alcohol.

BACKGROUND OF THE INVENTION As is well-known in the paper making industry, foam is an undesirable by-product which is encountered in different areas of the paper-making process. In any system where there is an aqueous medium which contains both dissolved and undissolved solids and where there is a great deal of agitation, foam is a potential problem. Since paper-making processes meet with all of the prerequisites, the systems are constantly being plagued by foam. Accordingly the industry is constantly seeking out new materials to either prevent or control foam during the paper-making process since the presence or absence of foam not only bears directly on the quality of the paper produced but also upon the economics of the process.

In this regard one might consider the Fourdrinier machine which although basically an excellent paper making system can be put out of operation by and until foam problems are brought within reasonable control.

Also of importance is the fact that although the foam situation may not be sufliciently severe to shut-down the machine, it may be so severe as to drastically affect its production speed. To mill personnel, this is not satisfactory since production is required to meet certain demands not only from the stand-point of quality but also from the stand-point of tons produced.

Areas in the Fourdriner machine where foam may become a problem, are areas such as the headbox, on the wire itself, the wire-pit, seal pits from the suction boxes and rolls, drop-leg and tray run-off, saveall, blend chest and machine chest.

One of the major finished products of integrated kraft pulp and paper mills is linerboard and linerboard is generally produced on large Fourdrinier Machines with dual headboxes. While most linerboard is made entirely from unbleached kraft with a minimum of additives (generally only rosin size and alum for pH adjustment), occasionally a better grade of linerboard is produced in which the top sheet, that portion of the board supplied by the second headbox, is of bleached or semi-bleached kraft. Foaming or air entrainment problems are frequently encountered on linearboard machines. In some cases the foam problem may occur ahead of the machine in the stock preparation system where it may be manifested by difficulty in pumping the stock. However, the most common foaming problems encountered in the production of linerboard are on the machine itself.

Foam and/or entrained air can cause bubbles on the wire, interference with drainage of water through the wire, breaks and uneven drying or poor moisture profile across the sheet. Foam formation in the wire pit can also 3,751,373 Patented Aug. 7, 1973 ice be a problem if the foam builds up to the point where it can touch the underside of the wire. Also it may be objectionable from an esthetic viewpoint or because the presence of such foam may have a disturbing influence on the operators who feel that something must be wrong when they see it. Although some mills do not feel that wire pit foam is harmful, it can entrap various types of debris that could contribute to problems in other areas of the machine system.

In most linerboard defoamer applications, continuous feed is required although some mills find that they require defoamer for only certain grades. In the majority of applications, the point of application is the wire pit or the suction side of the fan pump. Most mills feed the defoamer neat from the drum utilizing a diaphragm pump, sized to cover the maximum feed rate anticipated. Aspirator devices such as the Feedrator also can be used to feed the defoamer directly into a water line which then can be introduced to any desired point in the system. Some linerboard mills feed defoamer by gravity to the wire pit but this method of feed leads to very poor control.

In some linearboard applications the defoamer may be fed ahead of the machine at a point such as the machine chest or even ahead of the refiners. In such applications it may or may not be necessary to feed an additional amount of defoamer directly to the machine itself. In general, since the defoamer will tend to lose efficiency as it passes further along in the system, a lower total performance cost will be obtained feeding at one point in the stock preparation system with a supplementary feed at the machine rather than feeding enough at the one point ahead of the machine to control foam in the stock preparation system as well as on the machine.

Accordingly it was the present inventors goal to not only develop a foam control composition which was effective for the purpose but one which could also be fed easily and preferably automatically as with precision pumps.

The present inventors ascertained that the goals could be achieved with a composition comprising on a weight basis;

(i) from about 0.5% to about 30%, and preferably 2% to 15% of a tallow fatty acid having from 12 to 24 carbon atoms (preferably 16 to 18), and/or a tallow fatty alcohol having from 12 to 24 and preferably 16 to 18 carbon atoms;

(ii) from about 0.3% to about 20%, and preferably 0.3% to 4% of a petroleum sulfonic acid having a molecular weight from 400 to about 900, and preferably 400 to 500;

(iii) from about 0.1% to about 15% and preferably 0.5 to 12% of at least one mono or diester of polyethylene glycol with a fatty acid having from about 14 to 18, and preferably 16 to 18 carbon atoms; and preferably having a ethylene oxide content to produce a molecular weight of from 300 to 600;

(iv) from about 65% to 95%, and preferably to 93% of a water insoluble organic liquid such as vegetable oils, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated alicyclic hydrocarbons, halogenated aromatic hydrocarbons, long chain amines and the like.

The composition may additionally contain from about 0.5% to about 8% and preferably from about 2% to about 6% of a lower alkanol solubilizing agent such as the one to six carbon alcohols i.e. methanol, ethanol, isopropanol and hexanol.

Agents of this nature are used to provide cold temperature stability in those areas and applications which require this feature. The foregoing recitations relative to the composition, although the most effective are not necessarily the only percentages of each that may be utilized. The percentages recited represent the desirable ranges from both an effectiveness point of view and an economics point of consideration.

The effective and economic treatment levels for the inventive composition were determined to be within the range of from about 0.01% to about 1% b weight of the foam controlling composition based upon the weight of the dry solids content of the aqueous system. Although, as explained above, many factors can cause or contribute to the production, existence and maintenance of foam in an aqueous system, the prime factor is considered to be the solids content of the system. In many instances this factor has been used in the industry to approximate treatment levels. However the most general practice is to add on a weight basis from about 1 to about 100 parts of the composition per million parts of the aqueous systern, since most foam problems are controlled using treatment levels within this range. Although treatment levels above 1%, based upon solids content or 100 p.p.m. based weight of system, are quite effective in controlling foam, the use of excesses above these levels are prohibitive due to economic considerations. Accordingly the upper treatment level is predicated upon cost consideration rather than limit of effectiveness.

As a further explanation or description of the ingredients of the composition the following will be of help.

The tallow acids are basically the saturated and unsaturated mono and dicarboxylic fatty acids having from about 12 to 24 carbon atoms, and preferably 16 to 18 carbon atoms such as stearic acid, palmitic and oleic acid and mixtures thereof. In many instances the tallow acids as obtained are in fact mixtures of various fatty acids such as mixtures of palmitic, stearic and oleic acids. Likewise the tallow alcohols have from about 12 to 24 but normally from 16 to 18 carbon atoms.

Petroleum sulfonic acids and the metallic salts thereof e.g. calcium, magnesium, potassium and sodium salts, are usually obtained as a by-product of white oil manufacturing and lube stock refining, usually by the addition of sulfur trioxide to oils. The molecular weights of these particular derivatives range from about 400 to 900. Products of this type are obtainable under the trade names of Petronate HL and calcium Petronate.

The polyethylene glycol derivatives are those esters such as the mono-oleate, dioleate, mono and distearate, mono and dipalmitate esters. Moreover the derivatives may be the 300 to 600 derivatives such as polyethylene glycol 600 dioleate or the polyethylene glycol 300 monoleate. The number which appears after the polyethylene glycol in these designations represents the degree of polymerization of the polyethylene glycol. More specifically, this number indicates that the number of ethylene oxide units in the polymer is such as to yield a total molecular weight expressed in the number of the polymer designation.

The water-insoluble organic liquids which can be advantageously used in the composition are the vegetable oils, such as the water-insoluble edible oils which are extracted from seeds and which are generall considered to be mixtures of glycerides, the aliphatic hydrocarbons, the alicyclic hydrocarbons and the aromatic hydrocarbons and the halogenated derivatives thereof. These generic descriptions include many type carriers or liquids such as benzene, hexane, octane, mineral hydrocarbons such as the mineral oils (parafiinic oils, naphthenic oils, halogenated products thereof and kerosene). Mineral seal oil and similar petroleum fractions, synthetic polymers and halogenated products thereof, such as the liquid trifiuorovinyl chloride polymers, long chain alcohols such as nonyl alcohol and octyl alcohol, long chain esters such as diglycol laurate, and long chain amines such as octyl amine, nonyl amine and 2-ethyl-amino-heptane. In many instances these liquid carriers are not only water-insoluble but also hydrophobic.

The carrier liquid should be of such nature that its boiling point should be greater than 150 F. and its viscosity should be such as to be liquid at room temperature. In the case of mineral hydrocarbons a viscosity of about 30 to 400 SUS F.) has been found to be completely acceptable. From the vast number of water-insoluble liquids evaluated, it would appear that any liquid which possesses the aforementioned properties would be operable.

Spreading agents or surfactants which are commercially available such as sorbitan monostearate and the surfactants, decyl alcohol, silicone oils (Union Carbides L45) and the polyether triols of high molecular weight (Union Carbides LHT42) have been used successfully in the inventive compositions. These agents are generally included where rapid distribution of the defoamer in a particular system is required.

The composition of the invention can be made simply by mixing the ingredients thoroughly, heating the mixture to a temperature of from about to F. for a time to insure that the ingredients have been dissolved and thoroughly incorporated. The blend is then cooled slowly to 100 F. and at this point other ingredients such as the solubilizing agent may be added. The product is then ready for use. The heating is merely an expedient in the preparation, since products prepared without heating but with longer mixing times operate as effectively.

In order to determine the foam controlling capacity of the composition of the present invention, a test procedure was used which placed the sample stock solutions under agitation conditions similar to those experienced in the actual paper making process.

In order to more accurately assimulate the condition of a papermaking process, actual stock samples are either obtained directly from paper mills or the tests were conducted in the mill proper. These stock samples were approximately 0.5% consistency. More specifically, the stock is comprised of approximately 99.5% aqueous medium and approximately 0.5% fiber, filler, coloring agent, etc. The stock is that which would be fed from the headbox of a paper-making machine to the Fourdrinier wire Where paper or linerboard formation initially occurs.

The test procedure used required 600 milliliters of the stock solution.

TEST PROCEDURE The stock is circulated from a calibrated reservoir holding the stock to and through a pump and back to the reservoir. This action agitates the stock and simulates the conditions which are normally encountered during the paper making process. The reservoir is calibrated in centimeters in order to measure the foam height at various time intervals which is a mode of measuring the degree of foaming of a system or in other terms, the defoaming or antifoaming action of the composition. The height of the foam is noted at various intervals and the longer the time required for the foam to reach a certain level the better the inhibiting properties of the composition. The calibrations of the reservoir range from 0 to 300 centimeters with the normal slurry volume taking up the first 100 cm. A reading therefore of 100 means that essentially no foam formed during the respective period. The last reading is made when the foam overflows the reservoir or exceeds the 300 centimeter level.

When the overflow takes place, the pump is then turned oif. The test is an excellent measure of the defoaming characteristics of a composition since it is quite stringent.

SPECIFIC EXAMPLES In order to illustrate the effectiveness of the compositions of the present invention, the following compositions were prepared and tested in accordance with the test procedure outlined earlier. In order to accurately compare the various compositions, the compositions were all prepared in the same manner so as to avoid any variations in the composition other than the ingredients and the concentrations thereof. In order to obtain the best comparisons, the ingredients were, where desirable, kept the same.

The products were prepared by merely blending and mixing the ingredients and heating the blend at a temperature of 145 F. for a time suflicient to dissolve all of the soluble ingredients and to homogeneously mix the ingredients (e.g. 15 minutes). The composition was then allowed to cool, after which the lower alkanol, if used, was added and thoroughly mixed in and the product or composition was then ready for testing or use.

Example 1 The composition of this example contained the following ingredients in the respective percentage by weight listed:

Percent Kerosene. 79 Polyethylene glycol 600 dioleate 14 Tallow fatty acid (HCP, a mixture of primarily palmitic, stearic and oleic acids) Isopropanol 5 Example 2 The composition of this example was the same as Example 1 excepting that it contained 2% of a petroleum sultonic acid (Petronate HL) having a molecular weight ranging from about 400 to 460, an empirical formula of C H SO H, and an S content of about 17.5%. The amount of kerosene was proportionally decreased i.e. the composition contained 77% kerosene.

Example 3 The composition of the example contained:

Percent Acme S-l (a paraflinic oil having an SUS of 105 at 100 F.) 79 Polyethylene glycol 600 dioleate 14 Tallow fatty acid (mixture of primarily palmitic, stearic and oleic acids) Isopropanol 5 Example 4 The product was essentially the same as Example 3 except in that it contained 2% Petronate HL (see Example 1) and the polyethylene glycol 600 dioleate content was reduced to 12%.

Example 5 This product was essentially the same as that of Example 4 excepting that it contained 3% Petronate HL and the Acme S-lOS content was reduced to 78%.

Example 6 The composition of this example contained:

Percent Reprol (a paraifinic oil having an SUS of 40 at 100 Example 7 The composition of Example 6 excepting that it contains 2% Petronate HL and the Reprol content was reduced to 77%.

6 Example 8 The composition of this example contained:

Percent Reprol 76 Calcium Petronate (basic calcium salt of petroleum sulfonic acid and having a molecular weight of about 892) 3 HCP (note Example 1) 7 Sorbitan monostearate (surfactant) 0.5 Polyethylene glycol 600 monostearate 0.5 Alfol 1618C (see Example 6) 7.0 Isopropanol 6.0

Example 9 The composition of Example 8 excepting that Sodium Petronate was used in place of the Calcium Petronate. Sodium Petronate is the sodium salt of the petroleum sulfonic and the sodium Petronate has a molecular weight of about 450.

Example 10 This composition contained:

Percent Topas S-lOS (an oil composed of a mixture of paraffinic, naphthenic and aromati oils), SUS of at 100 F. 79 HCP (note Example 1) 8 Alfol 1618C (note Example 6) 3 Polyethylene glyol 400 dioleate 2 Polyethylene glycol 300 dioleate 2 Isopropanol 6 Example 11 This composition was essentially the same as that of Example 10 excepting that it contained 3% Petronate HL (see Example 1) and the oil content was reduced to 76% TESTS TABLE 1 Foam height after designated intervals in cm. Mill location from Composition which stock 30 60 90 Time (sec.) of sample obtained see. sec. sec. sec. of overflow 1 Example 1.... A S. Carolina mill 14. 5 Example 2 -.do 170 Example 3. 26. 0 Example 4. 81.3 Example 5. o... 106. 6 Example 6.... A Maryland milL- 30. 0 Example 7 ..do Example 6.-.- A Michigan mill 29.0 Example 7 ..do 225 270 62.0 Example 6..-- A Georgia mi 265 34. 0 Example 7 ..do 176 195 Example 6...- A Michigan mill.-. 255 37. 0 Example 8 ..do 160 205 245 118i ()1 Example 9 -do 73. 0 Example 10..- A Georgia mill.. 56. 3

Example 11 ..do

. 1 Time required for team to exceed 300 em, if measured.

1 N at measured.

From the foregoing tabulated results it is apparent that in every instance, the products containing the petroleum sulfonic acid or its metallic salt out-performed the products which were formulated essentially the same but did not contain the sulfonic acid derivative. The difference in efiectiveness in every case was quite substantial.

Because the test evaluations proved so successful for the inventive compositions, the following products were formulated together with a third product which did not contain the sulfonic acid derivative. These products were prepared as described for the earlier examples and composition-wise were as follows:

Products I and III were comparativey tested on the actual linerboard producing machine at a North Carolina mill. For the test all variables were maintained the same with respect to the paper making operation excepting the feed rates. In this type test the feed rates to control the foam within certain and acceptable limits is the comparison criteria. Product I to perform the particular function required a feed rate of approximately 14 cubic centimeters per minute. Product HI on the other hand required a feed rate of 25 cubic centimeters per minute and even at the feed rate control was sporadic.

Based upon the results of the mill test at the North Carolina mill, Products I and II were on-machine mill tested at a South Carolina mill which was producing Kraft linerboard. The products were fed at two locations on the machine, i.e. at the raw stock chest where the pH is 9-10 and at the machine chest when the pH is 5.2-5.3. Both Products I and II, on a cost-performance basis outperformed by 20% to 30% a competitor antifoam which was also being tested by mill personnel.

From the foregoing then it was evident that the inventive compositions operated effectively to achieve the goals demanded.

The foregoing examples were used as illustrations of the invention. Modifications of the invention i.e. increasing or decreasing the content of the respective materials within of course the range disclosed or the substitution of obvious equivalents also operate quite effectively for the purpose.

Accordingly having described the invention, what is claimed is:

1. A foam control composition comprising on a weight basis:

(i) from about 0.5% to about 30% of at least one tallow fatty acid or tallow fatty alcohol, said acid or alcohol having from about 12 to about 20 carbon atoms;

(ii) from about 0.3% to about 20% of a petroleum sulfonic acid having a molecular weight of from about 400 to about 900, or the metal salt of said sulfonic acid;

(iii) from about 0.1% to about 15% of a compound selected from the group consisting of polyethylene glycol mono-esters of fatty acids having from 14 to 18 carbon atoms, and polyethylene glycol diesters of fatty acids having from about 14 to 18 carbon atoms; and

(iv) from about 65% to about 98% of a water-insoluble liquid selected from the group consisting of vegetable oils, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated alicyclic hydrocarbons, halogenated aromatic hydrocarbons, and long chain amines.

2. A composition according to claim 1 which contains from about 0.5% to about 8% of a lower alkanol solubilizing agent.

3. A composition according to claim 1 wherein:

(i) the tallow fatty acid or alcohol has from about 16 to 18 carbon atoms and is present in an amount of from about 2% to about 15 (ii) the petroleum sulfonic acid has a molecular weight of from about 400 to 500 and is present in an amount of from about 1.0% to about 8%;

(iii) the polyethylene glycol ester is polyethylene glycol 6'00 dioleate and is present in an amount of from about 0.5% to 12%;

(iv) the organic liquid is a refined mineral oil and is present in an amount of about 75% to about 93%;

4. A composition according to claim 3 which contains from about 2% to about 6% of isopropanol.

5. A composition according to claim 3 wherein:

(i) the tallow acid is a mixture of stearic, palmitic and oleic acids and is present in an amount of about 2%;

(ii) the petroleum sulfonic acid is present in an amount of about 2%;

(iii) said glycol ester is present in an amount of about 8%; and

(iv) said mineral is paraflinic and is present in an amount of about 83%.

6. A composition according to claim 5 which contains about 5% of isopropanol.

7. A method of controlling foam in the aqueous system of a kraft pulp and paper mill system which comprises adding thereto an amount effective for the purpose of a composition comprising:

(i) from about 0.5 to about 30% of a tallow fatty acid or alcohol having from about 12 to about 20 carbon atoms;

(ii) from about 0.3% to about 20% of a petroleum sulfonic acid having a molecular weight of from about 400 to about 900, or the metal salt of said sulfonic acid;

(iii) from about 0.1 to about 15% of a compound se-- lected from the group consisting of polyethylene glycol mono-esters of fatty acids having from 14 to 18 carbon atoms and polyethylene glycol diesters of fatty acids having from about 14 to 18 carbon atoms; and

(iv) from about 65 to about 98% of a water-insoluble liquid selected from the group consisting of vegetable oils, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated alicyclic hydrocarbons, halogenated aromatic hydrocarbons, and long chain amines.

8. A method according to claim 7 wherein the compositron contains from about 0.5 to about 8% of a lower alkanol solubilizing agent.

9. A method according to claim 7 wherein:

(i) the tallow fatty acid or alcohol has from about 16 to 18 carbon atoms and is present in an amount of from about 2% to about 15%;

(ii) the petroleum sulfonic acid has a molecular weight of from about 400 to 500 and is present in an amount of from about 1% to about 8% (iii) the polyethylene glycol ester is polyethylene glycol 600 dioleate and is present in an amount of from about 0.5% to 12%.

(iv) the organic liquid is a mineral oil and is present in an amount of about 75 to about 93 10. A method according to claim 9 which contains from 13. A method according to claim 10 wherein the comabout 2% to about 6% of isopropanol. position is added to the aqueous system in an amount of 11. A method according to claim 9 wherein the; from about 1 to about 100 Parts P minion- (i) the tallow acid is a mixture of stearic, palmitic and oleic acids and is present in an amount of about 5 References C'ted 2%; UNITED STATES PATENTS (ii) the petroleum sulfonic acid is present in an amount 2,052,164 8/1936 Buc 252-358 ofabvutm; 2,544,564 3/1951 Peterson et a1. 252-321 (iii) said glycol ester is present in an amount of about 2,668,150 2/ 1954 Luvisi 25232l 8%;and 10 3,198,744 8/1965 Lamont 252-321 (iv) said mineral Oil is paraffinic and is present in an 1,9 ,641 6/1934 Mathias 25Z321 amount of about 83%. 12. A method according to claim 9 wherein the com- JOHN WELSH Primary Exammer position is added to the aqueous system in an amount of 5 U.S. C1. X.R. from about 1 to about 100 parts per million. 252-458