GB2041905A

GB2041905A - Defoamer for High Strength Acid Media

Info

Publication number: GB2041905A
Application number: GB7905781A
Authority: GB
Original assignee: Cities Service Co
Current assignee: Cities Service Co
Priority date: 1979-02-19
Filing date: 1979-02-19
Publication date: 1980-09-17

Abstract

A defoamer for controlling the foam in high strength acid media comprises a major part of a sulfonated petroleum oil and a minor part of a C4-C20-alcohol.

Description

SPECIFICATION Defoamer for High Strength Acid Media The invention is related to a surface active material, a defoamer. More particularly, this invention provides a defoamer and process for preparing such a defoamer, which controls the foam in high strength acid media, from petroleum products.

Conventional defoamers contain sulfonated tall oil-fatty acids. Some are produced from a refined oleic acid while others are produced from tall oil. The primary application of these defoamers is in the phosphate industry to control the foam in the digestion and concentration stages of wet-process phosphoric acid manufacture. In recent years cost of conventional defoamers has drastically increased because of the high cost of raw materials utilized in their manufacture. Therefore, what is needed is a defoamer which is at least as effective as the conventional defoamers being marketed, but can be prepared at low cost.

It is therefore an object of this invention to provide a process for preparing defoamers which uses comparatively low cost materials and an economically attractive preparation method. The defoamers are just as effective as conventional defoamers or more so.

In accordance with this invention, the defoamer comprises from about 57.1 wt% to about 97.6 wt% of sulfonated petroleum oil and the balance of an alcohol having from about 4 carbon atoms to about 20 carbon atoms. The process comprises mixing from about 57.1 wt% to about 97.6 wt% of a sulfonated petroleum oil with the balance an alcohol having from about 4 carbon atoms to about 20 carbon atoms.

The composition of matter of this invention is a defoamer for controlling the foam in high strength acid media which broadly comprises a majority of a sulfonated oil and a minority of a long chain alcohol. The oil may be any petroleum feedstock, mineral oil, fuel oils and/or lubricants derived from petroleum and its products including hydrocarbons. A preferred oil is one having a viscosity at 1 000F of between about 5 N SUS and 100 or 1000 N SUS. The oil is sulfonated by mixing it with a mixture of SO, and SO, at a temperature of between about -200F and 21 20F. A preferred temperature is room temperature (i.e. about 720F). The SO, is much too reactive alone; therefore, SO, is utilized to pacify the reaction.The SO2 doesn't enter into the reaction of the SO, and oil but merely acts as a diluent and coolant for the strong oxidizing tendencies of the SO3. The alcohol is used to disperse and/or dissolve the acid sludge. The alcohol not only disperses the sludge but also permits the formation of a synergistic product to produce a defoamer which is several-fold more effective than the sulfonate or the alcohol alone. The alcohol may be any alcohol that is soluble in the sulfonated oil. Preferably the alcohol may be any straight or branched cycle or linear long chain alcohol having between about 4 and 20 carbon atoms. More preferably the alcohol has between about 8 and 14 carbon atoms. Most preferably the alcohol is dodecyl alcohol.

The sulfonation ratio of SO, to oil may broadly be from about 0.025:1 to about 0.60:1. The more preferred sulfonation ratio of SO, to oil is from between about 0.1:1 to about 0.3:1, most preferably, the ratio is about 0.25:1.

The ratio of alcohol to the sulfonated oil may broadly be from about 0.025:1 to about 0.75:1. The more preferred ratio of alcohol to sulfonated oil is from between about 0.25:1 to about 0.50:1; most preferably, the ratio is about 0.38:1.

In the process for preparing the defoamer the oil is sulfonated with a minority of SO, dissolved in a majority of SO2. The mixing ratio of SO, to SO2 may be any suitable ratio such that SO, quiesces the reactive SO3. Preferably S03 and SO, are mixed in a ratio of from approximately 1:1 to about 1:10.

During the course of the reaction of the oil and the 503 SO, mixture, the temperature decreases. The mixture is preferably allowed to react from between about 1 5 minutes and 90 minutes whereafter the reacted product is a mixture of sulfonated oil and an acid sludge. The alcohol is subsequently added to the sulfonated oil to disperse the sludge. After the admixing of the alcohol to the sulfonated oil, the mixture is blended from between about 1 5 mins. and 90 minutes. It should be noted that the 90 minute upper limitation on the reaction time of the oil and SO3, SO, mixture, and the sulfonated oil and alcohol mixture is not to be construed as an unduly limitation. Longer reaction times would be superfluous because the reactions are completed after about 15 minutes.

In the following is set forth examples of our invention which are given by way of illustrations and, not by limitations. The specific concentrations, temperatures, times, compounds, etc., set forth in these examples are not to be construed to unduly limit the scope of the invention.

Example 1 Four hundred grams of a neutral lube oil having a viscosity of 350 N SUS at 1 000F were sulfonated at room temperature with 100 gms of liquid SO, dissolved in 500 gms of liquid SO2. During the course of the reaction, the temperature decreased to --1 00 F. The mixture was allowed to react for 1/2 hour at which time the temperature rose to 700 F. The product was then heated to 1 400F to strip residual SO2. The reacted product was a mixture of sulfonated oil and sludge. Dodecyl alcohol was added to the mixture to disperse the sludge. The alcohol was added in a ratio of 300 grams of alcohol to 500 grams of sulfonated oil.The mixture was blended for 30 minutes at 1400 F. to insure complete dispersion of the sludge. An acceptable alternative is to add the alcohol along with the lube oil before sulfonation.

This defoamer was added periodically to a reactor having a continuous flow of phosphate rock, 60% H2SO4, and recycled phosphoric acid (25% P205) in order to control the foaming. This defoamer was proved to be superior to conventional defoamers on a cost/ton of P205 basis and defoamer requirements/ton of P205 as evidenced in the following Table l: Table I Defoamer Requirements Cost per Ton per ton P2O5 {Ibs./ton) P2o5 {$) Applicants' Defoamer 2.59 .58 Conventional Defoamers including tall oil, fatty acids, by-products of paper industry:: Brand A 4.00 0.70 Brand B 2.87 0.65 Brand C 4.68 1.24 Brand D 6.62 1.16 Brand E 4.18 6.94 Brand F 9.60 1.63 Brand G 4.66 0.98 Example 2 Four hundred grams of a neutral lube oil having a viscosity of 350 N SUS at 1 000F were sulfonated at room temperature with 130 grams of liquid S03 dissolved in 650 grams of liquid 502.

During the course of the reaction, the temperature decreased to -1 00 F. The mixture was allowed to react for 1 hour at which time the temperature rose to 850 F. The product was then heated to 1 200F to strip residual SO2. The reacted product was a mixture of sulfonated oil and acid sludge. Dodecyl alcohol was added to the mixture to disperse the sludge. The alcohol was added in a ratio of 318 grams alcohol to 400 grams of sulfonate. The mixture was agitated for 30 minutes to insure complete dispersion of the sludge. Subsequently the defoamer was tested and compared to conventional defoamers in accordance with Example I and similar results were found.

Example 3 Four hundred grams of a neutral lubricating oil having a viscosity of 350 N SUS at 1 000F were sulfonated at room temperature with 80 grams of liquid S03 dissolved in 400 grams of liquid 502.

During the course of the reaction, the temperature dropped to -100F. The mixture was allowed to react for 45 minutes at which time the temperature of the mixture rose to 600 F. The reacted product was a mixture of sulfonated oil and acid sludge. Dodecyl alcohol was added to the mixture to disperse the sludge. The alcohol was added in a ratio of 288 grams of alcohol to 480 grams of the sulfonate.

The mixture was stirred at room temperature for 30 minutes to insure complete dispersion of the sludge. Subsequently the defoamer was tested and compared to conventional defoamers in accordance with Example I and similar results were found.

Example 4 Repeat Examples 1-3, but vary the mixing ratios of SO, to oil in 0.005 increments between 0.025 and 0.400 and find similar results.

Example 5 Repeat Examples 1-4 but vary the type of alcohol (both straight chain and branched) linear or cyclic in 1 carbon atom increments between 4 carbon atoms and 20 carbon atoms and find similar results.

Example 6 Repeat Examples 1-5 but vary the sulfonation temperature in increments of 50F between -200F and 2120F and find similar results.

Example 7 Repeat Examples 1-6 but vary the mixing ratio of the alcohol to the sulfonated oil in increments of 0.005 between 0.025 and 0.750 and find similar results.

Example 8 Repeat Examples 1-7 but vary the mixing ratio of the SO, to SO, in increments of 1:1 between 1:1 to 1:10 and find similar results.

Example 9 Repeat Examples 1-8 but lower the reaction time of S03 and SO2, and the agitation time of sulfonated oil and alcohol to 15 minutes and find similar results.

Example 10 Take the sulfonated oil of Example 1 and the alcohol of Example 1 and test the defoamer requirements of each and synergistically compare with the defoamer of Example 1. Find the following synergistic results: Table 2 Defoamer Requirements Cost per per ton P205 ton P3O5 Sulfonated oil 7.52 1-.88 Alcohol 6.03 1.20 Applicants' Defoamer 2.59 0.58 Example 11 Repeat Example 10 in accordance with each procedure of Examples 2-9 and find the similar results given in Example 10.

While the present invention has been described herein with reference to particular embodiments thereof, and specific examples, a latitude of modifications various changes and substitutions are intended in the foregoing disclosure, and in some instances some features of the invention will be employed without a corresponding use of other features without departing from the scope of the invention as set forth.

Claims

1. A defoamer for controlling foam in high strength acid media including: a). from about 57.1 wt% to about 97.6 wt % of sulfonated petroleum oil; and b). the balance of an alcohol having from about 4 carbon atoms to about 20 carbon atoms.

2. The defoamer of Claim 1 wherein said alcohol comprises a linear alcohol of from about 8 carbon atoms to about 14 carbon atoms.

3. The defoamer of Claim 1 wherein said alcohol is a branched chain alcohol from about 8 carbon atoms to about 14 carbon atoms.

4. The defoamer of Claim 1 wherein said alcohol is a branched cyclic chain alcohol of from approximately 4 carbon atoms to about 20 carbon atoms.

5. The defoamer of Claim 2 wherein said alcohol is dodecyl alcohol.

6. A process for preparing a defoamer for controlling the foam in high strength acid media comprising mixing from about 57.1 wt% to about 97.6 wt% of a sulfonated petroleum oil with the balance an alcohol having from about 4 to about 20 carbon atoms.

7. The process of Claim 6 wherein said alcohol is a linear alcohol of from about 8 carbon atoms to about 14 carbon atoms.

8. The process of Claim 6 wherein said alcohol is a branched chain alcohol of from about 8 carbon atoms to about 14 carbon atoms.

9. The process of Claim 7 wherein said alcohol is dodecyl alcohol.

10. The process of Claim 6 wherein said sulfonated oil is from about 66.7 wt% to about 80 wt% of the defoamer.

11. The process of Claim 6 additionally comprising agitating said mixture of sulfonated oil and alcohol for at least 15 minutes immediately after adding said alcohol to insure complete dispersion of acid sludge resulting from sulfonation of the oil.

1 2. The process of Claim 6 wherein said oil is sulfonated with a ratio of SO, to oil of from approximately 0.025 to about .6.

13. The process of Claim 12 wherein said sulfonated oil comprises about 66.7 wt% to about 80 wt% of the defoamer.

14. The process of Claim 12 wherein said sulfonated oil is sulfonated at a temperature of from between about -200F to about 21 20F.

15. The process of Claim 11 additionally including mixing SO, with said SO3, said mixture of SO, and SO, being mixed in a ratio of from approximately 1:1 to about 1:10.

16. The process of Claim 15 wherein said sulfonation is performed at a temperature of between about -200F to about 21 20F.

17. The process of Claim 16 wherein said mixture of oil, SO, and S03 is allowed to react for at least 15 minutes.

18. The process of Claim 6 wherein said alcohol comprises a branched cyclic chain alcohol of from approximately 4 carbon atoms to about 20 carbon atoms.

19. A process for preparing a defoamer substantially as herein described and exemplified.

20. Defoamers substantially as herein described and exemplified.