BACKGROUND OF THE INVENTION In the propylene oxide styrene monomer (POSM) process, methyl oxirane (propylene oxide) and ethenyl or vinyl benzene (styrene monomer) are co-produced. Molecular oxygen is reacted with ethylbenzene to form a-hydroperoxy ethylbenzene which is then subsequently reacted with propene to form propylene oxide and a-hydroxyethylbenzene, also known as methylbenzyl alcohol.

After removing the more volatile propylene oxide, the methylbenzyl alcohol is dehydrated to water and styrene monomer. These are co-distilled overhead and condensed into a water/oil separator, where the water forms a separate phase and is drained. The crude styrene phase is then extracted in a caustic wash drum with 5 to 10% of an aqueous caustic solution containing about 2 to 3% NaOH, sometimes with about an equal amount of a caustic solution recycled to remove phenolic byproducts of the above-described oxidation and epoxidation reactions.

The caustic extracted styrene is then rinsed in a water wash drum with 5 to 10% fresh water, also sometimes with about an equal amount recycled, to remove residual caustic and phenate salts from the crude styrene prior to distillation. Typically, the temperature of the extraction is about 100 to 110°F. The pH in the second stage is about 11.5 and in the first stage is about 14.

The present inventor has discovered a means to improve this extraction process while minimizing residual carryover of caustic and phenates to the styrene distillation towers. This method also helps eliminate the production and disposal as toxic waste of stable dispersion layers which otherwise accumulate in separation vessels.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides for an improved method for extracting phenols from crude styrene with aqueous caustic, the improvement comprising adding to the styrene an effective amount for the purpose of aiding extraction of an aromatic or alkylammonium tailed multi-polyether headed surfactant or a quaternary polyamine.

The aromatic or alkylammonium tailed multi-polyether headed surfactants (MPEHS) include those with hydrophobic"tails"comprising C, to C, s alkylaryl diols to polyols and C3 to <BR> <BR> <BR> <BR> <BR> C22 alkyl or alkylaryl I'or 2'amines. These are adducted with C, to C3 alkylene oxides to form two or more hydrophilic heads per hydrophobe comprising separate polyether chains of degree of polymerization (dp) 3 to 30. The backbone and branches of the polymer contain only ether or amine linkages, and not, for example, esters or amides. Quaternary amines employ any convenient counterions, such as halides, sulfates, nitrates, phosphates, carboxylates, phenates, silicates, carbonates, or hydroxides. <BR> <BR> <BR> <BR> <BR> <P> Preferably, the multi-polyether headed surfactant comprises C4 to C9<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> alkylphenol-formaldehyde condensates of dp 4 to 8 adducted with ethylene oxide to form 4 to 8 polyether chains of dp 4 to 7 blended with the halide salt of linear C,, to C2, alkyl 2° amines adducted with ethylene oxide to form 2 polyether chains of dp 5 to 10.

The quaternary polyamines used in the present invention are those in which the backbone and branches of the polymer contain only ether or amine linkages and not, for example, esters or amides. The polyamine should have a degree of polymerization of about 60 to 6000 monomer units and an overall carbon to nitrogen or oxygen ratio of less than 10. These compounds are water soluble.

The quaternary polyamines include but are not limited to halides, sulfates, nitrates, phosphates, carboxylates, phenates, silicates, carbonates, or hydroxides of alkyl or alkylaryl quaternary amines. The preferred polyamines include but are not limited to poly (diallyldimethylammonium chloride), or poly (DADMAC), having the formula: poly (N, N-dimethyl, 2-hydroxypropyleneammonium chloride), or poly (DMHPAC), having the formula:

and poly (N, N-dimethyl, 3- (2-hydroxypropyleneamine) propylammonium chloride), or poly [DM (HPA) PAC], having the formula: The poly (DMHPAC) compound may be formed by reacting about equimolar amounts of 3-chloromethyl-1,2-oxirane (epichlorohydrin or EPI) with dimethylamine (DMA).

The poly [DM (HPA) PAC] may be formed by reacting about equimolar amounts of EPI and dimethylaminopropylamine (DMAPA).

The present inventor has discovered that these extraction aids assist in fluidizing, solubilizing and removing the surfactant barrier to improve extraction efficiency. This minimizes the caustic carryover to the crude styrene distillation section and eliminates the production and disposal of the dispersion layer.

The multi-polyether headed surfactants are preferably fed as solutions in aqueous or organic solvents that are compatible with both the MPEH's and the POSM process. The organic solvents include high boiling (i. e. greater than 400°F) aromatic hydrocarbons, glycol ethers, such as 2-n-butoxy-2-ethoxyethanol (butyl carbitol), and native aromatic alcohols such as «-hydroxyethylbenzene, which is most preferred.

Preferably the solutions are fed to the influent, unwashed styrene. The solutions may also be fed to the interstage, washed but not rinsed styrene. Preferably from about 3 to about 30 parts of MPEH per million parts of styrene are fed.

The quaternary polyamines are preferably fed as an aqueous solution to the influent caustic wash water or the fresh rinse water or most preferably both the caustic wash and rinse water, prior to mixing with the styrene.

The quaternary polyamines are fed in amounts ranging from about 1 part to about 100 parts polyamine per million parts of water with a range of about 3 to about 30 preferred, or about 0.1 part to about 10 parts per million parts of styrene with a range of about 0.2 parts to about 2.0 parts preferred.

The following examples are intended to show the efficacy of the present invention and should not be construed as limiting the scope of the invention.

EXAMPLES In order to find a counteractant to the barrier soaps, which tend to accumulate at the interface of the extraction vessels, a sample of concentrated soap in an 18% oil-in-water emulsion from the second stage of a Southwestern U. S. POSM caustic wash unit was taken.

Selected candidates were screened using the following procedure: 1. Add 100 mL of sample to 6 oz. Rx bottle 2. Heat the bottle to 105 °F in a 105°F water bath 3. Treat the sample with chemical at 105 ° F 4. Shake the bottle with a 3 inch stroke at 60 cps for 1 minute on a mechanical shaker 5. Place the bottle back into a 105°F bath 6. Record rate and degree to which soapy appearance disappears.

Table A lists the chemicals that were tested.

TABLE A A Branched nonylphenol-formaldehyde condensate of dp 4-8 adducted with propyl-and ethylene oxides to form 4-8 polyether chains of dp 7-10 each B 2,2-bis-p-phenoxyhydroxypropyletherpoly (propylether) propane of dp 0-2 adducted with ethylene oxide to form 4-8 polyether chains of dp 4-8 each C Poly (N, N-dimethyl, 2-hydroxypropyleneammonium and 3- (2-hydroxypropyleneamine) propylammonium, chlorides) D Poly (diallyldimethyl ammonium chloride) The results of this screening are shown in Tables I & II. The"top oil"described as "opaque white"was found to be a water continuous phase."Translucent" (or"transluc.") and "transparent" (or"transpar. ") indicate an oil continuous phase, with and without significant entrained water, respectively."Transparent"indicates text is readable through the phase, though

some dispersed material remains."Clear"indicates phase is substantially free of any dispersed material. Within a given opacity classification, the color indicates the relative amount of foreign material present in the phase, with brown > tan > amber > yellow > white.

TABLE I Post-Treatment Appearance Readings Treatment 5 Minutes 30 Minutes 60 Minutes Chemical ppm Top Oil Bottom I/F Top Bottom I/F Top Oil Bottom I/F Act Water Oil Water Water blank 0 opaque opaque much opaque opaque much opaque opaque much white white soap white white soap white white soap A 3 opaque opaque much opaque opaque much opaque opaque much white white soap white white soap white white soap 7 7. 5 opaque opaque much opaque opaque much opaque opaque much white white soap white white soap white white soap A 15 opaque opaque much opaque opaque much opaque opaque much white white soap white white soap white white soap A 30 opaque opaque much opaque opaque much opaque opaque much white white soap white white soap white white soap A 60 opaque opaque much opaque opaque much opaque opaque much white white soap white white soap white white soap A 120 opaque opaque much opaque opaque much opaque opaque much white white soap white white soap white white soap A 240 opaque opaque much opaque opaque much opaque opaque much white white soap white white soap white white soap C 1.5 50% trans-trans-much 75% trans-trans-much 80% trans-opaque much lucent brown lucent soap lucent brown lucent soap parent white soap C 3.75 80% trans-trans-little 90% trans-trans-little 90% trans-translucent much lucent brown lucent soap lucent brown parent soap parent amber soap C 7.5 all trans-trans-no soap 100% trans-trans-no soap 100°/o trans-transparent no soap lucent brown parent parent parent parent c 15 25% trans-much 50% traiis-much 80% transparent much trans-parent parent soap trans-parent parent soap trans-parent soap opaquetrans-muchopaquetrans-much25%trans-translucentmuchC30 white lucent soap white lucent soap parent soap C 60 opaque opaque much opaque opaque much 10% trans-opaque much white white soap white white soap parent white soap C 120 opaque opaque much opaque opaque much 10% trans-opaque much white white soap white white soap parent white soap TABLE I. continued

Post-Treatment Appearance Readings Treatment- 5Minutes30 Minutes 60 Minutes Chemical ppm Top Oil Bottom I/F Top Bottom I/F Top Oil Bottom I/F Act Water Oil Water Water D 1.5 opaque opaque much opaque opaque much 10% opaque much white white soap white white soap transparent white soap 3.75 opaque opaque much 25% opaque much 25% opaque much white white soap translucent white soap transparent white soap brown D 7.5 50% opaque much 50% opaque much 50% opaque much transluc. white soap translucent white soap transparent white soap brown brown amber 15 90% trans-little 90% clear little 90% clear little transluc. parent soap translucent soap transparent soap brown brown D 30 25% trans-much 50% transparent much 50% transparent much transluc. parent soap translucent soap transparent soap brown brown D 60 opaque trans-much opaque translucent much much soap opaque much white lucent soap white soap white soap D 120 opaque trans-much opaque translucent much much soap opaque much white lucent soap white soap white soap TABLE II Post-Treatment Appearance Readings Treatment 5 Minutes 15 Minutes 30 Minutes 60 Minutes Chemical ppm Top Oil Bottom I/F Top Oil Bottom I/F Top Bottom I/F Top Oil Bottom I/F Act Water Water Oil Water Water blank 0 opaque opaque much opaque opaque little opaque opaque little opaque opaque little white whitesoapwhite whitesoapwhite whitesoapwhite white soap B 2.3 opaque opaque much opaque opaque little opaque trans-little opaque opaque little white whitesoapwhite whitesoapwhite) ucentsoapwhite white soap B 4 6 opaque opaque much opaque opaque little opaque trans- little opaque opaque little white white soap white white soap white lucent soap white white soap B 9.2 opaque opaque much opaque opaque little opaque trans-little opaque opaque little white white soap white white soap white lucent soap white white soap B 18.4 opaque opaque much opaque opaque little opaque trans-little opaque opaque little white white soap white white soap white lucent soap white white soap B 36.8 opaque opaque much opaque opaque little opaque trans-little opaque opaque little white white soap white white soap white lucent soap white white soap B 73.6 opaque opaque much opaque opaque little opaque trans-little opaque opaque little white white soap white white soap white lucent soap white white soap Tables I and II show that D from 1.5 to 30 ppm active and, even more so C, from 1.5 to 60 ppm active, per emulsion, were able to remove the barrier surfactants and allow the dispersed crude styrene to coalesce into a recoverable, phenate and caustic depleted, clear organic phase on top, an emulsion free interface between the oil and water layers and a clearer, less wasteful and

hazardous water layer. The MPEH's, which have broken other types of emulsions not containing synthetic stabilizers in other applications at near neutral pH (5-9), had no significant effect on accumulated surfactants such as these at alkaline pH (11-14).

These results imply that the phenol extraction process would be improved by feeding about 9 ppm of C per water (0-6 ppm active per oil at 6.6% water wash) into the water to the vessel accumulating soapy emulsion. The sample above was taken from stage 2 but if the treatment were applied either additionally or instead to stage 1 to keep soap from carrying over, better extraction may result.

A second test was run to test an agent's ability to promote formation of an emulsion with which to extract the phenol but which would also not impede the reaction of the phenols with the caustic, the transfer of the phenate to the water droplets, or the subsequent coalescence and removal of the droplets from the styrene. Samples of the first stage crude styrene effluent and the first stage caustic brine effluent (containing 0.8% sodium hydroxide and 0.5% sodium phenates) were taken and used to recreate the first stage extraction step in the laboratory. A variety of candidate extraction aids were screened using the following procedure: 1. Pour 86 mL crude styrene and 14 mL caustic water into Rx bottle 2. Heat to 105°F in a water bath 3. Treat with chemical at 105°F in duplicate 4. Shake the bottle with a 3 inch stroke at 240 cps for 1 minute on a mechanical shaker 5. Place the bottle into 105 °F bath 6. Record degree to which an initial milky appearance forms 7. Record the rate and degree the milky appearance disappears for 60 minutes.

Table B presents the additional chemicals tested.

TABLE B E Linear dodecylbenzene sulfonic acid, nonylphenol-formaldehyde condensates of dp 4-8 adducted with ethylene oxide to form 4-8 polyether chains of dp 4-7, and a nonylphenol ethoxylate F Branched nonylphenol-formaldehyde condensate of dp 4-8 adducted with ethylene oxide to form 4-8 polyether chains of dp 4-7 and poly (propylether diol) adducted with ethylene oxide to form 2 polyether chains of dp 12-24 G Branched nonylphenol-formaldehyde condensates of dp 4-8 adducted with ethylene oxide to form 4-8 polyether chains of dp 4-7 H Branched nonylphenol-formaldehyde condensates of dp 4-8 adducted with ethylene oxide to form 4-8 polyether chains of dp 4-7 and halide salts of linear Cl2 to C22 alkyl 2° amines adducted with ethylene oxide to form 2 polyether chains of dp 5-10

I Poly (propylether diol) adducted with ethylene oxide to form 2 polyether chains of dp 12-24 J Halide and carboxylate salts of linear C12 to C22 alkyl 2°aminesadductedwithand ethylene oxide to form 2-3 polyether chains of dp 1-10 The results of this testing are presented in Tables III to VII.

TABLE III Post-Treatment Appearance Readings Treatment 15Minutes30Minutes60MinutesMinutes Chemical ppm Top Oil Bottom I/F Top Oil Bottom I/F Top Bottom I/F Top Oil Bottom I/F Act Water Water Oil Water Water blank 0 trans-trans-little trans-trans-little trans-trans-little trans-trans-little lucent, lucent, soap lucent, lucent, soap parent, lucent, soap parent, parent, soap amber brown amber amber amber amber amber amber B 5.8 trans-trans-little trans-trans-little trans-trans-little clear, trans-little parent, lucent, soap parent, parent, soap parent, parent, soap yellow parent, soap amber amber yellow yellow yellow yellow yellow B 12 trans-trans-little trans-clear, little trans-trans-little clear, trans-little parent, lucent, soap parent, yellow soap parent, parent, soap yellow parent, soap amber amber yellow yellow yellow yellow B 2= trans-trans-little trans-clear, little trans-trans-little trans-trans-little lucent, lucent, soap parent, yellow soap parent, parent, soap parent, parent, soap amber amber amber amber yellow yellow yellow B 46 trans-trans-little trans-clear, little trans-trans-little trans-trans-little lucent, lucent, soap lucent, yellow soap lucent, parent, soap lucent, parent, soap amber amber amber amber yellow amber yellow B 92 trans-trans-little trans-clear, little trans-trans-little trans-trans-little lucent, lucent, soap lucent, yellow soap lucent, parent, soap lucent, parent, soap amber brown brown brown yellow amber yellow B 184 opaque trans-little opaque clear, little trans-trans-little trans-trans-little brown lucent, soap brown yellow soap lucent, parent, soap lucent, parent, soap amber brown yellow brown yellow D 7. s u-ans-opaque little trans-trans-little trans-trans-little trans-trans-little lucent, brown soap lucent, lucent, soap lucent, lucent, soap parent, parent, soap amber amber amber amber amber amber yellow D 15 trans-opaque little trans-clear, little trans-trans-little trans-trans-little lucent, brown soap lucent, yellow soap lucent, lucent, soap lucent, parent, soap amber amber amber amber amber yellow D 30 trans-opaque much trans-clear, little trans-trans-little trans-trans-little lucent, brown soap lucent, yellow soap lucent, lucent, soap lucent, parent, soap tan tan tan amber amber yellow D 60 trans-opaque much trans-clear, much trans-trans-much trans-trans-little lucent, brown soap lucent, yellow soap lucent, lucent, soap lucent, parent, soap brown brown tan amber brown yellow D 120 trans-opaque much trans-clear, much trans-trans-much trans-trans-much lucent, brown soap lucent, yellow soap lucent, lucent, soap lucent, parent, soap brown brown brown amber brown yellow 240 opaque opaque much trans-clear, mucll trans-trans-much trans-trans-much brown brown soap lucent, yellow soap lucent, lucent, soap lucent, parent, soap amberbrownyellowbrownbrown TABLE IV

Post-Treatment Appearance Readings Treatment- 5 Minutes 60 Minutes Chemical ppm Top Oil Bottom I/F Top Bottom I/F Top Oil Bottom I/F Act Water Oil Water Water blank 0 trans-trans-little trans-trans-little trans-trans-little lucent, lucent, soap lucent, lucent, soap parent, parent, soap brown brown amber amber amber amber B 1 trans-trans-little trans-trans-little trans-trans-little lucent, parent, soap parent, parent, soap parent, parent, soap amber amber amber yellow yellow yellow B 3 trans-trans-little trans-trans-little clear, trans-I ittle parent, parent, soap parent, parent, soap yellow parent, soap amber amber yellow yellow yellow B 5.8 trans-trans-little trans-trans-little clear, trans-little parent, parent, soap parent, parent, soap yellow parent, soap amber amber yellow yellow yellow B/D 5.8/0.15 trans-trans-little trans-trans-little trans-trans-little parent, parent, soap parent, parent, soap parent, parent, soap amber yellow yellow yellow yellow yellow B/D 5.8/0.3 trans-trans-little trans-trans-little trans-trans-little lucent, parent, soap parent, parent, soap parent, parent, soap amber yellow yellow yellow yellow yellow B/D 5.8/0.6 trans-trans-little trans-trans-little trans-trans-little lucent, parent, soap parent, parent, soap parent, parent, soap amber. yellow amber yellow yellow yellow B/D trans-trans-little trans-trans-little trans-trans-little lucent, parent, soap parent, parent, soap parent, parent, soap amber yellow amber yellow yellow yellow B/D 2.3/0.3 trans-trans-little trans-trans-little trans-trans-little lucent, parent, soap parent, parent, soap parent, parent, soap amber yellow amber yellow yellow yellow B/D 2.3/0. 6 trans-trans-little trans-trans-little trans-trans-little lucent, parent, soap parent, parent, soap parent, parent, soap amber yellow amber yellow yellow yellow D 3.8 trans-trans-little trans-trans-little trans-trans-little lucent, lucent, soap lucent, parent, soap parent, parent, soap brown amber amber amber amber yellow TABLE V

Post-Treatment Appearance Readings Treatment 5 Minutes 30 Minutes 60 Minutes Chemical ppm Top Oil Bottom I/F Top Bottom I/F Top Oil Bottom I/F act Water Oil Water Water blank 0 trans-trans-little trans-trans-little trans-trans-little lucent, lucent, soap lucent, lucent, soap parent, parent, soap amber brown amber amber amber amber E 8.2 trans-trans-little trans-trans-little trans-trans-little parent, lucent, soap parent, parent, soap parent, parent, soap amber amber yellow yellow yellow yellow F 6.2 trans-trans-little trans-trans-little trans-trans-little parent, lucent, soap parent, parent, soap parent, parent, soap amber amber yellow yellow yellow yellow G 6 trans-trans-little almost trans-little clear, trans-little parent, lucent, soap clear, parent, soap yellow parent, soap amber amber yellow yellow yellow A 6 trans-trans-little clear, trans-little clearer, trans-little parent, lucent, soap yellow parent, soap yellow parent, soap amber amber yellow yellow H 4 trans-trans-little clearer, trans-little clearest, trans-little parent, lucent, soap yellow parent, soap yellow parent, soap amber amber yellow yellow J 3 trans-trans-little trans-trans-little almost trans-little parent, lucent, soap parent parent, soap clear, parent, soap amber amber yellow yellow yellow yellow B 4.6 trans-trans-little trans-trans-little almost trans-little parent, lucent, soap parent parent, soap clear, parent, soap amber amber yellow yellow yellow yellow 1 7.2 trans-trans-little trans-trans-little trans-trans-little lucent, lucent, soap lucent lucent, soap lucent, parent, soap brown amber amber amber amber yellow TABLE VI 5 10 15 Post-Treatment Appearance Readings Treatment 30Minutes605Minutes Minutes Chemical ppm Top Oil Bottom I/F Top Bottom I/F Top Oil Bottom I/F act Water Oil Water Water C 0.3 trans-opaque, little trans-trans-Iittle trans-trans-little lucent, brown soap lucent, lucent, soap parent, parent, soap amber amber amber amber yellow C 0.6 trans-trans-little trans-trans-little trans-trans-little lucent, lucent, soap parent, lucent, soap parent, parent, soap amber amber amber amber amber yellow C 1.2 trans-trans-little trans-trans-little trans-trans-little lucent, lucent, soap parent, lucent, soap parent, parent, soap amber amber amber amber amber yellow C 2.4 trans-trans-little trans-trans-little trans-trans-little lucent, lucent, soap parent, lucent, soap parent, parent, soap amber amber amber amber amber yellow C 4.8 trans-opaque, little trans-trans-little trans-trans-little lucent, brown soap parent, lucent, soap parent, parent, soap amber amber amber amber yellow trans-opaque,littletrans-trans-littletrans-trans-littleC9.6 lucent, brown soap lucent, lucent, soap parent, parent, soap brown amber amber amber yellow B 2.3 trans-trans-little trans-trans-little almost trans-little parent, lucent, soap parent, parent, soap clear, parent, soap amber amber yellow yellow yellow yellow B 4.6 trans-trans-little almost trans-little almost trans-little parent, lucent, soap clear, parent, soap clear, parent, soap amber amber yellow yellow yellow yellow H 2.0 trans-trans-little clear, trans-little clear, trans-no parent, lucent, soap yellow parent, soap yellow parent, soap yellowyellowamberamber H 4.0 littletrans- clear, trans-little notrans- parent, lucent, soap yellow parent, soap yellow parent, soap amber amber yellow yellow TABLE VII

Post-Treatment Appearance Readings Treatment 30Minutes 60Minutes Chemical ppm Top Oil Bottom I/F Top Bottom I/F Top Oil Bottom I/F act Water Oil Water Water blank 0 trans-trans-little trans-trans-little trans-trans-little lucent, lucent, soap parent, lucent, soap parent, parent, soap amber brown amber amber amber amber A 6 trans-trans-little clear, trans-little clearer, trans-no parent, lucent, soap yellow parent, soap yellow parent, soap amber amber yellow yellow A/C 6/0.3 trans-trans-little clear, trans-little clearer, trans-no parent, lucent, soap yellow parent, soap yellow parent soap amber amber yellow yellow A/C 6/0.6 trans-trans-little trans-trans-little clear, trans-no parent, lucent, soap parent, parent, soap yellow parent, soap amber amber yellow yellow yellow A/C 6/0.9 trans-trans-little trans-trans-little trans-trans-no parent, lucent, soap parent, parent, soap parent, parent, soap amber amber amber yellow yellou yellow H 4 trans-trans-little clear, trans-little clearest, trans-no parent, lucent, soap yellow parent, soap yellow parent, soap amber amber yellow yellow H/C 4/0.3 trans-trans-little clear, trans-little clearest, trans-no parent, lucent, soap yellow parent, soap yellow parent, soap amber amber yellow yellow H/C 4/0.6 trans-trans-little trans-trans-little trans-trans-no parent, lucent, soap parent, parent, soap parent, parent, soap amber amber yellow yellow yellow yellow H/C 4/0.9 trans-trans-little trans-trans-little trans-trans-no parent, lucent, soap parent, parent, soap parent, parent, soap amber amber yellow yellow yellow yellow B 4.6 trans-trans-little trans-trans-little almost trans-no parent, lucent, soap parent, parent, soap clear, parent, soap amber amber yellow yellow yellow yellow B/C 4.6/0.3 trans-trans-little trans-trans-little trans-trans-little parent, lucent, soap parent, parent, soap parent, parent, soap amber amber yellow yellow yellow yellow B/C 4.6/0.6 trans-trans-little trans-trans-little trans-trans-little parent, lucent, soap parent, parent, soap parent, parent, soap amber amber yellow yellow yellow yellow B/C trans-trans-little trans-trans-little trans-trans-little lucent, lucent, soap parent, parent, soap parent, parent, soap brown brown amber amber amber yellow

The data in Tables III and IV show that the aromatic tailed MPEH's achieved the best results for fonning a fluid, extractive emulsion of caustic-in-styrene.

The data in Table V demonstrate that aromatic and alkylammonium tailed MPEH's were effective while blends of aromatic and alkylammonium tailed MPEH's were even more effective.

The data in Table VI also show the aromatic and alkylammonium tailed MPEH blend to be best based on caustic removal. Table VII demonstrates that small amounts of a quaternary polyamine can be added in conjunction with the aromatic and/or alkylammonium tailed MPEH's without harm to the extraction process.

Clarifie top oil from the previous test and additional DI water were used to simulate the second stage rinse. Additional treatments and controls with no further treatment were tested using the following procedure: 1. Thief 70 mL clarified top oil from previous test and place in another Rx bottle.

2. Add 5.25 mL (7%) DI water to 2nd bottle.

3. Heat to 105 °F in water bath.

4. To one of each duplicate, add an additional 1 ppm (product) C.

5. Shake the bottles with a 3 inch stroke at 240 cps for 1 minute on a mechanical shaker.

6. Place the bottles back into 105 °F bath.

7. Record degree to which an initial milky appearance forms.

8. Record the rate and degree the milky appearance disappears for 60 minutes.

The results of this testing are presented in Table VIII.

TABLE VIII

Post-Treatment Appearance Readings Treatment Treatment Minutes 30 Minutes 60 Minutes Chemical ppm ppm Top Oil Bottom I/F Top Bottom I/F Top Oil Bottom I/F orig add Water Oil Water Water blank 0 0 trans-clear, very trans-clear, much trans-clear, much lucent. yellow much lucent, white soap parent, white soap brown soap amber amber A 6 0 trans-trans-much clear, clear, much clear, clear, little lucent, lucent, soap white white soap white white soap brown amber A/C 6/0.3 0/0 trans-tarns-much trans-clear, much trans-clear, much lucent, lucent, soap lucent, white soap parent, white soap brown brown brown amber A/C 6/0.6 0/0 trans- trans- much trans- clear, much trans- clear, much lucent, lucent, soap lucent, white soap lucent, white soap brownbrownbrownbrown A/C 6/0. 9 0/0 trans-trans-much trans-clear, much trans-clear, much lucent, lucent, soap lucent, white soap lucent, white soap brown brown brown brown H 4 0 trans-clear, little clear, clear, no clearer, clear, no parent, white soap white white soap white white soap yellow H/C 4/0.3 0/0 trans-clear, little soap clear, clear, no soap clearer, clear, no parent, white white white white white soap yellow H/C 4/0. 6 0/0 trans-clear, little soap clear, clear, no soap clearer, clear, no parent, white white white white white soap yellow H/C 4/0.9 0/0 trans-clear, little soap clear, clear, no soap clearer, clear, no parent, white white white white white soap yellow B 4. 6 0 trans- clear, no trans- clear, much clear, clear, little lucent, white soap parent, white soap yellow white soap brown yellow B/C 4.6/0.3 0/0 trans- clear, no soap trans-clear, much trans-clear, little lucent, white lucent, white soap lucent, white soap brown brown yellow B/C 4.6/0.6 0/0 trans-clear, no soap trans-clear, much trans-clear, much lucent, white lucent, white soap lucent, white soap brown brown amber B/C 4.6/0.9 0/0 trans-clear, no soap trans-clear, much trans-clear, much lucent, white lucent, white soap lucent, white soap brown brown amber A/C 6/0 0/0.3 trans-trans-much trans-clear, much clear, clear, much lucent, lucent, soap lucent, white soap yellow white soap brown brown brown A/C 6/0. 3 0/0.3 trans-trans-much trans-clear, much trans- clear, much lucent, lucent, soap lucent, white soap lucent, white soap brown brown brown amber A/C 6/0.6 0/0.3 trans-trans-much trans-clear, much trans-clear, much lucent, lucent, soap lucent, white soap lucent, white soap brown brown brown amber A/C 6/0.9 0/0.3 trans-trans-much trans- clear, much trans-clear, much lucent, lucent, soap lucent, white soap lucent, white soap brown brown brown amber TABLE VIII, continued

Post-Treatment Appearance Readings Treatment 5 Minutes 30 Minutes 60 Minutes Chemical ppm ppm Top Oil Bottom I/F Top Bottom I/F Top Oil Bottom I/F orig add Water Oil Water Water H/C 4/0 0/0.3 trans-clear, clear,noclearestclear, clear, stays lucent, clean on whitewhitesoapwhitewhitewhitesoap agit'n amber H/C 4/0.3 0/0.3 nosoapclear,clear,nosoapclearestclear,clear, stays lucent, white white white white white cleanest amber on agit'n* H/C 4/0.6 0/0.3 trans-clear, no soap clear, clear, no soap clearest clear, stays lucent, white white white white white clean on amber agit'n H/C 4/0.9 0/0 3 trans-clear, no soap clear, clear, no soap clearest clear, stays lucent, white white white white white clean on amber agit'n B/C 4.6/0 0/0.3 trans-trans-much trans-clear, much clear, clear, much lucent,soaplucent,parent, soap white soap yellow white brownbrownvesicles B/C 4.6/0.3 0/0.3 trans-trans-much trans-clear, much trans-clear, much lucent, parent, soap lucent, white soap parent, white soap* brown vesicles brown amber B/C 4.6/0.6 0/0.3 trans-trans-much trans-clear, much trans-clear, much lucent, parent, soap lucent, white soap parent, white soap brown vesicles brown amber B/C 4.6/0.9 0/0.3 trans-trans-much trans-clear, much trans-clear, much I parent, soap lucent, white soap parent, white soap brown vesicles brown amber *Cleans up and doesn't redisperse after sitting overnight.

These data demonstrate that treatment H at 4 ppm active or at 4 ppm active combined in Stage 1 with Treatment C at 0.3 to 1.0 ppm active would produce improved extraction (crystal clear top oil), less waste (crystal clear on bottom) and better process control and consistency (emulsion free interface in 30 minutes). The addition of an additional 0.3 ppm active Treatment C in Stage 2 provides this all at an increased throughput capacity.

To find a more robust treatment capable of recovering from intermittent excursions or cumulative retention of soap production and/or entrainment, such as the initial state to the system studied, a realistic amount of the accumulated emulsion withdrawn from the interface of the 2nd stage, used in the initial tests (Table I and II), was added into each of the test bottles from the previous test and reshaken using the following procedure: 1. Add 2 mL 2nd stage interface emulsion to each bottle from previous test 2. (Do not add more chemical treatment.) 3. Maintain at 105 °F in water bath.

4. Shake the bottles with a 3 inch stroke at 240 cps for 1 minute on a mechanical shaker.

5. Place the bottles back into 105 °F bath.

6. Record degree to which an initial milky appearance forms.

7. Record the rate and degree the milky appearance disappears for 60 minutes.

The results are shown in Table IX, where the treatment histories are those of Table VIII.

TABLE IX Post Treatment Appearance Readings Treatment 6030Minutes Minutes Chemical ppm total Top Oil Bottom I/F Top Oil Bottom Water I/F Water blank 0 translucent, translucent, much soap clear, translucent, much soap amber brown white brown A 6 transparent, translucent, much soap clear, translucent, much soap yellow amber white brown A/C 6/0.3 transparent, translucent, much soap clear, yellow translucent, much soap amber brown brown A/C 6/0.6 translucent, translucent, much soap transparent, translucent, much soap amber brown yellow brown A/C 6/0.9 translucent, translucent, much soap translucent, translucent, much soap brown brown amber brown H 4 clear, translucent, little clear, white translucent, little soap yellow brown soap amber H/C 4/0.3 transparent, translucent, little soap clear, white translucent, little soap yellow brown amber H/C 4/0.6 transparent, translucent, little soap clear, white translucent, little soap yellow brown amber H/C 4/0.9 transparent, translucent, little soap clear, white translucent, little soap amber brown amber B 4.6 transparent, translucent, much soap clear, white translucent, much soap yellow brown brown B/C 4.6/0.3 transparent, translucent, much soap transparent, translucent, much soap amber brown yellow brown B/C 4.6/0.6 transparent, translucent, much soap transparent, translucent, much soap amber brown yellow brown B/C 4.6/0.9 transparent, translucent, much soap transparent, translucent, much soap amber brown amber brown A/C 6/0.3 translucent, translucent, much soap translucent, translucent, much soap amberbrownbrownbrown A/CA/C6/0.6 translucent, translucent, much soap translucent, translucent, much soap brown brown amber brown TABLE IX, continued

Post Treatment Appearance Readings Treatment 30 Minutes 60 Minutes Chemical ppm total Top Oil Bottom I/F Top Oil Bottom Water I/F Water A/C 6/0.9 translucent, translucent, much soap translucent, translucent, much soap brown brown amber brown A/C 6/1.2 translucent, translucent, much soap translucent, translucent, much soap brown brown amber brown H/C 4/0.3 transparent, translucent, little soap clear, yellow transparent, little soap* amber brown amber H/C 4/0.6 transparent, translucent, little soap transparent, transparent, little soap amber brown yellow amber H/C 4/0.9 transparent, translucent, little soap transparent, transparent, little soap amber brown yellow amber H/C 4/1.2 transparent, translucent, little soap transparent, transparent, little soap amber brown yellow amber B/C 4.6/0.3 transparent, translucent, much soap transparent, translucent, much soap* amber brown yellow brown B/C 4.6/0.6 transparent, translucent, much soap transparent, translucent, much soap amber brown yellow brown B/C 4.6/0.9 translucent, translucent, much soap translucent, translucent, much soap brown brown amber brown B/C 4.6/1.2 translucent, translucent, much soap translucent, translucent, much soap brown brown amber brown *no soap on reshaking after sitting overnight.

These data demonstrate the Treatment H by itself at 4 ppm active clarifie the oil the fastest. This treatment combined with treatment C at 0.3 ppm active in Stage 2 was almost as fast, produced the cleanest water and was the best treatment on reshaking after sitting overnight (a measure of complete interfacial emulsion resolution/emulsifier removal when detained at the interface of the process vessels).

To measure the effects of these extraction aids on an actual POSM wash unit, a 30 day trial was conducted. The throughput of crude styrene was varied to optimize the treatment under various conditions. The build up of soapy emulsion was monitored in both stages by examining samples taken from the mid vessel trilines. Extraction performance was measured by analyzing the second stage effluent oil for free phenol, by GC, and sodium, by AA, and by measuring the water removed from the overhead accumulator in the downstream styrene distillation unit.

Treatment H was fed at 2 to 6 ppm active to the first stage influent styrene. Treatment C was fed at 0.3 to 0.5 ppm active to either the second stage influent water or the aqueous influents to both stages.

These results are reported in Table X.

TABLE X Baseline Low Rate Test High Rate Test Styrene Rate (MPPH) 208 180 167 167 167 167 214 214 214 H to Stage 1 (ppm Act) 0 0 4 4 6 2 2 4 6 C to Stage I (ppm A) 0 0 0 0.3 0.3 0.3 0.3 0.4 0.5 C to Stage 2 (ppm Act) 0 0 0.3 0.3 0.3 0.3 0. 3 0.4 0.5 Trilines of Stable 3-4 2-4 2.0 0.5 1.0 0 5 0. 5 Emulsion St 1 (#) avg. 3.5 avg. 3.0 _ Trilines of Stable 3-4 2-4 0.5 0.5 0.5 0.5 0.5 Emulsion St. 2 (#) avg. 3.5 avg. 3.0 Frequency of 1/F 4 I 0 0 0 0 0 0 0 Dumpings(#/mo.) Water Distilled 600-2400 200-150-550, avg. 350 500-900, avg. 700 Overhead (PPH) avg 1300 2000 avg. 900 Na in Washed 2-55 5-9 2-8, avg. 5 2-6, avg. 4 Styrene (ppm) avg. 10 avg. 7 Phenol in Washed 6-12 2-6 2-4 2.3 2 2-3 3-5 5-7 5 Styrene (ppm) avg. 9 avg. 4 avg. 3 avg. avg. 2.5 avg. 4 avg. 6 2. 5 1 These data demonstrate that the co-addition of these two extraction aids improved the conversion of phenol to Na phenate while also improving the removal of phenates to the water or interface, and the dissolution of the phenate soaps into the water. This improved the quality of the finished styrene monomer and eliminated the withdrawal and disposal of stable emulsion.

While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.