CA2068013A1 - Cationic polyelectrolyte demulsifier and coagulator - Google Patents

Cationic polyelectrolyte demulsifier and coagulator

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Publication number
CA2068013A1
CA2068013A1 CA 2068013 CA2068013A CA2068013A1 CA 2068013 A1 CA2068013 A1 CA 2068013A1 CA 2068013 CA2068013 CA 2068013 CA 2068013 A CA2068013 A CA 2068013A CA 2068013 A1 CA2068013 A1 CA 2068013A1
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CA
Canada
Prior art keywords
cationic
range
starch
oil
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA 2068013
Other languages
French (fr)
Inventor
David B. Mitchell
Thomas P. Curran
Mark W. Salihar
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Veolia WTS USA Inc
Original Assignee
WR Grace and Co Conn
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by WR Grace and Co Conn filed Critical WR Grace and Co Conn
Publication of CA2068013A1 publication Critical patent/CA2068013A1/en
Abandoned legal-status Critical Current

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Abstract

ABSTRACT OF THE INVENTION

A cationic polyelectrolyte demulsifier and coagulator for use in demulsifying and coagulating oil in water emulsions comprising a mixture of three cationic polyelectrolytes wherein the polyelectrolytes comprise (a) an inorganic polyelectrolyte, (b) a cationically modified starch and (c) an epihalohydrin. The inorganic polyelectrolyte component (a) is selected from the group consisting of polyaluminum chloride, alum, calcium hydroxide, and mixtures thereof.

Description

FIELD OF THE INVENTION
This invention r~lates to a composition and method for treating various waste streams to separate oil from water and more specifically to novel cationic polyelectrolyte blends which exhibit surprising and unexpected demulsifying and coagulating effects on oil in water emulsions.

BACKGROUND OF THE INVENTION
In water chemistry, there are basically two types of emulsions that are commonly found, oily waste water and waste oil emulsions. An oily waste water emulsion (oil in water emulsion) is comprised of a continuous water phase and a dispersed oil phase, and may contain a variety of oil types in a wide range of concentrations, and may ~lso contain other contaminants such as emulsifiers, detergents, cleaners, solvents, etc. as well as suspended solids, such as silicates, metal hydroxides and the like. The treatment of oily wastewater is normally divided into two steps: 1) coagulation - where the emulsifying properties of the oil droplet is destroyed, and 2) flocculation - where the neutralized oil droplets are agglomerated into large separate globules.
It is well known in the art that the demulsification and separation of oil in water emulsions has been very difficult. The coagulation of oil in water emulsions involves the neutralization of the stabilizing factors to allow the emulsified oil droplets to coalesce. Since the emulsified oil droplets are negatively charged (anionic), chemical demulsifiers are generally positively charged (cationic). Various inorganic emulsion breakers are known including polyvalent metal salts such as alum (Al2(S04~3), AlCl3, FeCl3, Fez(SO4)3, Na2Al2O4 or NaAlO2 calcium hydroxide; mineral acids such as H2SO4, HCl, HNO3;
and adsorbents such as pulverized clay and lime. In addition, various organic emulsion breakers have been used for breaking oil in water emulsions which include polyamines, polyacrylates, their substituted copolymers, cationic starches, and the like.
However, due to the complexity of the various types of oil in water emulsions, the above inorganic and organic emulsion breakers are not always successful. It has now been discovered that certain blends of these emulsion breakers not only aid in coagulation, but noticeably speed the coagulating reaction.

SUMMARY OF THE INVENTION
It is an object of this invention to provide a composition for coagulating oil in water emulsions.
It is another object of this invention to provide a composition for treating waste streams containing oil in water emulsions to break the emulsion and thereby separate the oil from the water.
In accorclance with the present invention there have been provided certain novel compositions comprising a mixture of three cationic polyelectrolytes wherein the three polyelectrolytes include a) an inorganic polyelectrolyte selected from the group consisting of polyaluminum chloride, alum, calcium hydroxide and mixtures thereof, b) a cationically modified starch, and c) an epihalohydrin~ The above three component blends of cationic polyelectrolytes exhibit surprising and unexpected synergy in demulsifying and coagulating oil in water emulsions.
Also in accordance with the present invention, there has been provided a method of treating waste streams containing oil in water emulsions which method comprises 2~68~ 3 adding to the waste stream a mixture of three cationic polyelectrolytes wherein the three polyelectrolytes include a) an inorganic polyelectrolyte selected from the group consisting of polyaluminum chloride, alum, calcium hydroxide and mixtures thereof, b) a cationically modified starch, and c) an epihalohydrin in an amount effective to break the oil in water emulsions.

DETAILED DESCRIPTION
This invention is directed to a composition useful for demulsifying and coagulating oil in water emulsions.
More specifically, the invention is directed to a three component mixture comprising certain cationic polyelectrolytes comprising a) an inorganic polyelectrolyte, b) a cationically modified starch and c) an epihalohydrin. The relative proportions of a:boc supra, are generally in the range (l-99):(1-99):(1-99) and are preferably in the range (20-75):(5-30):(5-30).
Suitable inorganic polyelectrolytes (a) for use in this invention include those selected from the group consisting of polyaluminum chloride, alum, calcium hydroxide, and mixtures thereof. The inorganic polyelectrolyte preferably contains aluminum ion, and is most preferably polyaluminum chloride because it is amphoteric and has a branched polymeric structure. It appears that these particular characteristics aid in precipitation.
Suitable cationically modified starches (b) for use in this invention include the quaternary ammonium alkyl ether type as disclosed in U.S. Patent No. 4,088,600 which is hereby incorporated by reference in its entirety. The preparation of these cationic starch quaternary ammonium ethers is well known to those skilled in the art. They are prepared by reacting a starch and, 206~ 3 e.g. a quaternary halohydrin salt with an alkali. See "Starch: chemistry and Technology", Whistler, R.C., and Paschall~ E.F., eds. Chapter 16, Production and Uses of Cationic Starches, by Paschall, C.F. ~1967).
The cationically modified starches may also comprise cationic quaternary ammonium modified blends of a starch and a natural gum in accordance with USSN 499,939 which is hereby incorporated by reference in its entirety. As disclosed therein, the cationically modified blends are prepared by reacting a mixture of a starch and a natural gum with a quaternary ammonium compound in the presence of an alkali catalyst at a pH in the range 12-13.
Suitable gums include carboxymethyl cellulose, guar, locust bean, karaya, alginate and xanthum gum, and is preferably guar, carboxymethyl cellulose or alginate gum.
Examples of starches which are suitable for use in this invention include corn, potato, tapioca, sago, rice, wheat, waxy maize, grain sorghum, grain starches in raw or modified forms, and the like.
The quaternary ammonium compound can be expressed by the following formula:

X
~Rl Y - N+ - R2 wherein X is any monovalent anion including, for example, chloride, bromide, iodide, methyl sulfate, and the like;
Y is selected from the group consisting of 2, 3 epoxy propyl, 3-halo-2 hydroxy propyl, 2 haloethyl, o, m, or p (~ hydroxy haloethyl) benzyl; Rl, R2 and R3 are independently selected from the group consisting of hydrogen, hydroxyl, alkyl, substituted alkyl, aryl and 2(~6~ 3 aralkyl, and in which two of the R's may be joined to form a heterocyclic or homocyclic ring compound, further in which the total number of carbon atoms in all three of Rl, R2 and R3 should not exceed 14 carbons. If all three of ~1l R2 and R3 are different and R3 contains more than 3 carbon atoms, but not mor~ than 12, then R1 and R2 should preferably be from the group consisting of methyl and ethyl; and if R1 and R2 are joined to form a ring compound, R3 should preferably not be greater than ethyl.
The cationically modified starches generally have a charge den~ity in the range 0.2 to 4.0 meq/g and preferably have a charge density in the range 0.7 to 3.5 meq/g. The cationically modified starches generally have a molecular weight in the range from 25,000 to 750,000 and are preferably between 50,000 to 500,000.
Epihalohydrin~ (c) suitable for use in this invention are disclosed in U.S. Patent No. 3,738,945 which is hereby incorporated by reference in its entirety. The epihalohydrin is preferably dimethylamine epichlorohydrin having a charge density of +7.5 meq/g and a molecular weight in the range 50,000 to 100,000, preferably about 75,000.
In general, the cationic polyelectrolyte demulsifiers of the instant invention may be added directly to the waste stream containing the oil in water emulsion in an amount effective to break the oil in water emulsion, generally at a dosage concentration in the range 10 ppm to 5000 ppm, depending of course, on the concentration of oil in the waste stream, and is preferably added at a dosage concentration of between 500 to 3000 ppm. The cationic polyelectrolyte demulsifiers may optionally be diluted with a suitable solvent, typically water, prior to adding them to the waste stream.

68~3 Without further elaboration, it is believed that one of ordinary skill in the art, using the preceding detailed description can utilize the present invention to its fullest extent.
The following examples are provided to illustrate the invention in accordance with the principles of this invention, but are not to be construed as limiting the invention in any way except as indicated in the appended claims. All parts and percentages are by weight unless otherwise indicated.

Example 1 This example illustrates the surprising synergy exhibited by the claimed invention when tested on twc separate oil in water emulsions which resulted from waste water streams from two separate nylon extruding processes each of which utilized various distinct lubricants, and additionally, a third oil in water emulsion was obtained hereinafter indicated as Emulsion A and Emulsion B from the waste oil stream of a locomotive degreasing process.
The two emulsions from the nylon extrusion waste stream were diluted to 1% concentrations. The efficacy of the three component blended formulations were evaluated on their ability to break these emulsions when compared to efficacy of the individual components. The formulation dosages screened upon Emulsion A (Table 2) ranged from 2500 ppm to 5000 ppm. The formulation dosages screened upon Emulsion B (Table 3) ranged from 1000 ppm to 5000 ppm. The treated emulsions were mixed for approximately 5 minutes and allowed to stand, without mixing, for thirty minutes. The subnatant was sampled and transferred to a colorimeter and the percent transmittance (%T) was recorded. The higher the %T
translated to a more effective demulsifier.

Z(~61~ 3 Table 1 describes the nature and rela~ive proportions of the components in the various formulations screened against these emulsions. Tables 2 and 3 indicate that the three component formulations provided a more effective treatment than any of the individual components and were in fact more effective than would have been expected from the combination of the individual components. In particular, it should be noted that the formulations designated A and C not only outperformed all of the individual components, but two of the components;
DMA-EPI and PAC failed to break the emulsion at all.

Table 1 INITIAL STARCH COAGULANT BLENDS
FORMULATION (%) ACTIVES
FORMULATION STARCH PAC DMA-EPI

lCorn starch with a molecular weight 50-200,000 and charge density 2-4.0 meq/g.
2Corn starch with a molecular weight 25 150,000 and charge density 0.5 to 2.0 meq/g.
3Corn starch-guar gum with a molecular weight 200-750,000 and charge density 0.2 to 2 meq/g.

9~ 8~)13 o o ~ In o o o o o ~ ;o o ~ o o o o o o o o ~ U~ ~
z o U o ~ o ~ o o o o ~ O ~

H _ H
~ Z Z ou~ mo ooooo ~ O ~ ~: N O O O O

.~_ O O O O O O O O O O O
I
E~
v v ~n o\O
O O O

U P: ~ X ~o ~o ~ ~ O
O V ~ ~ ~, C~ O O O X ~

~ tn X X E U
o o o ~ o ~
u~ ~ ~ ~ u ~ u u p~ ~ ~; ~

u~ o u~ o 68~3 o ~ ~o ~ ~ CO ~ ~Q U~
O ~ ~ ~ ~D

O ~ ~ r7 N N ~ U~
O ~`I N N

C
H
E~
Z U ~ o ~ cn ~ ~ o O 0~ ~4 0 1` 1` ~

H o~ H

O O ~ O d ' 1~') N ~1 ~n N

C ~ ~ ~
O ID ~O O O ~
~ ~ m ~ u~
O ,¢ 0\
o o o ~
~ o H ~ ~ ~o u~
O~ ~ U ,~ a) x x E J~ ~ ~ .~C C.~ ~I E3 ~ u ~ a ~ o In o E.~ample 2 This example contrasts the performance of the C.M.S.
in Formation C and the three most effective formulations of this invention for breaking an oil in water emulsion obtained from the waste stream of a locomotive degreasing process. The results are reported as turbidities (NTU) and accordingly, a lower number reflects a more e~fective treatment. All of the products were screened at the optimum dosage for the C.M.S. in Formulation C, which was the most effective individual modified starch. As indicated in Table 4, all three formulations provided superior performance to the C.M.S. (in Formulation C) by itself. Of these, the sample treated with Formulation C
was the most effective as evidenced by a relative decrease in turbidity of 49 NTU less than the C.M.S. used in Formulation C. This was surprising and unexpected since the PAC and DMA-EPI which are present in Formulations A-C failed to break the emulsion at all.
That is, it would have been expected that a blend of these ineffective components would have negatively arfected the performance of the C.M.S. used in Formulation C.

Table 4 FIELD TESTING AT UNION PACIFIC RAILROAD LN!_PLATTE
POLYMER CONCENTRATION TURBIDITY
(PPM) tNTU) Cationic starch in 120 68 Formulation C*
Formulation C 120 19 Formulation B 120 28 Formulation A 120 22 * ~ost effective cationi~ modified starch when tested by itself upon the above emulsion.

Claims (9)

1. A composition for use in demulsifying and coagulating oil in water emulsions comprising a mixture of three cationic polyelectrolytes wherein the polyelectrolytes include (a) an inorganic polyelectrolyte selected from the group consisting of polyaluminum chloride, alum, calcium hydroxide and mixtures thereof, (b) a cationically modified starch, and (c) an epihalohydrin.
2. A composition according to Claim 1 wherein the ratio of the cationic polyelectrolytes a:b:c is in the range (1-99):(1-99): (1-99).
3. A composition according to Claim 2 wherein the ratio of the cationic polyelectrolytes a:b:c is in the range (20-75):(5-30):5-30).
4. A composition according to Claim 1 wherein the inorganic polyelectrolyte (a) is polyaluminum chloride, the cationic starch (b) is a cationic quaternary ammonium modified blend of a starch and a natural gum, and the epihalohydrin (c) is dimethylamine epichlorohydrin.
5. A composition according to Claim 1 wherein the cationic starch has a charge density in the range 0.2 to 4.0 meq/g and a molecular weight of at least 25,000 and less than 750,000.
6. A composition according to Claim 1 wherein the cationic starch has a charge density in the range 0.7 to 3.5 meq/g and a molecular weight in the range 50,000 to 500,000.
7. A method for demulsifying and coagulating oil in water emulsions comprising contacting the emulsion with the composition according to Claim 1.
8. A method according to Claim 7 wherein the effective amount is a dosage concentration in the range of from 10 ppm to 5000 ppm.
9. A method according to Claim 8 wherein the dosage concentration is in the range of from 500 ppm to 3000 ppm.
CA 2068013 1992-01-30 1992-05-05 Cationic polyelectrolyte demulsifier and coagulator Abandoned CA2068013A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US82809692A 1992-01-30 1992-01-30
US828,096 1992-01-30

Publications (1)

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AU (1) AU646733B2 (en)
BR (1) BR9202070A (en)
CA (1) CA2068013A1 (en)
ZA (1) ZA923161B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100300962A1 (en) * 2009-06-02 2010-12-02 Delaval Holding Ab Methods for treating wastewater using an organic coagulant
US20150090667A1 (en) * 2012-03-28 2015-04-02 Halosource, Inc. Water treatment compositions and methods of use
US20180327673A1 (en) * 2017-05-09 2018-11-15 Baker Hughes, A Ge Company, Llc Demulsifier or water clarifier activity modifiers
US11174374B2 (en) * 2016-12-01 2021-11-16 Dober Chemical Corporation Water-enriching and water depleting compositions and methods

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100300962A1 (en) * 2009-06-02 2010-12-02 Delaval Holding Ab Methods for treating wastewater using an organic coagulant
US20150090667A1 (en) * 2012-03-28 2015-04-02 Halosource, Inc. Water treatment compositions and methods of use
US20160221847A1 (en) * 2012-03-28 2016-08-04 Dober Chemical Corp. Water treatment compositions and methods of use
AU2013239687B2 (en) * 2012-03-28 2017-11-30 Dober Chemical Corp. Water treatment compositions and methods of use
US12172911B2 (en) * 2012-03-28 2024-12-24 Dober Chemical Corp. Water treatment compositions and methods of use
US12180099B2 (en) * 2012-03-28 2024-12-31 Dober Chemical Corp. Water treatment compositions and methods of use
US11174374B2 (en) * 2016-12-01 2021-11-16 Dober Chemical Corporation Water-enriching and water depleting compositions and methods
US20180327673A1 (en) * 2017-05-09 2018-11-15 Baker Hughes, A Ge Company, Llc Demulsifier or water clarifier activity modifiers
US11124711B2 (en) * 2017-05-09 2021-09-21 Baker Hughes Holdings Llc Demulsifier or water clarifier activity modifiers
US12371623B2 (en) 2017-05-09 2025-07-29 Baker Hughes, A Ge Company, Llc Demulsifier or water clarifier activity modifiers

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BR9202070A (en) 1993-08-03
ZA923161B (en) 1993-07-30
AU646733B2 (en) 1994-03-03
AU1514392A (en) 1993-08-26

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