GB2085433A - Poly quaternary ammonium compounds; flocculating agents - Google Patents
Poly quaternary ammonium compounds; flocculating agents Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C10G33/00—Dewatering or demulsification of hydrocarbon oils
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Abstract
Bifunctional compounds represented by the formula <IMAGE> in which Y represents alkylene, 2-hydroxy-1,3-propylene, -CH2CH2NHCONHCH2CH2- or -CH2CH2CH2NHCONHCH2CH2CH2 and x represents 0 or an integer from 1-7 obtained by the reaction of epihalohydrins and secondary amines, having two reactive terminal halogen atoms and at least one cationic group, are reacted with ammonia, monofunctional amines or bifunctional amines to give linear cationic products. The compounds I, their hydrolysis products and their reaction products with ammonia or amines are useful as demulsifiers for flocculating or breaking oil-in-water or water-in-oil emulsions. Certain of the reaction products II are novel. The compound I may be reacted with ammonia or a mono or tri- functional amine in a ratio 1:2 to provide compounds having terminal amino groups or with bifunctional amines in a ratio 2:1 to provide compounds having terminal halogen atoms which may be further reacted with ammonia or a monofunctional amine.
Description
SPECIFICATION
Improvements in or relating to organic compounds
This invention relates to compounds containing multiple cationic groups.
It is known from British Patent 1 213745 to prepare bifunctional compounds of formula I
in which Hal is chlorine or bromine, preferably chlorine each of R, and R2 are selected from C alkyl and C2 5 hydroxyalkyl radicals
Y is selected from C2 6alkylene radicals, 2-hydroxy-1 ,3-propylene radicals, and the radicals -CH2CH2NHCONHCH2CH2- and -CH2CH2CH2NHCONHCH2CH2CH2 A0 is an anion
and x is an integer of from 0 to 7, provided that when x is greater than 2, each of the symbols Y need not necessarily have the same significance.
According to the above patent, compounds of formula I are used to crosslink polyamides by reaction with secondary amine groups in the polymer chain.
It has now been found that compounds of formula I, together with their hydrolysis products and their reaction products with compounds selected from ammonia and non-polymeric monofunctional amines and bifunctional amines are useful as demulsifiers for the flocculation or breaking of oil-in-water emulsions. Although compounds of formula I and their reaction products with primary and secondary lower alkylamines are known, their reaction products with other amines are novel.
Accordingly, the present invention provides a process for the flocculating or breaking of an emulsion characterised in that the emulsion is treated with a compound of formula II
X~[~Cp~B~]~k~Cp~X [ Ac3 ] m II
In which Cp represents the residue of a compound of formula I from which the halogen atoms have been removed, i.e. it has the formula:
in which R1, R2, Y and x are as defined above;B represents a group of formula Ill
in which the groups R', which may be the same or different, are selected from hydrogen, C, 20alkyl, C2#20aIkenyl, C2#6hydrnxyalkyl, aralkyl and groups of formula iV
where n is from 2 to 150, preferably 2 to 50, and each R5 independently is hydrogen or methyl and D is C2#20aIkylene, a group of formula V -[-(CH2)-d-NR6-]-e-(CH2)-f- V in which e is 1 to 5,
d and f are independently 2 to 5 and
R6 is hydrogen, Cl 6alkyl, C2#6-hydroxyalkyI, or C1#6haloaIkyl, or a group of formula -(-CH2-)-g-R7-(-CH2-)-h where g and h are independently 0 to 3 and
R7 is a 5- to 7-membered ring system which may be saturated or wholly or partially unsaturated and which may contain all carbon atoms or a mixture or carbon, oxygen and/or nitrogen atoms, or B represents a group of formula VI
in which D' together with the two nitrogen atoms represents a ring system comprising one or more 5- to 7-membered rings, which may be saturated, unsaturated or aromatic and which may contain further nitrogen atoms,
R' and d are as defined above, each p is independently 0 or 1 and q is O or 1; each X, independently, is chlorine; bromine; hydroxyl; a group of formula VII
in which the groups R, which may be the same or different, are selected from hydrogen, C, 20alkyl, C2#20aIkenyI, C;2#6hydrnxyalkyl, C;;3#8cycIoaIkyl, phenyl, aralkyl, alkaryl and groups of formula IV above or two groups R, together with the nitrogen atom to which they are attached, form a saturated or unsaturated 5- to 7-membered ring which may contain one or more oxygen or one or more further nitrogen atoms and which may be alkyl substituted in positions not adjacent to the quaternary nitrogen atom or three groups R together with the nitrogen atom to which they are attached form a polycyclic ring system which may contain further oxygen or nitrogen atoms, or represent an aromatic ring system which may contain one or more further nitrogen atoms, or a group of formula Vlil
in which R' and D are as defined above,
k is an integer, preferably from 0 to 10, more preferably from 0 to 5, particularly 0 or 1, A# is an anion; and m is an integer equal to the number of cationic sites in the molecule.
The invention provides novel compounds of formula Ia X'-[-Cp-B-]-k-Cp-x' #AG ] m Ila
in which Cp, B, k, A and m are as defined above and X' has any of the significances of X above, with the provisos that when k = 0, then 1) X' is other than chlorine or bromine
2) when each X' is a group of formula VII, then when two groups R on each of the groups X' are C1 4alkyl, then at least one of the other two groups R in the molecule is other than hydrogen, and when one group R on each of the groups X' is C1 4alkyl, then at least one of the other four groups R in the molecule is other than hydrogen
and 3) when each X' is a group of formula VEIL, then in each X', at least one group R' is other than hydrogen.
Preferably X' is a group of formual VII, more preferably one in which all groups R are other than hydrogen, or one in which at least one group R is C8 ,8alkyl. Preferably both X' groups are the same.
When k > O, so that 2 or more groups Cp are present in the molecule, these may be the same or different but are preferably the same. Similarly when k > 1, so that 2 or more groups B are present these may also be the same or different but are preferably the same.
According to British Patent 1 213 745, compounds of formula I in which X is chlorine or bromine are prepared by the reaction of a specific excess of epihalohydrin, preferably epichlorohydrin, with a mono-functional secondary amine for example dimethylamine or a bifunctional tertiary amine, for example tetramethyl ethylenediamine, or mixtures of these in the presence of an acid which partially converts the amine to the amine salt. The preferred compounds of formula I are those in which, independently, R1 and R2 are methyl, x is O or 1, more preferably 1 and Y is 2-hydrnxy-1-3-prnpylene.
The compound of formula I (hereinafter referred to as the 'coupling agent') has two reactive halogen end groups, and it is known that it can be reacted further with monofunctional primary or secondary lower alkylamines to give products having terminal amine salt groups. The process according to the invention may be carried out using these known compounds, that is, by flocculating or demulsifying with a compound of formula lIb X"#Cp#X" LAO ] m l l b in which Cp, A- and m are as defined above and each X", which may be the same or different, is chlorine, bromine or a group of formula
in which R3 is hydrogen or C1 4alkyl, and R4 is C1 4alkyl.
Under basic conditions the amine salt end groups may lose a proton to give end groups of the formula R3R4N-, and formula llb is intended to include the reaction products both in amine salt and in free base form.
It is also known that the coupling agent may be reacted with an excess of a di-primary amine such as diethylene triamine to give compounds of formula llc H2N#D#NO+H2-L-Q-NO+ H2-D-N#H2-#-Cp-NO+ H2-D-NH2 [ A(3 ] m llc in which Cp, D, k, AO and m are as defined above. The process of the invention may also be carried out using compounds of formula llc.
The coupling agent may also be reacted with ammonia, monofunctional amines or bifunctional amines. A preferred class of monofunctional amines are monofunctional tertiary amines of formula (R)3N in which all groups R are other than hydrogen, preferably C1 20alkyl or C2#6hydrnxyaIkyI. A further preferred class are primary, secondary or tertiary amines having at least one C8 18alkyl group.
Preferred tertiary amines are those in which either all three R groups are C2 4hydroxyalkyl (particularly hydroxyethyl) or one R group is C8 18alkyl (preferably C10 14) and the remaining two
R groups are C1 4alkyl (preferably methyl) or C2 4hydroxyalkyl (preferably hydroxyethyl).
Preferred primary and secondary amines are those in which the R groups which are other than hydrogen are C1 20alkyl, C2#6hydrnxyaIkyl, or benzyl. Particularly preferred primary and secondary amines are those having at least one C8 18alkyl group, for example coconut or hardened tallow fatty acid amines.
Reaction with monofunctional tertiary amines will result in the formation of one quaternary ammonium group for each molecule of amine reacted, and these quaternary end groups will then be incapable of reacting further. Monofunctional tertiary amines may therefore be regarded as terminating groups, having the function of terminating the reaction sequence. Similarly, ammonia or monofunctional primary or secondary amines will give rise to cationic amine salt groups, which will be incapable of further reaction as long as they are not neutralised by base.
On the other hand, reaction with bifunctional amines may be controlled by varying the molar ratio of the reactants in such a way that either free active halogen groups or free amino groups are left at the ends of the molecule, and these groups are capable of further reaction. A bifunctional amine may thus be regarded as a bridging group capable of extending the size of the molecule. An amine is described herein as "bifunctional" if it has two reactive amino groups which readily react with coupling agent, even if it may in addition have one or more less reactive nitrogen atoms which will not react as readily. Thus for example diethylene triamine,
H2N-C2H4-NH-C2H4-NH2, may be regarded as a bifunctional amine.
Preferred groups B are of formula III in which each R' is independently hydrogen or methyl and D is D" where D" is C2#12aIkyIene, preferably -C2H4-, -(-CH2-)-s or -(-CH2-)-12, or a group of formula V in which e is 1, d and f are independently 2 or 3 and R6 is hydrogen; or B is a group of formula Vl in which D' forms with the nitrogens a piperazine ring, each p = 1, R' is
H, d is 2 and q = O or 1.
A further preferred class of groups B are those of formula III in which three groups R' are hydrogen and one group R' is C8#20aIkyI, preferably C11 15alkyl, and D is D" as defined above.
Thus, for example, two moles of a coupling agent Cl-Cp-CI may be reacted first with one mole of a diamine (R')2N-D-N(R')2 to produce the structure IX
and this may then be further reacted with 2 moles of a monofunctional amine (R)3N to act as a terminator giving the structure of formula X.
By increasing the ratio of bifunctional amine to coupling agent in the first step, the number of units in the molecule may be increased, until with equimolar amounts a linear polymer may be obtained. By further increasing the amine ratio, compounds having free amino end groups will be obtained, a 2:1 ratio of bifunctional amine to coupling agent giving structures of formula Xl
Such compounds may then be reacted for example with a different coupling agent Cl-Cp'-CI and then terminated with a tertiary amine, for example giving structures such as XII
It will be seen that by such stepwise reaction sequences a wide range of linear structures may be built up.
It will be appreciated that when any of R1 are hydrogen, the cationic grouping -NL+#(R')2- will be an amine salt group, not a quaternary ammonium group. By treatment with base such groups will lose HJ and revert to secondary amine groups -NH- or tertiary amine groups -NR'- where R' is other than 11. This will of course affect the acid-base properties and the water solubility of the product molecule. The same considerations apply to end groups (R)3N'3- - where one or more groups R are hydrogen.
The properties of such compounds will in general depend upon their chain length, the spacing of quaternary groups along the chain, and the nature of the side groups which are present. For example while the compounds will normally be water-soluble, it is possible by incorporating a relatively high number of lipophilic side chains to produce water-insoluble products.
The anion AG will generally be composed of the anion of the acid employed in the formation of the coupling agent and the halide anion derived from the epihalohydrin. When hydrochloric acid is used and the reagent is epichlorohydrin, the anion A^- will be CIG. It is of course possible to exchange the anion for another in the finished product. If a polyvalent anion is present, for example SO',~, the symbol Ar is to be understood as referring to one equivalent of anion, for example 2SOt-74-S.
Mixtures of products of formula II may be obtained by the use of mixtures of reagents at one or more steps of the reaction sequence, after the initial preparation of the coupling agent 1.
The coupling agent itself, or any compound such as IX having terminal halogen atoms, may be hydrolysed by aqueous alkali to the corresponding compound having terminal hydroxyl groups.
The conditions employed for preparation of any adduct will depend both on the desired end products and the nature of the starting materials for each step of the particular reaction sequence planned. In the case of the more reactive amines, the reaction usually is exothermic even when the coupling agent is in aqueous solution, and one reagent will be added slowly to the other at a starting temperature such that the reaction exotherm will commence. The rate of addition of reagent is then used to control the reaction temperature in the manner usual in such cases with application of external cooling if necessary. Starting temperatures are usually between 0 to 1 0O'C, preferably 20-60 C, whilst the reaction temperature upper limit is dictated by the boiling point of the amine employed and the nature of the product desired.In some cases, the addition of water to the reaction mass or one or both of the reagents may be required, in others the coupling agent may itself have been prepared in aqueous solution and require no further water addition. Conversely, the preparation of certain materials may require their production by reaction in the absence of water. Alternative organic solvents of suitable polarity may also be employed where required.
Amines of low water solubility or reactivity, will usually require rather different reaction conditions and may require careful control of reaction pH. A polar solvent is usually employed to ensure that the reaction mixture is homogenous, the two reactants normally but not necessarily being mixed together in the solvent at ambient temperature and then brought to reaction temperature. In such cases, the reaction temperatures will be higher than those employed for the more reactive amines, and a reaction exotherm is not usually detected. The nature of the solvent taken is a matter or choice dectated by the nature of the reactants used, the temperature of reaction and the final product properties required. Clearly the boiling point of the solvent must be equal to or greater than the maximum temperature of reaction.Such reaction temperatures generally lie in the range 60-100 C. Suitable solvents include the lower alcohols, e.g. ethanol; glycols, e.g. ethylene glycol and glycol ethers. The solvent may then be distilled off from the reaction mass before proceeding, or allowed to remain for subsequent steps or even remain as a component of the final product formulation should it be so desired.
Where the amine is of low water solubility or reactivity, it may also be advantageous to use a coupling agent prepared using the minimum quantity of water.
The progress of any reaction step may be monitored by following the disappearance of amine or coupling agent functional groups, or the formation of ions where this occurs during the reaction, for instance when the coupling agent contains the a-chloro-ss-hydroxy-ethyl reactive site in which case the appearance of chloride ion may be monitored. Reaction is continued until the theoretical quantity of chloride ion has been liberated, or until the concentration of chloride ion becomes constant.
The hydrolysis of halogen end groups to hydroxyl may be carried out for example in dilute aqueous sodium hydroxide at temperatures of about 60 C.
The compounds of formula II have surface-active properties which render them useful for example in the flocculation and demulsification of oil-in-water or water-in-oil emulsions. By flocculation is meant the initial stage in the breaking of an emusion in which, for an oil-in-water emulsion, the oil droplets coagulate into aggregations or 'flocs' of individual oil droplets. The breaking of the emulsion may not go beyond this stage, in which case the flocs, which still contain large quantities of water, are not useable as fuel or as oil feedstock without further processing.
The second stage in the breaking of the emulsion is the coalescence of the oil droplets in the floc to give larger and larger drops until eventually a continuous oil phase containing very little water may be produced. The conversion of a flocculate to a continuous oil phase may be assisted by heating.
The following Examples, in which all parts and percentages are by weight and temperatures are in degrees Centigrade, illustrate the invention.
Examples 1-4: Preparation of coupling agents
Example 1
To a mixture of 3514 parts of deionised water and 1131 parts (2 mol) of 60% dimethylamine solution is slowly added 883 parts of 30% hydrochloric acid, maintaining the temperature of the reaction mixture between 35 and 40 . While cooling continuously and stirring, 2093 parts (3 mol) epichlorohydrin are added slowly at such a rate that the temperature remains between 35 and 40 . When all the epichlorohydrin has been added, the mixture is allowed to react for a further 8 hours at 35-40 and then cooled to 25 . The 3:2 adduct so produced contained 2 moles of ionic CIG and 2 moles of nonionic reactive chlorine per mole of product.
Example 2: Using less water
104.3 Parts of 35% aqueous hydrochloric acid (1 mol) is slowly added to 150 parts of 60% aqueous dimethylamine (2 moles) with stirring and cooling to maintain the temperature below 40 . The mixture is further cooled to 35 and 277.5 parts (3 moles) epichlorohydrin is added at a rate such that the temperature is maintained at 35 to 40 . The product is stirred for 1 hour at 50 and left to stand overnight.
Example 3
121.67 parts of 30% aqueous hydrochloric acid (1 mole) is slowly added to 210 parts of diethanolamine (2 moles) with stirring and cooling to maintain the temperature below 40 . The mixture is further cooled to 35 and 277.5 parts (3 moles) epichlorohydrin is added at a rate such that the temperature is maintained at 35 to 40 . The product is stirred for 1 hour at 50 and left to stand overnight.
Example 4
86.3 Parts of 36.5% aqueous hydrochloric acid (2 moles) is slowly added to 110 parts of deionised water at 15'. 50 parts (1 mole) of tetra methyl ethylenediamine is then added slowly, with sufficient cooling to maintain the temperature between 35-40 . The mixture is then cooled to 25 and 79.8 parts (2 moles) of epichlorohydrin added over one hour, during which time temperature is maintained at 25 . The product is then stored overnight at 40 .
Examples 5-20: Termination reactions
In each of the following Examples, 1 mole of coupling agent is reacted with 2 moles of a monofunctional amine, to give compounds of the type R3N+ -Q-N4 R3 2C1 In all cases reaction is continued until a constant level of chloride is observed. Table 1 gives the reagents and reaction conditions. Where additional solvent is indicated, the quantity is given in parts by weight based on amine = 1 part.
Table 1
Ex. coupling anine additional reaction No. agent of R3 solvent conditions example 5 1 CH 3SN ethanol reflux 5 hr, then 2 5 3 (3.7 parts) distil off ethanol 6 2 SXH2 - reflux 8 hr maintain pH 7 by addition of 30% NaOH.
7 2 H(c2H4OH)3 - 85-95 / 4 hr 8 2 EN(C2H40H)2 - 60-70 / 4 hr 9 1 9NH2 - 65 > 75 t 3 hr 10 1 tCn2NS2 - 60 /4 hr,then 80/1hr 90'/21/2 hr# 95'l3hr' 11 2 (n-C41i9)3N 3N ethylene glycol 850 / 20 hr 3N nonoethyl ether (0.8 ether ethanol (3.9 parts) 12 2 coconut fatty - 1100 / 20 hr dialkylamine (product is a Cr ) 2NH waxy solid) (see below) 13 1 dietho'::ylated - 95 / 10 hr hardened tallow product is n oft, fatty nine pasty, solid ntN(C2H40H)2 soluble in ethanol) (see below) 14 1 C 60-70 / 31/2 hr Table 1 (continued)
EX coupling amine additional reaction No. agent of R3N solvent conditions example 15 1 fatty monoalkylamine ethylene glycol 750 / 1 hr then RfNH2 monoethyl 900 /21 hr (see below) ether (0.33 parts) 16 1 fatty dialkylamine as Ex. 15 as Ex. 15 RfN (CH3)2 (see below) 17 1 dimethyl mono - 700 / 1 hr then coconut fatty amine 900 / 2 hr RCN(GH3)2 (see below) 18 3 N(C2H4OH)3 - 85-95 / 4 hr 19 4 (CH3)3N - 90 / 10 hr (27.5Z aqueous solution) 20 4 as Ex. 13 - g50 I 10 hr Table 2
Ex. difunctional amine additional reaction No. solvent conditions 22 U2NcH2CH2NH2- 600 / 2 hr 23 - 400/2hr,then 60 /1hr 850/2hr and 950I1hr 24 H2NCH2CH2CH2NH2 - 600 / 2 hr 25 H2N(cH2)6NH2 - 600 / 1 hr then 800 I 4 hr 26 H2N(cH2)12NH2 - 600 / 1 hr then 80 I 4 hr 27 HN ~IN-CH2CH2NH2 85 / 4 hr 28 H2NCH2CH2NXCH2CH2NH2 - 400 / 4 hr then 600 1 2 hr Table No. 2 (continued)
Ex. difunctional amino additional reaction No. solvent conditions 29 RcNHCH2CH2Cl12t#H2 industrial methylated 85-90 /18 hr (Rc=coconut fatty alkyl spirits (1 part) see above) 30 ns 1,4-diaza- - 500 1 1 hr then 30 U bicyclooctane . 50 / 2 hr The coconut fatty alkyl group Rc has the following typical analysis:
Caproyl (C6) 0.5 parts
Caprylyl (C8) 8.0 parts
Capryl (C10) 7.0 parts
Lauryl (C12) 50.0 parts
Myristyl (C14) 18.0 parts
Palmityl (C16) 8.0 parts
Stearyl (C18) 1.5 parts
Oleyl (C18) 6.0 parts
Linoleyl (C18) 1.0 parts
The hardened tallow fatty alkyl group R, has the following typical analysis: fK# Myristyl (C14) 3.5 parts
Pentadecyl (C15) 0.5 parts
Palmityl (C16) 30.0 parts
Margaryl (C17) 1.5 parts
Stearyl (C18) 62.5 parts
Myristoleyl (C14) 0.5 parts
Palmitoleyl (C16) 0.5 parts
Oleyl (C18) 1.0 parts
The fatty alkyl group Rf has the following typical analysis::
C13 alkyl 70 parts
C15 alkyl 30 parts of which 50 parts is straight chain and 50 parts is branched chain, mainly methyl.
Example 21: Termination with a difunctional amine
The aqueous reaction product prepared as in example 1 (1 mole) is heated to between 40 and 50 , and 174 parts (2 moles) of a commercially available diamine mixture, containing 30-36% hexamethylene diamine and 64-70% diamino-cyclohexane, is added dropwise over 13 hours.
The mixture is then stirred at 50 C for a further 4 hours or until analysis shows the theoretical concentration of chloride ion.
The resulting product is of the type of formula Xl above.
Examples 22-30: Bridging Reactions
In each of the following reactions, 2 moles of the coupling agent of Example 1 is reacted with 1 mole of difunctional amine to give structures of the type: Cl-Cp-B-Cp-CI Table 2 gives the amine reagent and the reaction conditions.
Examples 31-41: Termination of bridged compounds
In each of the following Examples, 1 mole of a bridged compound from Examples 22-30 is reacted with 2 moles of a monofunctional amine, to give structures of the type: P3NO+#Cp#B#Cp#N~P3 2CI9 Table 3 gives the reagents and reaction conditions used
Table 3
Ex. bridged amine R3N additional reaction No. compound solvent conditions oi Example ~ IOf.Examplo 31 22 N(CH2CH20H)3 - 85-950 / 4 hr 32 23 N(CH2CH20H)3 - 95-980 / 3 hr 33 22 iN(CH2CH20H)2 ---;;- 60-700 / 4 hr 34 25 (CH3)2NH 40013 hr then (60Z aqueous solna - 700/1 hr 35 25 as Ex. 13 - 500/1 hr, 80017 hr 60-70"/31/2 hr 37 26 (CH3)2NH (60% aqueous 40 /3 hr then solution) 700/1 hr 38 26 tNH2 600/4 hr then 80'Ii hr 90 /21/2 hr, 95013 hr 39 26 N(CH2CH20H)3 85 -95 / 4hr 40 30 N(CH2CH20H)3 - 950/16 hr 41 30 CRf)N(CH3)2 isopropanol 90#950/16 hr (4.7 parts) CRf= fatty alkyl, + ethylene see above) glycol see (4.7 parts) Application Examples-Dem ulsification Samples of industrial effluent were obtained, containing approximately 4% of rolling oils, along with other contaminants. Varying applications of demulsifier were added to aliquots of the effluent samples, which were then shaken to an equivalent degree, and left to stand.
Any separation or flocculation was then observed, as well as the clarity of the aqueous phase, and the optimum concentration of chemical noted.
Application Example A
The effluent contained 4% of a rolling oil containing fatty esters and mineral oil, with other additives, and industrial waste contaminants.
Treatments:
Non-ionic, such as polyethylene glycols, ethoxylated alcohols and ethoxylated alkyl phenols, had a slight effect only, and only at high application levels.
Aluminium chloride: at high application levels (2000-5000 ppm) caused fast flocculation, but also incorporated water into the flocculate and left a hazy aqueous phase.
Aluminium chloride, calcium chloride and ferric chloride were all ineffective at less than 1000 ppm.
The product of Example 7 was effective at 200 ppm, and produced a homogenous oil layer and a clear, colourless aqueous phase within 24 hours.
Application Example B
This effluent contained 4% of a rolling oil, this being a blend of animal grease and mineral oil with quantities of fatty esters, fatty alcohols, rolling additives and emulsifiers. This was heavily contaminated with industrial wastes.
Treatments
Inorganic flocculants had very little effect. The product of Example 8 was effective at 10,000 ppm. The product of Example 7 was effective at 5000 ppm. The product of Example 31 was effective at 1000 ppm.
These products caused separation to occur gradually over 2-3 days, producing a homogenous oil layer and a transparent pale yellow aqueous layer.
Application Example C
A waste rolling oil from a steelworks contained 1.03% oil in an aqueous phase.
a) The products of Examples 13, 17 and 19 were effective in the range 1000-5000 ppm to give a flocculated oil layer and a slightly cloudy aqueous layer.
b) The products of Examples 40 and 41 at 1000-5000 ppm gave a very turbid aqueous layer and a reasonably water-free oil layer.
c) The products of Examples 16, 34, 37 and 38 were effective at 500-1000 ppm with the same results as in a) above.
d) The product of Example 15 was effective at 500-750 ppm giving a clearer aqueous layer than that of a) above.
To 14,000 s of the oil emulsion was added 750 ppm of the product of Example 15. The tank contents were mixed by pumping for 6 min and left to stand at 28". After 40 hr, the oil content in the aqueous layer was 0.046%. The flocculated oil in the upper layer when heated to 60 gave oil of 1.3% water content within 1 hr.
Application Example D
A bitumen oxidation plant produced a distillate containing 60% water and 40% oil, with oil as the continuous phase.
The products of Examples 5, 13, 14 and 19 were effective at 1000-2000 ppm to give an oil layer and a clear light brown aqueous layer either in the cold or at the initial temperature of the distillate (40-50ç). Separation was faster at the higher temperature.
To 29,000 1 of the water-in-oil emulsion containing 62.4% water at pH 9.6, 50 was added 1000 ppm of the product of Example 13. The pH was adjusted to 7 with hydrochloric acid and mixing was carried out by circulating pump for 30 min. Water separation began at once and was complete after standing for 15 hr. Water-free oil and clear water suitable for sewage discharge were produced.
Claims (24)
1. A process for the flocculation or breaking of an emulsion characterised in that the emulsion is treated with a compound selected from compounds of formula I
in which Hal is chlorine or bromine, each of R, and R2 are selected from C, 5alkyl and C2 5hydroxyalkyl radicals
Y is selected from C2 6alkylene radicals, 2-hydroxy-1 3-propylene radicals, and the radicals -CH2CH2NHCONHCH2CH2- and -CH2CH2CH2NHCONHCH2CH2CH2 A is an anion
and x is an integer of from 0 to 7, provided that when x is greater than 2, each of the symbols Y need not necessarily have the same significance, their hydrolysis products and their reaction products with compounds selected from ammonia and non-polymeric monofunctional and bifunctional amines.
2. A process as claimed in Claim 1 in which the emulsion is treated with a compound of formula II X~ [ ~Cp~B~ ] ~k~Cp~X [ A' ] m II in which Cp has the formula
in which R1, R2, Y and x are as defined in Claim 1,
B represents a group of formula III
in which the groups R', which may be the same or different, are selected from hydrogen, C, 20alkyl, C2-20alkenyl, C2#6hydrnxyaIkyI, aralkyl and groups of formula IV
where n is from 2 to 150, and each R5 independently is hydrogen or methyl and D is C2-20 alkylene, a group of formula V -[-(CH2)-d-NR6-]-e-(CH2)-f- V in which e is 1 to 5,
d and f are independently 2 to 5 and
R6 is hydrogen, C1#6alkyI, C2#6-hydrnxyaIkyI, or C1-6haloalkyl.
or a group of formula -(-CH2-)-g-R7-(-CH2-)-h where g and h are independently 0 to 3 and R7 is a 5- to 7-membered ring system which may be saturated or wholly or partially unsaturated and which may contain all carbon atoms or a mixture of carbon, oxygen and/or nitrogen atoms, or B represents a group of formula VI
in which D' together with the two nitrogen atoms represents a ring system comprising one or more 5- to 7-membered rings, which may be saturated, unsaturated or aromatic and which may contain further nitrogen atoms, R' and d are as defined above, each p is independently 0 or 1 and q is O or 1; each X, independently, is chlorine; bromine; hydroxyl; a group of formula VII
in which the groups R, which may be the same or different, are selected from hydrogen, C, 20alkyl, C2-20alkenyl, C2#6hydrnxyaIkyI, C3#8cycIoalkyl, phenyl, aralkyl, alkaryl and groups of formula IV above or two groups R, together with the nirogen atom to which they are attached, form a saturated or unsaturated 5- to 7-membered ring which may contain one or more oxygen or one or more further nitrogen atoms and which may be alkyl substituted in positions not adjacent to the quaternary nitrogen atom or three groups R together with the nitrogen atom to which they are attached form a polycyclic ring system which may contain further oxygen or nitrogen atoms, or represent an aromatic ring system which may contain one or more further nitrogen atoms, or a group of formula VIII
in which R' and D are as defined above,
k is an integer, from 0 to 10, A' is an anion; and m is an integer equal to the number of cationic sites in the molecule.
3. A process as claimed in Claim 2 in which the emulsion is treated with a compound of formula lIb X"#Cp#X" [A@]m llb in which Cp, A# and m are as defined in Claim 2 and each X", which may be the same or different, is chlorine, bromine or a group of formula
in which R3 is hydrogen of C1 4alkyl and R4 is C1 4alkyl the end groups being in amine salt or free base form.
4. A process as claimed in Claim 2 in which the emulsion is treated with a compound of formula II@ H2N~D~N#H2~[Cp~N#H2~D~N#H2~]~k~Cp~N#H2~D~NH2 [ AG ] m llc in which Cp, D, k, A- and m are as defined in Claim 2.
5. A compound of formula Ila
X'-[-Cp-B-]-k-Cp-X' [ A3 ] m Ila in which Cp, B, k, A and m are as defined in Claim 2 and X' has any of the significances of X in Claim 2, with the provisos that when k = 0, then
1) X' is other than chlorine or bromine
2) when each X' is a group of formula VII, then when two groups R on each of the groups X' are C, 4alkyl, then at least one of the other two groups R in the molecule is other than hydrogen, and when one group R on each of the groups X' is C, 4alkyl, then at least one of the other four groups R in the molecule is other than hydrogen and
3) when each X' is a group of formula Villi, then in each X', at least one group R' is other than hydrogen.
6. A compound as claimed in claim 5 in which both groups X' are the same.
7. A compound as claimed in Claim 6 in which X' is a group of formula
in which R is as defined in Claim 2.
8. A compound as claimed in Claim 7 in which all groups R are other than hydrogen.
9. A compound as claimed in Claim 8 in which all groups R are selected from C1-20alkyl and C2#6-hydroxyaIkyI.
10. A compound as claimed in Claim 9 in which all groups R are hydroxyethyl.
11. A compound as claimed in Claim 7 in which at least one group R in each group X' is C8 ,8alkyl
12. A compound as claimed in Claim 11 in which in each group X', one group R is C818alkyl and the other two are hydrogen.
13. A compound as claimed in Claim 11 in which in each group X', one group R is C8 ,8alkyl and the other two are methyl or hydroxethyl.
14. A compound as claimed in any one of Claims 5-13 in which, in the group Cp R1 and R2 are methyl
x is Oor 1 and
Y is 2-hydroxy-1,3-propylene.
15. A compound as claimed in any one of Claims 5-14 in which k > O and B is a group of formula a)
in which each R" is independently hydrogen or methyl and D" is C212alkylene or a group of formula -(-CH2-##d,-N H-(#CH2-)-v in which d' and f' are independently 2 or 3, or b) take in block no 14 in which q is O or 1.
16. A compound as claimed in any one of Claims 5-14 in which k > O and B is a group of formula
where D" is as defined in Claim 14 and R"' is C8#20aIkyI.
17. A compound as claimed in any one of Claims 5-14 in which k is O.
18. A compound as claimed in any one of Claims 5-1 6 in which k is 1.
19. A process for the preparation of a compound as claimed in Claim 17 (as dependent upon Claim 7) by the reaction of 1 mole of a compound of formula I, stated in Claim 1, with at least 2 moles of ammonia or a monofunctional amine other than a primary or secondary lower alkylamine, in aqueous medium or in a polar organic solvent.
20. A process for the preparation of a compound as claimed in Claim 18 (as dependent upon Claim 7) by the reaction of 2 moles of a compound of formula I, stated in Claim 1, with 1 mole of a bifunctional amine, followed by reaction of the intermediate product with at least 2 moles of ammonia or a monofunctional amine, both reaction steps being carried out in aqueous medium or in a polar organic solvent.
21. A compound as claimed in Claim 17 or Claim 18 (as dependent on Claim 7) whenever prepared by the process of Claim 19 or Claim 20.
22. A compound as claimed in Claim 5 as described in any one of Examples 5-20 and 22-41.
23. A process for the flocculation or breaking of an emulsion comprising treating the emulsion with a compound as claimed in any one of Claims 5-18 and 21-22
24. A process for the flocculation or breaking of an emulsion as described in any one of
Application Examples A to D.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8011212 | 1980-04-03 | ||
GB8011214 | 1980-04-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2085433A true GB2085433A (en) | 1982-04-28 |
GB2085433B GB2085433B (en) | 1985-03-06 |
Family
ID=26275069
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8110408A Expired GB2085433B (en) | 1980-04-03 | 1981-04-02 | Poly quaternary ammonium compounds flocculating agents |
Country Status (6)
Country | Link |
---|---|
CH (1) | CH655248A5 (en) |
DE (1) | DE3111386A1 (en) |
FR (1) | FR2483456A1 (en) |
GB (1) | GB2085433B (en) |
IT (1) | IT1170864B (en) |
NL (1) | NL8101586A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4692317A (en) * | 1984-11-08 | 1987-09-08 | W. R. Grace & Co. | Corrosion control in aqueous systems using cationic polymers in combination with phosphonohydroxyacetic acid |
US4692315A (en) * | 1984-04-25 | 1987-09-08 | Dearborn Chemicals Limited | Method of inhibiting corrosion in aqueous systems |
US4692316A (en) * | 1984-03-20 | 1987-09-08 | Dearborn Chemicals Limited | Method of inhibiting corrosion in aqueous systems |
US5223097A (en) * | 1986-01-09 | 1993-06-29 | W. R. Grace Ab | Method for controlling pitch on a paper-making machine |
US5626720A (en) * | 1986-01-09 | 1997-05-06 | W.R. Grace & Co.-Conn. | Method for controlling pitch on a papermaking machine |
US10563042B2 (en) | 2016-12-14 | 2020-02-18 | Ecolab Usa Inc. | Quaternary cationic polymers |
US11427964B2 (en) | 2018-06-12 | 2022-08-30 | Ecolab Usa Inc. | Quaternary cationic surfactants and polymers for use as release and coating modifying agents in creping and tissue papers |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH655092A5 (en) * | 1981-04-02 | 1986-03-27 | Sandoz Ag | METHOD FOR PRODUCING BRANCHED POLYCATIONIC CONNECTIONS. |
EP0434223A1 (en) * | 1989-11-22 | 1991-06-26 | ARCO Chemical Technology, L.P. | Oxyalkylene/n-acylalkylenimine block copolymers useful as surfactants |
WO2015033281A1 (en) * | 2013-09-03 | 2015-03-12 | Saudi Basic Industries Corporation | Phase transfer catalyst for breaking emulsions of oil in water |
-
1981
- 1981-03-23 CH CH195481A patent/CH655248A5/en not_active IP Right Cessation
- 1981-03-23 DE DE19813111386 patent/DE3111386A1/en not_active Withdrawn
- 1981-03-31 NL NL8101586A patent/NL8101586A/en not_active Application Discontinuation
- 1981-04-01 IT IT4818081A patent/IT1170864B/en active
- 1981-04-02 FR FR8106644A patent/FR2483456A1/en active Granted
- 1981-04-02 GB GB8110408A patent/GB2085433B/en not_active Expired
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4692316A (en) * | 1984-03-20 | 1987-09-08 | Dearborn Chemicals Limited | Method of inhibiting corrosion in aqueous systems |
US4692315A (en) * | 1984-04-25 | 1987-09-08 | Dearborn Chemicals Limited | Method of inhibiting corrosion in aqueous systems |
US4692317A (en) * | 1984-11-08 | 1987-09-08 | W. R. Grace & Co. | Corrosion control in aqueous systems using cationic polymers in combination with phosphonohydroxyacetic acid |
US5223097A (en) * | 1986-01-09 | 1993-06-29 | W. R. Grace Ab | Method for controlling pitch on a paper-making machine |
US5626720A (en) * | 1986-01-09 | 1997-05-06 | W.R. Grace & Co.-Conn. | Method for controlling pitch on a papermaking machine |
US10563042B2 (en) | 2016-12-14 | 2020-02-18 | Ecolab Usa Inc. | Quaternary cationic polymers |
US11319427B2 (en) | 2016-12-14 | 2022-05-03 | Ecolab Usa Inc. | Quaternary cationic polymers |
US11427964B2 (en) | 2018-06-12 | 2022-08-30 | Ecolab Usa Inc. | Quaternary cationic surfactants and polymers for use as release and coating modifying agents in creping and tissue papers |
Also Published As
Publication number | Publication date |
---|---|
FR2483456B1 (en) | 1985-05-03 |
CH655248A5 (en) | 1986-04-15 |
NL8101586A (en) | 1981-11-02 |
DE3111386A1 (en) | 1982-03-04 |
IT1170864B (en) | 1987-06-03 |
FR2483456A1 (en) | 1981-12-04 |
GB2085433B (en) | 1985-03-06 |
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