CA2025785A1 - Organic sludge dehydrater - Google Patents
Organic sludge dehydraterInfo
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- CA2025785A1 CA2025785A1 CA002025785A CA2025785A CA2025785A1 CA 2025785 A1 CA2025785 A1 CA 2025785A1 CA 002025785 A CA002025785 A CA 002025785A CA 2025785 A CA2025785 A CA 2025785A CA 2025785 A1 CA2025785 A1 CA 2025785A1
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- organic sludge
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Abstract
ABSTRACT OF THE DISCLOSURE
An organic sludge dehydrater of a water-in-oil form amphoteric copolymer emulsion containing an amphoteric polyelectrolite represented by the general formula:
An organic sludge dehydrater of a water-in-oil form amphoteric copolymer emulsion containing an amphoteric polyelectrolite represented by the general formula:
Description
ORGANIC SLUDGE DEHYDRATER
BACKGROUND OF THE INVENTION
Field of the Invention:
This invention relates to an organic sludge dehydrator.
Description of the Prior Art:
Heretofore, the disposal of various plant effluents and the disposal of sewage and excrements have given rise to sludge of sedimented particles and excess sludge. As a dehydrator for the sludge of this type, an organic flucculant has come to find utility. In the methods for flocculation and dehydration of sludge, the method which resorts to exclusive addition of a cationic organic macromolecular flocculant and the method which resorts to simultaneous addition of a cationic organic polymeric flocculant and an anionic organic polymeric flocculant have been famous.
The method which relies on the sole addition of a cationic organic polymeric flocculant, however, is not fully effective in disposing thoroughly of the sludge and bringing about a satisfactory result in terms of cake content and speed of filtration, for example.
Further, in case of the method relying on combined use of a cationic organic polymeric flocculant and an anionic organic polymeric flocculant, though it possibly allows improvement in cake content and speed of filtration, it has a disadvantage that the operation thereof necessitates installation of a plurality of flocculant dissolving tanks and flocculant reacting tanks, the equipment therefor is expensive, and the disposal of sludge calls for heavy consumption of additives and boosts the cost of chemicals.
In recent years, a method has been proposed which uses a cationic organic macromolecular flocculant and an anionic organic macromolecular flocculant as dissolved jointly in a solution with the pH of the solution controlled as disclosed in Japanese Patent Publication SHO 60(1985)-43,800 and Japanese Patent Laid-Open SHO 58(1983)-216,706.
In the case of this method, however, there is imposed a restriction on the kind of the cationic organic polymeric f]occulant to be effectively usable for this method. Then, in the case of an amphoteric organic polymeric flocculant using as a cationic component thereof a monomer containing a tertiary amine or a quaternary salt as disclosed in Japanese Patent Laid-Open SHO 62(1987)-205,112, a restriction is imposed on the balance of composition of the flocculant.
When an organic polymeric flocculant containing both a cationic and an anionic component is used as an organic sludge dehydrator, the dehydrated cake content is smaller than when a cationic or an anionic flocculant is used alone as disclosed in Japanese Patent Publication SHO 60(1985)-43,800, Japanese Patent Laid-Open SHO 58 (1983) -216,706, and Japanese Patent Laid-Open SHO 63(1988)-205,112. The use found for this flocculant, however, is limited.
In the case of an amphoteric organic macromolecular flocculant having as a cationic component thereof a monomer containing a tertiary amine, since the balance of composition is limited, the value of equivalent weight of cation, that of anion, and the equivalent weight ratio of cation/anion have their own limits. An amphoterioc organic sludge dehydrator which combines ability of flocculation and ability of dehydration remains yet to be developed.
When the dehydraters is in the form of powder, it necesitales to dissolve them when using. It needs to require a long time for dissolving, sometimes there is occurred problems of stability of the polymer, and it also require a special dilution equipment.
An object of the present invention is, accordingly, to provide a novel organic sludge dehydrater.
SUMMARY OF THE INVENTION
The object described above is accomplished by an organic sludge dehydrater of a water-in-oil form amphoteric copolymer emulsion containing an amphoteric polyelectrolite represented by the general formula I:
7 ~ R2 IR3 [-CH2- -]a [- CH2-C-]b [-CH2-C-] (I) O(CH2fH- I )nH n(HY) wherein n is an integer in the range of 1 to 5, providing the average value of n is not less than 2, a, b, and c are proportions such that the sum, a + b + c is 1, or a + b is 1, R1, R2, R3 and R4 are independently hydrogen atom or an alkyl group, R5 is hydrogen atom, an alkyl group, or an alkyl group substituted with a ~-hydroxy group, HY is a monobasic acid, and Z is an amide group represented by the general formula II:
-CoNR6R7 (II) wherein R6 and R7 are independently hydrogen atom or an alkyl group, a hydroxyalkyl group represented by the general formula m:
--C02CH-CHOH (m) wehrein R8 and R9 are independently hydrogen atom or an alkyl group, or a nitrile group represented by the general formula N:
-CN (N) or an ester group represented by the general formula ~:
-C02R10 (~) wherein R10 is an alkyl group, an aromatic group, or an alicyclic group.
The object is also accomplished by an organic sludge dehydrater of a water-in-oil type amphoteric polyelectrolite emulsion, represented by the general formula I, having an aminoalkyl group and a carboxyl group, which method comprises emulsifying either at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid or a mixture of the anionic monomer (A) with a nonionic monomer (B) in water-in-oil form in the presence of water, a surfactant, and a hydrophobic organic solvent, causing an alkylene imine to react on the resultant water-in-oil form vinylic carboxylic acid emulsion (C) resulting from the polymerization or copolymerization by the use of a radical polymerization catalyst thereby aminoalkylating the emulsion, and subsequently acidifying the aminoalkylated emulsion with a monobasic acid.
The object is also accomplished by an amphoteric sludge dehydrater containing an amphoteric polyelectrolite having aminoalkyl group and a carboxyl group and represented by the general formula ~:
Z I ]d [ CH2 f - ]e [-CH2-lc-]f [-CH2_ 7, C=O COOH A B
(CH2CH-N)nH n(HY) (V) wherein n is an integer in the range of 1 to 5, d, e, f, and g are proportions such that the sum, d + e + f + g, is 1, or d + e + f is 1, R1, R2, R3, R4 and R10 are independently hydrogen atom or an alkyl group, R5 is hydrogen atom, an alkyl group, or an alkyl group substituted with a ~-hydroxy group, HY is a monobassic acid, A is an ester group represented by the general formula ~:
-C02R 1 1 ( vl ) wherein Rll is an alkyl group, an aromatic group, or an alicyclic group, an unsubstituted or a p-substituted phenyl group represented by the general formula ~:
~R 12 (V[l) wherein R12 is hydrogen atom, an alkyl group, or a hydroxy group, or a nitrile group represented by the general formula N :
-CN (N) B is an amide group represented by the general formula II:
-CoNR6R7 (II) wherein R6 and R7 are independently hyrogen atom or an alkyl group, a hydroxyalkyl group represented by the general formula m:
--C02CH-CHOH (m) wherein R8 and R9 are independently hydrogen atom or an alkyl group, or a nitrile group represented by the general formula ~:
-CN (~) The object is accomplished by an organic sludge dehydrater of an amphoteric polyelectrolite, represented by the general formula (V), having an aminoalkyl group and a carboxyl group, which method comprises either emulsion polymerizing in water at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid and a nonionic monomer (D) corresponding to A in the general formula V to be added for the purpose of emulsification or effecting in water the emulsion polymerization in the presence of a nonionic monomer (B) corresponding to B in the general formula v, causing an alkylene imine to react on the resultant vinylic carboxylic acid polymer emulsion (E) thereby aminoalkylating the polymer emulsion, and subsequently acidifying the aminoalkylated polymer emulsion with a monobasic acid.
The organic sludge dehydrator of this invention can be used on organic sludge by the same method as the conventional cation flocculant formed of the quaternized dimethylamino methacrylate, for example. It is so effective as to form tenaceous flocs, which on being dehydrated with a press produce sludge of a conspicuously lowered water content. This effect manifests itself particularly conspicuously when the treatment of dehydration is effected with a press. During the course of gravitational filtration in a press dehydrating device, owing to the interaction between the cation group and the anion group in the polymer, the speed of filtration is conspicuously heightened, the water content of filtration residue is notably lowered, and the peelability of the filtration case from the filter cloth is improved to a great extent. The dehydrated sludge has small viscosity and low water content and, therefore, allows ease of handling and enables the fuel and cost of incineration to be lowered greatly. The species of organic sludge which are subjectable to the dehydration treatment herein include initially sedimented raw sludge occurring in sewage treatment, excess sludge occurring in activated sludge treatment and mixtures thereof with other refuses, digested sludge, and excess sludge produced in the treatment with activated sludge of various organic substance-containing waste waters, for example.
EXPLANATION OF THE PREFERRED EMBODIMENT
Also, this invention relat~es to an organic sludge dehydrator of a water-in-oil form~amphoteric polyelectrolite emulsion represented by the general formula I possessing an aminoalkyl group and a carboxyl group, comprising emulsifying either at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid or a mixture of said anionic monomer (A) with a nonionic monomer (B) in water-in-oil form in the presence of water, a surfactant, and a hydrophobic organic solvent, then polymerizing or copolymerizing the emulsified monomer with a radical polymerization catalyst thereby forming a water-in-oil form vinylic carboxylic acid emulsion (C), then aminoalkylating said emulsion with an alkylene imine, and subsequently acidifying the aminoalkylated emulsion with a monobasic acid.
The anionic monomer (A) is preferable to be acrylic acid or methacrylic acid. The nonionic monomer (B) is required to be selected in consideration of the characteristic of acid dissociation. The neutralization degree of anionic monomer (A) is from 5-100 mol%, preferably 20-95 mol%.
The nonionic monomer (B) may be any nonionic monomer copolymerizable with the monomer (A) mentioned above. For example, a vinylic monomer possessing an amide group represented by the general formula ~ can be used:
R3--e C N<R7 (~, In the general formula X, R3, R6, and R7 are independently hydrogen atom or an alkyl group. The vinylic monomers of the general formula X include, for example, acrylamide, methacrylamide, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N,N-diethyl acrylamide, and N,N-diethyl methacrylamide.
A vinylic monomer possessing a hydroxyalkyl group represented by the general formula X is also usable:
Il R8 R9 (X) , In the general formula X, R3, R8, and R9 are independently hydrogen atom or an alkyl group. The vinylic monomers of the general formula X include, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.
A vinylic monomer having an ester group represented by the following general formula XI is also usable:
R3-C - C-O-Rl (XI) wherein R3 is hydrogen atom or an alkyl group and R10 is an alkyl group, an aromatic group, or an alicyclic group. The compounds of the general formula XII include, for example, methyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and phenyl methacrylate.
The nonionic monomer (B) is used herein for the purpose of adjusting the molecular weight and ion equivalent weight of the organic sludge dehydrator.
For the water-in-oil type amphoteric type copolymer emulsion to be produced by the method of this invention, the amounts of the anionic monomer (A) and the nonionic monomer (B) to be used during in the polymerization of the water-in-oil form vinylic carboxylic acid polymer emulsion (C) must be fixed so that the produced copolymer emulsion may acquire a cation equivalent weight value, Cv, in the range of 0.8 to 10.0 meq/g, and an anion equivalent weight value, Av, in the range of 0.1 to 6.0 meq/g.
When at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid or a mixture of the anionic monomer (A) with a nonionic monomer (B) is to be emulsified in water-in-oil form in the presence of water, a surfactant, and a hydrophobic organic solvent, the surfactant may be a nonionic surfactant in popular use.
The nonionic surfactants which are usable herein include, for example, sorbitan monooleate, sorbitan monostrearate, sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbin monolaurate, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, and glycerol monooleate.
These nonionic surfactants may be used either singly or in the form of a mixture of two or more members.
Optionally, the nonionic surfactant may be used in combination wit;h an anionic and a cationic surfactant of ordinary grade.
The hydrophobic organic solvents which are usable herein include, for example, hydrophobic aliphatic and aromatic hydrocarbons, vegetable and animal oils, and modified products of such oils. Typical examples are normal paraffin, isoparaffin, cyclohexane, naphtene, toluene, xylene, kerosine, mineral oils, and lamp oil, etc.
The total amount of the anionic monomer (A) and the nonionic monomer (B) to be used herein is preferable to account for a concentration in the range of 20 to 80% by weight, based on the amount of water. The concentration of the surfactant to be used is preferable to be in the range of 5 to 30% by weight, based on the amount of the hydrophobic organic solvent. The ratio of the hydrophobic organic solvent to the water is in the range of 1 : 10 to 10 :1, preferably l : 5 to 3 : 1.
When the water-in-oil form monomer emulsion obtained by emulsifying in water-in-oil form at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid or a mixture of the anionic monomer (A) with a nonionic monomer (B) in the presence of water, a surfact;ant, and a hydrophobic organic solvent is to be polymerized or copolymerized, a redox type or azo type radical polymerization initiator may be used as occasion demands. The redox type polymerization initiators include, for example, ammonium persulfate, potassium persulfate, hydrogen peroxide, benzoil peroxide, and t-butyl peroxide.
The azo type polymerization initiators usable herein include, for example, azobis(amidinopropane) Hcl, azobisisobutyronitrile, azobis(dimethylvaleronitrile), and azobis(cyclohexanecarbonitrile).
It is also permissible to add to the polymerization system a well-known chain transfer agent such as isopropyl alcohol, erythorubic acid, or 2-mercapto ethanol.
The polymerization temperature is preferable to be externally controlled, during the initial phase of the polymerization, in the range of 10 to 60C, and, during the normal phase of the polymerization, in the range of 30 to Though the polymerization time is variable with the concentration of monomers, the polymerization temperature, and the polymerization degree aimed at, for example, it is generally in the range of 10 minutes to 10 hours, preferably 1 to 7 hours.
Further, preparatory to the aminoalkylation, it is necessary to fix the amounts of the vinylic carboxylic acid polymer (C) and the alkylene imine to be used for the aminoalkylation.
If the cation equivalent weight value, Cv, is less than o.8 meq/g, the produced amphoteric polyelectrolite manifests its characteristics only with difficulty. If the cation equivalent weight value, Cv, exceeds 10.0 meq/g, the produced amphoteric polyelectrolite does not easily manifest its characteristics. If the anion equivalent weight value, Av, is less than 0.1 meq/g, the produced amphoteric polyelectrolite manifests its characteristics only with difficulty. Conversely, if the anion equivalent weight value, Av, exceeds 6.0 meq/g, there arises a disadvantage that the produced amphoteric polyelectrolite tends to suffer a decrease in its solubility in water.
t~
The reaction of aminoalkylation can be effected by causing an alkylene imine to react on the water-in-oil form vinylic carboxylic acid polymer emulsion (C).
Preparatory to the aminoalkylation, it is necessary to fix the amounts of the water-in-oil form vinylic carboxylic acid polymer emulsion (C) and the alkylene imine.
The aminoalkylation is effected by causing reaction of the acid group of the vinyl type carboxylic acid polymer (C) with the alkylene imine as indicated below.
The alkylene imine for exchanging the free carboxyl group of the vinylic polymer for an aminoester group is a 1,2-alkylene imine (aziridine). Among other 1,2-alkylene imines, 1,2-propylene imine and ethylene imine prove to be particularly desirable because of their ready availability and relatively low prices. Optionally, n-alkyl-substituted or unsubstituted 1,3-alkylene imines (azetidine) are usable because their imines, in forming an aminoester group, exhibit chemical reactivity and other properties similar to those of 1,2-imines.
The acidification of a suspended aminoalkyl group is effected with a monobasic acid, which is used in an amount in the range of 50 to 100 mol% (preferably 60 to 90 mol~), based on the amount of the added alkylene imine. The addition of the monobasic acid to the reaction system is carried out either collectively or peacemeal during the course of the aminoalkylation. The monobasic acid is selected from among mineral acids such as hydrochloric acid, nitric acid, and carboxylic acids such as acetic acid, formic acid etc.
For the organic sludge dehydrator of water-in-oil form amphoteric copolymer emulsion to be obtained by the method of this invention, it is preferable to control suitably the molecular weight thereof in addition to the cation equivalent weight and the anion equivalent weight value mentioned above. With intrinsic viscosity as an index to molecular weight, the composition of the component f ~ ~
monomers, the polymerization conditions, etc. are preferable to be suitably set so that the produced water-in-oil form amphoteric copolymer emulsion may acquire intrinsic viscosity [~] in the range of 0.1 to 25, preferably 1 to 15.
Also, this invention relates to an organic sludge dehydrator of an amphoteric polyelectrolyte represented by the general formula V having an aminoalkyl group and a carboxyl group obtained by either emulsion polymerizing in water at least one anionic monomer (A) selected from the group cons.isting of acrylic acid and methacrylic acid and a nonionic monomer (B) corresponding to A in the general formula V and added for the purpose of emulsification or effecting said emulsion polymerization in water in the presence of a hydrophilic nonionic monomer (C) corresponding to B of said general formula (V), allowing the resultant vinylic carboxylic acid polymer emulsion to be reacted upon by an alkylene imine thereby aminoalkylating said vinylic carboxylic acid polymer emulsion, and subsequently acidifying said aminoalkylated polymer emulsion with a monobasic acid.
The anionic monomer (A) to be used herein is as already described.
The nonionic monomer (D) may be any nonionic monomer which is emulsifiable and, at the same time, copolymerizable with the aforementioned monomer (A). The nonionic monomers which are usable herein include vinylic monomers possessing an ester group represented by the general formula X I .
Typical examples are as already cited. Further, vinyl compounds possessing an unsubstituted or p-substituted phenyl represented by the general formula XII:
R3-C ~ R12 (XII) wherein R3 and R12 have the meanings defined above, are also usable. Typical examples are styrene, p-methylstyrene, and p-vinylphenol. Acrylonitrile may be cited as another example.
The nonionic monomer (D) is used herein for the purpose of enabling the vinylic carboxylic acid polymer emulsion (E) to be obtained as an emulsion possessing low viscosity and allowing an increase in molecular weight.
Generally it is added in an amount of not more than 20 mol%, based on the amount of the vinylic carboxylic acid polymer emulsion (E). If this amount exceeds 20 mol%, there arises a disadvantage that the produced amphoteric polyelectrolite exhibits inferior solubility in water.
As the nonionic monomer (D), any of the nonionic monomers which are copolymerizable with the aforementioned monomers (A) and (B) can be used.
The nonionic monomer (B) is used for the purpose of adjusting the molecular weight and ion equivalent weight of the amphoteric polyelectrolite. Generally, it is preferable to be used in an amount of not more than 70 mol% based on the amount of the vinyl type caboxylic acid polymer emulsion (E).
For the amphoteric polyelectrolite to be produced by the method of this invention, it is necessary to fix the amounts of the anionic monomer (A) and the nonionic monomers (B) and (D) to be used in the polymerization of the vinylic carboxylic acid polymer emulsion (E) so that the produced amphoteric polyelectrolite may acquire a cation equivalent weight value, Cv, in the range of 0.8 to 10.0 meq/g and an anion equivalent weight value, Av, in the range of 0.1 to 6.0 meq/g. The amounts of monomers [the total amount of the anionic monomer (A) and the nonionic monomers (B) and (D) (hereinafter referred to as "total amount of monomers")] are preferable to account for a concentration approximately in the range of 10 to 80% by weight. If the concentration is less than 10% by weight, there arises a disadvantage that the polymerization betrays poor productivity. Conversely, if the concentration exceeds 80% by weight, there ensure at disadvantage that the polymerization generates a large volume of heat and the polymerization system suffers from undue rise of temperature.
In emulsion polymerizing in water at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid and a nonionic monomer (D) corresponding to A in the general formula V to be added for the purpose of emulsification with the anionic monomer or in effecting the emulsion polymerization in the presence of a hydrophilic nonionic monomer (B) corresponding to B of the general formula V, it is permissible to use a surfactant for the purpose of ensuring thorough dispersion of the monomers (A), (D), and (B). Though the surfactant to be used is not specifically defined, it is preferable to possess relatively high hydrophylicity enough for the formation of an 0/W form emulsion in consequence of the emulsification. The surfactants which are usable herein for this purpose include nonionic surfactants such as polyoxyethylene nonylphenyl ether and polyoxyethylenestearyl ether, anionic surfactants such as sodium lauryl sulfate and polyoxyethylene nonylphenyl ether sodium sulfate, and cationic surfactants such as stearyl amine acetate and stearyl trimethyl ammonium chloride, for example. The amount of the surfactant to be used is in the range of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of monomer~.
In the production of the vinylic carboxylic acid polymer emulsion (E), it is permissible to use a redox type or azo type radical polymerization initiator, as occasion demands. The kinds of the polymerization initiator and the amount of the polymerization initiator to be used are as already described.
The polymerization temperature is required to be controlled externally, during the initial phase of the polymerization, in the range of 10 to 40C, preferably 20 to 40C, and, during the normal course of the :~ `
polymerization, in the range of 30 to 100C, preferably 40 to 80C.
Though the polymerization time is variable with the concentration of the monomers, the polymerization temperature, and the polymerization degree aimed at, for example, it is generally in the range of 10 minutes to 10 hours, preferably 1 to 7 hours.
Preparatory to the reaction of aminoalkylation, it is necessary to fix the amounts of the vinylic carboxylic acid polymer emulsion (E) and the alkylene imine.
If the cation equivalent weight value, Cv, is less than 0.8 meq/g, the produced amphoteric polyelectrolite does not manifest its characteristics easily. Conversely, if the cation equivalent weight value, Cv, exceeds 10.0 meq/g, the characteristics expected of the produced amphoteric polyelectrolite do not easily manifest themselves. If the anion equivalent weight value, Av, is less than 0.1 meq/g, the produced amphoteric polyelectrolite manifests its characteristics only with difficulty. If this value exceeds 6.0 meq/g, there is a disadvantage that the produced amphoteric polyelectrolite tends to exhibit inferior solubility in water.
The aminoalkylation can be carried out by causing the vinylic carboxylic acid copolymer emulsion (E) to be acted upon by an alkylene imine.
Specifically, the aminoalkylation is conventional manner as described above between the carboxylic acid group of the vinylic carboxylic acid polymer emulsion (E) and the alkylene imine. The typical examples of the alkylene imine and the amount of the alkylene imine to be used are as already described. The conditions for the aminoalkylation are also as described above.
For the organic sludge dehydrator containing the amphoteric polyelectrolite by the method of this invention, it is preferable to control suitably the molecular weight thereof in addition to the cation equivalent weight value and the anion equivalent weight value mentioned above. With intrinsic viscosity as an index to molecular weight, the composition of the component monomers, the polymerization conditions, etc. are preferable to be suitably set so that the produced amphoteric polyelectrolite may acquire intrinsic viscosity [~] in the range of 0.1 to 25, preferably 1 to 15.
The organic sludge dehydrator of this invention, in addition to organic sludge, gives rise to flocs. These flocs are destined to be dehydrated by the conventional method. The dehydrating devices which are usable for this purpose include, for example, screw-press type dehydrating devices, filter-press type dehydrating devices, belt-press type dehydrating devices, screw decanters, and centrifugal devices.
Now, the present invention will be described more specifically below with reference to working examples. It should be noted, however, that the present invention is not limited in any sense by these examples.
Referential Example 1 [Method for production of organic sludge dehydrator]
In a four-neck flask fitted with a stirrer, a thermometer, a condenser, a dropping funnel, and a nitrogen gas inlet tube, 100 g of Isoper M (isoparaffin solvent produced by Exxon Chemical) was placed and 11.6 g of sorbitan monooleate was dissolved therein and the resultant mixture was emulsified by gradual addition thereto of a mixed solution prepared as an aqueous monomer solution by the combination of 80 g of acrylic acid, 20 g of acrylamide, 52.9 g of aqueous 28 wt% ammonia solution, and 33.9 g of deionized water. After the internal gas of the reaction system had been thoroughly displaced with nitrogen gas, the reaction mixture was heated to 60C and, in the presence of 0.7 g of azobis(dimethyl valeronitrile) added thereto as a catalyst, was heated at 60C and, at the same time, stirred for 4 hours. Consequently, there was obtained a water-in-oil form vinylic carboxylic acid polymer emulsion.
Ethylene imine (23.9 g) was added dropwise while keeping at 50C, and stirring was continued for 30 min. To the resultant solution, were added dropwise 57.4 g of 61 wt~
of nitric acid, then stirring was continued for 30 min.
Further ethylene imine (76.1 g) were added dropwise, then stirring was continued for 30 min. Additional 61 wt% of nitric acid( 110.7 g) were added dropwise, then stirring was continued for 30 min. give rise to an organic sludge dehydrator aimed at. The reaction condition are shown in Table 1.
Referential Examples 2-10 The procedure of Referential example 1 was repeated, except that the conditions indicated in Table 1 were used.
Referential Example 11 [Production of organic sludge dehydrator]
In a four-neck flask fitted with a stirrer, a thermometer, a condenser, a dropping funnel, and a nitrogen gas inlet tube, 820 g of deionized water and 0. 8 g of sodium lauryl sulfate were stirred for thorough solution. To the resultant solution, were added 25.6 g of acrylic acid (AA), 3.2 g of acrylamide (AAm), and 3.2 g of styrene (St). The reaction mixture was kept stirred and the internal gas of the reaction system was thoroughly displaced with nitrogen gas. After the nitrogen displacement, the reaction mixture was heated to 50C and 0.288 g of ammonium persulfate (APS) and 0.288 g of sodium hydrogen sulfite were added as catalyst thereto. Immediately, 102.4 g of acrylic acid (AA), 12.8 g of acrylamide (AAm), and 12.8 g of styrene (St?
were added dropwise through the dropping funnel to the reaction mixture over a period of 2 hours, with the temperature kept at 50C. The resultant mixture was left aging for 2 hours. Consequent;ly, there was obtained a vinylic carboxylic acid polymer emulsion.
The emulsion obtained was kept at 50C throughout the entire course of reaction and, after dropwise addition of 38.2 g of ethylene imine thereto, was stirred for 30 minutes. The resultant mixture and 91.8 g of an aqueous 61 wt~ nitric acid solution added thereto were stirred for 30 minutes. Subsequently, the ensuant mixture and 121.8 g of ethylene imine added thereto were stirred for 30 minutes.
After addition of an aqueous 61 wt% nitric acid solution (177.2 g), stirring was continued for 30 minutes.
Consequently, there was obtained an amphoteric polyelectrolite. The reaction conditions and the physical properties of the reaction product were as shown in Table 1.
Referential Examples 12 to 20 The procedure of Referential Example 11 was repeated, except that the conditions indicated in Table 1 were used instead.
Tablel ____ . - . .
Rererential Organic sll1dge dehydration agent Example Composition in weight 1 El/AAm/AA = 50/10/40 . . El/AAm/AA = 50/15/35 3 El/AA = 50/50 . EI/AAm/AA = 50/20/30 EIMEA/AA = 50/10/40 EVMAm/AN/AA = 50/1515/30 El/AAm/AA = 30128142 El/AAm/AA = 28M3129 . ~ ~ El/AAm/AA -- 24146130 El/AAm/AA = 15/64/21 11 EllAAmlSt/AA = 501515140 12 EIlAAmlSt/AA = 50/10/5/35 13 EIlAAmlBA/AA = 501515140 14 EIMEA/MMA/AA = 50/15/5/30 11~ ET/MAm/MA/AA = 5017.512.5140 16 EVAAm/St~AA = 5017.512.5140 17 ~ ETMEA/MMA/AA--3012V7142 18 ET/AAm/MA/AA = 2813617129 .
__ EllAAm/MAlAA = 2413818130 ET/AAm/AN/AA = 15151/13/21 AA: acrylic acid AAm: acrylamide HEA: 2-hydroxyethyl acrylate AN: acrylonitrile MAm: methacrylamide EI: ethylene imine St: styrene MA: methyl acrylate BA: butyl acrylate MMA: methyl methacrylate Examples 1 to 6 Flocs were formed by stirring 150 ml of mixed raw sludge from a sewage disposal plant (pH 6.1, SS 1.8 wt%, VSS/SS 76.3~) and an organic sludge dehydrator added thereto in an amount stated in Table 1 at 300 rpm for 30 seconds.
Into a Buchner funnel draped with a 100-mesh nylon filter cloth, was poured 100 ml of the flocs of sludge. The amount of water passed through the filter cloth over a period of 10 seconds was measured. The sludge which passed through the filter cloth over a period of 5 minutes was nipped between two filter cloths and squeezed under 0.5 kg/cm2 for 2 minutes. The sludge (cake) resulting from the dehydration was tested for water content. The results and the physical properties are shown in Table 2.
Controls 1 to 3 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 2 were polymerized by the known method and then subjected to the same flocculation test as in Example 1. The results and the physical properties are shown in Table 2.
_ a - ~ r ., o r r~ r ~
~' .~ ~ _ __ __ _ _ _ _ _ ,_ o . ~ , _ _ r _ ~ _ ~ _ ~ ~ ~4;~
O ~ 01 ~ G~ 0~ C~ t- t- C~ .C ;7J ~
_ ~ ~ _ _ _ ___ ~s ~
y E ¦ C E I 9 ~ E ' ~ c~ c.~ ~ ~n ~D _~ ~ C'~
';~ ~ E~ ¦ E ¦ E
Examples 7 and 8 The organic sludge dehydraters indicated in Table 1 were subjected to the same flocculation test as in Example 1, using mixed raw sludge (pH 6.4, SS 1.7 wt~, VSS/SS 73.6~) from a sewage disposal plant. The results and the physical properties are shown in Table 3.
Controls 4 and 5 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 3 were polymerized by the known method and subjected to the same flocculation test as in Example 7. The results and the physical properties are shown in Table 3.
Examples 9 and 10 The organic sludge dehydraters indicated in Table l were subjected to the same flocculation test as in Example 1, using mixed raw sludge (pH 6.2, SS 1.4 wt%, VSS/SS 74.6~) from a sewage disposal plant. The results and the physical properties are shown in Table 4.
Controls 6 and 7 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 4 were polymerized by the known method and subjected to the same flocculation test as in Example 7. The results and the physical properties are shown in Table 4.
~ ;~
~, ~
E E o, c~ _ _ ~J O E E = 3 _ O ~ .
_ __ _ ~ _ __ _ _ e~
Z
r5 _ O Z .E_ E E~ c r Z ~
C~ 5 C~ 5 The cation equivalent weight values, the anion equivalent weight values, and the intrinsic viscosity indicated in Tables 2 to 7 were determined by the following methods.
(1) Cation equivalent weight value This property was determined by placing 95 ml of distilled water in a beaker, adding thereto 5 ml of a solution of 1,000 ppm of a given sample, adjusting the pH
value of the resultant solution to 7.0 by addition of either 1% HCl or 1% NaOH, stirring the solution for about 1 minute, then adding two or three drops of toluidine blue indicator solution, and titrating the solution with N/400 PVSK
(polyvinyl sulfate potassium solution) at intervals of 2 ml.
The time at which an interval of at least 10 seconds elapsed after the color of the sample water had changed from blue to reddish purple was taken as the end point of this titration.
Cation equivalent weight value (Cv) (meq/g) =
(Amount of titrant [ml] for sample - amount of titrant [ml] for blank) x F/2 x (concentration of effective component (ppm) in sample) The term "effective component" as used herein refers to the component remaining after removal of neutralizing acid from the solids of the sample.
BACKGROUND OF THE INVENTION
Field of the Invention:
This invention relates to an organic sludge dehydrator.
Description of the Prior Art:
Heretofore, the disposal of various plant effluents and the disposal of sewage and excrements have given rise to sludge of sedimented particles and excess sludge. As a dehydrator for the sludge of this type, an organic flucculant has come to find utility. In the methods for flocculation and dehydration of sludge, the method which resorts to exclusive addition of a cationic organic macromolecular flocculant and the method which resorts to simultaneous addition of a cationic organic polymeric flocculant and an anionic organic polymeric flocculant have been famous.
The method which relies on the sole addition of a cationic organic polymeric flocculant, however, is not fully effective in disposing thoroughly of the sludge and bringing about a satisfactory result in terms of cake content and speed of filtration, for example.
Further, in case of the method relying on combined use of a cationic organic polymeric flocculant and an anionic organic polymeric flocculant, though it possibly allows improvement in cake content and speed of filtration, it has a disadvantage that the operation thereof necessitates installation of a plurality of flocculant dissolving tanks and flocculant reacting tanks, the equipment therefor is expensive, and the disposal of sludge calls for heavy consumption of additives and boosts the cost of chemicals.
In recent years, a method has been proposed which uses a cationic organic macromolecular flocculant and an anionic organic macromolecular flocculant as dissolved jointly in a solution with the pH of the solution controlled as disclosed in Japanese Patent Publication SHO 60(1985)-43,800 and Japanese Patent Laid-Open SHO 58(1983)-216,706.
In the case of this method, however, there is imposed a restriction on the kind of the cationic organic polymeric f]occulant to be effectively usable for this method. Then, in the case of an amphoteric organic polymeric flocculant using as a cationic component thereof a monomer containing a tertiary amine or a quaternary salt as disclosed in Japanese Patent Laid-Open SHO 62(1987)-205,112, a restriction is imposed on the balance of composition of the flocculant.
When an organic polymeric flocculant containing both a cationic and an anionic component is used as an organic sludge dehydrator, the dehydrated cake content is smaller than when a cationic or an anionic flocculant is used alone as disclosed in Japanese Patent Publication SHO 60(1985)-43,800, Japanese Patent Laid-Open SHO 58 (1983) -216,706, and Japanese Patent Laid-Open SHO 63(1988)-205,112. The use found for this flocculant, however, is limited.
In the case of an amphoteric organic macromolecular flocculant having as a cationic component thereof a monomer containing a tertiary amine, since the balance of composition is limited, the value of equivalent weight of cation, that of anion, and the equivalent weight ratio of cation/anion have their own limits. An amphoterioc organic sludge dehydrator which combines ability of flocculation and ability of dehydration remains yet to be developed.
When the dehydraters is in the form of powder, it necesitales to dissolve them when using. It needs to require a long time for dissolving, sometimes there is occurred problems of stability of the polymer, and it also require a special dilution equipment.
An object of the present invention is, accordingly, to provide a novel organic sludge dehydrater.
SUMMARY OF THE INVENTION
The object described above is accomplished by an organic sludge dehydrater of a water-in-oil form amphoteric copolymer emulsion containing an amphoteric polyelectrolite represented by the general formula I:
7 ~ R2 IR3 [-CH2- -]a [- CH2-C-]b [-CH2-C-] (I) O(CH2fH- I )nH n(HY) wherein n is an integer in the range of 1 to 5, providing the average value of n is not less than 2, a, b, and c are proportions such that the sum, a + b + c is 1, or a + b is 1, R1, R2, R3 and R4 are independently hydrogen atom or an alkyl group, R5 is hydrogen atom, an alkyl group, or an alkyl group substituted with a ~-hydroxy group, HY is a monobasic acid, and Z is an amide group represented by the general formula II:
-CoNR6R7 (II) wherein R6 and R7 are independently hydrogen atom or an alkyl group, a hydroxyalkyl group represented by the general formula m:
--C02CH-CHOH (m) wehrein R8 and R9 are independently hydrogen atom or an alkyl group, or a nitrile group represented by the general formula N:
-CN (N) or an ester group represented by the general formula ~:
-C02R10 (~) wherein R10 is an alkyl group, an aromatic group, or an alicyclic group.
The object is also accomplished by an organic sludge dehydrater of a water-in-oil type amphoteric polyelectrolite emulsion, represented by the general formula I, having an aminoalkyl group and a carboxyl group, which method comprises emulsifying either at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid or a mixture of the anionic monomer (A) with a nonionic monomer (B) in water-in-oil form in the presence of water, a surfactant, and a hydrophobic organic solvent, causing an alkylene imine to react on the resultant water-in-oil form vinylic carboxylic acid emulsion (C) resulting from the polymerization or copolymerization by the use of a radical polymerization catalyst thereby aminoalkylating the emulsion, and subsequently acidifying the aminoalkylated emulsion with a monobasic acid.
The object is also accomplished by an amphoteric sludge dehydrater containing an amphoteric polyelectrolite having aminoalkyl group and a carboxyl group and represented by the general formula ~:
Z I ]d [ CH2 f - ]e [-CH2-lc-]f [-CH2_ 7, C=O COOH A B
(CH2CH-N)nH n(HY) (V) wherein n is an integer in the range of 1 to 5, d, e, f, and g are proportions such that the sum, d + e + f + g, is 1, or d + e + f is 1, R1, R2, R3, R4 and R10 are independently hydrogen atom or an alkyl group, R5 is hydrogen atom, an alkyl group, or an alkyl group substituted with a ~-hydroxy group, HY is a monobassic acid, A is an ester group represented by the general formula ~:
-C02R 1 1 ( vl ) wherein Rll is an alkyl group, an aromatic group, or an alicyclic group, an unsubstituted or a p-substituted phenyl group represented by the general formula ~:
~R 12 (V[l) wherein R12 is hydrogen atom, an alkyl group, or a hydroxy group, or a nitrile group represented by the general formula N :
-CN (N) B is an amide group represented by the general formula II:
-CoNR6R7 (II) wherein R6 and R7 are independently hyrogen atom or an alkyl group, a hydroxyalkyl group represented by the general formula m:
--C02CH-CHOH (m) wherein R8 and R9 are independently hydrogen atom or an alkyl group, or a nitrile group represented by the general formula ~:
-CN (~) The object is accomplished by an organic sludge dehydrater of an amphoteric polyelectrolite, represented by the general formula (V), having an aminoalkyl group and a carboxyl group, which method comprises either emulsion polymerizing in water at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid and a nonionic monomer (D) corresponding to A in the general formula V to be added for the purpose of emulsification or effecting in water the emulsion polymerization in the presence of a nonionic monomer (B) corresponding to B in the general formula v, causing an alkylene imine to react on the resultant vinylic carboxylic acid polymer emulsion (E) thereby aminoalkylating the polymer emulsion, and subsequently acidifying the aminoalkylated polymer emulsion with a monobasic acid.
The organic sludge dehydrator of this invention can be used on organic sludge by the same method as the conventional cation flocculant formed of the quaternized dimethylamino methacrylate, for example. It is so effective as to form tenaceous flocs, which on being dehydrated with a press produce sludge of a conspicuously lowered water content. This effect manifests itself particularly conspicuously when the treatment of dehydration is effected with a press. During the course of gravitational filtration in a press dehydrating device, owing to the interaction between the cation group and the anion group in the polymer, the speed of filtration is conspicuously heightened, the water content of filtration residue is notably lowered, and the peelability of the filtration case from the filter cloth is improved to a great extent. The dehydrated sludge has small viscosity and low water content and, therefore, allows ease of handling and enables the fuel and cost of incineration to be lowered greatly. The species of organic sludge which are subjectable to the dehydration treatment herein include initially sedimented raw sludge occurring in sewage treatment, excess sludge occurring in activated sludge treatment and mixtures thereof with other refuses, digested sludge, and excess sludge produced in the treatment with activated sludge of various organic substance-containing waste waters, for example.
EXPLANATION OF THE PREFERRED EMBODIMENT
Also, this invention relat~es to an organic sludge dehydrator of a water-in-oil form~amphoteric polyelectrolite emulsion represented by the general formula I possessing an aminoalkyl group and a carboxyl group, comprising emulsifying either at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid or a mixture of said anionic monomer (A) with a nonionic monomer (B) in water-in-oil form in the presence of water, a surfactant, and a hydrophobic organic solvent, then polymerizing or copolymerizing the emulsified monomer with a radical polymerization catalyst thereby forming a water-in-oil form vinylic carboxylic acid emulsion (C), then aminoalkylating said emulsion with an alkylene imine, and subsequently acidifying the aminoalkylated emulsion with a monobasic acid.
The anionic monomer (A) is preferable to be acrylic acid or methacrylic acid. The nonionic monomer (B) is required to be selected in consideration of the characteristic of acid dissociation. The neutralization degree of anionic monomer (A) is from 5-100 mol%, preferably 20-95 mol%.
The nonionic monomer (B) may be any nonionic monomer copolymerizable with the monomer (A) mentioned above. For example, a vinylic monomer possessing an amide group represented by the general formula ~ can be used:
R3--e C N<R7 (~, In the general formula X, R3, R6, and R7 are independently hydrogen atom or an alkyl group. The vinylic monomers of the general formula X include, for example, acrylamide, methacrylamide, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N,N-diethyl acrylamide, and N,N-diethyl methacrylamide.
A vinylic monomer possessing a hydroxyalkyl group represented by the general formula X is also usable:
Il R8 R9 (X) , In the general formula X, R3, R8, and R9 are independently hydrogen atom or an alkyl group. The vinylic monomers of the general formula X include, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.
A vinylic monomer having an ester group represented by the following general formula XI is also usable:
R3-C - C-O-Rl (XI) wherein R3 is hydrogen atom or an alkyl group and R10 is an alkyl group, an aromatic group, or an alicyclic group. The compounds of the general formula XII include, for example, methyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and phenyl methacrylate.
The nonionic monomer (B) is used herein for the purpose of adjusting the molecular weight and ion equivalent weight of the organic sludge dehydrator.
For the water-in-oil type amphoteric type copolymer emulsion to be produced by the method of this invention, the amounts of the anionic monomer (A) and the nonionic monomer (B) to be used during in the polymerization of the water-in-oil form vinylic carboxylic acid polymer emulsion (C) must be fixed so that the produced copolymer emulsion may acquire a cation equivalent weight value, Cv, in the range of 0.8 to 10.0 meq/g, and an anion equivalent weight value, Av, in the range of 0.1 to 6.0 meq/g.
When at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid or a mixture of the anionic monomer (A) with a nonionic monomer (B) is to be emulsified in water-in-oil form in the presence of water, a surfactant, and a hydrophobic organic solvent, the surfactant may be a nonionic surfactant in popular use.
The nonionic surfactants which are usable herein include, for example, sorbitan monooleate, sorbitan monostrearate, sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbin monolaurate, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, and glycerol monooleate.
These nonionic surfactants may be used either singly or in the form of a mixture of two or more members.
Optionally, the nonionic surfactant may be used in combination wit;h an anionic and a cationic surfactant of ordinary grade.
The hydrophobic organic solvents which are usable herein include, for example, hydrophobic aliphatic and aromatic hydrocarbons, vegetable and animal oils, and modified products of such oils. Typical examples are normal paraffin, isoparaffin, cyclohexane, naphtene, toluene, xylene, kerosine, mineral oils, and lamp oil, etc.
The total amount of the anionic monomer (A) and the nonionic monomer (B) to be used herein is preferable to account for a concentration in the range of 20 to 80% by weight, based on the amount of water. The concentration of the surfactant to be used is preferable to be in the range of 5 to 30% by weight, based on the amount of the hydrophobic organic solvent. The ratio of the hydrophobic organic solvent to the water is in the range of 1 : 10 to 10 :1, preferably l : 5 to 3 : 1.
When the water-in-oil form monomer emulsion obtained by emulsifying in water-in-oil form at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid or a mixture of the anionic monomer (A) with a nonionic monomer (B) in the presence of water, a surfact;ant, and a hydrophobic organic solvent is to be polymerized or copolymerized, a redox type or azo type radical polymerization initiator may be used as occasion demands. The redox type polymerization initiators include, for example, ammonium persulfate, potassium persulfate, hydrogen peroxide, benzoil peroxide, and t-butyl peroxide.
The azo type polymerization initiators usable herein include, for example, azobis(amidinopropane) Hcl, azobisisobutyronitrile, azobis(dimethylvaleronitrile), and azobis(cyclohexanecarbonitrile).
It is also permissible to add to the polymerization system a well-known chain transfer agent such as isopropyl alcohol, erythorubic acid, or 2-mercapto ethanol.
The polymerization temperature is preferable to be externally controlled, during the initial phase of the polymerization, in the range of 10 to 60C, and, during the normal phase of the polymerization, in the range of 30 to Though the polymerization time is variable with the concentration of monomers, the polymerization temperature, and the polymerization degree aimed at, for example, it is generally in the range of 10 minutes to 10 hours, preferably 1 to 7 hours.
Further, preparatory to the aminoalkylation, it is necessary to fix the amounts of the vinylic carboxylic acid polymer (C) and the alkylene imine to be used for the aminoalkylation.
If the cation equivalent weight value, Cv, is less than o.8 meq/g, the produced amphoteric polyelectrolite manifests its characteristics only with difficulty. If the cation equivalent weight value, Cv, exceeds 10.0 meq/g, the produced amphoteric polyelectrolite does not easily manifest its characteristics. If the anion equivalent weight value, Av, is less than 0.1 meq/g, the produced amphoteric polyelectrolite manifests its characteristics only with difficulty. Conversely, if the anion equivalent weight value, Av, exceeds 6.0 meq/g, there arises a disadvantage that the produced amphoteric polyelectrolite tends to suffer a decrease in its solubility in water.
t~
The reaction of aminoalkylation can be effected by causing an alkylene imine to react on the water-in-oil form vinylic carboxylic acid polymer emulsion (C).
Preparatory to the aminoalkylation, it is necessary to fix the amounts of the water-in-oil form vinylic carboxylic acid polymer emulsion (C) and the alkylene imine.
The aminoalkylation is effected by causing reaction of the acid group of the vinyl type carboxylic acid polymer (C) with the alkylene imine as indicated below.
The alkylene imine for exchanging the free carboxyl group of the vinylic polymer for an aminoester group is a 1,2-alkylene imine (aziridine). Among other 1,2-alkylene imines, 1,2-propylene imine and ethylene imine prove to be particularly desirable because of their ready availability and relatively low prices. Optionally, n-alkyl-substituted or unsubstituted 1,3-alkylene imines (azetidine) are usable because their imines, in forming an aminoester group, exhibit chemical reactivity and other properties similar to those of 1,2-imines.
The acidification of a suspended aminoalkyl group is effected with a monobasic acid, which is used in an amount in the range of 50 to 100 mol% (preferably 60 to 90 mol~), based on the amount of the added alkylene imine. The addition of the monobasic acid to the reaction system is carried out either collectively or peacemeal during the course of the aminoalkylation. The monobasic acid is selected from among mineral acids such as hydrochloric acid, nitric acid, and carboxylic acids such as acetic acid, formic acid etc.
For the organic sludge dehydrator of water-in-oil form amphoteric copolymer emulsion to be obtained by the method of this invention, it is preferable to control suitably the molecular weight thereof in addition to the cation equivalent weight and the anion equivalent weight value mentioned above. With intrinsic viscosity as an index to molecular weight, the composition of the component f ~ ~
monomers, the polymerization conditions, etc. are preferable to be suitably set so that the produced water-in-oil form amphoteric copolymer emulsion may acquire intrinsic viscosity [~] in the range of 0.1 to 25, preferably 1 to 15.
Also, this invention relates to an organic sludge dehydrator of an amphoteric polyelectrolyte represented by the general formula V having an aminoalkyl group and a carboxyl group obtained by either emulsion polymerizing in water at least one anionic monomer (A) selected from the group cons.isting of acrylic acid and methacrylic acid and a nonionic monomer (B) corresponding to A in the general formula V and added for the purpose of emulsification or effecting said emulsion polymerization in water in the presence of a hydrophilic nonionic monomer (C) corresponding to B of said general formula (V), allowing the resultant vinylic carboxylic acid polymer emulsion to be reacted upon by an alkylene imine thereby aminoalkylating said vinylic carboxylic acid polymer emulsion, and subsequently acidifying said aminoalkylated polymer emulsion with a monobasic acid.
The anionic monomer (A) to be used herein is as already described.
The nonionic monomer (D) may be any nonionic monomer which is emulsifiable and, at the same time, copolymerizable with the aforementioned monomer (A). The nonionic monomers which are usable herein include vinylic monomers possessing an ester group represented by the general formula X I .
Typical examples are as already cited. Further, vinyl compounds possessing an unsubstituted or p-substituted phenyl represented by the general formula XII:
R3-C ~ R12 (XII) wherein R3 and R12 have the meanings defined above, are also usable. Typical examples are styrene, p-methylstyrene, and p-vinylphenol. Acrylonitrile may be cited as another example.
The nonionic monomer (D) is used herein for the purpose of enabling the vinylic carboxylic acid polymer emulsion (E) to be obtained as an emulsion possessing low viscosity and allowing an increase in molecular weight.
Generally it is added in an amount of not more than 20 mol%, based on the amount of the vinylic carboxylic acid polymer emulsion (E). If this amount exceeds 20 mol%, there arises a disadvantage that the produced amphoteric polyelectrolite exhibits inferior solubility in water.
As the nonionic monomer (D), any of the nonionic monomers which are copolymerizable with the aforementioned monomers (A) and (B) can be used.
The nonionic monomer (B) is used for the purpose of adjusting the molecular weight and ion equivalent weight of the amphoteric polyelectrolite. Generally, it is preferable to be used in an amount of not more than 70 mol% based on the amount of the vinyl type caboxylic acid polymer emulsion (E).
For the amphoteric polyelectrolite to be produced by the method of this invention, it is necessary to fix the amounts of the anionic monomer (A) and the nonionic monomers (B) and (D) to be used in the polymerization of the vinylic carboxylic acid polymer emulsion (E) so that the produced amphoteric polyelectrolite may acquire a cation equivalent weight value, Cv, in the range of 0.8 to 10.0 meq/g and an anion equivalent weight value, Av, in the range of 0.1 to 6.0 meq/g. The amounts of monomers [the total amount of the anionic monomer (A) and the nonionic monomers (B) and (D) (hereinafter referred to as "total amount of monomers")] are preferable to account for a concentration approximately in the range of 10 to 80% by weight. If the concentration is less than 10% by weight, there arises a disadvantage that the polymerization betrays poor productivity. Conversely, if the concentration exceeds 80% by weight, there ensure at disadvantage that the polymerization generates a large volume of heat and the polymerization system suffers from undue rise of temperature.
In emulsion polymerizing in water at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid and a nonionic monomer (D) corresponding to A in the general formula V to be added for the purpose of emulsification with the anionic monomer or in effecting the emulsion polymerization in the presence of a hydrophilic nonionic monomer (B) corresponding to B of the general formula V, it is permissible to use a surfactant for the purpose of ensuring thorough dispersion of the monomers (A), (D), and (B). Though the surfactant to be used is not specifically defined, it is preferable to possess relatively high hydrophylicity enough for the formation of an 0/W form emulsion in consequence of the emulsification. The surfactants which are usable herein for this purpose include nonionic surfactants such as polyoxyethylene nonylphenyl ether and polyoxyethylenestearyl ether, anionic surfactants such as sodium lauryl sulfate and polyoxyethylene nonylphenyl ether sodium sulfate, and cationic surfactants such as stearyl amine acetate and stearyl trimethyl ammonium chloride, for example. The amount of the surfactant to be used is in the range of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of monomer~.
In the production of the vinylic carboxylic acid polymer emulsion (E), it is permissible to use a redox type or azo type radical polymerization initiator, as occasion demands. The kinds of the polymerization initiator and the amount of the polymerization initiator to be used are as already described.
The polymerization temperature is required to be controlled externally, during the initial phase of the polymerization, in the range of 10 to 40C, preferably 20 to 40C, and, during the normal course of the :~ `
polymerization, in the range of 30 to 100C, preferably 40 to 80C.
Though the polymerization time is variable with the concentration of the monomers, the polymerization temperature, and the polymerization degree aimed at, for example, it is generally in the range of 10 minutes to 10 hours, preferably 1 to 7 hours.
Preparatory to the reaction of aminoalkylation, it is necessary to fix the amounts of the vinylic carboxylic acid polymer emulsion (E) and the alkylene imine.
If the cation equivalent weight value, Cv, is less than 0.8 meq/g, the produced amphoteric polyelectrolite does not manifest its characteristics easily. Conversely, if the cation equivalent weight value, Cv, exceeds 10.0 meq/g, the characteristics expected of the produced amphoteric polyelectrolite do not easily manifest themselves. If the anion equivalent weight value, Av, is less than 0.1 meq/g, the produced amphoteric polyelectrolite manifests its characteristics only with difficulty. If this value exceeds 6.0 meq/g, there is a disadvantage that the produced amphoteric polyelectrolite tends to exhibit inferior solubility in water.
The aminoalkylation can be carried out by causing the vinylic carboxylic acid copolymer emulsion (E) to be acted upon by an alkylene imine.
Specifically, the aminoalkylation is conventional manner as described above between the carboxylic acid group of the vinylic carboxylic acid polymer emulsion (E) and the alkylene imine. The typical examples of the alkylene imine and the amount of the alkylene imine to be used are as already described. The conditions for the aminoalkylation are also as described above.
For the organic sludge dehydrator containing the amphoteric polyelectrolite by the method of this invention, it is preferable to control suitably the molecular weight thereof in addition to the cation equivalent weight value and the anion equivalent weight value mentioned above. With intrinsic viscosity as an index to molecular weight, the composition of the component monomers, the polymerization conditions, etc. are preferable to be suitably set so that the produced amphoteric polyelectrolite may acquire intrinsic viscosity [~] in the range of 0.1 to 25, preferably 1 to 15.
The organic sludge dehydrator of this invention, in addition to organic sludge, gives rise to flocs. These flocs are destined to be dehydrated by the conventional method. The dehydrating devices which are usable for this purpose include, for example, screw-press type dehydrating devices, filter-press type dehydrating devices, belt-press type dehydrating devices, screw decanters, and centrifugal devices.
Now, the present invention will be described more specifically below with reference to working examples. It should be noted, however, that the present invention is not limited in any sense by these examples.
Referential Example 1 [Method for production of organic sludge dehydrator]
In a four-neck flask fitted with a stirrer, a thermometer, a condenser, a dropping funnel, and a nitrogen gas inlet tube, 100 g of Isoper M (isoparaffin solvent produced by Exxon Chemical) was placed and 11.6 g of sorbitan monooleate was dissolved therein and the resultant mixture was emulsified by gradual addition thereto of a mixed solution prepared as an aqueous monomer solution by the combination of 80 g of acrylic acid, 20 g of acrylamide, 52.9 g of aqueous 28 wt% ammonia solution, and 33.9 g of deionized water. After the internal gas of the reaction system had been thoroughly displaced with nitrogen gas, the reaction mixture was heated to 60C and, in the presence of 0.7 g of azobis(dimethyl valeronitrile) added thereto as a catalyst, was heated at 60C and, at the same time, stirred for 4 hours. Consequently, there was obtained a water-in-oil form vinylic carboxylic acid polymer emulsion.
Ethylene imine (23.9 g) was added dropwise while keeping at 50C, and stirring was continued for 30 min. To the resultant solution, were added dropwise 57.4 g of 61 wt~
of nitric acid, then stirring was continued for 30 min.
Further ethylene imine (76.1 g) were added dropwise, then stirring was continued for 30 min. Additional 61 wt% of nitric acid( 110.7 g) were added dropwise, then stirring was continued for 30 min. give rise to an organic sludge dehydrator aimed at. The reaction condition are shown in Table 1.
Referential Examples 2-10 The procedure of Referential example 1 was repeated, except that the conditions indicated in Table 1 were used.
Referential Example 11 [Production of organic sludge dehydrator]
In a four-neck flask fitted with a stirrer, a thermometer, a condenser, a dropping funnel, and a nitrogen gas inlet tube, 820 g of deionized water and 0. 8 g of sodium lauryl sulfate were stirred for thorough solution. To the resultant solution, were added 25.6 g of acrylic acid (AA), 3.2 g of acrylamide (AAm), and 3.2 g of styrene (St). The reaction mixture was kept stirred and the internal gas of the reaction system was thoroughly displaced with nitrogen gas. After the nitrogen displacement, the reaction mixture was heated to 50C and 0.288 g of ammonium persulfate (APS) and 0.288 g of sodium hydrogen sulfite were added as catalyst thereto. Immediately, 102.4 g of acrylic acid (AA), 12.8 g of acrylamide (AAm), and 12.8 g of styrene (St?
were added dropwise through the dropping funnel to the reaction mixture over a period of 2 hours, with the temperature kept at 50C. The resultant mixture was left aging for 2 hours. Consequent;ly, there was obtained a vinylic carboxylic acid polymer emulsion.
The emulsion obtained was kept at 50C throughout the entire course of reaction and, after dropwise addition of 38.2 g of ethylene imine thereto, was stirred for 30 minutes. The resultant mixture and 91.8 g of an aqueous 61 wt~ nitric acid solution added thereto were stirred for 30 minutes. Subsequently, the ensuant mixture and 121.8 g of ethylene imine added thereto were stirred for 30 minutes.
After addition of an aqueous 61 wt% nitric acid solution (177.2 g), stirring was continued for 30 minutes.
Consequently, there was obtained an amphoteric polyelectrolite. The reaction conditions and the physical properties of the reaction product were as shown in Table 1.
Referential Examples 12 to 20 The procedure of Referential Example 11 was repeated, except that the conditions indicated in Table 1 were used instead.
Tablel ____ . - . .
Rererential Organic sll1dge dehydration agent Example Composition in weight 1 El/AAm/AA = 50/10/40 . . El/AAm/AA = 50/15/35 3 El/AA = 50/50 . EI/AAm/AA = 50/20/30 EIMEA/AA = 50/10/40 EVMAm/AN/AA = 50/1515/30 El/AAm/AA = 30128142 El/AAm/AA = 28M3129 . ~ ~ El/AAm/AA -- 24146130 El/AAm/AA = 15/64/21 11 EllAAmlSt/AA = 501515140 12 EIlAAmlSt/AA = 50/10/5/35 13 EIlAAmlBA/AA = 501515140 14 EIMEA/MMA/AA = 50/15/5/30 11~ ET/MAm/MA/AA = 5017.512.5140 16 EVAAm/St~AA = 5017.512.5140 17 ~ ETMEA/MMA/AA--3012V7142 18 ET/AAm/MA/AA = 2813617129 .
__ EllAAm/MAlAA = 2413818130 ET/AAm/AN/AA = 15151/13/21 AA: acrylic acid AAm: acrylamide HEA: 2-hydroxyethyl acrylate AN: acrylonitrile MAm: methacrylamide EI: ethylene imine St: styrene MA: methyl acrylate BA: butyl acrylate MMA: methyl methacrylate Examples 1 to 6 Flocs were formed by stirring 150 ml of mixed raw sludge from a sewage disposal plant (pH 6.1, SS 1.8 wt%, VSS/SS 76.3~) and an organic sludge dehydrator added thereto in an amount stated in Table 1 at 300 rpm for 30 seconds.
Into a Buchner funnel draped with a 100-mesh nylon filter cloth, was poured 100 ml of the flocs of sludge. The amount of water passed through the filter cloth over a period of 10 seconds was measured. The sludge which passed through the filter cloth over a period of 5 minutes was nipped between two filter cloths and squeezed under 0.5 kg/cm2 for 2 minutes. The sludge (cake) resulting from the dehydration was tested for water content. The results and the physical properties are shown in Table 2.
Controls 1 to 3 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 2 were polymerized by the known method and then subjected to the same flocculation test as in Example 1. The results and the physical properties are shown in Table 2.
_ a - ~ r ., o r r~ r ~
~' .~ ~ _ __ __ _ _ _ _ _ ,_ o . ~ , _ _ r _ ~ _ ~ _ ~ ~ ~4;~
O ~ 01 ~ G~ 0~ C~ t- t- C~ .C ;7J ~
_ ~ ~ _ _ _ ___ ~s ~
y E ¦ C E I 9 ~ E ' ~ c~ c.~ ~ ~n ~D _~ ~ C'~
';~ ~ E~ ¦ E ¦ E
Examples 7 and 8 The organic sludge dehydraters indicated in Table 1 were subjected to the same flocculation test as in Example 1, using mixed raw sludge (pH 6.4, SS 1.7 wt~, VSS/SS 73.6~) from a sewage disposal plant. The results and the physical properties are shown in Table 3.
Controls 4 and 5 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 3 were polymerized by the known method and subjected to the same flocculation test as in Example 7. The results and the physical properties are shown in Table 3.
Examples 9 and 10 The organic sludge dehydraters indicated in Table l were subjected to the same flocculation test as in Example 1, using mixed raw sludge (pH 6.2, SS 1.4 wt%, VSS/SS 74.6~) from a sewage disposal plant. The results and the physical properties are shown in Table 4.
Controls 6 and 7 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 4 were polymerized by the known method and subjected to the same flocculation test as in Example 7. The results and the physical properties are shown in Table 4.
~ ;~
~, ~
E E o, c~ _ _ ~J O E E = 3 _ O ~ .
_ __ _ ~ _ __ _ _ e~
Z
r5 _ O Z .E_ E E~ c r Z ~
C~ 5 C~ 5 The cation equivalent weight values, the anion equivalent weight values, and the intrinsic viscosity indicated in Tables 2 to 7 were determined by the following methods.
(1) Cation equivalent weight value This property was determined by placing 95 ml of distilled water in a beaker, adding thereto 5 ml of a solution of 1,000 ppm of a given sample, adjusting the pH
value of the resultant solution to 7.0 by addition of either 1% HCl or 1% NaOH, stirring the solution for about 1 minute, then adding two or three drops of toluidine blue indicator solution, and titrating the solution with N/400 PVSK
(polyvinyl sulfate potassium solution) at intervals of 2 ml.
The time at which an interval of at least 10 seconds elapsed after the color of the sample water had changed from blue to reddish purple was taken as the end point of this titration.
Cation equivalent weight value (Cv) (meq/g) =
(Amount of titrant [ml] for sample - amount of titrant [ml] for blank) x F/2 x (concentration of effective component (ppm) in sample) The term "effective component" as used herein refers to the component remaining after removal of neutralizing acid from the solids of the sample.
(2) Anion equivalent weight value This property was determined by placing 50 ml of distilled water in a beaker, adding thereto about 0.3 g of accurately weighed sample, stirring the resultant solution, and titrating this solution with a N/10 NaOH solution to obtain the scale reading of electroconductivity. The scale reading of titration corresponding to the last (the point at which neutralization of the whole acid present was completed) of several points of inflection was taken for reporting.
(3) Intrinsic viscosity (dl/g) In 100 parts by volume of water, 0.2 part by weight of a sample polymer was dissolved and adjusted to pH 4 with .~
hydrochloric acid. In a conical flask (200 ml) fitted with a ground stopper, 50 ml of the resultant solution was placed and gently stirred with 50 ml of 2N-NaN03 for thorough solution. Then, the resultant solution was diluted with 1N-NaN03 to concentrations of 0.02~, 0.04%, 0.06~, and 0.08%, diluted solutions were adjusted to pH 4.
In a constant temperature bath adjusted to 30C ~
0.1C and fitted with a Canon Fenske viscosimeter, 10 ml of a sample was placed in the viscosimeter and allowed to flow down spontaneously. The time required for the sample to pass through the distance between the vertically separated marks on the measuring bulb was measured. This procedure was repeated at least three times to determine the intrinsic viscosity as the average. A blank test was performed with an aqueous solution of 1N-NaN03.
This procedure was performed on each of the 0.02 to o . o8~ solutions mentioned above.
The reduced viscosity was calculated as follows.
Relative viscosity ~rel = t/to Specific viscosity nlsp = (t - to)/tO ~ ~rel ~ 1 Reduced viscosity ~sp/c wherein to is the time for downward flow of 1N-NaN03, t is the time for downward flow of sample solution, ~rel is the relative viscosity, rlsp is the specific viscosity, and c is the concentration of sample solution.
On a graph having the horizontal axis graduated for sample concentration and the vertical axis for reduced viscosity, the numerical values obtained by the measurement described above were plotted and straight lines were drawn across the points. The reading of the vertical axis against which the sample concentration was O was taken as the intrinsic viscosity of the sample.
to = the time required for 1N-NaN03 t - the time required the sample soln.
~rel = relative viscosity rlsp = specific viscosity c = the concentration of the sample soln.
Examples 11 to 16 Flocs were formed by stirring 150 ml of mixed raw sludge (pH 6.7, SS 1.9 wt~, VSS/SS 73.9~) from a sewage disposal plant and an organic sludge dehydrator added thereto in an amount stated in Table 1 at 300 rpm for 30 seconds. Into a Buchner fullen draped with a 100-mesh nylon filter cloth, 100 ml of the flocs was poured. The amount of water passed through the filter cloth over a period of 10 seconds was measured. Then, the sludge which had passed through the filter cloth over a period of 5 minutes was interposed between filter cloths and squeezed under pressure of 0.5 kg~cm2 for 2 minutes to expel the water. The sludge (cake) resulting from the dehydration was tested for water content. The results and the physical properties are shown in Table 5.
Controls 8 to 10 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 5 were polymerized by the known method and subjected to the same flocculation test as in Example 11. The results and the physical properties are shown in Table 5.
~ ~c~ ----- ----i~C, --~ ~
~`
L ~ ~ ¦ c E ~ c~ a .D
L~ Q e " , Examples 17 and 18 The organic sludge dehydraters indicated in Table 1 were subjected to the same flocculation test as in Example 11, using mixed raw sludge (p~l 6.5, SS 1.2 wt~, VSS.tSS
70.6%) from a sewage disposal plant. The results and the physical properties are shown in Table 6.
Controls 11 and 12 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 6 were polymerized by the known method and subjected to the same flocculation test as in Example 11. The results and the physical properties are shown in Table 6.
Examples 19 and 20 The organic sludge dehydraters indicated in Table 1 were subjected to the same flocculation test as in Example 1, using mixed raw sludge (pH 6.2, SS 1.5 wt%, VSS/SS 71.5%) from a sewage disposal plant. The results and the physical properties are shown in Table 7.
Controls 13 and 14 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 7 were polymerized by the known method and subjected to the same flocculation test as in Example 11. The results and the physical properties are shown in Table 7.
.~ - - .
a 3 ~ o e c u ~i ~ ~ ~o ~ .c ~ ~ ~ ~
O r ~ = E r ~
~ ~-~9~
hydrochloric acid. In a conical flask (200 ml) fitted with a ground stopper, 50 ml of the resultant solution was placed and gently stirred with 50 ml of 2N-NaN03 for thorough solution. Then, the resultant solution was diluted with 1N-NaN03 to concentrations of 0.02~, 0.04%, 0.06~, and 0.08%, diluted solutions were adjusted to pH 4.
In a constant temperature bath adjusted to 30C ~
0.1C and fitted with a Canon Fenske viscosimeter, 10 ml of a sample was placed in the viscosimeter and allowed to flow down spontaneously. The time required for the sample to pass through the distance between the vertically separated marks on the measuring bulb was measured. This procedure was repeated at least three times to determine the intrinsic viscosity as the average. A blank test was performed with an aqueous solution of 1N-NaN03.
This procedure was performed on each of the 0.02 to o . o8~ solutions mentioned above.
The reduced viscosity was calculated as follows.
Relative viscosity ~rel = t/to Specific viscosity nlsp = (t - to)/tO ~ ~rel ~ 1 Reduced viscosity ~sp/c wherein to is the time for downward flow of 1N-NaN03, t is the time for downward flow of sample solution, ~rel is the relative viscosity, rlsp is the specific viscosity, and c is the concentration of sample solution.
On a graph having the horizontal axis graduated for sample concentration and the vertical axis for reduced viscosity, the numerical values obtained by the measurement described above were plotted and straight lines were drawn across the points. The reading of the vertical axis against which the sample concentration was O was taken as the intrinsic viscosity of the sample.
to = the time required for 1N-NaN03 t - the time required the sample soln.
~rel = relative viscosity rlsp = specific viscosity c = the concentration of the sample soln.
Examples 11 to 16 Flocs were formed by stirring 150 ml of mixed raw sludge (pH 6.7, SS 1.9 wt~, VSS/SS 73.9~) from a sewage disposal plant and an organic sludge dehydrator added thereto in an amount stated in Table 1 at 300 rpm for 30 seconds. Into a Buchner fullen draped with a 100-mesh nylon filter cloth, 100 ml of the flocs was poured. The amount of water passed through the filter cloth over a period of 10 seconds was measured. Then, the sludge which had passed through the filter cloth over a period of 5 minutes was interposed between filter cloths and squeezed under pressure of 0.5 kg~cm2 for 2 minutes to expel the water. The sludge (cake) resulting from the dehydration was tested for water content. The results and the physical properties are shown in Table 5.
Controls 8 to 10 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 5 were polymerized by the known method and subjected to the same flocculation test as in Example 11. The results and the physical properties are shown in Table 5.
~ ~c~ ----- ----i~C, --~ ~
~`
L ~ ~ ¦ c E ~ c~ a .D
L~ Q e " , Examples 17 and 18 The organic sludge dehydraters indicated in Table 1 were subjected to the same flocculation test as in Example 11, using mixed raw sludge (p~l 6.5, SS 1.2 wt~, VSS.tSS
70.6%) from a sewage disposal plant. The results and the physical properties are shown in Table 6.
Controls 11 and 12 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 6 were polymerized by the known method and subjected to the same flocculation test as in Example 11. The results and the physical properties are shown in Table 6.
Examples 19 and 20 The organic sludge dehydraters indicated in Table 1 were subjected to the same flocculation test as in Example 1, using mixed raw sludge (pH 6.2, SS 1.5 wt%, VSS/SS 71.5%) from a sewage disposal plant. The results and the physical properties are shown in Table 7.
Controls 13 and 14 The DAM (N,N-dimethylaminoethyl methacrylate) type polymers indicated in Table 7 were polymerized by the known method and subjected to the same flocculation test as in Example 11. The results and the physical properties are shown in Table 7.
.~ - - .
a 3 ~ o e c u ~i ~ ~ ~o ~ .c ~ ~ ~ ~
O r ~ = E r ~
~ ~-~9~
Claims (14)
1. An organic sludge dehydrater of a water-in-oil form amphoteric copolymer emulsion containing an amphoteric polyelectrolite represented by the general formula I:
(I) wherein n is an integer in the range of 1 to 5, providing that the average value of n is not less than 2, a, b, and c stand for proportions such that the sum, a + b + c, is 1 or the sum, a + b, is 1, R1, R2, R3, and R4 are independently hydrogen atom or an alkyl group, R5 is hydrogen atom, an alkyl group, or an alkyl group substituted with a .omega.-hydroxy group, HY is a monobasic acid, Z is an amide group represented by the general formula II:
-CONR6R7 (II) wherein R6 and R7 are independently hydrogen atom or an alkyl group, a hydroxyalkyl group represented by the general formula III:
(III) wherein R8 and R9 are independently hydrogen atom or an alkyl group, or a nitrile group represented by the general formula IV:
-CN (IV) or an ester group represented by the general formula VIII:
-CO2R10 (VIII) wherein R10 in an alkyl group, an aromatic group, or an alicyclic group.
(I) wherein n is an integer in the range of 1 to 5, providing that the average value of n is not less than 2, a, b, and c stand for proportions such that the sum, a + b + c, is 1 or the sum, a + b, is 1, R1, R2, R3, and R4 are independently hydrogen atom or an alkyl group, R5 is hydrogen atom, an alkyl group, or an alkyl group substituted with a .omega.-hydroxy group, HY is a monobasic acid, Z is an amide group represented by the general formula II:
-CONR6R7 (II) wherein R6 and R7 are independently hydrogen atom or an alkyl group, a hydroxyalkyl group represented by the general formula III:
(III) wherein R8 and R9 are independently hydrogen atom or an alkyl group, or a nitrile group represented by the general formula IV:
-CN (IV) or an ester group represented by the general formula VIII:
-CO2R10 (VIII) wherein R10 in an alkyl group, an aromatic group, or an alicyclic group.
2. An organic sludge dehydrater according to claim 1, which possesses a cation equivalent weight value (Cv) in the range of 0.8 to 10.0 meq/g, an anion equivalent weight value (Av) in the range of 0.1 to 6.0 meq/g.
3. An organic sludge dehydrater according to claim 2, wherein said amphoteric polyelectrolyte is obtained by either polymerizing in water in oil emulsion form at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid or copolymerizing said anionic monomer (A) with a nonionic monomer (B), allowing the resultant vinylic carboxylic acid polymer (C) to be reacted upon by not less than 1.2 mols, per mol of said anionic monomer (A), of an alkylene imine thereby aminoalkylating said vinylic polymer (C), and subsequently acidifying the aminoalkylated vinylic carboxylic acid polymer (C) with a dibasic acid.
4. An organic sludge degydrater according to claim 3, wherein said nonionic monomer (B) accounts for a proportion in the range of 0 to 70 mol%, based on the amount of said vinylic carboxylic acid polymer (C).
5. An organic sludge dehydrater according to claim 4, wherein said nonionic monomer (B) is at least one member selected from the group consisting of vinyl monomers possessing an amide group and represented by the general formula IX:
(IX) wherein R3, R6, and R7 have the same meanings as defined above, vinyl monomers possessing a hydroxyalkyl group and represented by the general formula X:
wherein R3, R8, and R9 have the same meanings as defined above, and (meth)acrylonitriles.
(X)
(IX) wherein R3, R6, and R7 have the same meanings as defined above, vinyl monomers possessing a hydroxyalkyl group and represented by the general formula X:
wherein R3, R8, and R9 have the same meanings as defined above, and (meth)acrylonitriles.
(X)
6. An organic sludge dehydrater according to claim 3, wherein said alkylene imine is represented by the general formula, wherein R4 and R5 have the same meanings as defined above.
7. An organic sludge dehydrater according to claim 3, wherein said amphoteric polyelectrolite possesses an intrinsic viscosity [?] in the range of 0.1 to 25.
8. An organic sludge dehydrater containing amphoteric polyelectrolite possessing an aminoalkyl group and a carboxyl group and represented by the general formula V:
(V) wherein n is an integer in the range of 1 to 5, d, e, f, and g are proportions such that the sum, d, e + f + g, is l or the sum, d + e + f, is 1, R1, R2, R3, R4, and R10 are independently hydrogen atom or an alkyl group, R5 is hydrogen atom, an alkyl group, or an alkyl group substituted with a .omega.-hydroxy group, HY is a monobasic acid, A is an ester represented by the general formula VI:
-CO2R11 (VI) wherein R11 is an alkyl group, an aromatic group, or an alicyclic group, an unsubstituted or a p-substituted phenyl group represented by the general formula VII:
(VII) wherein R12 is hydrogen atom, an alkyl group, or a hydroxy group, or a nitryl group represented by the general formula IV:
-CN (IV) B is an amide group represented by the general formaula II:
-CONR6R7 (II) wherein R6 and R7 are independently hydrogen atom or an alkyl group, a hydroxyalkyl group represented by the general formula III:
(III) wherein R8 and R9 are independently hydrogen atom or an alkyl group, or an aminoalkyl group represented by the general formula IV:
-CN (IV)
(V) wherein n is an integer in the range of 1 to 5, d, e, f, and g are proportions such that the sum, d, e + f + g, is l or the sum, d + e + f, is 1, R1, R2, R3, R4, and R10 are independently hydrogen atom or an alkyl group, R5 is hydrogen atom, an alkyl group, or an alkyl group substituted with a .omega.-hydroxy group, HY is a monobasic acid, A is an ester represented by the general formula VI:
-CO2R11 (VI) wherein R11 is an alkyl group, an aromatic group, or an alicyclic group, an unsubstituted or a p-substituted phenyl group represented by the general formula VII:
(VII) wherein R12 is hydrogen atom, an alkyl group, or a hydroxy group, or a nitryl group represented by the general formula IV:
-CN (IV) B is an amide group represented by the general formaula II:
-CONR6R7 (II) wherein R6 and R7 are independently hydrogen atom or an alkyl group, a hydroxyalkyl group represented by the general formula III:
(III) wherein R8 and R9 are independently hydrogen atom or an alkyl group, or an aminoalkyl group represented by the general formula IV:
-CN (IV)
9. An organic sludge dehydrater according to claim 8, which possesses a cation equivalent weight value (Cv) in the range of 0.8 to 10.0 meq/g and an anion equivalent weight value (Av) in the range of 0.1 to 6.0 meq/g.
10. An organic sludge dehydrater according to claim 9, wherein said amphoteric polyelectrolite is obtained by emulsion polymerizing in water at least one anionic monomer (A) selected from the group consisting of acrylic acid and methacrylic acid and a nonionic monomer (D) corresponding to A in the general formula V and added for the purpose of emulsification or effecting said emulsion polymerization in water in the presence of a nonionic monomer (B) corresponding to B of said general formula V, allowing the resultant vinylic carboxylic acid polymer emulsion (E) to be reacted upon by an alkylene imine thereby aminoalkylating said vinylic carboxylic acid polymer emulsion, and subsequently acidifying said aminoalkylated polymer emulsion with a monobasic acid.
11. An organic sludge dehydrater according to claim 10, wherein said nonionic monomer (B) is at least one member selected from the group consisting of vinyl monomers possessing an amide group and represented by the general formula IX:
(IX) wherein R3, R6, and R7 have the same meanings as defined above, vinyl monomers possessing a hydroxyalkyl group and represented by the general formula X:
(X) wherein R3, R8, and R9 have the same meanings as defined above, (meth)acrylonitriles, vinyl monomers possessing an ester group and represented by the general formula XI:
(XI) wherein R3 and R10 have the same meanings as defined above, and vinyl monomers possessing an unsubstituted or p-substituted phenyl group and represented by the general formula XII:
(XII) wherein R3 and R12 have the same meanings as defined above
(IX) wherein R3, R6, and R7 have the same meanings as defined above, vinyl monomers possessing a hydroxyalkyl group and represented by the general formula X:
(X) wherein R3, R8, and R9 have the same meanings as defined above, (meth)acrylonitriles, vinyl monomers possessing an ester group and represented by the general formula XI:
(XI) wherein R3 and R10 have the same meanings as defined above, and vinyl monomers possessing an unsubstituted or p-substituted phenyl group and represented by the general formula XII:
(XII) wherein R3 and R12 have the same meanings as defined above
12. An organic sludge dehydrater according to claim 10, wherein said alkylene imine is represented by the general formula, wherein R4 and R5 have the same meanings as defined above.
13. An organic sludge dehydrater according to claim 10, wherein said nonionic monomer (B) accounts for a proportion in the range of 0 to 20 mol%, based on the amount of said vinylic carboxylic acid polymer emulsion (E).
14. An organic sludge dehydrater according to claim 10, wherein said amphoteric polyelectrolite possesses an intrinsic viscosity [n] in the range of 0.1 to 25.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-1036 | 1990-01-09 | ||
| JP2001036A JPH0787920B2 (en) | 1990-01-09 | 1990-01-09 | Organic sludge dehydrator |
| JP2003435A JPH03213200A (en) | 1990-01-12 | 1990-01-12 | Organic sludge dewatering agent |
| JP2-3435 | 1990-01-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2025785A1 true CA2025785A1 (en) | 1991-07-10 |
Family
ID=26334193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002025785A Abandoned CA2025785A1 (en) | 1990-01-09 | 1990-09-20 | Organic sludge dehydrater |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2025785A1 (en) |
-
1990
- 1990-09-20 CA CA002025785A patent/CA2025785A1/en not_active Abandoned
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |