JPS6150609A - Preparation of flocculant - Google Patents

Abstract

PURPOSE:To prepare a flocculant showing marked flocculation effect and easy in post-treament because of its reduced water content, by bonding a polymer derivative of N-substituted carbamoyl to dibenzalsorbit. CONSTITUTION:Dibenzalsorbit and halo-urea are mised under heating to introduce a carbamoyl group and glyceroyl dihalohydrin is succeedingly mixed under heating to form not only a cyclic derivative but also -NH-. Separately, ethyl urea and urea are mixed under heating to form a biuret derivative having an ethyl side chain and operation, such that epichlorohydrin is mixed with this derivative under heating to introduce an ethyl group into the chain terminal, is repeated and, further, the reaction product is reacted with hydroxylamines to obtain a straight chanin poly-N-methylcarbamoyl derivative having a hydroxyl group and a carbamoyl group at the terminal thereof and the abovementioned cyclic derivative of debenzalsorbit is reacted with the obtained derivative to be bonded thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a flocculant derived from dibenzalsorbit.

Although benzalsorbits have the ability to gel cicoloids due to their unique structure, they have the disadvantage that if used as is for wastewater treatment, they form aggregates with a high water content, making post-treatment difficult.

Most organic flocculants conventionally used in wastewater treatment were obtained by subjecting polymers such as polyacrylamide to various chemical treatments. It was presumed that the flocculation ability could be further strengthened if the properties of organic compounds having this ability were combined.

However, these existing flocculants are all vinyl-based macromolecules, and have the drawback that chemical treatment thereof is complicated and inconvenient.

The coagulation that acts on colloidal particles is achieved by neutralization of colloid charge and cross-linking of microflocs, but in actual wastewater treatment, the coagulant is easily dispersed in the wastewater to be treated, and at the same time adsorbs and permeates into oily substances. Therefore, it is necessary to have appropriate hydrophilicity and lipophilicity. However, since the main chain of conventional flocculants is a polyvinyl bond that has hydrophobic properties, it is difficult to obtain the above balance between oil-based properties and hydrophilicity when the side chains are subjected to various chemical treatments. is a novel composition in which an N-substituted carbomoyl polymer (NR-CO← derivative), which inherently has hydrophilicity in the main chain itself and is easy to balance with lipophilicity through the side chains, is bonded to nitrogen aqueous sorbitol. Preparation of flocculant I
This method is used in various wastewater treatments to provide aggregates with remarkable flocculation effects, low water content, and easy post-treatment.

That is, the present invention introduces a carbomoyl group into dibenzalsorbit by a dehydrochlorination reaction by mixing and heating dibenzalsorbit with a halogenated urea, and then mixing and heating glyceroyl dihalohydrin. At the same time as forming a cyclic derivative, -N1 (-, which is highly chemically reactive) is generated. Separately, ethyl urea and urea are mixed and heated to form a biuret derivative having an ethyl side chain, and epichlorohydrin is mixed with this. The operation of heating and introducing an ethyl group at the end of the chain is repeated to form a polyN-ethylcarbomoyl (NC, H5-Cob chain), which is then treated with hydroxyalkylamines such as ethanolamine, jetanolamine, and ethoxyethyl Ethanolamines Nf-r2(02H50)mH (In>2), jetoxyethylethanolamine, etc. are mixed and heated to form a linear chain having a water tfll group at one end and a carbomoyl group at the other end. The present invention provides a method for producing a flocculant in which a polyN-ethylcarbomoyl derivative is obtained, and a cyclic derivative of dibenzalsorbit is mixed and heated to bind the two.

Dibenzalsorbit has two hydroxyl groups, and 2 moles of halogenated urea reacts with 1 mole of dibenzalsorbit.

CH,OH As the urea halide used in this reaction, any of urea chloride, urea bromide, and urea iodide can be used, but urea chloride is preferred because dc-e can be easily separated. For the reaction, a method of mixing and heating in the presence of slightly boiling water to below the boiling point with IQ stirring can be adopted, but in the absence of water,
Good yields can be obtained even when stirring and mixing at temperatures up to 20°C.

The dicarbomoyl regulator a obtained in this way was subsequently reacted with glyceroyl dihalohydrin without lowering the mixture, and from the same dehydrochloric acidity LF5V, the cyclic compound a contained in dibenzalsorbitol was reacted with glyceroyldihalohydrin. Derivatives are
It is formed by the following equation.

This reaction, like the above reaction, is carried out in good yield by the mixing and heating method at 90 to 150°C to carry out the calculated equivalent amount of denorogenated hydrogenation reaction. Glyceroyldichlorohydrin can be suitably used as the glyceroyldihalohydrin.

In the reaction product, in addition to b in the above reaction formula, dimer production was also observed, but the production was extremely small. The two NHs shown in the east seal in the structural formula clearly occupy positions that are rich in chemical activity.

The N-substituted carbomoyl chain compound is synthesized as follows.

A chain compound with an unsubstituted carbomoyl group at one end and ethyl substitution at the other end, NH,C0tN(CtHfi)CO
lnNF((C2Hs) (n is a natural number including O, n
= O indicates ethyl urea) and urea are reacted with stirring in the presence or absence of hot water while maintaining the temperature at 90 to 110°C.

This chain compound has functional groups at both ends, but the highly reactive hydrogen of NH3 reacts and leaves NH3, and a chain compound with unsubstituted carbomoyl groups at both ends and an extended chain is formed. can get. Subsequently, epichlorohydrin was added in an amount of 1/2 equivalent or less of the unsubstituted carbomoyl group of the chain compound, and when mixed and heated under the same conditions in the presence of air, hydrogen chloride was eliminated and the oxirane ring was cleaved and oxidized. In combination with this, only one end is ethylated, and one end of the original has an unsubstituted carbomoyl, and the other end is an ethyl-substituted chain i.
A compound with an extended chain length is obtained.

By repeating the combination of (1) and (4) using ethyl urea as a starting base, a chain compound having multiple ethyl side chains is obtained, but the number of ethyl side chains is finally obtained. It affects the balance between hydrophilicity and lipophilicity or hydrophobicity of the flocculant, and in most cases, the number of ethyl side chains is suitable between 2 and 10, and more preferably between 6 and 8, giving a good flocculant. There are many.

Next, a hydroxyalkyl group is introduced into one end of this chain compound.

This reaction also undergoes similar deNH1 removal, and the hydrogen of >Nu at one end of the chain compound is extracted, producing a tertiary amine or quaternary amine.

As the hydroxyalkyl amine used in this reaction, monoethanolamine or jetanolamine is preferably used, but in order to finely adjust the balance between hydrophilicity and lipophilicity, monoethanolamines, I
01((CH2CH20)n l m NHs -m
(n is a natural number of 2 or more, m is 1 or 2) can also be used.

The tertiary amine derivative obtained by reaction formula (Ill) can of course be converted into a quaternary amine by a conventional method using an alkyl halide or the like.

The chain compound, which retains an unsubstituted carbomoyl group at one end and has cationic properties at the other end as described above, is mixed with the above-mentioned dipenzalusorbit derivative and bonded by the same heating and stirring operation. A flocculant is obtained as the final product.

This final reaction is a solid-state reaction between large molecules, and although its details are not necessarily clear, it is a de-Nf reaction similar to (1) to (1v) above, and (b in reaction formula (2)).
It is presumed that the H of the East seal in ) is extracted and the unsubstituted carbomoyl group retained at one end of the chain compound is bonded.

・OH-1-→ Construction is simply displayed. ) Since the pot nitrogen in flocculant (C) can be easily quaternized to give a + position, this flocculant has four colloidal charge neutralization centers.

After the above continuous mixing and heating process, the mixture was allowed to cool and a flocculant powder was obtained with a yield of 90 yen or more calculated from the raw materials. This flocculant is also soluble in alcohol-based and ketone-based organic solvents, but it is soluble in dimethylformamide.
% or more, and this was used to prepare wastewater treatment agents.

This wastewater treatment agent is applied to various wastewaters containing heavy oil, etc.
Colloids coagulate rapidly and instantaneously, and floating flocculation was observed in many wastewaters. The water content of the aggregates is small, and the solution of the wastewater treatment agent does not need to be used immediately after preparation, unlike commercially available products, and has good storage stability with no decline in flocculating ability observed even after approximately one year. showed his sexuality.

The present invention will be described below with reference to Examples, but the scope of the present invention is not limited to these Examples.

Example 1 Take 1 mole of diinthalsorbitol, add slightly more than 2 moles of urea chloride, and knead the two for 60 minutes. While adding boiling water three times the weight of the mixture, knead until a sufficiently uniform slurry state is obtained, then start heating, and
Stir for 50 minutes at 20-130°C, then collect 1/2 mole of glyceroyldichlorohydrin, and reduce the temperature to 13°C.
Adjust the temperature to 5 to 140°C, add gradually while stirring, and add at 30°C.
Continue stirring for a minute to obtain the dibenzalsorbit derivative.

Example 2 1 mole of ethyl urea was taken as a starting base, and 1 mole of urea was added to it.
1 mole of boiling water was added and stirred for 10 minutes at the boiling point, then 1 mole of epichlorohydrin was gradually added and stirred for 10 minutes, this operation was repeated 6 times, and then 1 mole of jetanolamine was added. After stirring for 30 minutes, the obtained slurry was combined with the slurry obtained in Example 1, and after mixing, the temperature was gradually increased while stirring was continued for 30 minutes to evaporate water, and the mixture was allowed to cool to form a powdery agglomerate. obtained the drug.

Example: 3 20 cc of 30% saline solution and 5 c of sludge precipitated on the fish bed
c was mixed to form a colloidal suspension. The flocculant obtained in Example 2 was dissolved in dimethylformamide to a concentration of 10φ, and when this solution 2 (C) was added and stirred, the sludge was
@Scoop up the aggregates that quickly aggregated and floated to the surface of the water.
Then, the water was immediately separated, forming an aggregate with almost no excess water.

Example 4 A colloidal suspension was prepared by vigorously stirring 5 cc of heavy crude oil and 20 cc of trichloride salt solution for 10 minutes. Next, 2 cc of the same flocculant solution as in Example 3 was added and stirred, and a strongly bonded aggregate was instantly flocculated.

Claims (1)

[Claims] Mix and heat dibenzalsorbit and halogenated urea, mix and heat glyceroyl dihalohydrin to obtain a dibenzalsorbit derivative, separately heat mix ethyl urea and urea, and mix epichlorohydrin with this. 1. A method for producing a flocculant, which comprises repeating a heating operation multiple times, mixing and heating a hydroxyalkylamine, and mixing and heating the dibenzalsorbit derivative.