JPS6150631A - Precursor substance of flocculant and its preparation - Google Patents

Abstract

PURPOSE:To obtain a precursor substance convertible to a flocculant with a low polymerization degree showing strong flocculation capacity, in a N-substituted carbamoyl polymer being a main chanin, by providing high hydrophilicity as compared with one having a vinyl macromolecular molecule as a main chain and imparting various functional groups thereto. CONSTITUTION:In the precursor substance of a flocculant based on a N-substituted carbamoyl polymer represented by formula [wherein R1 and R2 are same and different and selected from either one of the following molecular formulae I -IV and n is 2-10. The molecular formula I is HO-CH2-CH2-{N(C2H5)-C (O)}n-N(R2)-CO-, the molecular formula II is H2N-C(NH)-, the molecular formula III is C2H5- and the molecular formula IV is H-], high hydrophilicity as compared with a conventional one having a vinyl macromolecular molecule as a main chain is provided to the main chain thereof and various functional groups are imparted thereto to obtain the precursor substance convertible to various flocculants showing strong flocculation capacity in spite of a low polymerization degree.

Description

[Detailed description of the invention] The present invention relates to a precursor of a flocculant.

The flocculant that flocculates fine particles in the colloidal liquid has the function of neutralizing the colloid charge and cross-linking the microfloc, as well as facilitating dissolution and dispersion in the wastewater to be treated. It is necessary to have appropriate lipophilicity or hydrophobicity in consideration of the hydrophilicity of oil and adsorption and permeation of oily substances, and these properties are always imparted by total synthetic chemical methods.
It has been obtained via a precursor. In addition, even if such precursor substances themselves lack the performance as flocculants or are chemically unstable, they can easily exhibit the above-mentioned properties in their molecular structure through chemical modification. or a reactive atomic group that can easily combine with another atomic group that has the above-mentioned functions, and further, a flocculant that is finally obtained by these chemical operations. It is assumed that the chemical structure should be able to fit into the molecular structure of the compound.

The present invention relates to the chemical structure of a substance having various functions as a precursor and a method for producing the same.

It is.

Conventionally commercially available organic flocculants are vinyl polymers with extremely large molecular structures, such as polyacrylamide, and require a high degree of polymerization in order to satisfactorily exhibit the various functions described above as a flocculant. It is a well-established theory that 11M is a good flocculant for polymeric compounds with a low degree of polymerization.

As a result of examining the properties of various organic and inorganic flocculants or kelizing agents, the inventor has determined that the above-mentioned theory is #
This is due to the adoption of a polyvinyl chain, (-C)(t-Cf(Rk), which is essentially hydrophobic, as the main chain of the molecular structure, and if the main chain itself is given hydrophilicity. For example, as a result of studying the molecular structure of the main chain of Co-NR and its production method, we arrived at a precursor material that can increase good #aggregation, and completed the present invention. This is what I did.

That is, in the present invention, the general formula is selected from any one of the following chemical formulas 4'1lit+) to (1v).

n is 2-10. ) fill) c, H5- (1v) f(- Precursor of flocculant if...9 A chain compound t-base a having a novel molecular structure ethyl-substituted carbomol group, Ctl(sNHco-) , for example urea NHZCO
NHt or 1%J ef/l/substituted NHtN
When the base is a chain compound having carbomol groups at both ends, such as HtCONl((CtHs)CONHt, the base a and/or i', Lb and urea are mixed and heated while stirring. (ii) mixing and heating the bases a and/or b and echylchlorohydrin to remove hydrochloric acid and thermally decompose the oxirane ring; Simultaneously filtered, N placed 1α on the main chain or chain end of a chain compound,
A unit process of substituting l-f bonded to a boon with an ethyl group, (Ill) d base a and/or b, and monoethanolamine and/or ethylene as a hydroxyethyl grouping agent. A unit step of mixing and heating oxides and introducing a hydroxyethyl group by an addition reaction accompanied by removal of ammonia or cleavage of an oxirane ring. (1v) A chain compound having carbomol groups at the chain end (base C)
(v) mixing and heating the base C and guanidines, heating and deammonizing the base C and urea to bond them through a deammoniation reaction to approximately double the chain length; A continuous mixing and heating process that includes any three or more types of unit processes several times or multiple times, and connects these unit processes sequentially according to a predetermined plan. This is a novel and useful manufacturing method characterized in that it is carried out as follows.

The @ precursor material of the present invention is an ethanolamine derivative having an amino group, imino group, tertiary amine, or amidino group at one end and a hydroxyl group at the other end, and the intermediate main chain is poly(N
l! Carbomol (carbomol) is easy to realize the alkalinity or strong alkalinity, and when it is embedded in the agglomeration/j'1 and part of its structure is cut out, it has a large amount of rt in the wastewater to be treated.
The particles in the cage are in the middle and form a center that absorbs particles.Also, the liquid quality of wastewater is not necessarily acidic, but is often neutral. , it is advantageous for the N atoms at both ends to become monolithic when inserted into a flocculant, but in that case, the hydrophilicity of the J-base group of Ill-drive:ms will be further strengthened. Become.

In the molecule +4 +i& of the general formula, the N atom on the left end has hydrogen, which has high chemical activity, in cases other than tertiary amines, so it is affected by the hydroxyl group on the right end, and the aqueous solution of the precursor itself Although it impairs the stability of the flocculant, it is used in chemical reactions during the manufacturing process and should not be present in the structure of the final product.

It was determined that a hydroxyethyl group is suitable for imparting appropriate hydrophilicity and good flocculating ability as a flocculant to a polymer consisting of a tWpA carbomol main chain. When quaternizing the N atom on the right end, it is also possible to introduce an atomic group that has a hardening or gelling property here, but in many cases, one additional hydroxyalkyl-straddling carboxy group is also used. It is often advantageous to introduce an alkyl group.

Table All N atoms in the main chain are alkyl-substituted tertiary amines, and this alkyl group is lipophilic or 1a
However, methyl groups naturally lose their oil miscibility, and alkyl groups, which are larger than ethyl groups, are rarely used for manufacturing reasons. It casts a great shadow on the flocculent pass.ifJ water: raw and visible oil: /l balance, that is, moderate surface activity as a flocculant, and its pattern is suitable to be 2 to 10. and more preferably 6
~8 often gives good flocculating ability.

The main chain, Shinkin □□□n, is approximately 10 m long, and there is no need for it to have a high degree of polymerization, which requires complicated and inconvenient chemical operations, as was the case with Juita's Uomunori/W flocculant.

It is sprayed as a light-colored fine powder that is soluble in solvents.

The above unit steps (1) and (+V) are carried out for the purpose of elongating the main chain and increasing its degree of polymerization n.

~C0N(kt)H+ (N1(t)2CO→~~C
0N(R)CONt(,+NH,?...(1)2
N(R)H+(NH2)tCO-～-N(R)CQN(
R)-+2N(s """ (Iv) (where ~ indicates the main chain, and R indicates H or C2H) These thermal condensations are well-known as biuret production reactions, but they do not occur at high temperatures. ,@, Rapid temperature rise produces cyclic derivatives as by-products, and the presence of by-products does not provide a good flocculant, so operation is performed in the presence of water while removing heat near the boiling point where ammonia loses its solubility. When the functional group of the generated system is an imino group, the reaction is completed more smoothly and more conveniently than an amino group.

Unit labor when using monoethanolamine + 1 liter (
The unit Ov), which utilizes Ill and guanidines, is a similar deammonization reaction and is operated under the same conditions as above.

These deammoniation reactions involve -NH and -Nf in the base material.
(When (C, l(,) coexist, the latter reacts preferentially, so other N atoms in the base are tertiaryized and -N)((C!N5) By mixing and heating the amino acids with the same amount as the amount present, it is possible to obtain an intermediate that preserves the 1NH, which was originally present in the base, and this preserved 1NH, eventually becomes Used in chemical reactions as a terminal group.

Unit process (ii) using epichlorohydrin and single process +l (Ill
1 both utilize the heat content of the oxirane ring, and the above (1) magko has the same tanamijo +'F as (1v) etc.
Preferably, the mixture is heated under alkaline or slightly alkaline conditions. -Similar to the above, these reactions occur preferentially on -Ni((C, Nakaichi 5ix (CtHa
), a small amount of sodium carbonate is mixed and stirred into the base of the reaction system in advance, and the amount of ethylene oxide used is -Nl ((2 to It is preferable to use 3.5 times the amount to complete the reaction, and all the products will be tertiary amines, and if the above-mentioned monoethanolamine is used, a quaternary amine by-product will be produced. There aren't many.

In the unit step (ii), although the reaction mechanism in such a catalytic reaction of solids is not yet clear, the solids are first combined by oxidation, then stirred and heated in the presence of air. It is presumed that oxidative decomposition of the oxirane ring occurs to generate an ethyl group.

Some of these unit processes have been well known for similar reactions since ancient times, but in this project, each of these unit processes is placed in a slurry reaction system of a bent heating knife, and is stirred. Taking into account the common point that the solid particles of the formula t proceed rapidly and with relatively few main components of side reactions, we cleverly combined these unit processes to create a new series of mixing and heating processes. This is what we do.

How to combine medium-level technical species Kr: I. If ethyl urea is selected as the starting material, subsequent combinations will be easy. To this, fil + fll) + (ii+ tl++・
..., the combination of unit processes (1) and (ii) is repeated to form a chain compound, and then the unit process 4 (
For I+1, it is preferable to use 1/2 of this -Nl(!) of epichlorohydrin for one time in terms of quality control of the final product.

In this way, the base material that has reached the predetermined chain length is !
An active atomic group is introduced into the terminal by the unit steps (fil) and (V), or the chain length is doubled by the unit step (lv).
With L, the precursor is defeated by lv.

The invention will be described below based on an actual gun array, but the scope of the invention is not limited to these examples.

Example 1 1 mole each of ethyl urea and urea and 5 iJcc of boiling water are stirred and mixed into a slurry, and 20 to 40 cc of boiling water is poured into the slurry, and the mixture is brought to a boil for 15 minutes.Then, the temperature is raised to 120°C, and the ammonia odor is removed. Ryo epichlorohydrin 47 confirmed to have decreased? While gradually pouring water into the container, the temperature was maintained at 120°C and heated on a heating table for 10 minutes, and the temperature in the next chamber was lowered to around 100°C. Repeat this operation 4 times (return 4 times to get a slurry of approximately 600 deg (main component,
NH2(CONCtl(s)4[4)r acquired.

Example 2 In Example 1, ilV (coal content soaked 5% in slurry prepared
Aqueous solution 3 (l ee) was poured, and ethylene oxide 130y was gradually poured into the reflux stirring vessel while the temperature was raised. After reacting for 30 minutes, the flow was stopped and the temperature was raised to 140°C.

Next, gradually add 1/2 mole of urea and raise the temperature to 140~
After stirring for 15 minutes while maintaining the temperature at 150°C, the temperature was lowered to 90°C to form a cake (main component COINH (Co-NC)).
! Hs)*CHtCLOf(it), 2 mol of guanidine was added thereto, and stirring was continued for 30 minutes at 90 to 100 T until the separation of ammonia was no longer observed, to obtain a substance represented by the following formula.

Implementation row 3 The operation shown in Example 1 was repeated 6 times to obtain a slurry of about 7001 (main component, N) 1. (CONC!Ha)8 H
) was obtained, monoethanolamine 62) was added thereto, and after stirring and mixing at 100°C for 5 minutes, the temperature was gradually raised while stirring to reach 150°C after 30 minutes, and the m degree was 90°C. 1 mole of ethylguanisine was added and stirred at 90-100"C for 10 minutes (v) to obtain about 1 mole of cake-like material shown in the following formula.

C, l (5 Kari el + 114 fruit / lv I row: 1 mole of sodium benzimidazole sulfonate was added to the fake bouquet obtained in 3 and mixed with stirring, it reacted easily to generate ammonia. Then I
4. C, H having the following chemical formula.

(However, Ll, j indicate a benzimidazole heterocycle.) When this substance was dissolved in dimenalformamide to make a 10% solution and added to wastewater containing heavy oil, strong aggregation occurred. Fully demonstrated levitation ability.

Fuyuishi'1L1i, it is a precursor of t flocculant □ fiber which has N 11 + carbomol 1 wa 1 naru as seven bases, compared to Vζ whose main chain is a vinyl-based macromolecule. A compound that has hydrophilicity in its main chain and can be converted into various flocculants that exhibit strong flocculating ability despite having a low degree of polymerization by adding various (1) enu 4 fr: Since it is a product that provides fibers and its manufacturing method is a %4 method in which several unit steps are carried out consistently by a mixing and heating method, it can be applied to the production of flocculants. Useful.

Claims (4)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R_1 and R_2 are the same or different and are selected from any one of the following chemical species (i) to (iv). n is 2 ~10) (i) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (ii) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (iii) C_2H_5- (iv) Precursor of a flocculant represented by H- . (2) A chain compound having a carbomol group at one end and an N-ethyl-substituted carbomol group at the other end is used as the base a, and a chain compound having an N-ethyl-substituted carbomol group at both ends is used as the base b. a unit step (i) of mixing and heating agents a and/or b and urea to obtain a chain compound having carbomol groups at both ends and increasing the chain length of the main chain; and the base agents a and/or b. Or unit step (ii) of mixing and heating b and epichlorohydrin to obtain a chain compound having an ethyl group bonded to both ends or one end or to the N atom as a side chain.
and a unit step (iii) of mixing and heating the bases a and/or b and monoethanolamine and/or ethylene oxide to obtain a chain compound having a hydroxyethyl group at one or both ends; A unit process (iv) in which a chain compound having only hydroxyethyl groups is used as a base c, and this base c and urea are mixed and heated to obtain a chain compound having hydroxyethyl groups at both ends and having an increased chain length. ) and the base c and guanidine or ethylguanidine are mixed and heated to obtain a chain compound having a hydroxyethyl group at one end and an amidino group at the other end. There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by concatenating three or more types including ii) and (iii) individually or multiple times, and performing these consecutively ▼ (However, in the formula, R_1 and R_2 is the same or different and is selected from any one of the following chemical species (i) to (iv). n is 2 to 10.) (i) ▲ Numerical formula, chemical formula, table, etc. ▼ (ii) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (iii) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (iv) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A method for producing a precursor of a flocculant represented by. (3) a unit process of mixing and heating ethyl urea and urea;
The combination of the unit process of mixing and heating the substance obtained in this unit process and dichlorohydrin is repeated multiple times, and the unit process of mixing and heating the substance obtained by repeating the process multiple times with monoethanolamine, and then A general formula consisting of a unit process of mixing and heating a substance obtained by mixing and heating monoethanolamine and a unit process of mixing and heating ethylguanidine, and characterized in that the mixing and heating process in which these unit processes are connected is performed continuously. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, n is 2 to 10.) The method for producing a precursor of a flocculant according to claim 2, which is represented by the following. (4) a unit process of mixing and heating ethyl urea and urea;
The combination of a unit process of mixing and heating the substance obtained by this unit process and epichlorohydrin is repeated multiple times, and a unit process of mixing and heating the substance obtained by repeating the plurality of times and ethylene oxide, and mixing and heating the ethylene oxide. The unit process consists of a unit process of mixing and heating the substance obtained by the unit process of mixing and heating urea, and a unit process of mixing and heating the substance obtained by the unit process of mixing and heating the urea and guanidine. Claim 2, which is expressed by a general formula ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ (however, n is 2 to 10), characterized in that a mixing and heating step in which the steps are connected is performed continuously. A method for producing a precursor of a flocculant as described in 1.