LT4490B - Process for preparing cationic flockulant - Google Patents

Abstract

The proposed invention is attributed to manufacturing technologies of cationic floccules and sorbents, which may be used in water treatment, in particular for cleaning textile effluents, and for the extraction or concentration of reagents. Floccules are obtained when potassium or ammonium peroxide sulphates are added to an ammonium poly-quaternary salt solution at a component amount proportion of 1:(0.1-9) and mixed. White colour dispersion forms. The required amount of this dispersion is poured into solutions being cleaned, mixed and the floccules are let to settle down. Separately prepared poly-quaternary ammonia salt and peroxide sulphate solutions may be poured in succession into the solution being cleaned and mixed there. An insoluble dispersion with a component amount ratio of 1:(0.4-1.5) may be separated and used as filter aggregation for filtration of solutions needed to be cleaned.

Description

The invention relates to production technologies for cationic flocculants and sorbents which can be used in water treatment, in particular for the treatment of textile wastewater, as well as for the isolation or concentration of reagents.

Many flocculants are known to be based on polymeric quaternary ammonium salts [Floover M.F. Cationic àuatemary polyelectrolytes - a literature revievv // J. Macromol. Sci. Chem. - 1970. - A 4 (6). - pp. 1327-1417]. Of these, polydimethyldiallyl ammonium chloride (PDMDAAC1) is the most widely used flocculant in water treatment, mining and paper industry. It is prepared from monomer dimethyldiallylammonium chloride by radical polymerization using various initiators: peroxy-, diazo-, organophosphorus compounds [EofrpKHHa H.M., ΚριοΊκοΒ B.B. h jp. riojoiMepu Ha ocHOBe N, N-aHMeraji-N, NAHa-T-THjTaMMOHHft xnopima // nnacTii ^ ecKHe Maccu.— 1987.— N ° 8. - C.1720], sulfur dioxide or selenium [A. c. 1571048 (CCCP), C 08 G 73/06 (1980)].

PDMDAAC1, which is obtained when the inorganic peroxysulfates are used as initiators, has been selected as a prototype [Pat. 141029 (DDR), C 08 F 126/04, C 08 F4 / 34 (1979); Pat. 156979 (DDR), C 08 F 126/02, C 08 F 4/28 (1982)]. In the 30-70% o

the monomeric dimethyldiallylammonium chloride solution is added in small amounts - (0.3-10 '-4-10' ') mol / mol of monomer, to maintain an optimal pH of the medium (6.7-v 10.3) using buffer systems of inorganic salts or various amines . This produces high molecular weight linear soluble polymers in the form of aqueous solutions.

The disadvantage is that water-soluble cationic flocculants, including polyketide ammonium salts, need to be dosed very precisely into the solution to be cleaned, since these flocculants only bind and precipitate pollutants within a very narrow concentration range [Schulz G., Herlinger H. Entfernung von Reaktivfarbstoff aus Teilabvvasserstromen durch Fallungs - Flokuugreaktionen / 'Textūveredlung.1988, - <\ «1.2.- S. 445-448; 1990, - N> 1.- S. 23-27; Boothe J. E., Flock H. G., Hoover

M. F. Some homo- and copolymerization studies of dimethyldiallyl ammonium chloride // J. Macromol. Sci. Chem. - 1970. - A4 (6). - P. 1419-1430.] An overdose of flocculant has the opposite effect of stabilizing. The optimum concentration of the flocculant may be different for each individual pollutant deposition, and will depend on pH, low molecular weight salt additives, and other factors. This is a major impediment to the practice of treating wastewater or other reagents with flocculants, especially in the textile industry. In addition, conventional cationic flocculants are water-soluble and can only be used in precipitation-flotation operations.

The object of the present invention is to improve the flocculation properties of polyketric ammonium salts and to extend their application by using them as flocculants and sorbents.

The object is achieved by the addition of potassium or ammonium peroxysulphates to the polyketal ammonium salt solution. at a component weight ratio of 1: (0.1- ^ 9). When mixed, complexes of these compounds are formed. These polymeric condensates (PCs) are obtained by mixing component solutions in any range of their weight ratios. The presence of minor additions of potassium or ammonium peroxysulphates (up to ~ 0.3 g peroxysulphates / 1 g polydimethyldiallyl ammonium chloride) gives off-white solutions which, when concentrated, produce a fine white dispersion with a maximum yield of peroxysulphate: cationic polymer = 4: 6 ( Table 1). Both PK solutions and dispersions, once homogenized, can be used to bind and precipitate various classes of textile dyes or other chemicals (Table 2). PK solutions or dispersions, when added to the solutions to be cleaned, act as flocculants: after mixing, floccules begin to form in a few minutes, become coarser and eventually settle on the bottom.

Solution cleaning performance is superior to the prototype polymeric quaternary ammonium salt, polydimethyldiallyl ammonium chloride (Table 2, Νθ 15, 16), except in isolated cases, such as hydrolyzed active dye in a strongly alkaline medium, where table. Characteristics of polymeric condensates of various configurations

Efl. No. APS: PDMDAAC1, g / g Insoluble fractions iseiea,% Notes 1 1: 9 0 Almost clear solution 2 2: 8 - A strongly white solution 3 3: 7 ~ 70 The insoluble fraction is more difficult to separate 4 4: 6 ~ 95 Easily separable insoluble fraction 5 5: 5 —80 Easily separable insoluble fraction 6th 6: 4 ~ 65 Easily separable insoluble fraction 7th 7: 3 ~ 50 Easily separable insoluble fraction 8th 8: 2 —30 Easily separable insoluble fraction 9th 9: 1 ~ 15 Easily separable insoluble fraction

excess ammonium peroxysulfate (APS) (φ> 1) is not appropriate. The polyketide ammonium salt without peroxysulphates did not precipitate poorly the hydrolyzed active dye under similar conditions. and other chemicals poorly or not at all. Increasing PK concentrations up to 10-fold did not result in overdose (Table 2,. \ '2 5-7). One APS without cationic polymer did not bind active and disperse dyes and only 19% colored the acid dye solution (Table 2, N ° 14). Optimal binding of anionic and non-anhydrous disperse dyes and other chemicals was obtained when the weight ratio of PK constituent components - polymeric quaternary ammonium salt to peroxysulphate was 1: (0.67 + 1).

Mixing the components at a ratio of 1: (0.4 + 9) gives a PK dispersion (Table 1) which, after separation from the solution, can be used as a sorbent by filtration through the solution to be purified. It is expedient to prepare the sorbates from PK with a component weight ratio of 1 r (0.4 + 1.5), as this yields a sufficient amount of insoluble fraction (yield> 65%).

PKs can be formed in solutions or wastewater of directly treated chemicals. For this purpose, solutions of the polymeric salt and peroxysulphates are prepared separately, dosed one after the other in the solution to be purified and mixed there.

table. Binding of various reagents to polymeric condensates

1 C -2 £ 1 Here no c him Ή et c c V2 Lc sulfuric acid) j disodium salt (GOST 6848-65) f 1 1 so UO 1 1 I r- SO ra SO i ' 1 1 1 O 1 et 1— c Vi et _t o J _t ra 'RH 'TT · J ₍ cn U ₍ and _J SO cc and cn _t oo Vi E ra cit et 1- ^ 1 / —S c cs yr \ Ct - «- d o ra ra # * n ₁ c 3 £ d TT ¹ r- ra P £ tZ '. »* -« o. P— ¹ et C - : · Σ / 5 rs 'O SC CO TT i «= 3 < »—4 o o rn uo J _t ra TT '70 T? c O \ ra ₍ et C. Ό k-H u- TT and SO ra tn rr O C- 'C u u * s <υ v; u * r- ra i > —1 U 2- d u c. loose O ra ra c ra i / n cc Ό CC O · cc T * t co. 'Rr r— < o ra & Q. rt o. v * et X k— < u. . £ 3 C j d · —I > cs 1 k - t o SO UO so _t uo i SO t-H ΓΊ TT n B co ao c. c \ cc so uo cn Uh k-U Ό tS et «** k-Lt u * cz • —i d ra cc i rn r- o o SO m uo o CC ra CC CS r - l U Ct U £ S k - <l-C cn cn o. Thu Thu see c \ OC ra TT ra Γ4 * - et B C 3 et C > N Him et <· • —t CN and co. ra Λ F— ( _ < ra -2 u, oc d d d d d ¹ T - t d d ¹ id o o o O d: o CU o · * - •. - v .S " d ξ cc ra sC '* O so '70 and c *; ra o Ξ o > - » H << • » et S s r - t e ^ J m -T - -T * n and SO r- oc Thu s o? o v: B- c V? - U s * s s et 0 oz? s co < 22nd £ 0 ε 7- o T3 C c A -> z · ^ ·. c · _> LC JJ p- £ έ - ΓΊ TT Ό ra cc Thu 2 d ra r ^ _t · - · 4 2 «Λ SO

¹ - »- -...... * ...... ·· -!» - —.......- ,, ¹ - - - ^{1 1} - · · ».... ......- - - i —- -----. i.

Notes: - Technical grade paints which correspond to the Color Index classification have been used .;

- detergent Sulfonate - a mixture of sodium alkanesulfonate (Ο ,, ΙΒ ,,, j C, _r i), where n I m = l 1 = 17;

- initial concentration of reagent in solution - 0,1 g / l.

The proposed method of preparing flocculants is accomplished by adding the required amounts of aqueous polyketal ammonium salts and (NH (SsOg or K2S2O5) solutions to the prepared vessel. The polycetate ammonium salt and peroxysulphate solutions are blown successively into the solution to be cleaned and mixed in order to use the PK dispersion as a sorbent, filter it, apply it to the filter filler and filter through the solutions to be purified.

Specific examples of the preparation and application of flocculants are given.

example

To 600 ml of a 1% solution of PDMDAAC1 (TU 6-05-2009-86) is added 400 ml of a 1% solution of ammonium peroxysulphate, (NLD ^ Og (GOST 20478-75)) with stirring. A white dispersion is formed. 10 ml of the dispersion are added to 11 solutions of dye, detergent or disodium salt of 2,2'-methylenebis (6-naphthalenesulphonic acid) in 0,1 g / l concentration, mixed and left to settle on the flocculates. photovoltaic colorimeters ΚΦΚ-3 or Specord UV VIS at the following wavelengths: CI Reactive red 2-540 nm, CI Disperse blue 7-592 nm, CI Acid red 186-520 nm, potassium palmitate 364 nm, 2.2 ^; Methunebis (6-naphthalensulphonic acid) disodium salts - 285 nm Calculate the degree of purification by comparing the starting and light absorbance of the purified solutions. chloroform extracts to absorb light at 650 nm. After precipitation, the concentration of CI Reactive red 2 in solution was reduced by 90%, hydrolyzed CI Reactive red 2 - 96%, CI Disperse blue 7 - 70%, CI Acid red 186 - 75%, 2,2-methylenebis (6-naphthalenesulfonic acid) disodium salts 56%, sulfonate 50%.

example

Similarly, for example 1, only another polymeric quaternary ammonium salt is used, polyvinylbenzyltrimethylammonium chloride (PVBTALACl) (TU 6-09-4145-75).

This results in a less sedentary PK dispersion and finer floccules than in Example 1. Degree of Purification: C.I. Reactive red 2 - 74%, C.I. Disperse blue 7 - 78%.

example

Similarly, for example 1, only potassium peroxysulfate (GOST 4146-74) is used instead of ammonium peroxysulfate. By precipitation of the resulting PK C.I. Reactive red 2 dye was reduced by 92% in solution.

example

In analogy to Example 1, only 150 ml of the resulting PK dispersion is filtered and filled with a glass filter to form a sorbent layer of 2 cm diameter and 11 cm height, through which a 0.1 g / l C.I. Reactive red 2 solution. > 400 ml of a colorless filtrate is obtained.

example

In 11 0.1 g / L dyes, C.I. Reactive red 2 and C.I. Disperse blue 7 solutions are added in 5 mL of 1% PDMDAAC1 solution and mixed. After 10 minutes, add 5 ml of a 1% solution of ammonium peroxysulphate in the same solutions. The solutions are left to settle. After a day, sample solutions and determine the degree of purification. It is obtained that, after deposition, C.I. Reactive red 2 concentration in solution decreased by 95%, C.I. Disperse blue 7-82%.

The following examples demonstrate that the proposed polycondensates can bind both ionic and non-ionic disperse dyes in alkaline, acidified and neutral solutions, as well as in the cleaning of various detergents and some aromatic compounds. The flocculants obtained in this way have better properties than the prototype: the degree of binding of various classes of dyes is increased by 20 to 90%, the detergents by S-30% and some aromatic compounds by up to 70%. In addition, the risk of an overdose of flocculant is avoided. Polycondensates can be isolated in solid form and used as sorbents, thus expanding their technological applications.

Claims (3)

Definition of the Invention CLAIMS 1. A process for preparing a cationic flocculant from a polyketric ammonium salt by addition of a solution of potassium or ammonium peroxysulfates to the polymeric quaternary ammonium salt in a weight ratio of 1: (0.1 + 9). 2. A process for the preparation of a cationic flocculant according to claim 1, wherein, separately, the solutions of the polyketric ammonium salt and peroxysulphates are successively added to the solution to be purified and mixed therein. 3. A process for the preparation of a cationic sorbent according to claim 1, characterized in that at a component weight ratio of 1: (0.4 + 1.5), after mixing, it separates the insoluble dispersion.