SU1564156A1 - Method of obtaining water-soluble cation-active polymer - Google Patents

Abstract

The invention relates to the production of polymer dewatering and retaining agents and flocculants and can be used in the pulp and paper industry, as well as in the treatment of municipal and industrial wastewater. The invention allows to simplify the process of obtaining a water-soluble cationic polymer with enhanced reproducibility and stability. This problem is solved by using polyethylene polyamine mol as the feedstock. 200-400 m, to the aqueous 15-20% solution of which epichlorohydrin is added in the amount of 40-100% by weight of polyethylene polyamines with stirring, the mixture is heated to 75-95 ° C and stirred at this temperature until viscosity is reached 20 ° C 0.2-0.8 P, after which dichlorohydrin or polyethylene glycol diepoxide mol mol. 200-400 in the amount of 1-15% by weight of polyethylene polyamines and stirred at 74-95 ° C until the resulting polymer solution has a viscosity at 20 ° C 2-8 P. Table 3.

Description

This invention relates to methods for producing cationic polymers used as dewatering agents in the pulp and paper industry and as flocculants in wastewater treatment.

The purpose of the invention is to simplify the method of obtaining the polymer.

PRI me R 1. A periodic process for the preparation of a cationic polymer (CP) is carried out in a capacitance reactor made of X18H10T steel with a capacity of 100 liters, equipped with a chisel for cooling and heating with water, a root stirrer (rpm), a reflux brine-cooled refrigerator, and a thermocouple

and a circulation system including a plunger pump, a brine cooled heat exchanger and a BBH-3M industrial viscometer sensor. Using the circulation system during the synthesis of KN, a continuous selection of the reaction mass at a rate of 200 l / h from the reactor to the viscometer sensor is provided, followed by its return to the reactor.

In a reactor with a mixture of 10 kg of technical polyethylenepolydmines (NEP) with an average MM of 265 (PE11A grade A according to TU 6-02-594-80) with a solution of NEPA with 40 liters of water. To dissolved pep when cooled with water, taught in

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a j

sd

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the jacket of the reactor, and stirring over a period of 1 h, was added 6.5 kg of epichlorohydrin (EPH) from the measuring device (65% by weight of NEPA), preventing the temperature from rising above 30 ° C. At the end of the dosage EIH, the reaction mixture is heated to 95 ° C. Maintain the mixture at the specified temperature and stirring, continuously monitoring its viscosity using an industrial viscometer. After 6 hours, upon reaching a viscosity of 63 cps (at 20 ° C), in the resulting 29.2% solution of the pre-polymer at 95 ° C, 0.3 kg of technical dichlorohydrin polyethylene glycol (DHP) ( 3% by weight of PEPA) synthesized from EPH and polyethylene glycol (PEG) 400 and having a hydrin chlorine content of 11.7%.

The reaction mass is maintained at 95 ± 5 ° C and stirring, continuously monitoring its viscosity. After 6 hours, upon reaching a viscosity of 230 cP, the process is terminated. Received 29.8% aqueous solution KP with. The content of ionic chlorine 4.4% is a light brown liquid, it has a density of 1.08 g / cm2, pH 10. The viscosity of the polymer solution remains almost unchanged during storage for 15 months. Example 2. The process of producing CP is carried out analogously to example 1, but using PEPA with an average W of 397 (PEP grade G according to TU 6-02-594-80) and technical diepoxidol ethylethylene glycol (DEP) obtained from EPH and PEG 400 and having an epoch C content of 10.5%.

In a reactor, an 18% aqueous solution of PEP is prepared from 8 kg of PEPA and 36.4 l of water. 3.3 kg of EPH (40% of the mass of PEP) was added to the NEP solution at 15–20 ° C and stirring for 0.5 h, after which the mixture was heated to 80 ° C and stirred for 8 h until viscosity 25 ell (at 20 ° C). 1.2 kg DEP (15% by weight of NEPA) was added to the obtained 23.5% aqueous prepolymer solution at 80 ° C and stirring, and the reaction mixture was stirred for 10 hours until the viscosity reached 787 cP at 20 ° C. The resulting 25.4% aqueous KP solution has a density of 1.12 g / cm3, pH 11. After storage for 16 months, the viscosity of the solution was 1260 cP.

0

5 5

five

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II g. 3. KP synthesis is carried out in a glass round-bottom three-tube flask with a capacity of 0.5 liters, equipped with a stirrer in a stopper, a reflux condenser, a thermometer and an addition funnel. As the amine component, a technical mixture of tetraethylenepentamine (74 wt.%), Pentaethylenehexamine (18 wt.%) And other ethylene amines having an average MM 203 is used. In a flask of 45 g of this mixture and 2.25 g of water is prepared 15% - niy solution. 36 g of AIM (80% by weight of ethylene amine mass) are gradually added to the solution at 25–30 ° C and with stirring. The reaction mixture is heated with an oil bath to 90 ° C and kept with stirring at this temperature, periodically, every 2 hours, taking samples of the reaction mass, measuring their viscosity and returning the samples to the reactor. After 5 hours, upon reaching a viscosity of 27.0 ell (at 20 ° C), 4.5 DHP (10% by weight by weight) was added to the obtained 24.1% aqueous solution of prepolymer at 90 ° C and stirring for 1 hour. ethylene amines) obtained from PEG with MM 200. The reaction mixture was stirred for 7 hours at 90 ° C until viscosity reached 427 cP (at 20 ° C). The viscosity of a 25.1% aqueous solution of KP with a density of 1,128 g / cm3, pH 10.5 after storage for 20 months was 574 cP.

Data on the preparation of the cationic polymer in the form of examples reflecting the essence of the invention (examples 1 to 12), and control examples 13 to 25 are presented in Table. one.

The synthesis of KP in examples 4-12 was carried out similarly to examples 1 to 3; The table presents the conditions for the synthesis of KP according to the proposed technical solution.

Example 13 (control). KP synthesis is carried out using the laboratory setup of Example 3.

By dissolving 40 g of technical PEPA with an average molecular weight of 255 in 160 ml, flasks in a flask are prepared with a 20% solution of PEPA.

At 20 + 5 ° C and stirring, 2 g (5% by weight of PEP) of technical HPP synthesized from EPH and SG 400 and containing 11.7% hydrin chlorine are added dropwise to the NEP solution within 0.5 h. After heating for 10 hours at 90 ° C, the viscosity of the reaction mixture is 8 cP (at 20 ° C).

To the reaction mixture cooled to 20 ° C with stirring for 1 hour, 26 g of ENH (65% by weight of NEP) are gradually added. The mixture is stirred for 3 hours at 20 ° C, heated to 90 ° C and maintained at this temperature, the viscosity is controlled by analyzing the samples on a Hepler viscometer.

After 4 hours, the reaction mixture was gelled, insoluble in water.

Examples 14-15 are analogous to example 13 with a modified mixing sequence of reagents, with the only difference that in example 14 and 15 different crosslinking agents are used and PE11A of different molecular weights are used as starting materials.

In examples 16-18 and 19-21, 22-25 presents the results of experiments on the preparation of KP using as a cross-linking agent one EPH in two (16-18) and one stages (19-21) and DHP or SS in one stage (22 - 25)

In tab. 1 The following notation is used:

MM,

 papa

MM

- molecular weight of polyethylene polyamine;

M is the mass amount of ENH based on the mass of the PEPA involved in the reaction in the preparation of the pre-polymer;

T (is the temperature of the synthesis of the prepolymer;

li is the viscosity of the prepolymer solution at 20 ° С; AHP (Dep) molecular weight

PEG taken for the synthesis of DHP (DEP); M is the mass amount of DHP (DEP) from the mass of the PEPA involved in the reaction when filing the prepolymer;

ten

15641566

C is the mass concentration of the polymer solution.

The effectiveness of the obtained water-soluble cationic polymer (CP) as an intensifier of the main processes of paper and paperboard production was investigated. For comparison, KPs of a similar purpose were used by a number of foreign firms. The criteria for the effectiveness of the use of additives were the following indicators: the degree of retention of the filler (kaolin) in the paper sheet and the dehydration rate., Paper pulp (by changing the degree of grinding)

KP samples synthesized under the conditions of examples 1-3 were tested; paper furnish composition, wt%: henbele pulp 56; kaolin 39; rosin glue 2; alumina 3,

The specific consumption of KP for dry matter is 0.15% to absolutely dry paper stock. 25 The results are presented in Table. 2

In tab. 3 shows the results of tests of KP as flocculant during the precipitation of a suspension of mineral

15

20

white soot filler (high-dispersed, 0 persistent SiO). KP samples obtained under the conditions of examples 4 and 5 were used. The concentration of the solid phase was 1.45 g / l, pH 6.6.

In tab. 3 for comparison, the test data for cationic flocculus n-35 ta based on polyacrylamide AK-617-04.

In Table 3, the following conventions are accepted:

g l

40

 axis

 "Rl

min y

mg / l

45

Name 7m

2 „

50

solution clarification rate;

the degree of compaction of the sludge;

flocculant concentration;

filtering method

sediment content;

relative to the speed control acceleration of clarification of the precipitate; relative, compaction of sediment; relative filter sedimentation ability.

V; / VK. У, / У к - Ф; / ФК synthesis temperature

polymer;

viscosity of the polymer solution at 20 ° C; storage time - 55

no polymer; the viscosity of the polymer solution after storage at 20 ° C;

white soot filler (high dispersed SiO). KP samples obtained under the conditions of examples 4 and 5 were used. The concentration of the solid phase was 1.45 g / l, pH 6.6.

In tab. 3, for comparison, presents test data for cationic flocculant n-5ta based on polyacrylamide AK-617-04.

In Table 3, the following conventions are accepted:

g l

0

 axis

 "Rl

min y

mg / l

five

Name 7m

2 „

0

five

solution clarification rate;

the degree of compaction of the sludge;

flocculant concentration;

filtering method

frequency of sediment;

relative to the speed control acceleration of clarification of the precipitate; relative, compaction of sediment; relative filter sedimentation ability.

KP is highly effective when applied to silica suspensions, which increases both the rate of sludge and the degree of compaction of the precipitate.

V; / VK. Y, Y Y K - F; / FC Formula of Invention A method of producing a water soluble cationic polymer by reacting an aliphatic amine with bifunctional compounds in an aqueous solution by heating in two stages, characterized in that, in order to simplify the process, polyethylene polyamine is used as an aliphatic amine with mol.m. 200-, 400 in the form of a 15-20% aqueous solution, as bifunctional co.

In the first stage, epichlorohydrin is used in an amount of 40-100% by weight of polyethylene polyamine, and in the second stage, dichlorohydrin or polyethylene glycol di-epoxide with mol.m. 200-400 in amounts of 1-15% by weight of polyethylene polyamine, the first stage being carried out at 75-95 ° C until a polymer solution with a viscosity of 0.2-0.8.11 is obtained at 20 ° C, and the second stage at 75 -95 ° C to obtain a polymer solution with a viscosity of 2-8 P at 20 ° C.

T a b l p 1

1 76

62

Zvolvee uvachie u ° M corresponds to the freedom of the effectiveness of the additive.

Tavlitsa2

15

18

14

17

74

IN

 70

74

Table3

Claims (1)

SUMMARY OF THE INVENTION A method for producing a water-soluble cationic polymer by reacting an aliphatic amine with bifunctional compounds in an aqueous solution by heating in two stages, characterized in that, in order to simplify the method, polyethylene polyamine with a mol.m is used as an aliphatic amine. 200; 400 in the form of a 15-20% aqueous solution, epichlorohydrin in the amount of 40-100% by weight of polyethylene polyamine is used as bifunctional compounds in the first stage, and dichlorohydrin or polyethylene glycol diepoxide with mol.m. 200-400 in quantities of 1-15% by weight of polyethylene polyamine, the first stage being carried out at 75-95 ° C until a polymer solution with a viscosity of 0.2-0.8 .P at 20 ° C is obtained, and the second stage at 75-95 C to obtain a polymer solution with a viscosity of 2-8 P at 20 ° C. Table!* Straight NEP number Cas.X 'from t *. cp when on the beam yam DHL (power lines) us"? 2 carried f ,, eP s, wt .X Note 1 255 "5.0 95 63.0 400 i 3.0 95 230 fifteen 238 29.8 2. 397 40,0 80 25.0 (400J 15.0 80 787 16 1260 25,4 3 203 80.0 80 27.0 200 10.0 90 427 20 574 25.1 4 255 67.0 75 79.2 (200) 1,0 75 242 18 248 29.8 5 397 45.0 95 55.0 200 5,0 * 95 548 fifteen 725 25,4 6 203 100.0 90 74.1 (400) 2.0 90 285 18 302 28.1 7 255 62.0 80 21.0 200 14.0 80 301 20 322 29.8 8 255 67.0 90 "9.2 200 4.0 90 348 20 356 29.8 9 297 42.0 83 36.0 400 8.0 85 457 18 503 25,4 to 397 42.0 75 22.4 (200) 15.0 75 246 .20 253 25,4 eleven 203 80.0 75 66.5 (200) 5,0 75 273 20 298 25.1 12 203 90.0 SO 69.0 400 2.0 80 290 20 310 25.1 thirteen 255 65.0 90 80 400 5,0 90 Gel •. 29.8 Follower changed ^- 14 391 40,0 75 12.0 (200) 2.0 75 Gel • 25,4 Reagent mixing reagent: thirteen 203 100.0 83 11.0 200 12.0 85 Gel • · 28.1 I stage * DHP (power transmission line) II stage “EPH 1" 203 80.0 90 29.0 10.0 90 249 4 Gel 28.1 EPH prepolymer graft 17 255 65.0 80 58.0 5,0 80 285 4 Gel 29.9 · "* · 18 397 42.0 75 23.0 12.0 75 426 3 Gel 25,4 19 203 110 80 24 " - - - 3 Gel 28.1 Carrying out the process in one 20 255 70.0 75 466 •a • - - 1 Gel 29.8 Stage: Somma Agent 21 397 50,0 80 Gay - - - - • • 25.1 EPH 22 397 • (200) 110 90 874 4 Gel 35.5 Carrying out the process in one 23 397 • 400 130 75 742 4 Gel 36.5 stage: saivac agent 2 * 203 * • • 200 150 95 1220 3 Gel 35.5 DI (power transmission line) 25 255 - - - (400) 140 80 925 3 Gel 36.5 Table 2 Indicators Carteretia-K Savdoz Ziejzarya Retaminol-K Bayer Germany Kknene-709 Herkofinn Finland Full-KN BASF Germany Synthesized samples KP according to examples 1 2 3 Speeding up the dehydration process. d’shr * eleven 4 9 fifteen 18 14 17 Retention of kaolin, X from a given amount 76. 62 73 74 80  70 74 In the longer term, evacuation of ° Р соответствует corresponds to the free effectiveness of the supplement. Table 3 Flocculant mg / l " Rpm At F.10 ^_T , and ¹ jv; / v _K F; / f _to KP 29, BX water solution 5,0 1,59 20,4 0.292 69.1 14.2 2.15 2.3 P viscosity at 20 ^e C 10.0 4.16 19.9 0.361. 180.0 13.8 2.65 KP 25.4% water plant thief 5,0 6.11 26.9 0.336 265.0 18.7 2.47 viscosity 5.5 P at 20 ° C 10.0 1.83 21,2 0.445 79.9 14.7 3.27 AK-617-04 25 1,67 23.3 0.212 73.0 16,2 1,56 5,0 5.19 24.2 0.180 225.5 16.8 1.33 The control 0.00 0,023 1.44 0.136 1.00 1.00 1.00