Process for purifying effluents from dyes or optical bleaching agents

专利摘要:
A novel process for the purification of industrial effluents, wherein the effluents are brought into contact with cationically modified cellulose-containing materials, the cationic constituent of which is bonded to the cellulose part via the grouping of the general formula -O-CH2-N< in which the nitrogen belongs to an amide group of the cationic constituent and the oxygen is bonded to the cellulose part.
公开号:SU997604A3
申请号:SU762420356
申请日:1976-11-12
公开日:1983-02-15
发明作者:Хаазе Ярослав；Лихти Петер；Вегмюллер Ханс；Вурстер Рудольф；Бовес Квентин
申请人:Циба-Гейги Аг. (Фирма)；
IPC主号:

专利说明:

or formula. K-Qj-ir-Oi-CO-lT-GH-Q-, H RS Y where Q is C | -C3 alkylene, R. R. and (J are lower alkyl, or lower g-radicals, substituted by lower alkoxy groups or —Q — CO — lyCH, jOR or R, and R together with a bound nitrogen atom form a 5-membered heterocyclic the residue, or Kf and Rj together with the group 7 N-UJ, -N form a bivalent piperazine new residue, where Vj is hydrogen, or lower alkyl, or lower alkyl, are replaced by a nitrile or hydroxyl group, or benzyl, Rj, R and V together with the nitrogen atom bound to them form a pyridine ring; An is an organic anion or an inorganic; an oh-acid, or a formula: a- CO-T5 N.-CH, -0I or the formula where R, R, V, R and R are lower alkyl, Dg D, D g or R and Ri together with the associated az atom form a morpholine cycle; K - hydrogen or f-p-Q -CO-NH-CHiOH, and Ql-methylene or propylene) Q-alkyl and cellulosic materials differ from known agents, for example from activated carbon, by high absorption capacity and absorption rate of dissolved or dispersed in water, especially anionic substances. The proposed 1 st method is used in dp cleaning solutions that contain organic, ionic, i.e. anionic or cationic substances or mixtures thereof. Anionic or cationic dyes, bleaching agents, dyeing or textile aids, surfactants and tannins and their mixtures are particularly well removed from wastewater. The proposed method purifies wastewater, which contain mixtures of anionic and / or cationic dyes with anionic, cationic and / or non-ionic auxiliary agents. In addition, not only largely not fully selected dye and bleaching vanngle and treatment solutions from these substances, but also purify waste (sewer) solutions containing appropriate non-ionic textile and dye auxiliary agents and / or non-ionic dyes or bleaches, as well as a breakdown: solutions washed with flushing wastewater, which most often contain mixtures of dyes and 1 means, Wastewater treatment is carried out at 20-100 ° C, preferably at 30-70s and under pressure or in vacuum. Cationic cellulosic materials contain 0.4 wt.%, Preferably 0.71, 5 wt.%, Of basic nitrogen. The total nitrogen content, which also includes amide nitrogen, is 0.6 wt.%, Preferably 0.8, 3 wt. % The cationic-modified cellulosic material is mixed with active carbon and / or other known filtration aids, such as peat, kieselguhr, or diatomaceous. In this case, for example, the active carbon is added to the cellulosic materials in an amount of 2 to 95% by weight, preferably 1070% by weight, based on the / total weight of the cellulosic material. The proposed method removes water-soluble dyes, dispersed anionic or cationic dyes or optical brighteners, G preferably anionic dyes or optical brighteners. The use of modified cellulosic material also partially removes non-ionic, anionic and cationic surfactants and textile aids and aids used in dyeing, and also phosphates from aqueous residual baths. By selecting a suitable pulp material, the wastewater is free from impurities dissolved in them by 100%, which is 50 g of residual, i.e. dyestuff, optical bleach, excipients, tannins, per 100 g of cellulosic material. When the complete bleaching or removal of residues in the result of a single treatment of the residual substance with a cellulosic material is not achieved, the cleaning process is repeated. After the adsorption of impurities, the spent cellulosic material is easily regenerated using, for example, a dilute aqueous solution of sodium hydroxide. The used cell-modified cellulosic material, after its saturation, residual substances} are removed from the wastewater, dried, then burned or used as additives, for example, in the preparation of packaging or building materials. In addition, the cation-modified material can be easily converted into the desired form of application, for example, fiber, crumb, - filter paper. Cation-modified cellulosic materials EFF; |) effectively used. instead of coagulating agents in wastewater treatment, they do not overdose. When using good dehydrating agents, sludge is absent. Cation-modified. Cellulose materials have a high capacity for anionic substances in the neutral pH range, especially in the form of chips and a fixed layer. Preparation of cation-modified target material, A. a / 115 g of adduct, obtained by adding 2 mol of acyl amide to 1 mol M of 1-dimethyl ethylenediamine, dissolved in 93 ml of water and allowed to react njpHO-lO With 85 ml of 35.1% formaldehyde solution until the free formaldehyde content is O , 7%. 293 g of a 50% aqueous solution of dimethylol compound are obtained. (CH%) j, N-CH2: H2-M / CH4CH / rCONH-CHgpH (a. ("I)) The solution is then diluted with 1172 g of water and adjusted to pH 3 by adding concentrated hydrochloric acid: acid. .9.1 g of filter paper (weight 1 g) is impregnated with rastat, obtained according to paragraph. AH in such a way that the paper has 25.7 g of an acidic solution. Soaked paper 10 NMH is maintained with JB-IO C and then with a rapidly rotating agitator After that, the paper is filtrated, distilled with water and dried in a vacuum. The total nitrogen content of this fibrous The adsorption agent consisted of 2.15%, of which 1.07% is basic nitrogen. A similar adsorption agent is obtained if the same amount of sulphite-cellulose pulp, cotton yarn, and cotton fabric is used instead of filter paper. 2 g of the adduct, obtained by adding 1 mole of diethylamine to 1 mole of acrylamide, is dissolved in 35.4 g of water, and adding 0.1 g of sodium hydroxide is reacted. Methylene emission 25.8 g of a 35% formaldehyde solution for 5 hours at 50 ° C. . . . . A 50% yellowish solution of the methylol compound of the formula / C H IdN-CH / iCHa-CONH-CHeOH ({Oi) with 0.77% free formaldehyde is obtained. This solution is diluted with 417.5 g of water and the pH is adjusted to 3 with the addition of concentrated hydrochloric acid. c) - 9.5 g of filter paper are soaked in an acidic solution, obtained according to a), that it takes 30.4 g of an acidic solution. The impregnated paper is dried with 10 mi at. and then treated the same as in paragraph A. c). The nitrogen content of this adsorption material is 2.07%, of which 1.03% is basic nitrogen. C.a.) 63.2 g of the adduct, obtained by adding acrylic to morpholine, add 18 g of paraformaldehyde and O to the suspension, 2 g of sodium hydroxide in 80 g of ethanol. The reaction mixture is then heated up and left to react with stirring, for 5 hours until a clear, colorless solution is obtained, which is diluted with 550 ml of ethanol and cooled with dry ice to obtain 29 g of a crystalline methyl compound of the formula; about 1g- (21 C1csoin -sndan (wiz.) pp. 92-930C. c). 9.3 g of filter paper are soaked in with a 10% aqueous solution by a thief of the methylol compound of formula (103) s, that the paper absorbs 33.3 g of an acidic solution. The paper is dried for 10 minutes at. And then treated the same way as in A.v. The nitrogen content of this adsorption material is 1.6%, of which O, 8% is basic nitrogen, p.a. 68., 5 g of the adduct obtained by adding 2 mol of acrylamide to 1 molpiperazine (m.p., 236-231 ° C), Pc: lay in 313 MP of water and expoHO-H2CHl -OC-H2C-HjC-l / l - CHj-CH5i-CO - NH-CHiOH (W)
Have
from m.p. 151-153 0.
at. 9.6 g of filter paper are soaked in with a 10% aqueous solution of the methylol compound of formula (104), the pH of which is adjusted by adding hydrochloric acid to 3, so that the paper absorbs 34.6 g of the acidic solution. The paper treated in this way is dried for 10 minutes at and then treated in the same way as in point A. c. The nitrogen content in the resulting adsorption material composition HOH C-HN-OC-H C-lTjr-CH J-SNgOL (1D 5)
with a formaldehyde content of 0.06%, diluted with 242 ml of water and adjusted to the pH of the solution by adding concentrated hydrochloric acid to 3.
at. 964 g of filter paper is soaked in an acidic solution of the methylol compound of formula (105), prepared according to a), that the paper absorbs 33.7 g of this solution. The impregnated paper is dried for 10 minutes at and then treated in the same way as in paragraph A.v. The nitrogen content of the adsorption material obtained is 2.5%, of which 1.25% is basic nitrogen.
F.a). 22.6 g morpholine compound of the formula
Ojr -CH2-CO-l HjCl is dissolved in 110 ml of water. When added, 0.05 g of sodium hydroxide is added .55. 9/6 g of a 36.5% formaldehyde solution is distilled in methylolation for 5 hours at 50.55 seconds to obtain the methylol compound of the formula
(106)
about V-cng-so-nn-c% he cI
with formaldehyde content of 0.04%. .The plant obtained as a result of the reaction is 5
Methylation reactions are carried out when O is added, 1 g of sodium hydroxide with 51.3 g of a 35.1% formaldehyde solution for 5 hours at 30 ° C. A clear solution is formed, the formaldehyde content in which is 0.09%. Then this solution is completely evaporated. and the residue is recrystallized from ethanol: methanol in a 1: 1 ratio. 27 g of methylol compound of the formula are obtained.
It is 2.52%, of which 1.26% is basic nitrogen.
E. a /. 50 g of the product obtained as a result of the interaction of pipaRazine and chloroacetamide (m.p. 278282 s) are dissolved in 315 ml of water and subjected to a methylolation reaction by adding 0.1 g of sodium hydroxide and 42.8 g of a 35.1% formaldehyde solution . The resulting solution, which contains a methylol compound of the formula
The thief immediately after that is diluted with 118 ml of water and the pH is adjusted to 3 with concentrated hydrochloric acid.
Bj. 9.4 g of filter paper are soaked in an acidic solution of a methylol compound of formula (10 prepared in accordance with point a) that the paper absorbs 34.9 g of this solution. The impregnated paper is dried at 1400 ° C for 10 minutes and processed as in paragraph A.v. The nitrogen content of the resulting adsorption material is 0.8%, of which 0.4% is basic nitrogen.
G.a) 27.2 g of the adduct obtained in . The result of the addition of 2 mol of acrylamide to 1 mol of N, N-diethylaminopropylamine is dissolved in 150 ml of ethanol and 11 g of ethyl bromide are quentized for 5 hours at. The resulting solution is then evaporated at, after which 35.9 is obtained. g of a partially flattened ammonium compound as a thick oil. The ammonium compound is dissolved in 185 ml of water and, with the addition of 0.05 g of sodium hydroxide, 15/4 g of a 36.5% formaldehyde solution is subjected to methylolation for 5 hours at 50-60 0 to half a methyl compound of the formula:
/ CaHg / N-CHaCHjCHjN / CHiCHaCONHCH OHkBr l
 .uoi;
have a formaldehyde content of 0.04%. The resulting solution of methylol is diluted with 182 g of water and adjusted to pH 3 by adding concentrated hydrochloric acid, with
in /, 9.6 g of filter paper is impregnated with an acidic solution, obtained according to a) a), so that the resin absorbs 36.2 g of this solution. The impregnated paper with a height of ayut .. 10 minutes at and treated as in point A, in. The nitrogen content of the obtained adsorption material is 2%, of which 1.6% is basic nitrogen.
On . A solution of 34.9 g of 2-dimethyl-5-aminopropionamide in 22.5 ml of water (taken up from 22.5 g of a 36.8% hydrochloric acid solution. 30.4 g of 35.1% are added with stirring at room temperature a solution of formaldehyde 20 and 20 ml of water.After 2 days of reaction, the conversion of formaldehyde is 98% of theory. A 35% aqueous solution of the methanol compound of formula 25 is obtained.
) CH% / 2.N-CHaCHi-CHMH-CHiOH (S8)
which is 80% hydrochloride form
By adding 18% hydrochloric acid, the pH of 46 g of this solution is adjusted to 4 and diluted with 30 ml of water.
in |. With an acidic solution, obtained according to a), impregnate with 7-, 7 gz5 filter paper so that the paper absorbs 25.5, g of an acidic solution. The impregnated paper is thermofixed for 10 minutes at and then treated as in point A.v. The Q content of nitrogen of this adsorption material is 2.0%, of which 1% comes from basic nitrogen.
(.but). € 9.7 g of the product of the reaction of a bis- (2-ethoxyethyl) -amine with acrylamide is dissolved in 22.5 ml of water and 22.5 g of 36.5% hydrochloric acid are mixed while cooling. Then, with stirring at 25 ° C, 15 ml of water, 30.4 g of a 35.5% formaldehyde solution, 15 ml of 50 water and 30 ml of 2N sodium hydroxide solution are added. After a 14-day reaction, formaldehyde conversion is 96% of theory.
This gives 207 g of a 38% aqueous 55 solution of a methylol compound of the formula
 C C OCHENING I N-CHiCHa-CONH-CHaOH (iOO;
which is 80% 60 hydrochloride chloride.
The pH of this solution was adjusted to 4 with dilute hydrochloric acid and diluted with water until a 20% solution was obtained. j
in J. The acidic solution prepared according to paragraph a is treated with filter paper, as in paragraph H.c., and heat-set so that g adsorption material is obtained. The nitrogen content of the adsorption material is 1.6%, of which 0.8% is attributed to basic nitrogen.
J. a). With stirring for 40 minutes at 96–98 ° C, 144 g of 2-diethylaminopropionamide, 90 g of paraformaldehyde, and 0.6 g of magnesium oxide are reacted with stirring, resulting in a formaldehyde conversion of 100% of theory. After that, the reaction product is cooled to and immediately mixed with water.
Get it. 430 g of a 47% solution of dimethylol compound of the formula
 slN-CHiCHa-eOAlCMaOHIi (.Y.)
33.4 g of this solution is adjusted to a value of 4 with 5N hydrochloric acid and diluted with water to high. sa 80
at). Acidic solution prepared according to paragraph a /, / impregnate the filter paper, as in paragraph B. b, and heat-set, so that 9.0 g of the adsorption substance are obtained. The nitrogen content of this adsorption material is 2.5%, of which 1.25% is basic nitrogen.
K.a. 144 g of 2-diethyl-1-Minopropionamide, dissolved in 300 ml of benzene and mixed with 31.2 g of paraformaldehyde and 0.2 g of sodium methoxide, are reacted with stirring for 10 hours at. 91.4 g of a 36.9% hydrochloric acid solution and 92 g of methanol are added to it at room temperature. The resulting emulsion is slowly heated to boiling point and water is azeotropically distilled. The residue is evaporated, after which 198 g of compound of the formula are obtained.
. /С2.Н5/2Н-СНгСН2Г- СОЫН- СНгОСН5НСе (
at. The filter paper, as in paragraph N.b, is impregnated with a 20% acidic solution of the compound obtained under point a, and thermo-fixed in such a way that 8.7 g of adsorption material is obtained. The nitrogen content of this adsorption material is 2.6%, of which 1.3% is basic nitrogen.
L.a). A solution of 75.2 g of 2-chloropropionamide in 750 ml of dioxane is mixed with 56 g of pyridine and then 18 hours. The residue which is formed upon cooling, is filtered and recrystallized from ethanol.
65 g of compound of the formula are obtained.
(±)
A 24% methylol iHoro solution of the compound of formula
soon
and O.- JhUH-ff TiH. .HIRG
C1 The dye bath is heated up and mixed with 1 g of the cationic modified cellulose material prepared according to paragraphs A-G, which is pre-mixed with 100 ml of water. In each experiment, after 10–30 min of adsorption, a sample is taken, which is filtered through a folded filter, and the dye concentrations in the filtrate are determined as indicated in Table. 1. The same removal results: stains are obtained in a method with a fixed catalyst, if using
/
and-h but (/%
four.
(201)
SOjNQ are adsorption material specified in examples 1-7, in the form of chips. ExampleB If the residual bath of example 7 with a pH value of 8 is used and the experiment is carried out as in example 7, a sample that is taken after 10 and 30 minutes of adsorption - has a dye concentration of only 0.7 mg / l or shows complete bleaching . If in examples 1-8 a residual bath is replaced, instead of dyestuff containing formula (201), the EDIN of dyes of formula (202) - (209) / is replaced after 10 and 3 min of adsorption, the selected samples show / almost complete bleaching.
13997604
A-m-iTY
.

V / - / - -rVcK.
R
,
SOjbTQ o-CI-HK- | iJY MYI Cl OT dws YI -uK-fVcH m. : 1G-S L-:; irocRiCHi SOjUa TToOj fVm I irAu, i (HflCHiCHj) -jjQQ g
14
(202)
TO.
(203)
sc.
5opiQ
$ 0} iia x / L-tA-ij ciT-C-C-CH, s-n / gOjH rt ° ccHgO “g
g,
1Haz $ h
(208)
HHOC- /)
(209) EXAMPLE 9. A 50-liter purple-colored, heated to a residual bath after pressure washing, which has a TOC content of 39 mg / l, is brought into contact as described in Examples 1-8, from 60 g adsorbent obtained according to clauses Ab) -C, b). After processing for 10 min, the sample of the filtrate is completely discolored, it has a TOC content of only 8 mg / l (TOC is total organic carbon). Examples 10-18. A 5 l red colored residual dye bath with a pH value of 7, which contains 1UO mg / l of the dye of formula (201) in dissolved form, is placed in a mixing reactor. The dyebath is heated to and mixed with 0.5 g of prepared coagulum: finely with H-O points of cation-modified cellulosic material, which has been previously stirred up with 50 ml of water. In each experiment, after 30 minutes of adsorption, the sample was cut, which was filtered through a folding filter, and the capacity of the adsorbents used was shown in Table. 2
rlir-Q-CO-lT-CH -O, /
de R and R. are lower alkyls, or
lower alkyls substituted by lower alkoxy groups. pami, or R and R together with the bound nitrogen atom form a 5-6 membered heterocyclic residue;
Q.у-alkylene / h) is hydrogen, or C -C-alkyl, or, where R is hydrogen or methyl, whether the formula
K, TT-Q G -CO-: K-CH2- o R,

权利要求:
Claims (1)
[1]
"5 Continued from Table 2. Amount of adsorbing capacity. Amount of adsorbent dye. Amount of adsorbent. Formula of the invention. Method of wastewater purification from dyes or optical brighteners. For the purpose of increasing the degree of purification, cationic modified cellulosic material is used as an adsorbent, the cationic part of which is attached to the cellulosic part through the grouping of the general formula - С-1 T-CH „-0I -co- or -CO-Hydrogen, or C —C.-alkyl, or CHj.OR- where R is hydrogen or methyl, and corresponds to the formula where Q is.-alkylene nj, n -.- lower alkyls, or lower 2i alkyls substituted by lower alkoxy groups, or groups - (C-CO-TT-CH-OK I U or R and R f together with the bound nitrogen atom form a 5-b-membered heterocyclic residue, or R and R together with the group form a bivalent piperazine residue, or the formula Rч © y-Ql-CO- -CH -0- | Arf where V. is hydrogen, or lower alkyl, substituted alkyl with a nitrile or hydroxyl group, or benzyl , R., V- together with the associated atom of the az form pyridine cycle.A - anion of an organic or inorganic acid, whether the formula 1® An®, i T-Q-CO-TiH.-C-HiK I. formula Gk; , 1 LB Tf-vf- - - “СНо-о i Ч-1 1 j where, R2 .Ri.Ri is a neisch alkyl, or f and Rjj together with the nitrogen atom associated with them form a morpholine, cycle ,. , Ri is hydrogen or -OH-CO- M-ssAOH, Q and methylene or propylene group, Q - C-C-alkylene. Sources of information taken into account during the examination 1. French Patent No. 2184030, p. C 02 C 5 / 02-, published 1974 prototype).

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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CH1479875A|CH602501A5|1975-11-14|1975-11-14|

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