Classifications

• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
  • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
  • C02F1/56—Macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
  • B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F11/00—Treatment of sludge; Devices therefor
  • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
  • C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents

Definitions

• Powdery, water-soluble cationic polymer composition process for its preparation and its use
• the present invention relates to powdered water-soluble cationic polymers which consist of at least two different cationic
• polymer components which differ in the cationic component and in the molecular weight, as well as a process for their preparation and the use of the polymer products in the solid-liquid separation, e.g. in paper production as a retention aid and in sludge dewatering / wastewater treatment.
• the task of adding flocculants is to achieve the best possible result with regard to the parameters of dry solids and clarity of the filtrate, i.e. effect as complete a separation of solid from the liquid phase.
• the parameters of dry solids and clarity of the filtrate i.e. effect as complete a separation of solid from the liquid phase.
• the separated filtrate must also be disposed of. The clearer this is, i.e. the fewer non-flocculated solids are still in the filtrate, the better and easier this disposal is.
• a flocculant provides a flocculated sludge with a high solids content, but an unsatisfactory clarification of the supernatant. With another flocculant it may be the other way around.
• Flocculants are produced in the form of powdered granules or water-in-water or water-in-oil emulsions and added to the medium to be flocculated before they are used in dilute aqueous solutions.
• Powdery granules are preferred because, due to their almost water-free state, they are cheaper to transport and, as with the W / O emulsions, do not contain any water-insoluble oil or solvent components It has been shown in practice that the combination of two flocculants often gives better overall results than the use of a single flocculant.
• DE-OS 1 642 795 and EP 346 159 A1 describe the successive metering of different polymeric flocculants.
• cationic flocculants and processes for their production consist of two different polymer components. They do not arise by mixing the polymer components, but are formed by polymerizing cationic monomers into a high molecular weight cationic polymer component (flocculant) in the presence of a low molecular weight cationic polymer component (coagulant). This polymerization reaction can lead to grafting reactions on the polymer initially charged. Because of their incompatibility with the flocculant based on acrylate monomers, the following coagulant polymers are preferably used: polymers made from allyl monomers, in particular poly-DADMAC and amine-epichlorohydrin polymers (page 4, lines 40f).
• the ratio of coagulant to the high molecular weight polyelectrolyte component is given as 10: 1 to 1: 2, preferably 5: 1 to 1: 1.5 (page 3, lines 48-49), ie in the preferred embodiment the proportion is Coagulants on the polymer mixture 83 to 40% by weight.
• the properties of the flocculants disclosed do not meet the requirements as they are placed on technical flocculation processes in terms of speed and effectiveness.
• Polymer composition which contains at least two cationic polymers of different composition in the cationic groups, a first cationic polymer being formed in the presence of a second cationic polymer in aqueous solution from its monomer components by free-radical polymerization, characterized in that
• the polymerization of the first cationic polymer in an aqueous solution of the second cationic polymer is carried out according to the adiabatic gel polymerization method.
• the polymer composition is formed by a ratio of second cationic polymer to first cationic polymer of 0.01: 10 to 1: 4, preferably 0.2: 10 to ⁇ 1:10.
• the two cationic polymers differ in the type of their cationic groups, which are structured differently, ie the first cationic polymer is formed from a different cationic monomer species than the second cationic polymer.
• the first cationic polymer is a copolymer of cationic and nonionic monomers.
• Suitable cationic monomer components are, for example, cationized esters of (meth) acrylic acid, such as of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminobutyl (methacrylate), diethylaminobutyl (meth) acrylate, cationized amides of (meth) acrylic acid such as eg of dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dimethyla
• the basic monomers are used in a form neutralized or quaternized with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride. In a preferred embodiment, the monomers quaternized with methyl chloride or benzyl chloride are used.
• Preferred cationic monomer components are the cationized esters and amides of (meth) acrylic acid, each containing a quaternized nitrogen atom and Quaternized dimethylaminopropylacrylamide and quaternized dimethylaminoethyl acrylate are particularly preferably used.
• Suitable nonionic monomer components are, for example, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, N, N-dimethylacrylamide, vinylpyridine, vinyl acetate, hydroxyl-containing esters of polymerizable acids, the hydroxyethyl and propyl esters of acrylic acid and methacrylic acid, and further esters containing amino groups polymerizable acids such as the dialkylamino esters, for example Dimethyl and diethylamino esters of acrylic acid and methacrylic acid, for example dimethylaminoethyl acrylate and the corresponding amides such as dimethylaminopropylacrylamide.
• Acrylamide is preferably used as the nonionic monomer component. Limited water-soluble monomers are only used to the extent that they do not impair the water-solubility of the resulting copolymer.
• the first cationic polymer is a high molecular polymer. Its average molecular weight Mw is over 1 million, preferably over 3 million. The molecular weight of the first cationic polymer is higher than that of the second cationic polymer. The high molecular weight of the first cationic polymer improves the effect of the polymer composition according to the invention in the flocculation process.
• the charge density of the first cationic polymer can be freely selected and must be matched to the respective application.
• the first cationic polymer is formed from 20 to 90% by weight of cationic monomers, preferably from 40 to 80% by weight.
• the second cationic polymer can be polymerized from the same cationic monomers as described for the first cationic polymer, but supplemented by the monomer diallyldimethylammonium chloride.
• Preferred cationic monomers are the cationized esters and amides of (meth) acrylic acid, each containing a quaternized N atom, and quaternized dimethylaminopropylacrylamide and quaternized dimethylaminoethyl acrylate and the diallyldimethylammonium chloride are particularly preferred.
• copolymers with preferably water-soluble nonionic monomers can also be used. They are the same nonionic monomers that have already been described for the first cationic polymer.
• Acrylamide is preferably used as a comonomer.
• the second cationic polymer is formed from 70 to 100% by weight of cationic monomers, preferably from 75 to 100% by weight and particularly preferably from 100% by weight
• the second cationic polymer is lower in molecular weight than the first cationic polymer, its average molecular weight Mw is less than 1 million, preferably between 50,000 to 700,000 and particularly preferably between 100,000 and 500,000.
• the first cationic polymer has a lower cationic charge density than the second cationic polymer.
• the water-soluble cationic polymer compositions according to the invention are produced by the adiabatic gel polymerization process, a first cationic polymer being formed from its monomer components in aqueous solution by a radical polymerization in the presence of a second cationic polymer.
• a first cationic polymer being formed from its monomer components in aqueous solution by a radical polymerization in the presence of a second cationic polymer.
• an aqueous solution of cationic and optionally nonionic monomers and the second cationic polymer is first prepared, the starting temperature for the polymerization is set in a range from -10 to 25 ° C. and oxygen is removed from it by an inert gas.
• the exothermic polymerization reaction of the monomers is started and the polymerization batch is heated to form a polymer gel.
• the solid polymer gel which forms can be processed further immediately or only after a holding time, preferably the polymer gel is further processed immediately after the maximum temperature has been reached.
• the aqueous mixture of monomers and the second cationic polymer is usually used in a concentration of 10 to 60% by weight, preferably 15 to 50% by weight and particularly preferably 25 to 45% by weight.
• the solution obtained in the polymerization of the second cationic polymer is used directly for the production of the products according to the invention.
• the starting temperature for the polymerization reaction is set in a range from -10 ° C to 25 ° C, preferably in a range from 0 ° C to 15 ° C. Higher starting temperatures lead to polymer gels, which due to their softness can no longer be processed in the subsequent comminution and drying processes.
• the polymerization of the first cationic polymer is carried out as an adiabatic polymerization and can be started either with a redox system or with a photoinitiator. A combination of both start variants is also possible.
• the redox initiator system consists of at least two components: an organic or inorganic oxidizing agent and an organic or inorganic reducing agent.
• Compounds with peroxide units are frequently used, for example inorganic peroxides such as alkali metal and ammonium persulfate, alkali metal and ammonium perphosphates, hydrogen peroxide and its salts (sodium peroxide, barium peroxide) or organic peroxides such as benzoyl peroxide, butyl hydroperoxide or peracids such as peracetic acid.
• inorganic peroxides such as alkali metal and ammonium persulfate, alkali metal and ammonium perphosphates, hydrogen peroxide and its salts (sodium peroxide, barium peroxide) or organic peroxides such as benzoyl peroxide, butyl hydroperoxide or peracids such as peracetic acid.
• other oxidizing agents can also be used, for example
• Sulfur-containing compounds such as sulfites, thiosulfates, sulfinic acid, organic thiols (ethyl mercaptan, 2-hydroxyethanethiol, 2-mercaptoethylammonium chloride, thioglycolic acid) can be used as reducing agents become.
• Ascorbic acid and low-valent metal salts are also possible [copper (l); Manganese (II); Iron (II)].
• Phosphorus compounds can also be used, for example sodium hypophosphite.
• the reaction is preferably started with UV light, which causes the starter to disintegrate.
• starters examples include benzoin and benzoin derivatives, such as benzoin ethers, benzil and its derivatives, such as benzil ketals, acryldiazonium salts, azo initiators such as, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-amidinopropane) hydrochloride or acetophenone derivatives be used.
• the amount of the oxidizing and reducing components is in the range between 0.00005 and 0.5% by weight, preferably from 0.001 to 0.1% by weight, based on the monomer solution and, for photoinitiators, between 0.001 and 0.1% by weight. preferably 0.002 to 0.05% by weight.
• the polymerization is carried out batchwise in an aqueous solution in a polymerization vessel or continuously on an endless belt, as described, for example, in DE 35 44 770.
• This document is hereby introduced as a reference and is considered part of the disclosure.
• the process is carried out at atmospheric pressure without the addition of external heat, the heat of polymerization resulting in a maximum final temperature of 50 to 150 ° C. which is dependent on the content of polymerizable substance.
• polymers with significantly better product properties are obtained than those for products according to of EP 262945 were measured, which were synthesized by an isothermal polymerization.
• the polymer present as a gel is comminuted in industrially customary apparatus.
• the ratio of second to first cationic polymer is decisive for the further processing of the polymer gel. If the ratio exceeds the value of 0.01: 10 to 1: 4, very soft gels are formed, which immediately stick again after comminution and make drying on an industrial scale almost impossible.
• Polymers with cationic monomer contents of more than 60% by weight are particularly critical. It has often proven useful to set the ratio of the second to the first cationic polymer to 0.2: 10 to ⁇ 1:10.
• the comminuted gel is dried discontinuously in a circulating air drying cabinet at 70 ° C. to 150 ° C., preferably at 80 ° C. to 120 ° C. and particularly preferably 90 ° C. to 110 ° C. Drying is carried out continuously in the same temperature ranges, for example on a belt dryer or in a fluidized bed dryer. After drying, the product preferably has a moisture content of less than or equal to 12%, particularly preferably less than or equal to 10%.
• the product After drying, the product is ground to the desired grain size. In order to achieve rapid dissolution of the product, at least 90% by weight of the product must be less than 2.0 mm, preferably 90% by weight, less than 1.5 mm. Fine fractions below 0.1 mm should be less than 10% by weight, preferably less than 5% by weight.
• the polymers according to the invention are suitable as flocculants in the course of the solid / liquid separation.
• they are suitable for use in the purification of waste water and in the treatment of drinking water.
• they can advantageously be used as retention aids in the flocculation processes during the production of paper.
• the viscosities were determined using a Brookfield viscometer on a 0.5% by weight solution in 10% by weight NaCl solution. The solving time was one hour.
• DIMAPA-Quat 3-Dimethylammoniumpropyl (meth) acrylamide, which was quaternized with methyl chloride
• ADAME-Quat 2-Dimethylammoniumethyl (meth) acrylate, which was quaternized with methyl chloride
• DADMAC Diallyldimethylammoniumchlorid
• the second cationic polymers used in the examples are solution polymers made from DADMAC and DIMAPA-Quat, which were produced with different polymer contents and different molecular weights (Mw according to GPC). The more detailed properties of these products are listed in the table:
• This test method is adapted to the drainage process used in practice, namely continuous pressure filtration using filter presses or centrifugal dewatering in centrifuges.
• This method usually tests organic cationic polymers for their suitability for conditioning and dewatering municipal or industrial sludges.
• Polymers according to the invention are produced by the gel polymerization process.
• Polymer 3 378.0 g of 50% by weight aqueous acrylamide solution were initially introduced into a polymerization vessel and mixed with 303.6 g of water and 210 mg of Versenex 80. After the addition of 260.0 g of 80% by weight of ADAME-Quat and 57.8 g of the 40% by weight solution of K3, the pH was adjusted to 5.0 with 0.6 g of 50% by weight of sulfuric acid adjusted, cooled to 0 ° C and blown out with nitrogen. After the addition of 0.45 g ABAH (2,2'-azobis (2-methylpropionamidine) dihydrochloride), the polymerization was started with UV light. The polymerization runs from 0 ° C to 80 ° C within 25 min. The polymer was ground with a meat grinder and dried at 100 ° C for 90 min. The product was ground to a grain size of 90-1400 ⁇ m.
• Polymer 4 The synthesis was carried out like that of polymer 3, except that 29.0 g of the 40% by weight solution of K3, 274.3 g 80% by weight of ADAME-Quat and 318.2 g of water were added.
• the synthesis was carried out like that of polymer 3, only 78.8 g of the 40% by weight solution of K3, 354.4 g 80% by weight of ADAME-Quat, 270.0 g of 50% by weight of acrylamide solution and 296. 1 g of water added.
• the synthesis was carried out like that of polymer 3, except that 39.4 g of the 40% by weight solution of K3, 374.1 g 80% by weight ADAME-Quat, 270.0 g 50% by weight acrylamide solution and 316, 0 g of water added.
• the synthesis was carried out as for polymer 2, except that 70.0 g of K1 and 210.7 g of water were used.
• the synthesis was carried out as for polymer 2, except that 90.0 g of K1 and 192.4 g of water were used.
• Polymer 11 The synthesis was carried out as described in polymer 1, but was started at 10 ° C.
• the synthesis was carried out as described in polymer 1, but was started at 15 ° C.
• the synthesis was carried out as described in polymer 1, but was started at 20 ° C.
• Comparative Polvmer 6 The synthesis was carried out as described in Comparative Example 5, except that 250.0 g of K1, 106.7 g of MADAME-Quat, 40.0 g of acrylamide and 270.3 g of water were used.
• Comparative Polvmer 8 (according to EP 262945 B1) - starting temperature The synthesis was carried out as described in Comparative Example 6, only starting at 3 ° C. with 1000 ppm Na 2 S 2 O 8 , 7 ppm FeSO 4 and 2000 ppm Na 2 S 2 O 5 . The temperature of the mixture rose to 33 ° C. in 24 minutes. The mixture was then stirred for 60 minutes.
• Comparative Polvmer 9 (according to EP 262945 BP - starting temperature The synthesis was carried out as described in Comparative Example 7, only starting at 3 ° C. with 500 ppm Na 2 S 2 ⁇ 8 , 7 ppm FeSO 4 and 1000 ppm Na 2 S 2 O 5 The temperature of the mixture rose in 40 minutes to 31 ° C. The mixture was then stirred for 60 minutes.
• Polymer 1 according to the invention is compared with comparative polymer 1 as well as with a separate metering of first second cationic polymer and then first cationic polymer in the form of the comparative polymers without a second cat. Polymer.
• the stirring time was 10 s, the amount of filtrate was 200 mL.
• WS amount of polymer ("active substance")
• TS dry substance in sewage sludge
• Polymer 2 according to the invention is compared with comparative polymer 2 as with a separate metering of first second cationic polymer and then first cationic polymer in the form of the comparative polymers without a proportion of second cat. Polymer.
• the stirring time was 10 s, the amount of filtrate was 200 mL.
• WS amount of polymer ("active substance")
• TS dry substance in sewage sludge
• Polymers 3, 4, 5 and 6 according to the invention are compared with comparative polymers 3 and 4.
• the stirring time was 10 s, the amount of filtrate was 200 mL
• WS amount of polymer ("active substance")
• TS dry substance in sewage sludge
• Polymers 7, 8, 9 and 10 according to the invention are compared with comparative polymer 1, 5, 6 and 7.
• the stirring time was 10 s, the amount of filtrate was 200 mL.
• WS amount of polymer ("active substance")
• TS dry substance in sewage sludge
• the comparative examples according to EP262945 B1 are clearly inferior to the polymers according to the invention. At metered amounts with which the polymers according to the invention provide good dewatering results, the comparative examples do not yet show any approximately satisfactory dewatering.
• Application Example 5 Polymers 11, 12 and 13 according to the invention are compared with comparative polymers 1, 8 and 9. The stirring time was 10 s, the amount of filtrate was 200 mL. S: amount of polymer ("active substance"), TS: dry substance in sewage sludge
• Application example 6 wastewater treatment plant
• a cationic polyacrylamide (Praestol® 644 BC, a commercial product from Stockhausen GmbH & Co. KG based on 55% by weight DIMAPA-Quat. And 45% by weight acrylamide) was mixed with polymer 2 with regard to the flocculation performance at municipal Sewage sludge compared.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Hydrology & Water Resources (AREA)
• Life Sciences & Earth Sciences (AREA)
• Environmental & Geological Engineering (AREA)
• Water Supply & Treatment (AREA)
• Separation Of Suspended Particles By Flocculating Agents (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polymerisation Methods In General (AREA)
• Treatment Of Sludge (AREA)
• Graft Or Block Polymers (AREA)
• Paper (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

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