Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
  • D21C5/02—Working-up waste paper
  • D21C5/025—De-inking
  • D21C5/027—Chemicals therefor
• • 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
  • C02F1/24—Treatment of water, waste water, or sewage by flotation
• • 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
  • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
  • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/64—Paper recycling

Definitions

• the invention relates to a process for waste paper processing and the use of hydroxysulfonate salts for removing printing inks from printed waste paper and / or paper cycle water.
• waste paper For the production of, for example, newspaper printing and hygiene papers, waste paper is used in large quantities today. The quality of these types of paper is determined by their brightness and color. In order to be able to produce high-quality paper types, the printing inks must be removed from the printed waste paper. This is usually done using deinking processes, which essentially take place in two steps:
• the second process step can be carried out by washing or flotation (Ullmann's Enzyclopadie der Technischen Chemie, 4th edition, volume 17, pages 570-571 (1979)).
• flotation where the different wettability of printing inks and paper fibers is used, air is pressed or sucked through the pulp suspensions. Small air bubbles combine with the ink particles and form a foam on the water surface, which is removed with fabric catchers.
• the deinking of waste paper is usually carried out at alkaline pH values in the presence of alkali hydroxides, alkali silicates, oxidative bleaches and surface-active substances at temperatures between 30 and 50 ° C.
• Surface-active substances of an anionic and / or nonionic nature are predominantly used as surface-active substances which cause the detachment and separation of the printing ink particles, for example soaps, ethoxylated fatty alcohols and / or ethoxylated alkylphenols (Wochenblatt für Textilfabrikation j, 646 to 649 (1985)). From JP 61/207686, referenced in Chem. Abstr. 106.
• the object on which the invention is based was therefore to develop a method for processing waste paper with which a clear improvement in the ink removal from printed waste paper is achieved. It has now been found that by using certain hydroxysulfonate salts in waste paper processing processes, waste paper with very high degrees of whiteness is obtained. In addition, it was found that printing inks can also be removed from circulating water with hydroxysulfonate salts.
• the invention accordingly relates to a process for recovering waste paper, which is characterized in that printed waste papers in the presence of alkali, alkaline earth and / or ammonium salts of hydroxysulfonates, prepared by sulfonation of alkenyl esters and / or alkenyl polyoxyalkyl esters of the general formula
• radicals R 1 contain a linear Ci6-22- A T en y ⁇ 9 ru PP e ° - er e ⁇ ne palmitoleyl, oleyl, linoleyl, gadoleyl and / or erucyl groups and R2 H or a C ⁇ _3 ⁇ Represent alkyl group and the indices n 2, 3 and / or 4 and x represent a number from 0 to 30, followed by hydrolysis of the sultone and ester groups, are opened and then in a manner known per se from the detached ink particles by flotation or washing the pulp suspensions are removed.
• Another subject of the invention is the use of alkali, alkaline earth and / or ammonium salts of hydroxysulfonates, prepared by sulfonation of alkenyl esters and / or alkenyl polyoxyalkyl esters of the general formula
• radicals R 1 represent a linear Ci6-22 " lken y 1 9 ru PP e or a fatty alkenyl group and RH or a C ⁇ _3 alkyl group containing palmitoleyl, oleyl, linoleyl, gadoleyl and / or erucyl groups and the indices n 2, 3 and / or 4 and x represent a number from 0 to 30, and subsequent hydrolysis of the sulton and ester groups, for removing printing inks from printed waste papers and / or paper circulation waters.
• hydroxysulfonate salts to be used according to the invention are accessible by the process described in German Offenlegungsschrift DE-OS 37 25 030.
• Straight-chain alkenyl alcohols of natural and / or synthetic origin are used as starting materials for the esters of the general formula, for example palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, gadoleyl alcohol and / or erucyl alcohol and / or technical alcohol mixtures containing one or more of the aforementioned unsaturated alcohols.
• Naturally occurring alkenyl alcohols with 18 carbon atoms such as oleyl alcohol or technical alcohol mixtures containing oleyl alcohol, for example cetyl / oleyl and / or oleyl / linoleole alcohol mixtures with iodine numbers of 50 to 130 are preferred. Parts of saturated alcohols, such as cetyl alcohols and / or stearyl alcohol, do not interfere in technical alcohol mixtures.
• the commercially available alkenyl alcohols and alkenyl alcohol mixtures can be prepared by hydrogenating unsaturated carboxylic acids or mixtures containing technical grade unsaturated fatty acids.
• alkenyl alcohols are reacted by known industrial processes with ethylene oxide, propylene oxide and / or butylene oxide, preferably with ethylene oxide (see, for example, in "Chemical Technology" Volume 7, pages 131 to 132, Carl-Hanser -Verlag, Kunststoff-Vienna (1986)).
• the average degree of alkoxylation x of the mixtures of homologous alkoxylates obtained corresponds to the molar amount of the alkylene oxides attached and is preferably at most 10.
• the esterification of the hydroxyl group of the alkenyl alcohols and / or the alkoxylated alkenyl alcohols is carried out in a manner known per se, for example by reacting the unsaturated alcohols with carboxylic acids of the general formula R2-C00H in the presence of catalysts, for example concentrated sulfuric acid or tin grinding, at the boiling point with simultaneous distillation ver removal of the water of reaction formed. Furthermore, the esterification can also be carried out with carboxylic anhydrides of the general formula R 2 C00C0R 2 in a manner known per se.
• Suitable carboxylic acids and carboxylic acid anhydrides are formic acid, acetic acid, propionic acid and / or butyric acid and / or the corresponding anhydrides of these acids.
• acetic acid and / or acetic anhydride are preferably used.
• the sulfonations of the esters of the general formula are carried out with SO 3 -containing gas mixtures, preferably with gas mixtures of SO3 and air or inert gases, such as nitrogen, in which the SO 3 content is between 1 and 8% by volume at temperatures between 10 and
• SO3 is usually used in an equi-olar amount or in a molar excess of up to 50%.
• the sulfonations are used in the usual for Sulfation of fatty alcohols or the sulfonation of fatty acid esters, alkylbenzenes or olefins suitable and customary reactors, for example of the falling film reactor type, carried out continuously or batchwise (see, for example, in Kirk-Othmer: Encyclopedia of Chemical Technology 22, 28 ff ( 1983)).
• the product obtained is added to an aqueous solution of alkali metal hydroxides, alkaline earth metal hydroxides and / or ammonium hydroxide. 1 to 2.5 moles of hydroxides are used per mole of sulfur trioxide added.
• the aqueous solutions containing hydroxides are heated to, for example, boiling temperature under atmospheric pressure.
• the hydroxysulfonate salts to be used according to the invention are preferably added to pulp suspensions in amounts of 0.02 to 2% by weight, particularly preferably from 0.1 to 0.8% by weight, in each case based on air-dry pulp.
• Air-dry paper stock means that an equilibrium state of internal moisture has set in the paper stock. This equilibrium state depends on the temperature and the relative humidity of the air.
• the deinking result that is to say the removal of printing inks from printed waste paper
• the hydroxysulfonate salts to be used according to the invention in combination with, for example, CIO-22 " fatty acids: such as 01inor R 4010, 01inor R 4020 and / or Olionor R DG40 (manufacturer of all Henkel KGaA products), ethoxylated Alkyl alcohols with 6 to 22 carbon atoms, ethoxylated alkylphenols, polymers such as polyacrylics and / or polydimethylaminoethyl methacrylates and / or copolymers, described for example in DE 3839 479, in amounts of 0.01 to 1% by weight, based on air-dry Paper pulp, and / or with layer compounds of the general composition precipitated in situ
• M (II) stands for divalent metal cations
• M (III) for trivalent metal cations
• a z "for anions of mono- and / or polybasic acids the indices x a number between 0.01 and 0.5 and n is a number between 0 and 20, described in DE 39 09 568.
• the molar ratio of divalent metal cations to trivalent metal cations in layer compounds precipitated in situ is preferably between 20: 1 and 1: 1.
• trivalent metal cations can Amounts between 0.3 and 2 wt .-% are used.
• hydroxysulfonate salts for example newspaper rotary inks, letterpress inks, off-set printing inks, gravure inks, flexographic inks, laser printing inks and / or gravure inks from printed waste paper, for example newspapers, magazines, computer papers, magazines, Remove brochures, forms, phone books and / or catalogs.
• the waste papers deinked by the process according to the invention are distinguished by very high degrees of whiteness.
• Printed waste papers are, for example, between 1 and 5% by weight in a cloth dissolver in aqueous solution, which typically contains 0 to 1.5% by weight hydrogen peroxide (100%), 0 to 2.5% by weight.
• the detached ink particles are separated from the paper stock suspensions in a manner known per se by washing out or flotation.
• Flotation is preferably carried out in a manner known per se, for example in a Denver flotation cell.
• the compounds according to the invention When using the compounds according to the invention, printing inks are removed from the waste paper and from the circuit.
• the compounds according to the invention can also be used for the separate cleaning of paper circulation waters. In these cases, after the addition of 2 to 100 mg of compounds according to the invention per liter of circulating water, the ink particles are excreted, for example by filtration or flotation.
• E0 means ethylene oxide
• a technical mixture of oleyl and cetyl alcohol in a weight ratio of 1: 1 (HD-Ocenol R 50/55, iodine number 55, hydroxyl number 215; commercial product from Henkel KGaA) was mixed with acetic anhydride (20 mol% excess) at 118 ° C. within Converted into the appropriate acetate for 4 hours. The reaction mixture was then poured onto ice water, the organic phase washed several times with water, dried over sodium sulfate and then distilled.
• reaction mixture was cooled, stirred into an aqueous solution of 68 g (1.7 mol) of NaOH and 1500 g of water and then hydrolyzed for 4 hours on a steam bath at 95 to 100 ° C. After cooling to 20 ° C by adding Hydrochloric acid solution, the pH of the reaction mixture is adjusted to 7.0.
• a technical mixture of oleyl and cetyl alcohol in a weight ratio of 1: 1 (HD-0cenol R 50/55) was alkoxylated at 170 ° C. in the presence of sodium methylate as a catalyst with 5 moles of ethylene oxide per mole of alcohol mixture and then the alkoxylation product obtained with acetic anhydride (20 mol% excess) at 118 ° C within 4 hours in the corresponding acetate.
• the reaction mixture was then poured onto ice water, the organic phase washed several times with water, dried over sodium sulfate and then distilled.
• Sulfur trioxide was driven off from a corresponding amount of oleum by heating, diluted to a concentration of 5% by volume with nitrogen and introduced into the oleyl ether acetate within 10 minutes, the temperature of the reaction mixture being kept below 40 ° C. by cooling. After the sulfonation had ended, the reaction mixture was cooled, stirred into an aqueous solution of 96 g (2.4 mol) of sodium hydroxide and 2000 g of water and then hydrolyzed for 4 hours on a steam bath at 95 to 100 ° C. After cooling to 20 ° C., the pH of the reaction mixture was adjusted to 7.0 by adding hydrochloric acid solution.
• the paper pulp was then diluted to 1.84 l with water and left to stand at 45 ° C. for 1.5 hours.
• the flotation was then carried out for 12 minutes at 45 ° C. in a Denver laboratory flotation cell at 300 revolutions per minute.
• the respective paper pulp was separated from water (circulating water) on a suction filter and formed into a sheet between two filter papers on a photo drying press and dried at 100 ° C. for 90 minutes.
• the denaturability measure (DEM) was calculated from the reflection factors R457nm (whiteness) of the printed (BS), deinked (DS) and unprinted (US) paper stock using the following formula:

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• Chemical & Material Sciences (AREA)
• Water Supply & Treatment (AREA)
• Life Sciences & Earth Sciences (AREA)
• Hydrology & Water Resources (AREA)
• Engineering & Computer Science (AREA)
• Environmental & Geological Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Toxicology (AREA)
• Health & Medical Sciences (AREA)
• Paper (AREA)
• Fats And Perfumes (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1989
  • 1989-10-27 DE DE3935761A patent/DE3935761A1/de not_active Withdrawn
• 1990
  • 1990-10-18 KR KR1019920700978A patent/KR927003919A/ko not_active Application Discontinuation
  • 1990-10-18 AU AU65288/90A patent/AU637839B2/en not_active Expired - Fee Related
  • 1990-10-18 US US07/849,401 patent/US5234545A/en not_active Expired - Fee Related
  • 1990-10-18 EP EP90915115A patent/EP0500559A1/de not_active Withdrawn
  • 1990-10-18 CA CA 2071823 patent/CA2071823A1/en not_active Abandoned
  • 1990-10-18 JP JP2514135A patent/JPH05501430A/ja active Pending
  • 1990-10-18 WO PCT/EP1990/001765 patent/WO1991006701A1/de not_active Application Discontinuation
  • 1990-10-26 PL PL28752990A patent/PL287529A1/xx unknown
• 1992
  • 1992-04-23 FI FI921815A patent/FI921815A0/fi not_active Application Discontinuation

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