FI90573B - Method for improving retention or purification of cellulose fiber suspensions or waste water in the paper, pulp and paperboard industry - Google Patents
Method for improving retention or purification of cellulose fiber suspensions or waste water in the paper, pulp and paperboard industry Download PDFInfo
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- FI90573B FI90573B FI875123A FI875123A FI90573B FI 90573 B FI90573 B FI 90573B FI 875123 A FI875123 A FI 875123A FI 875123 A FI875123 A FI 875123A FI 90573 B FI90573 B FI 90573B
- Authority
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- Finland
- Prior art keywords
- cationic
- polyethylene oxide
- pulp
- purification
- phenol
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- 230000014759 maintenance of location Effects 0.000 title claims description 18
- 239000000725 suspension Substances 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 13
- 238000000746 purification Methods 0.000 title claims description 11
- 239000002351 wastewater Substances 0.000 title description 13
- 229920003043 Cellulose fiber Polymers 0.000 title 1
- 239000000123 paper Substances 0.000 title 1
- 239000011087 paperboard Substances 0.000 title 1
- 125000002091 cationic group Chemical group 0.000 claims description 36
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 25
- 239000000835 fiber Substances 0.000 claims description 23
- 229920000881 Modified starch Polymers 0.000 claims description 19
- 235000019426 modified starch Nutrition 0.000 claims description 19
- 229920002678 cellulose Polymers 0.000 claims description 17
- 239000001913 cellulose Substances 0.000 claims description 17
- 229920001568 phenolic resin Polymers 0.000 claims description 16
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 14
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 229920000867 polyelectrolyte Polymers 0.000 description 6
- -1 formaldehyde formaldehyde formaldehyde formaldehyde formaldehyde formaldehyde Chemical compound 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920002488 Hemicellulose Polymers 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- KUGRPPRAQNPSQD-UHFFFAOYSA-N OOOOO Chemical compound OOOOO KUGRPPRAQNPSQD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 102100031260 Acyl-coenzyme A thioesterase THEM4 Human genes 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 102100035861 Cytosolic 5'-nucleotidase 1A Human genes 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101000638510 Homo sapiens Acyl-coenzyme A thioesterase THEM4 Proteins 0.000 description 1
- 101000802744 Homo sapiens Cytosolic 5'-nucleotidase 1A Proteins 0.000 description 1
- DIWRORZWFLOCLC-UHFFFAOYSA-N Lorazepam Chemical compound C12=CC(Cl)=CC=C2NC(=O)C(O)N=C1C1=CC=CC=C1Cl DIWRORZWFLOCLC-UHFFFAOYSA-N 0.000 description 1
- RSPISYXLHRIGJD-UHFFFAOYSA-N OOOO Chemical compound OOOO RSPISYXLHRIGJD-UHFFFAOYSA-N 0.000 description 1
- DTAFLBZLAZYRDX-UHFFFAOYSA-N OOOOOO Chemical compound OOOOOO DTAFLBZLAZYRDX-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/48—Condensation polymers of aldehydes or ketones with phenols
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/53—Polyethers; Polyesters
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
1 905731 90573
Tapa parantaa paperi-, massa- tai kartonkiteollisuudessa sellukuitususpensioiden tai jätevesien retentiota tai puhdistusta 5 Käsiteltävänä oleva keksintö koskee tapaa paran taa paperi-, massa- tai kartonkiteollisuudessa sellukuitususpensioiden tai jätevesien retentiota ja/tai puhdistusta käsittelemällä niitä yhdistelmällä, joka muodostuu fe-noliformaldehydihartsista ja suurimolekyylisestä polyetee-10 nioksidista sekä kationisesta tärkkelysjohdannaisesta tai kationisesta seiluloosajohdannaises ta.The present invention relates to a method for improving the retention and / or purification of pulp fiber suspensions or effluents in the paper, pulp or board industry by treating them with a combination of polyol and formaldehyde formaldehyde formaldehyde formaldehyde formaldehyde formaldehyde formulation -10 nioxide and a cationic starch derivative or a cationic cellulose derivative.
Paperi-, massa- ja kartonkiteollisuudessa tunnetaan useita tapoja retention parantamiseksi sellukuitususpensioiden vedenpoiston yhteydessä lisäämällä erilai-15 siä polyelektrolyyttejä kuten kationista polyamiinia, kationista polyakryyliamidia ja kationista selluloosajohdannaista. Sellukuitususpensiot voivat sellukuitujen ohella sisältää myös vaihtelevia määriä epäorgaanisia täyteaineita, esim. savea, dolomiittikalkkia ja kipsiä, epä-20 orgaanisia ja orgaanisia sideaineita, ligniiniä ja hemi-selluloosia. Lisäämällä polyelektrolyyttejä helpotetaan massasuspension sisältämien tuotteiden flokkautumista ja tämä edistää puolestaan retentiota. Länsi-saksalaisesta patenttijulkaisusta 2 549 089 tunnetaan myös retention 25 parantaminen sellukuitususpensioiden vedenpoiston yhteydessä käyttämällä suurimolekyylisen polyeteenioksidin, fenoliformaldehydihartsin, vaihtoehtoisesti fenolirikki-hartsin, ja polyamidin yhdistelmää.Several ways are known in the paper, pulp and board industry to improve retention in the dewatering of pulp fiber suspensions by the addition of various polyelectrolytes such as cationic polyamine, cationic polyacrylamide and cationic cellulose derivative. Pulp fiber suspensions may contain, in addition to the pulp fibers, varying amounts of inorganic fillers, e.g., clay, dolomite lime and gypsum, inorganic and organic binders, lignin and hemicellulose. The addition of polyelectrolytes facilitates the flocculation of the products contained in the pulp suspension and this in turn promotes retention. West German Patent 2,549,089 also discloses the improvement of retention in the dewatering of pulp fiber suspensions using a combination of high molecular weight polyethylene oxide, phenol-formaldehyde resin, alternatively phenol-sulfur resin, and polyamide.
Kun vesi on poistettu sellukuitususpensiosta, saa-30 daan suuria määriä jätevettä, joka hyvälläkin retentiolla sisältää pienehköjä määriä hienokuitua, ns. nollakuitua, täyteaineita ja sideainetähteitä sekä ligniinistä ja hemi-selluloosasta liuenneita aineosia. Jäteveden puhdistuksessa pyritään tunnetusti flokkaamaan epäpuhtaudet lisää-35 mällä epäorgaanisia ja/tai orgaanisia polyelektrolyyttejä 2 90S73 kuten alumiinisulfaattia, rautakloridia, polyakryyliami-dia, polyakrylaattia, polyeteeni-imiiniä ja kationista tärkkelysjohdannaista.After the water has been removed from the pulp fiber suspension, large amounts of wastewater are obtained, which, even with good retention, contain smaller amounts of fine fiber, the so-called zero fiber, fillers and binder residues, and components dissolved from lignin and hemicellulose. Wastewater treatment is known to flocculate impurities by the addition of inorganic and / or organic polyelectrolytes 2 90S73 such as aluminum sulfate, iron chloride, polyacrylamide, polyacrylate, polyethyleneimine and a cationic starch derivative.
Kanadalaisesta patenttijulkaisusta CA 1 004 782 5 tunnetaan myös fenoliformaldehydin käyttö yhdistelmänä suurimolekyylisen polyeteenioksidin kanssa parantamaan retentiota sellukuitususpensioiden vedenpoiston yhteydessä. Sekä sellukuitususpensioiden vedenpoiston että jäteveden puhdistuksen yhteydessä polyeteenioksidiaddukti hel-10 pottaa fenoliformaldehydihartsin kanssa muodostuvien flok-kien agglomeroitumista, jolloin retentio ja puhdistus helpottuvat .Canadian patent publication CA 1 004 782 5 also discloses the use of phenol formaldehyde in combination with high molecular weight polyethylene oxide to improve retention in the dewatering of pulp fiber suspensions. In both the dewatering of pulp fiber suspensions and the treatment of wastewater, the polyethylene oxide adduct facilitates the agglomeration of Flocks formed with phenol-formaldehyde resin, thereby facilitating retention and purification.
Vaikka suurimolekyylisen polyeteenioksidin ja feno-liformaldehydihartsin yhdistelmä mahdollistaa hyvän reten-15 tion ja puhdistumisen, on osoittautunut, että osa hieno-kuiduista ja kolloidisista hiukkasista ja liuenneesta aineksesta ei pidäty kuiturainaan tai ei saada poistetuksi jätevedestä ehdotetulla menettelyllä. Siten on tarvetta saada käyttöön menettelyjä, jotka parantavat edelleen 20 retentiota ja puhdistusta. Tällaisia ongelmia esiintyy mm. poistettaessa vesi uusiomassasta tai mekaanisesta massasta saaduista kuitususpensioista tai puhdistettaessa näistä massoista tai kuorimoista syntyviä jätevesiä. Siten on olemassa tarve saada käyttöön menettelyjä, joilla 25 retentio ja puhdistus paranevat entisestäänkin.Although the combination of high molecular weight polyethylene oxide and phenol-liformaldehyde resin allows good retention and purification, it has been found that some of the fine fibers and colloidal particles and solute are not retained in the fibrous web or cannot be removed from the wastewater by the proposed procedure. Thus, there is a need for procedures that further improve retention and purification. Such problems occur e.g. when removing water from fiber suspensions obtained from recycled pulp or mechanical pulp or when treating waste water from these pulps or peelings. Thus, there is a need to provide procedures that further improve retention and purification.
Nyt on osoittautunut, että retentiota ja puhdistusta voidaan parantaa, jos kuitususpensioon tai jäteveteen lisätään formaldehydihartsin ja suurimolekyylisen polyeteenioksidin lisäksi kationista tärkkelysjohdannais-30 ta tai kationista selluloosajohdannaista. On osoittautunut, että kationisen tärkkelysjohdannaisen läsnäolo parantaa nollakuitujen ja flokkautuneen aineksen, joita on tai muodostuu käsittelyn aikana, "siepattavuutta". Kun vesi poistetaan kuitususpensiosta, nollakuidut, sideainehiuk-35 kaset, flokit ym. sitoutuvat enenevässä määrin sellukuitu- 3 90573 rainaan, mikä merkitsee suurempaa saantoa, nopeampaa vedenpoistoa ja puhtaampaa jätevettä. Jäteveden puhdistuksessa on voitu havaita, että keksintöä sovellettaessa nol-lakuidut, sideainehiukkaset, täyteaineet, pigmentit, lig-5 niini ja hemiselluloosa agglomeroituvat huomattavasti suuremmassa määrin kuin ennen flokeiksi. Flokit ovat hyvin pysyviä ja ne on helppo poistaa sedimentoinnin, vaahdotuk-sen tai sentrifugoinnin jälkeen.It has now been found that retention and purification can be improved if, in addition to formaldehyde resin and high molecular weight polyethylene oxide, a cationic starch derivative or a cationic cellulose derivative is added to the fiber suspension or wastewater. The presence of a cationic starch derivative has been shown to improve the "traceability" of zero fibers and flocculated material present or formed during processing. When water is removed from the fiber suspension, zero fibers, binder particles, flocs, etc. become increasingly bound to the pulp fiber web, which means higher yields, faster dewatering, and cleaner wastewater. In wastewater treatment, it has been found that in the application of the invention, the zero fibers, binder particles, fillers, pigments, lig-5ine and hemicellulose agglomerate to a much greater extent than before into flocs. The flocs are very stable and easy to remove after sedimentation, flotation or centrifugation.
Keksinnön mukaisessa tavassa käyttökelpoisen suu-j^q rimolekyylisen polyeteenioksidin molekyylipainon on oltava yli 500 000 ja mieluiten yli 2 000 000. Mitään kriittistä ylärajaa ei ole voitu havaita ja siten on hyviä tuloksia saavutettu polyeteenioksidilla, jonka molekyylipaino on 12 000 000. Huomattavasti suurempien molekyylipainojen ^5 saavuttaminen on osoittautunut vaikeaksi valmistuksessa tapahtuvan ketjunlyhenemisen vuoksi. Keksinnön mukainen polyeteenioksidi rakentuu suurimmaksi osaksi oksieteeni-ryhmistä, mutta siinä voi olla pienehkö määrä muita ryhmiä/ esim. oksipropeeniryhmiä. Muiden kuin oksieteeniryh-2Q mien määrää rajoittaa ehto, että polyeteenioksidin on oltava vesiliukoinen.The molecular weight of the oral polyethylene oxide useful in the process of the invention should be greater than 500,000 and preferably greater than 2,000,000. No critical upper limit could be observed and thus good results have been obtained with polyethylene oxide having a molecular weight of 12,000,000. 5 has proved difficult to achieve due to chain shortening in manufacturing. The polyethylene oxide according to the invention is composed mainly of oxyethylene groups, but may have a smaller number of other groups / e.g. oxypropylene groups. The number of non-oxyethylene groups is limited by the condition that the polyethylene oxide must be water-soluble.
Keksinnön mukainen fenoliformaldehydihartsi on suhteellisen vesiliukoinen, joskin voidaan käyttää hartseja, joiden liukoisuus on rajallinen neutraaleissa tai emäksi-25 sissä pH-arvoissa. Hartsi saostuu yleensä happamissa pH-arvoissa.The phenol formaldehyde resin of the invention is relatively water soluble, although resins with limited solubility at neutral or basic pH values may be used. The resin usually precipitates at acidic pH values.
Keksinnön mukaisesti käytettävänä kationisena tärkkelys johdannaisena on edullisesti peruna-, maissi- tai vehnätärkkelys, joka on substituoitu kvartaarisilla ammo-3Q niumryhmillä. Substituutioaste on edullisesti 0,01-0,1.The cationic starch derivative used according to the invention is preferably potato, corn or wheat starch substituted with quaternary ammonium groups. The degree of substitution is preferably 0.01 to 0.1.
Kationisesta selluloosajohdannaisesta tulee modifioimalla vesiliukoinen. Kationisen selluloosajohdannaisen on oltava vesiliukoinen ja se voi edellä mainittujen kationisten ryhmien lisäksi sisältää myös alempi-alkyyliryhmiä kuten 35 metyyli- tai etyyliryhmiä sekä alempi-hydroksialkyyliryhmiä 4 90573 kuten hydroksietyyli-, hydroksipropyyli- ja hydroksibutyy-liryhmiä. Selluloosajohdannaisen kationisten ryhmien, edullisesti kvartaaristen ammoniumryhmien sopiva substi-tuutioaste on 0,01-0,5 anhydroglukoosiyksikköä kohti ja 5 molekyylipaino noin 10 000 - noin 1 000 000.The cationic cellulose derivative becomes water-soluble by modification. The cationic cellulose derivative must be water-soluble and may contain, in addition to the above-mentioned cationic groups, lower alkyl groups such as methyl or ethyl groups and lower hydroxyalkyl groups such as hydroxyethyl, hydroxypropyl and hydroxybutyl groups. A suitable degree of substitution of the cationic groups of the cellulose derivative, preferably the quaternary ammonium groups, is 0.01 to 0.5 per anhydroglucose unit and the molecular weight is from about 10,000 to about 1,000,000.
Fenoliformaldehydihartsin, polyeteenioksidin ja ka-tionisen tärkkelysjohdannaisen tai kationisen selluloosa-johdannaisen määrät eivät ole kriittisiä. Lisäysmäärä sovitetaan edullisesti nollakuitujen, täyteaineiden, side-X0 aineiden, pigmenttien, ligniinin ja hemiselluloosan määrän ja tyypin mukaan. Fenoliformaldehydihartsimäärä on normaalisti yli 1, edullisesti yli 5 ppm, polyeteenioksidin määrä on yli 0,1 ppm, edullisesti yli 1 ppm ja kationisen tärkkelysjohdannaisen määrä yli 1, edullisesti yli 5 ppm 15 jätevedestä laskettuna. Sopivat ylärajat ovat vastaavasti noin 100, 20 ja 200 ppm jätevedestä laskettuna. Reten-tiolle edulliset lisäysmäärät ovat 0,01-0,5 paino-% feno-liformaldehydihartsia, 0,001-0,1 paino-% polyeteenioksi-dia ja 0,01-1,0 paino-% kationista tärkkelysjohdannaista 20 tai kationista selluloosajohdannaista suspension sisältämistä aineksista laskettuna. Fenoliformaldehydin ja polyeteenioksidin suhde on edullisesti 1:5 - 50:1 ja kationisen tärkkelysjohdannaisen tai kationisen selluloosajohdannaisen ja polyeteenioksidin suhde on ».«dull isosti 1:5 -25 100:1 riippumatta siitä, käytetäänkö komponentteja veden- puhdistukseen vaiko retentioon.The amounts of phenol formaldehyde resin, polyethylene oxide and cationic starch derivative or cationic cellulose derivative are not critical. The amount of addition is preferably adjusted according to the amount and type of zero fibers, fillers, binders-X0 substances, pigments, lignin and hemicellulose. The amount of phenol formaldehyde resin is normally more than 1, preferably more than 5 ppm, the amount of polyethylene oxide is more than 0.1 ppm, preferably more than 1 ppm and the amount of cationic starch derivative is more than 1, preferably more than 5 ppm based on wastewater. Suitable upper limits are about 100, 20 and 200 ppm of wastewater, respectively. Preferred addition amounts for retention are 0.01 to 0.5% by weight of phenol-liformaldehyde resin, 0.001 to 0.1% by weight of polyethylene oxide and 0.01 to 1.0% by weight of cationic starch derivative 20 or cationic cellulose derivative contained in the suspension. calculated on the basis of the ingredients. The ratio of phenol formaldehyde to polyethylene oxide is preferably 1: 5 to 50: 1 and the ratio of cationic starch derivative or cationic cellulose derivative to polyethylene oxide is preferably 1: 5 to 25 to 100: 1, regardless of whether the components are used for water purification or retention.
Kolmea keksinnön mukaista komponenttia voidaan lisätä mielivaltaisessa järjestyksessä. Kationinen tärkkelys johdannainen ja kationinen selluloosajohdannainen voi-30 daan esim. lisätä ensin, ja sitten fenolitormaldehydi- hartsi ja polyeteenioksidi mainitussa järjestyksessä. Voidaan myös toimia siten, että ensin lisätään fenoliform-aldehydihartsi ja sitten polyeteenioksidin ja kationisen tärkkelysjohdannaisen tai kationisen selluloosajohdannai-35 sen muodostama seos.The three components of the invention may be added in any order. The cationic starch derivative and the cationic cellulose derivative may be added, for example, first, and then the phenol tormaldehyde resin and the polyethylene oxide, respectively. It is also possible to proceed by first adding a phenol formaldehyde resin and then a mixture of polyethylene oxide and a cationic starch derivative or a cationic cellulose derivative.
5 905^35,905 ^ 3
Seuraavat toteutusesimerkit selventävät keksintöä ja niiden tehtävänä ei ole rajoittaa keksinnön piiriä.The following embodiments illustrate the invention and are not intended to limit the scope of the invention.
Esimerkki 1Example 1
Lasiastiaan kaadettiin 800 ml jätevettä, joka muo-5 dostui CTMP-valmistuksessa ja kartonginvalmistuksessa syntyneiden jätevesien seoksesta. Jäteveden pH oli 6,5 ja kuiva-ainepitoisuus 2,5 g per litra. Jätevettä sekoitettiin nopeudella 500 kierr/min ja lisättiin polyelektro-lyytti. Kun oli sekoitettu yksi minuutti, lisättiin feno-10 liformaldehydihartsi ja yhden lisäminuutin kuluttua lisättiin suurimolekyylinen eteenioksidiaddukti samalla sekoittaen nopeudella 500 kierr/min. Kun viimeisestä lisäyksestä oli kulunut 10 sekuntia, sekoitusnopeus pienennettiin arvoon 100 kierr/min ja kun oli vielä kulunut 50 se-15 kuntia, sekoitus lopetettiin. Jätevedessä muodostuneet flokit saivat sitten laskeutua ja sitten kirkkaasta faasista otettiin näytteitä ja sameus mitattiin nefelometri-sesti. Lisätyt kemikaalit, niiden määrät ja saavutettu selkeytys ilmenevät taulukosta 1.800 ml of wastewater formed from a mixture of effluents from CTMP and board production was poured into a glass vessel. The pH of the wastewater was 6.5 and the dry matter content was 2.5 g per liter. The effluent was stirred at 500 rpm and a polyelectrolyte was added. After stirring for one minute, pheno-10 liformaldehyde resin was added, and after one additional minute, a high molecular weight ethylene oxide adduct was added with stirring at 500 rpm. After 10 seconds from the last addition, the stirring speed was reduced to 100 rpm and after another 50 se-15 cycles, stirring was stopped. The flocs formed in the effluent were then allowed to settle and then the clear phase was sampled and turbidity was measured nephelometrically. The chemicals added, their amounts and the clarification achieved are shown in Table 1.
20 Tuloksista käy ilmi, että keksinnön mukaisissa ko keissa 2 ja 3 saavutettiin huomattavasti parempi selkeytys kuin kokeessa 1, joka on kanadalaisen patentin CA 1 004 782 mukainen. Kokeeseen 1 verrattuna muiden po-lyelektrolyyttien kuin kationisen tärkkelysjohdannaisen 25 lisääminen ei parantanut tuloksia.It appears from the results that Experiments 2 and 3 of the invention achieved significantly better clarification than Experiment 1, which is in accordance with Canadian Patent CA 1,004,782. Compared to Experiment 1, the addition of polyelectrolytes other than the cationic starch derivative 25 did not improve the results.
Esimerkki 2 Jätevesi, joka saatiin valkaisemattoman keräyspaperin pesusiistausvaiheesta, puhdistettiin 25°C:ssa samalla tavoin kuin esimerkissä 1. Jäteveden kuiva-ainepitoisuus 30 oli 2,5 g/1 ja pH-arvo 7. Lisätyt kemikaalit, niiden määrät ja tulokset ilmenevät taulukosta 1.Example 2 Wastewater obtained from the bleaching step of unbleached recovered paper was purified at 25 ° C in the same manner as in Example 1. The wastewater had a dry matter content of 2.5 g / l and a pH of 7. The added chemicals, their amounts and results are shown in Table 1. .
Tuloksista käy ilmi, että keksinnön mukaisen kationisen tärkkelysjohdannaisen tai kationisen selluloosajoh-dannaisen lisääminen aikaansaa huomattavasti paremman puh-35 distumisen kuin tavanomainen fenoliformaldehydihartsin ja suurimolekyylisen polyeteenioksidin yhdistelmä. Mitään pa- 6 90573 rantumista ei tapahtunut yhdistelmillä, jotka sisälsivät fenoliformaldehydihartsia ja suurimolekyylistä poly-eteenioksidia ja muita polyelektrolyyttejä.The results show that the addition of the cationic starch derivative or the cationic cellulose derivative according to the invention provides a significantly better purification than the conventional combination of phenol formaldehyde resin and high molecular weight polyethylene oxide. No improvement occurred with combinations containing phenol-formaldehyde resin and high molecular weight polyethylene oxide and other polyelectrolytes.
Esimerkki 3 5 Jätevesi, joka saatiin valkaistun keräyspaperin pesusiistausvaiheesta, puhdistettiin 25°C:ssa samalla tavoin kuin esimerkissä 1. Jäteveden kuiva-ainepitoisuus oli 4,4 g per litra ja pH-arvo 8. Lisätyt kemikaalit, niiden määrät ja tulokset ilmenevät taulukosta 3. Tuloksista 10 käy ilmi, että keksinnön mukaisissa kokeissa saavutettiin huomattavasta parempi puhdistuminen kuin käytettäessä pelkkää fenoliformaldehydihartsia tai suurimolekyylistä polyeteenioksidia tai näiden yhdistelmää.Example 3 5 The effluent from the bleached recovered paper scrubbing step was purified at 25 ° C in the same manner as in Example 1. The effluent had a dry matter content of 4.4 g per liter and a pH of 8. The chemicals added, their amounts and results are shown in Table 3. It appears from the results 10 that the experiments according to the invention achieved a significantly better purification than the use of phenol-formaldehyde resin alone or high molecular weight polyethylene oxide or a combination thereof.
Esimerkki 4 15 Massasuspensiolla, jonka sellukuitukonsentraatio oli 0,55 paino-% ja pH-arvo 7, suoritettiin retentiokokei-ta 35°C:ssa. Sellukuidun koostumus oli 60 % pesusiistat-tua massaa, 30 % sulfaattimassahylkyä ja 10 % valkaistua sulfaattimassaa. Retentiokokeet suoritettiin Brittin mu-20 kaan. Ks TAPPI 56(10), 46(1973). Lisätyt kemikaalit, niiden määrät ja tulokset ilmenevät alla olevasta taulukosta. Tuloksista käy ilmi, että tulokset keksinnön mukaisesti suoritetussa retentiossa olivat olennaisesti paremmat kuin vertailukokeissa.Example 4 Retention tests were performed on a pulp suspension having a pulp fiber concentration of 0.55% by weight and a pH of 7 at 35 ° C. The composition of the pulp fiber was 60% scrubbed pulp, 30% sulfate scrap and 10% bleached sulfate pulp. Retention experiments were performed according to Britt-20. See TAPPI 56 (10), 46 (1973). The chemicals added, their amounts and results are shown in the table below. The results show that the results in the retention according to the invention were substantially better than in the comparative experiments.
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Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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SE8604975 | 1986-11-21 | ||
SE8604975A SE454507B (en) | 1986-11-21 | 1986-11-21 | PUT IN THE PAPER, MASS OR BOARD INDUSTRIES IMPROVE RETENTION OR CELLULOSA FIBER SUSPENSION RESP RESP |
Publications (4)
Publication Number | Publication Date |
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FI875123A0 FI875123A0 (en) | 1987-11-19 |
FI875123A FI875123A (en) | 1988-05-22 |
FI90573B true FI90573B (en) | 1993-11-15 |
FI90573C FI90573C (en) | 1994-02-25 |
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Application Number | Title | Priority Date | Filing Date |
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FI875123A FI90573C (en) | 1986-11-21 | 1987-11-19 | A way to improve the retention or treatment of pulp fiber suspensions or wastewater in the paper, pulp or board industry |
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FI (1) | FI90573C (en) |
NO (1) | NO166456C (en) |
SE (1) | SE454507B (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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US5230808A (en) * | 1991-06-17 | 1993-07-27 | Nalco Canada Inc. | Liquid suspension of polyethylene oxide for use in treating paper and pulp wastewater |
US5173208A (en) * | 1991-06-17 | 1992-12-22 | Nalco Canada Inc. | Liquid suspension of polyethylene oxide for use in treating paper and pulp wastewater |
US5178770A (en) * | 1991-07-12 | 1993-01-12 | Nalco Canada Inc. | Method of treating bctmp/ctmp wastewater |
US5670021A (en) * | 1992-01-29 | 1997-09-23 | Kemira Kemi Aktiebolag | Process for production of paper |
SE500783C2 (en) * | 1992-05-05 | 1994-09-05 | Eka Nobel Ab | Ways to clean wood resin-containing process or wastewater |
SE509777C2 (en) * | 1997-07-07 | 1999-03-08 | Kemira Kemi Ab | Methods to improve retention in dewatering a cellulose fiber suspension using an agent comprising a phenol formaldehyde resin and a polyethylene oxide |
GB9800497D0 (en) * | 1998-01-09 | 1998-03-04 | Allied Colloids Ltd | Dewatering of sludges |
-
1986
- 1986-11-21 SE SE8604975A patent/SE454507B/en not_active IP Right Cessation
-
1987
- 1987-11-19 FI FI875123A patent/FI90573C/en not_active IP Right Cessation
- 1987-11-19 NO NO874840A patent/NO166456C/en not_active IP Right Cessation
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NO166456B (en) | 1991-04-15 |
NO874840D0 (en) | 1987-11-19 |
NO874840L (en) | 1988-05-24 |
FI875123A0 (en) | 1987-11-19 |
NO166456C (en) | 1991-07-24 |
FI875123A (en) | 1988-05-22 |
SE8604975D0 (en) | 1986-11-21 |
FI90573C (en) | 1994-02-25 |
SE454507B (en) | 1988-05-09 |
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