NO160666B - PROCEDURE FOR PREPARING PAPER WITH HIGH DEFINITION - Google Patents
PROCEDURE FOR PREPARING PAPER WITH HIGH DEFINITION Download PDFInfo
- Publication number
- NO160666B NO160666B NO813548A NO813548A NO160666B NO 160666 B NO160666 B NO 160666B NO 813548 A NO813548 A NO 813548A NO 813548 A NO813548 A NO 813548A NO 160666 B NO160666 B NO 160666B
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- Norway
- Prior art keywords
- melamine
- paper
- mixing
- solution
- formaldehyde
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 33
- 239000000084 colloidal system Substances 0.000 claims abstract description 27
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229920001131 Pulp (paper) Polymers 0.000 claims description 14
- 150000007974 melamines Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- -1 ammonia Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000010198 maturation time Effects 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- 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
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
- D21H17/51—Triazines, e.g. melamine
-
- 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
- D21H21/14—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 characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Replacement Of Web Rolls (AREA)
Abstract
Description
Det har lenge vært kjent å tilsette kolloidale vandige løsninger av melamin-formaldehyd-harpikser som fremstilles ved oppløsning av et eventuelt modifisert metylolmelamin i vandig syre og aldring av den dannede løsning, til papirmassen for oppnåelse av høyere papir-våtfasthet. Harpikskolloid-oppløs-ningenes pH-verdi ligger i området 0,5-5, og faststoff-innhol-det er maksimalt 15 vekt%. Ved høyere faststoffinnhold blir harpikskolloid - oppløsningene ustabile. It has long been known to add colloidal aqueous solutions of melamine-formaldehyde resins, which are produced by dissolving any modified methylolmelamine in aqueous acid and aging the resulting solution, to the paper pulp to achieve higher paper wet strength. The pH value of the resin colloid solutions is in the range 0.5-5, and the solids content is a maximum of 15% by weight. At higher solids content, the resin colloid solutions become unstable.
Fra DE-utlegningsskrift 10 90 078 er det kjent å forbedre melamin-formaldehyd-harpikskolloiders virkning ved tilsetning av formaldehyd og påfølgende aldring av de erholdte løsninger. Man tar derved sikte på å oppnå en forhøyelse av papirets våtfasthet. Ved de hittil kjente fremgangsmåter til fremstilling av melamin-formaldehyd-harpikskolloider er det nødvendig å la løsningene etter tilsetning av en syre aldres en bestemt tid, From DE specification 10 90 078 it is known to improve the effect of melamine-formaldehyde resin colloids by adding formaldehyde and subsequent aging of the solutions obtained. The aim is thereby to achieve an increase in the wet strength of the paper. In the hitherto known methods for the production of melamine-formaldehyde resin colloids, it is necessary to allow the solutions to age for a certain time after adding an acid,
i regelen 3-12 timer, før løsningene kan anvendes som våtfast-hetsmidler ved papirfremstillingen. For å aldre de surgjorte melamin-formaldehyd-harpikskolloider trenger man i praksis lagertanker. Ved den diskontinuerlige fremstilling av melamin-formaldehyd-harpikskolloider er man dessuten alltid tvunget til å inngå et kompromiss mellom virkningen av harpikskolloidene og de kolloidale løsningers lagrings-stabilitet. Forsøker man eksempelvis å nedsette modningstiden ved å forandre pH-verdien eller temperaturen, så vil den modnede løsnings virkeevne avta etter kort tid. as a rule 3-12 hours, before the solutions can be used as wet strength agents in paper production. In order to age the acidified melamine-formaldehyde-resin colloids, storage tanks are needed in practice. In the discontinuous production of melamine-formaldehyde resin colloids, one is also always forced to enter into a compromise between the effect of the resin colloids and the storage stability of the colloidal solutions. If, for example, you try to reduce the maturation time by changing the pH value or the temperature, the effectiveness of the matured solution will decrease after a short time.
Den foreliggende oppfinnelse tar således sikte på å til-veiebringe en fremgangsmåte til fremstilling av papir med høy våtfasthet ved tilsetning av melamin-formaldehyd-harpikskolloider til papirmassen og avvanning av papirmassen i papirmaskinen, ved hvilken man ikke er tvunget til å aldre melamin-formaldehyd-harpikskolloidene over lengre tid, slik at lagertanker bortfal-ler, og ved hvilken man lett kan innstille harpikskolloid-opp-løsningenes virkeevne. The present invention thus aims to provide a method for the production of paper with high wet strength by adding melamine-formaldehyde resin colloids to the paper pulp and dewatering the paper pulp in the paper machine, in which one is not forced to age the melamine-formaldehyde- the resin colloids over a longer period of time, so that storage tanks disappear, and by which one can easily adjust the effectiveness of the resin colloid solutions.
Fremgangsmåten-.ifølge oppfinnelsen går ut på at det som melamin-formaldehyd-harpikskolloider anvendes et produkt som er fremstilt ved kontinuerlig blanding av en 40-80-prosentig vandig løsning av et eventuelt modifisert melamin med vann og syre i en blandesone under anvendelse av turbulent strømning, The method according to the invention involves using as melamine-formaldehyde resin colloids a product which is produced by continuously mixing a 40-80 percent aqueous solution of a possibly modified melamine with water and acid in a mixing zone using turbulent flow,
en temperatur på 40-110°C, en pH-verdi på 2-4 og en oppholdstid a temperature of 40-110°C, a pH value of 2-4 and a residence time
mellom blandesonen og tilsatsstedet til papirmassen på 1-300 sekunder, hvorved faststoffinnholdet i melamin-formaldehyd-harpikskolloid-løsningen utgjør 5-20 vekt%. between the mixing zone and the point of addition to the paper pulp in 1-300 seconds, whereby the solids content in the melamine-formaldehyde-resin colloid solution amounts to 5-20% by weight.
Da det i henhold til fremgangsmåten ifølge oppfinnelsen anvendes høykonsentrerte, eventuelt modifiserte melaminoppløs-ninger, fortrinnsvis 60-70 prosents vandige løsninger, oppnår man i forhold til kjente fremgangsmåter en avgjørende nedset-telse i transportomkostninger. For fremstilling av harpikskolloid-oppløsningene kommer alle hittil herfor anvendte metylolmelaminer såvel som modifiserte metylolmelaminer i betraktning. Fortrinnsvis anvender man slike metylolmelaminer ved hvilke molforholdet. mellom melamin og formaldehyd er 1:2 til 1:6. Fremstillingen av vandige løsninger av metylolmelaminer og de tilsvarende modifiserte metylolmelaminer er kjent. Van-ligvis oppvarnter man for fremstilling av metylolmelaminer en As, in accordance with the method according to the invention, highly concentrated, possibly modified melamine solutions are used, preferably 60-70 percent aqueous solutions, compared to known methods, a decisive reduction in transport costs is achieved. For the production of the resin colloid solutions, all previously used methylol melamines as well as modified methylol melamines are taken into consideration. Such methylolmelamines are preferably used in which the molar ratio. between melamine and formaldehyde is 1:2 to 1:6. The production of aqueous solutions of methylolmelamines and the corresponding modified methylolmelamines is known. A warning is usually given for the production of methylolmelamines
•vandig løsning av melamin til temperaturer mellom 70 og 95°C •aqueous solution of melamine at temperatures between 70 and 95°C
og tilsetter formaldehyd, eksempelvis formalin eller paraform-aldehyd. Reaksjonsblandingens pH-verdi blir i regelen innstilt på verdier mellom 7,5 og 11. MetyloImelaminene er, som kjent, stabile i det alkaliske pH-område. Dé kan meget lett foretres med alkoholer i det sure pH-område. Fortrinnsvis anvender man for foretringen metanol, etanol og n- eller iso-propanol eller and adds formaldehyde, for example formalin or paraformaldehyde. As a rule, the pH value of the reaction mixture is set to values between 7.5 and 11. Methylomelamines are, as is known, stable in the alkaline pH range. It can very easily be etherified with alcohols in the acidic pH range. Preferably, methanol, ethanol and n- or iso-propanol or are used for the etherification
n- eller iso-butanol. Spesielt enkel og derfor også foretrukket er foretringen med metanol. Det er mulig å foretre metylol-melaminene delvis eller fullstendig. De herved dannede produk-ter kan inneholde 1-6, fortrinnsvis 2-5, etergrupperinger. Etter foretringen blir pH-verdien av den vandige løsning innstilt på verdier over 7, slik at kondensasjon forebygges. De eventuelt foretrede metylolmelaminer fremstilles med høy konsentrasjon, eksempelvis som 40-80-prosents vandig løsning. De kan også fremstilles ved oppkonsentrering av fortynnede løsninger. De høykonsentrerte modifiserte metylolmelamin-oppløsninger kan også modifiseres med alkalisulfitter, alkalibisulfitter eller med aminer. Molforholdet mellom metylolmelamin og sulfitt henholdsvis bisulfitt ligger fortrinnsvis i et område på 1:0,5 til 1:5. Som aminer kommer hovedsakelig ammoniakk, primære og sekundære alkylaminer, di- og polyaminer såvel som eksempelvis mono-, di- og trietanolamin, i betraktning. Molforholdet mellom metylolmelamin og amin ligger her fortrinnsvis i et område på n- or iso-butanol. Particularly simple and therefore also preferred is the etherification with methanol. It is possible to partially or completely etherify the methylol melamines. The products thus formed may contain 1-6, preferably 2-5, ether groupings. After the etherification, the pH value of the aqueous solution is set to values above 7, so that condensation is prevented. The optionally etherified methylolmelamines are produced with a high concentration, for example as a 40-80 percent aqueous solution. They can also be produced by concentrating dilute solutions. The highly concentrated modified methylolmelamine solutions can also be modified with alkali sulfites, alkali bisulfites or with amines. The molar ratio between methylolmelamine and sulphite or bisulphite is preferably in a range of 1:0.5 to 1:5. As amines, mainly ammonia, primary and secondary alkylamines, di- and polyamines as well as, for example, mono-, di- and triethanolamine, come into consideration. Here, the molar ratio between methylolmelamine and amine is preferably in a range of
1:0,5 til 1:5. 1:0.5 to 1:5.
Den konsentrerte vandige løsning av det eventuelt modifiserte metylolmelamin blandes kontinuerlig i en blandesone ved tilsetning av vann og en syre - hvor en reaksjonspartner allerede på forhånd kan være tilblandet vannet - ved en temperatur på 40-110°C, fortrinnsvis 70-90°C, slik at polykondensasjonen av det eventuelt modifiserte metylolmelamin forløper på meget kort tid i en etter-tilkoblet oppholdstid-beholder som også gjennomstrømmes kontinuerlig. Ved temperaturer over 100°C må trykkapparatur anvendes. The concentrated aqueous solution of the possibly modified methylolmelamine is continuously mixed in a mixing zone by adding water and an acid - where a reaction partner can already be mixed with the water in advance - at a temperature of 40-110°C, preferably 70-90°C, so that the polycondensation of the optionally modified methylolmelamine takes place in a very short time in a subsequently connected residence time container which is also continuously flowed through. At temperatures above 100°C, pressure equipment must be used.
Ved den kontinuerlige blanding av de to reaksjonspartnere - eller bare den ene reaksjonspartner, fortrinnsvis syren, når den ene av disse allerede på forhånd er tilblandet vannet - By the continuous mixing of the two reaction partners - or only one reaction partner, preferably the acid, when one of these has already been mixed with the water in advance -
må en homogen løsning, uten konsentrasjons-gradienter, fremstilles på meget kort tid, da det eventuelt modifiserte metylolmelamin på grunn av den høye reaksjons-akselerasjon i området for lave syrekonsentrasjoner ellers vil polymeriseres til en uløselig harpiks i løpet av få sekunder. a homogeneous solution, without concentration gradients, must be prepared in a very short time, as the potentially modified methylolmelamine will otherwise polymerize into an insoluble resin within a few seconds due to the high reaction acceleration in the area of low acid concentrations.
Blandingen utføres derfor i blandeutstyr med lite blande-volum. Blandingskomponentene gjennomløper blandesonen med høy turbulent strømning. Under disse betingelser virker høye energitettheter på de komponenter som skal blandes med hver-andre. For fremgangsmåten ifølge oppfinnelsen er eksempelvis følgende vanlige blandeinnretninger egnet: a) Stråleblandere - Blanding med en hurtig væskestråle; herfor anvendes fortrinnsvis vannet eller den vandige, The mixing is therefore carried out in mixing equipment with a small mixing volume. The mixing components pass through the mixing zone with high turbulent flow. Under these conditions, high energy densities act on the components to be mixed with each other. For the method according to the invention, for example, the following common mixing devices are suitable: a) Jet mixers - Mixing with a fast liquid jet; for this, the water or the watery one is preferably used,
eventuelt modifiserte metylolmelamin-løsning, possibly modified methylolmelamine solution,
b) In-line-miksere (propellblander innbygget i en rørledning), b) In-line mixers (propeller mixer built into a pipeline),
c) Statiske blandere og c) Static mixers and
d) Rotor - stator - blandere. d) Rotor - stator - mixers.
Fortrinnsvis utføres blandingen av reaksjonskomponentene Preferably, the mixing of the reaction components is carried out
med- vannet i en stråleblander som rager inn i et etter-tilkoblet with the water in a jet mixer that projects into a downstream
. oppholdstidsrom - utført som reaksjonsrør eller -beholder. . residence time space - designed as a reaction tube or container.
For tilførsel av den nødvendige blandeenergi til stråleblanderen anvendes vannet, fortrinnsvis den med vannet for-blandede, eventuelt modifiserte metylolmelamin-oppløsning, To supply the necessary mixing energy to the jet mixer, water is used, preferably the water-premixed, optionally modified methylolmelamine solution,
idet det tilføres som drivstråle med turbulent strømning ved as it is supplied as a driving jet with turbulent flow at
hastigheter på 5-50 m/s, fortrinnsvis 10-20 m/s, gjennom stråle-blanderens dyse. Energitettheten i blandesonen utgjør fortrinns--vis minst 20 kW/m 3 , mer foretrukket over 50 kW/m 3. speeds of 5-50 m/s, preferably 10-20 m/s, through the nozzle of the jet mixer. The energy density in the mixing zone is preferably at least 20 kW/m 3 , more preferably over 50 kW/m 3 .
Harpiksløsningen kan, når den ikke allerede er forhånds-blandet med vannet, i likhet med den syre som behøves for opp-starting av kondensasjons-reaksjonen, tilføres såvel gjennom dysen - som i dette tilfelle er utformet som flerstoffdyse - som med separate tilførselsrør ved siden av dysen eller til side for blanderøret i høyde med dysen. The resin solution, when it has not already been pre-mixed with the water, like the acid needed to start the condensation reaction, can be supplied both through the nozzle - which in this case is designed as a multi-material nozzle - and with separate supply pipes on the side of the nozzle or to the side for the mixing pipe at the height of the nozzle.
Gjennom impulsutveksling mellom drivstrålen og den reak-sjonsløsning som omgir denne, bevirkes en hurtig og intensiv blandevirkning i hele det som rør utformede blanderom. Dia-meterforholdene mellom drør og d<3riVstrå;Le er 2-20, fortrinnsvis 3-6; forholdet mellom lengden av røret og rørets diameter er lrør</d>rør = 5-20. Through impulse exchange between the drive jet and the reaction solution that surrounds it, a rapid and intensive mixing effect is produced throughout the tube-shaped mixing chamber. The diameter ratio between tube and d<3riVstra;Le is 2-20, preferably 3-6; the ratio between the length of the pipe and the diameter of the pipe is lpipe</d>pipe = 5-20.
Komponentene forlater røret homogent blandet. På grunn av den korte blandetid og den med blandeinnretningene tilførte høye energitetthet på 50-7000, fortrinnsvis 50-2000 kW/m 3, er det mulig å forkorte den nødvendige reaksjonstid frem til op-timal modning ved innstilling av egnede reaksjonsbetingelser {pH på 3-4, temperatur på 40-110°C) til 1-300 sekunder, uten forstyrrelser på grunn av flokkulering ved for langt fremskre-det kondensasjon eller på grunn av tap av virkeevne ved for kort oppholdstid. The components leave the tube homogeneously mixed. Due to the short mixing time and the high energy density of 50-7000, preferably 50-2000 kW/m 3 supplied with the mixing devices, it is possible to shorten the necessary reaction time until optimal ripening by setting suitable reaction conditions {pH of 3 -4, temperature of 40-110°C) for 1-300 seconds, without disturbances due to flocculation due to too far-advanced condensation or due to loss of effectiveness due to too short a residence time.
Modningen - polykondensasjon av det eventuelt modifiserte metylolamin - skjer i blandesonen såvel som i det etter-tilkoblede oppholdstid-rom, fortrinnsvis i et med stråleblanderen integrert og turbulent gjennomstrømmet reaksjonsrør. Etter å ha forlatt blandeinnretningen gjennomstrømmer den homogent blan-dede løsning - uavhengig av den anvendte blandeinnretning - The maturation - polycondensation of the possibly modified methylolamine - takes place in the mixing zone as well as in the subsequent residence time space, preferably in a reaction tube integrated with the jet mixer and turbulently flowed through. After leaving the mixing device, the homogeneously mixed solution flows through - regardless of the mixing device used -
et rør eller dessuten en beholder i hvilken den ønskede oppholdstid oppnås. DenN-nødvendige oppholdstid utgjør alt etter reaksjonsbetingelsene (temperatur, pH-verdi, konsentrasjon og arten av det eventuelt modifiserte metylolmelamin) fra noen ' sekunder til flere minutter, fortrinnsvis 15 sekunder til 1 mi-nutt. a tube or furthermore a container in which the desired residence time is achieved. Depending on the reaction conditions (temperature, pH value, concentration and the nature of the possibly modified methylolmelamine), the necessary residence time is from a few seconds to several minutes, preferably 15 seconds to 1 minute.
For å innstille den. nødvendige temperatur under blandeoperasjonen kan man enten på forhånd oppvarme alle de komponenter som skal blandes, til denne temperatur, eller man oppvarmer bare det for fortynning anvendte vann og da til en høyere temperatur, slik at temperaturen under blandeoperasjonen ligger i det angitte område. Dette kan eksempelvis skje ved at damp ledes inn i fortynningsvannet. To set it. required temperature during the mixing operation, you can either pre-heat all the components to be mixed to this temperature, or you only heat the water used for dilution and then to a higher temperature, so that the temperature during the mixing operation is in the specified range. This can happen, for example, by introducing steam into the dilution water.
Som syrer anvender man fortrinnsvis saltsyre og fosforsyre eller karboksylsyrer, såsom maursyre, eddiksyre og propion-syre. As acids, hydrochloric acid and phosphoric acid or carboxylic acids, such as formic acid, acetic acid and propionic acid, are preferably used.
Det oppnås en meget effektiv melamin-f ormaldehyd-hairpiks-kolloid-oppløsning med et faststoffinnhold på 5-20 vekt%. hvilken doseres direkte til papirmassen eller tilsettes papir-masse-suspensjonen etter en ytterligere kontinuerlig eller diskontinuerlig fortynning med vann i vektforholdet 1:10 til 1:20. De således fremstilte kolloidoppløsninger er effektive og anvendes fortrinnsvis direkte etter utløp fra blandeappara-turen. De kan også lagres noen timer; etter lengre tid avtar imidlertid deres effektivitet som våtstyrkeforbedrende midler. A very effective melamine-formaldehyde-hairpinx colloid solution is obtained with a solids content of 5-20% by weight. which is dosed directly to the paper pulp or added to the paper-pulp suspension after a further continuous or discontinuous dilution with water in a weight ratio of 1:10 to 1:20. The colloid solutions produced in this way are effective and are preferably used directly after discharge from the mixing apparatus. They can also be stored for a few hours; however, over time their effectiveness as wet strength improvers decreases.
De i eksemplene angitte deler er vektdeler, og prosent-angivelsene er basert på vekten av stoffene. Tørr-slitlengde ble bestemt i henhold til DIN 53 112, Blatt 1 og våt-slit-lengden i henhold til DIN 53 112, Blatt 2. Papirets lutfast-het ble bestemt etter den arbeidsmåte som er angitt for våt-slitlengden, dog ble de normerte papirstrimler ikke lagret i vann, men i 3% natronlut i 5 minutter ved 80°C. The parts given in the examples are parts by weight, and the percentages are based on the weight of the substances. The dry wear length was determined according to DIN 53 112, Blatt 1 and the wet wear length according to DIN 53 112, Blatt 2. The alkali resistance of the paper was determined according to the working method specified for the wet wear length, however, they were standardized paper strips not stored in water, but in 3% caustic soda for 5 minutes at 80°C.
Fremstilling av en foretret metylolmelamin-oppløsning i Preparation of an etherified methylolmelamine solution i
vann: water:
127 deler (ca. 1 mol) melamin ble blandet med 365 deler av en 37% vandig løsning av formaldehyd (ca. 4,5 mol C^O) . Blandingen innstilles på pH 8,5 med natronlut og oppvarmes 127 parts (approx. 1 mol) of melamine were mixed with 365 parts of a 37% aqueous solution of formaldehyde (approx. 4.5 mol C₂O). The mixture is adjusted to pH 8.5 with caustic soda and heated
til 70°C, inntil det samlede melamin er fullstendig gått i oppløsning. Man lar blandingen etter-reagere i ytterligere 5 minutter ved 70°C pg tilsetter deretter 640 deler (ca. 20 mol) metanol. Med fosforsyre blir nå løsningens pH-verdi innstilt på ca. 4,0, og temperaturen holdes ved 40°C i 30 minutter. Etter forhøyelse av pH-verdien til ca. 7 med natronlut opp-konsentreres løsningen deretter under vakuum (ca. 10 mbar) to 70°C, until the total melamine has completely dissolved. The mixture is left to react for a further 5 minutes at 70°C and 640 parts (approx. 20 mol) of methanol are then added. With phosphoric acid, the solution's pH value is now set to approx. 4.0, and the temperature is maintained at 40°C for 30 minutes. After raising the pH value to approx. 7 with caustic soda, the solution is then concentrated under vacuum (approx. 10 mbar)
ved 60°C til et faststoffinnhold på 70%, hvoretter den kjøles hurtig til 20°C. Den 70%-ige vandige løsning oppviser én vis-kositet på ca. 500 mPas (Brookfield, 20^/min) og er blandbar med vann i alle forhold. at 60°C to a solids content of 70%, after which it is rapidly cooled to 20°C. The 70% aqueous solution has a viscosity of approx. 500 mPas (Brookfield, 20^/min) and is miscible with water in all conditions.
Eksempel 1 Example 1
226 kg/time vann av 80°C og 38,3 kg/time 70%-ig 226 kg/hour of 80°C water and 38.3 kg/hour of 70%
vandig løsning av det ovenfor beskrevne foretrede metylolmelamin bg 3,8 kg/time konsentrert saltsyre (37%) ble, under anvendelse av en. stråleblander bestående av en tostoffdyse med en innvendig diameter på 2 mm og en rihgspalte med en spaltebredde på 1 mm, hvilken raget inn i et blanderør med 100 mm lengde og 20 mm diameter og en anslagsplate i en av-stand på 85 mm fra dysemunningen, blandet kontinuerlig ved at vannet som drivstråle ble tilsatt gjennom dysens indre boring med en strålehastighet på 20 m/s (turbulent strømning). Den foretrede metylolmelamin-oppløsning ble tildosert gjennom ringspalten, og den konsentrerte saltsyre ble tildosert gjennom en stuss anbrakt på blanderørets side i høyde med dysemunningen. - I det rørformede blanderom ble komponentene blandet intensivt og hurtig til en homogen løsning. Blanderommets energitetthet var 4 70 kW/m 3 . . For komplette-ring av polykondensasjonen (modning) var et oppholdstid-rom i form av et reaksjonsrør tilsluttet blanderøret. Reaksjons-røret hadde en innvendig diameter på 10 mm og en lengde på 30 m. Reaksjonsblandingens oppholdstid i blandesonen og det etter-tilkoblede reaksjonsrør frem til tilsetningsstedet til papirmassen var 30 sekunder, temperaturen 75°C og blandingens pH 3,0. - Det erholdtes på denne måte en 10%-ig harpiks-kolloidoppløsning, som tilsvarende en doseringsmengde på 5% harpikskolloid-oppløsning, beregnet på tørt fibermateriale, ble tilsatt direkte til papirmassen i en planviremaskin med en arbeidsbredde på 75 cm. Papirmaskinens arbeidshastighet var 66 m/min. Papiret besto av bleket sulfittmasse og hadde en flatevekt på 60 g/m 2. Massesuspensjonens pH-verdi ble ved tilsetning av 2% aluminiumsulfat og ved tilsetning av fortynnet svovelsyre innstilt på en verdi på 4,5. Malegra-den var 35° SR. Papirmaskinen ble tilført 3 kg/min. av sul-fittmassen. Det erholdte papirs egenskaper'er sammenstillet i Tabell 1. aqueous solution of the above-described etherified methylolmelamine bg 3.8 kg/hour concentrated hydrochloric acid (37%) was, using a. jet mixer consisting of a two-material nozzle with an internal diameter of 2 mm and a vertical slot with a slot width of 1 mm, which protruded into a mixing tube with a length of 100 mm and a diameter of 20 mm and a stop plate at a distance of 85 mm from the nozzle mouth, mixed continuously by the water being added as a driving jet through the inner bore of the nozzle with a jet speed of 20 m/s (turbulent flow). The etherified methylolmelamine solution was dosed through the annular gap, and the concentrated hydrochloric acid was dosed through a spigot placed on the side of the mixing tube at the height of the nozzle mouth. - In the tubular mixing chamber, the components were mixed intensively and quickly into a homogeneous solution. The mixing room's energy density was 4 70 kW/m 3 . . For completion of the polycondensation (ripening), a residence time space in the form of a reaction tube was connected to the mixing tube. The reaction tube had an internal diameter of 10 mm and a length of 30 m. The residence time of the reaction mixture in the mixing zone and the subsequently connected reaction tube until the point of addition to the paper pulp was 30 seconds, the temperature 75°C and the pH of the mixture 3.0. - A 10% resin colloid solution was obtained in this way, which corresponding to a dosage amount of 5% resin colloid solution, calculated on dry fiber material, was added directly to the paper pulp in a planar wire machine with a working width of 75 cm. The paper machine's working speed was 66 m/min. The paper consisted of bleached sulphite pulp and had a basis weight of 60 g/m 2. The pH value of the pulp suspension was adjusted to a value of 4.5 by adding 2% aluminum sulphate and by adding dilute sulfuric acid. The Malegra one was 35° SR. The paper machine was fed at 3 kg/min. of the sulphite mass. The properties of the obtained paper are compiled in Table 1.
Eksempel 2 Example 2
148,3 kg/time vann av 80°C ble sammen med 28,8 kg/time av 70%-ig vandig løsning av det ovenfor beskrevne foretrede 148.3 kg/hour of 80°C water was combined with 28.8 kg/hour of a 70% aqueous solution of the above-described ether
metylolmelamin kontinuerlig tilført sugesiden av en sentrifugal-pumpe, blandet i pumpen og inndyset i en stråleblander gjennom en 1-stoff-dyse med 2 mm boring under anvendelse av en strålehastighet på 15 m/s (turbulent strømning)., tilsvarende en energitetthet på 200 kW/m<3>. 2,8 kg/time konsentrert saltsyre ble tildosert i blanderommet som angitt i/Eksempel 1. Reak-sjonsrøret hadde de samme dimensjoner som i Eksempel 1. Reaksjonsblandingens oppholdstid frem til tilsetningsstedet til papirmassen var 50 sekunder, temperaturen 75°C og blandingens pH-verdi 3,0. methylolmelamine continuously supplied to the suction side of a centrifugal pump, mixed in the pump and injected into a jet mixer through a 1-substance nozzle with a 2 mm bore using a jet velocity of 15 m/s (turbulent flow), corresponding to an energy density of 200 kW/m<3>. 2.8 kg/hour of concentrated hydrochloric acid was dosed into the mixing room as indicated in Example 1. The reaction tube had the same dimensions as in Example 1. The residence time of the reaction mixture until the point of addition to the paper pulp was 50 seconds, the temperature 75°C and the mixture's pH value 3.0.
Av denne 10%-ige harpikskolloid-oppløsning ble det til papirmaskinen, med.samme massetilførsel som i Eksempel 1, tildosert 10%, beregnet på tørt fibermateriale. Egenskapene av det således fremstilte papir er sammenstillet i Tabell 1. Of this 10% resin colloid solution, 10%, calculated on dry fiber material, was dosed to the paper machine, with the same pulp supply as in Example 1. The properties of the paper produced in this way are compiled in Table 1.
Sammenligningseksempel 1 Comparative example 1
84,5 kg vann med en temperatur på 40°C ble oppvarmet i en 250 liters beholder forsynt med oppvarmningsinnretninger og et røreverk. Man holdt temperaturen konstant og tilsatte 1,4 kg konsentrert saltsyre (37%), og etter at en fortynnet syreløs-ning var dannet, tilsattes 14,3 kg av den ovenfor beskrevne 70%-ige vandige løsning av det foretrede metyloIme1amin. For oppnåelse av en grundig blanding av reaksjonspartnerne ble opp-løsningen omrørt under anvendelse av en energitetthet på 0,4 kW/m 3. Den grundige blanding ble fullført på ca. 5 minutter. 84.5 kg of water with a temperature of 40°C was heated in a 250 liter container equipped with heating devices and an agitator. The temperature was kept constant and 1.4 kg of concentrated hydrochloric acid (37%) was added, and after a dilute acid solution had been formed, 14.3 kg of the above-described 70% aqueous solution of the etherified methylimamine was added. To achieve a thorough mixing of the reaction partners, the solution was stirred using an energy density of 0.4 kW/m 3 . The thorough mixing was completed in approx. 5 minutes.
Deretter ble røringen stanset og blandingen aldret i 3 timer ved en temperatur på 40°C. Blandingens pH var 2,2. The stirring was then stopped and the mixture aged for 3 hours at a temperature of 40°C. The pH of the mixture was 2.2.
For utprøvning av melamin-formaldehyd-harpikskolloid-oppløsningen som våtfasthetsforbedrende middel ble harpiks-kolloidet i en mengde på 150 g/min. (tilsvarende 5%), beregnet på.tørt fibermateriale, tilsatt til papirmassen. Massesuspensjonens.pH ble innstilt på 4,5 med 2% aluminiumsulfat og enn videre med fortynnet svovelsyre. Denne massesuspensjon, med en malegrad på 35°SR, ble avvannet på den i Eksempel 1 beskrevne papirmaskin under anvendelse av en hastighet på 66 m/min. Det ble således fremstilt ca. 3 kg/min. av et papir av bleket sulfittmasse med en flatevekt på 60 g/cm 2. Papirets egenska-per er angitt i tabellen. For testing the melamine-formaldehyde-resin colloid solution as a wet strength improver, the resin colloid was added in an amount of 150 g/min. (equivalent to 5%), calculated on dry fiber material, added to the paper pulp. The pH of the mass suspension was adjusted to 4.5 with 2% aluminum sulphate and further with dilute sulfuric acid. This pulp suspension, with a grinding degree of 35°SR, was dewatered on the paper machine described in Example 1 using a speed of 66 m/min. It was thus produced approx. 3 kg/min. of a paper made of bleached sulphite pulp with a basis weight of 60 g/cm 2. The properties of the paper are indicated in the table.
Sammenligningseksempel 2 Comparative example 2
Sammenligningseksempel 1 ble gjentatt med unntagelse av at papirmassen ble tilsatt 300 g/min., tilsvarende 10%, beregnet på fibermaterialet, av den 10%-ige melamin-formaldehyd-harpikskolloid-oppløsning. Det således fremstilte papirs egen-skaper er angitt i tabellen. Comparative example 1 was repeated with the exception that 300 g/min., corresponding to 10%, calculated on the fiber material, of the 10% melamine-formaldehyde-resin colloid solution was added to the pulp. The properties of the paper produced in this way are indicated in the table.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803039762 DE3039762A1 (en) | 1980-10-22 | 1980-10-22 | METHOD FOR PRODUCING PAPER WITH HIGH WET RESISTANCE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO813548L NO813548L (en) | 1982-04-23 |
| NO160666B true NO160666B (en) | 1989-02-06 |
| NO160666C NO160666C (en) | 1989-05-16 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO813548A NO160666C (en) | 1980-10-22 | 1981-10-21 | PROCEDURE FOR PREPARING PAPER WITH HIGH DEFINITION |
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| Country | Link |
|---|---|
| EP (1) | EP0050223B1 (en) |
| AT (1) | ATE4826T1 (en) |
| DE (2) | DE3039762A1 (en) |
| ES (1) | ES506403A0 (en) |
| FI (1) | FI66943C (en) |
| NO (1) | NO160666C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5286347A (en) * | 1992-05-05 | 1994-02-15 | Calgon Corporation | Melamine formaldehyde polymer for pitch control method |
| DE9214170U1 (en) * | 1992-10-17 | 1993-03-11 | Gustav Demmler GmbH & Co, 12247 Berlin | Paper Biedermeier cuff |
| GB2293612B (en) * | 1994-09-30 | 1997-04-16 | Ricoh Kk | Recording material, method of producing the same and method of recycling recording material |
| DE102019127563A1 (en) | 2019-05-10 | 2020-11-12 | Hauni Maschinenbau Gmbh | Manufacture of paper drinking straws |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US2233965A (en) * | 1937-05-14 | 1941-03-04 | Bennett Inc | Method of delivering and diluting aqueous dispersions of wax, rosin, and the like |
| DE921300C (en) * | 1948-10-10 | 1954-12-13 | Cassella Farbwerke Mainkur Ag | Process for refining fiber material |
| GB866103A (en) * | 1956-10-08 | 1961-04-26 | American Cyanamid Co | Improved melamine resin colloid and manufacture of wet-strength paper therewith |
| CA986634A (en) * | 1971-12-20 | 1976-03-30 | Richard D. Sundie | Curable amino resins |
| FR2446889A1 (en) * | 1979-01-17 | 1980-08-14 | Protex Manuf Prod Chimiq | Paper pulp pigmentation - by in situ formation or organic pigments from an aminoplast foam |
-
1980
- 1980-10-22 DE DE19803039762 patent/DE3039762A1/en not_active Withdrawn
-
1981
- 1981-09-15 FI FI812880A patent/FI66943C/en not_active IP Right Cessation
- 1981-09-21 AT AT81107478T patent/ATE4826T1/en not_active IP Right Cessation
- 1981-09-21 DE DE8181107478T patent/DE3161038D1/en not_active Expired
- 1981-09-21 EP EP81107478A patent/EP0050223B1/en not_active Expired
- 1981-10-21 ES ES506403A patent/ES506403A0/en active Granted
- 1981-10-21 NO NO813548A patent/NO160666C/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES8303580A1 (en) | 1983-02-01 |
| EP0050223B1 (en) | 1983-09-28 |
| DE3039762A1 (en) | 1982-05-27 |
| FI66943B (en) | 1984-08-31 |
| FI812880L (en) | 1982-04-23 |
| EP0050223A1 (en) | 1982-04-28 |
| FI66943C (en) | 1984-12-10 |
| DE3161038D1 (en) | 1983-11-03 |
| ES506403A0 (en) | 1983-02-01 |
| ATE4826T1 (en) | 1983-10-15 |
| NO160666C (en) | 1989-05-16 |
| NO813548L (en) | 1982-04-23 |
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