NO309012B1 - Procedure for preventing the deposition of inorganic material on paper machine felt - Google Patents
Procedure for preventing the deposition of inorganic material on paper machine felt Download PDFInfo
- Publication number
- NO309012B1 NO309012B1 NO964374A NO964374A NO309012B1 NO 309012 B1 NO309012 B1 NO 309012B1 NO 964374 A NO964374 A NO 964374A NO 964374 A NO964374 A NO 964374A NO 309012 B1 NO309012 B1 NO 309012B1
- Authority
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- Norway
- Prior art keywords
- felt
- felts
- accordance
- paper
- fatty
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 27
- 230000008021 deposition Effects 0.000 title description 9
- 229910010272 inorganic material Inorganic materials 0.000 title 1
- 239000011147 inorganic material Substances 0.000 title 1
- 238000011282 treatment Methods 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- -1 lauryl ether sulfonates Chemical class 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 229920000847 nonoxynol Polymers 0.000 claims description 3
- 229920002113 octoxynol Polymers 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical class CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 150000003138 primary alcohols Chemical class 0.000 claims description 2
- 150000003333 secondary alcohols Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 229940048842 sodium xylenesulfonate Drugs 0.000 claims description 2
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000000123 paper Substances 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000003518 caustics Substances 0.000 description 10
- 239000000356 contaminant Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 239000004927 clay Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000011306 natural pitch Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F7/00—Other details of machines for making continuous webs of paper
- D21F7/08—Felts
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/30—Protecting wire-cloths from mechanical damage
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/32—Washing wire-cloths or felts
Landscapes
- Paper (AREA)
- Storage Of Web-Like Or Filamentary Materials (AREA)
- Prevention Of Fouling (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
Description
Den foreliggende oppfinnelse vedrører en fremgangsmåte for behandling av papirmaskinfilt som kontinuerlig sirkulerer mellom papirarkkontakttrinnet og et sugebokstrinn for å opprettholde porøsiteten i filtene. The present invention relates to a method for treating paper machine felt that continuously circulates between the paper sheet contact stage and a suction pad stage in order to maintain the porosity of the felts.
Fremstillingen av papir omfatter bearbeidingen av en vandig fibersuspensjon for å produsere et uniformt tørt papirark. Ved drift i forbindelse med papirfremstilling er man alltid opptatt av problemet med å kontrollere avleiringer, spesielt i trinnet for arkpressing der papirduken passerer gjennom presser som er dekket med porøs pressfilt for å ekstrahere gjenværende vann fra duken. Det er viktig å ekstrahere så mye vann som mulig fra papirduken før den entrer tørkeseksjonen, idet den mekaniske fjerning av vann gjennom pressfiltene er en mer kostnads-effektiv fremgangsmåte for å tørke papirduken enn å frembringe damp for tørkere. Moderne pressfilt fremstilles ikke lenger av naturlige ull-materialer, men er av syntet-iske fibre, såsom nylon og polyesterblandinger. Følgende egenskaper er ønskelige for en pressfilt: The manufacture of paper involves the processing of an aqueous fiber suspension to produce a uniform dry sheet of paper. In papermaking operations, one is always concerned with the problem of controlling deposits, especially in the sheet pressing step where the paper web passes through presses covered with porous press felt to extract residual water from the web. It is important to extract as much water as possible from the paper web before it enters the drying section, as the mechanical removal of water through the press felts is a more cost-effective method of drying the paper web than generating steam for dryers. Modern pressed felt is no longer made from natural wool materials, but is made from synthetic fibres, such as nylon and polyester blends. The following properties are desirable for a press felt:
- tettes ikke igjen, - does not clog again,
- blir ikke ru, - doesn't get rough,
- gjennomtrengelighet for vannbevegelse, - permeability to water movement,
- en ikke-sammenpressbar base som gir hulrom, - a non-compressible base that provides voids,
- en glatt overflate som hindrer uregelmessigheter i papiroverflaten. - a smooth surface that prevents irregularities in the paper surface.
En ren filt, som har små porer som er relativt åpne, er spesielt ønskelig for effektiv papirfremstilling idet dette muliggjør effektiv fjerning av vann fra papirarkene uten å etterlate merker eller uregelmessigheter i papiret. Imidlertid blir filt i presseksjoner fylt eller tettet igjen med forurensninger og krever derfor ofte periodiske nedstenginger, og behandling med kaustiske løsninger (dvs. utkoking), eller eventuell erstatning. Tetting av filt har blitt et stort problem i moderne papirfremstillingsprosesser på grunn av økt anvendelse av resirkulert vann og økt anvendelse av resirkulert papir, samt et ønske om å redusere porestørrelsen for å minimere filt-avmerking. A clean felt, having small pores that are relatively open, is particularly desirable for efficient papermaking as this enables efficient removal of water from the paper sheets without leaving marks or irregularities in the paper. However, felt in press sections becomes filled or clogged with contaminants and therefore often requires periodic shutdowns, and treatment with caustic solutions (ie boiling), or eventual replacement. Clogging of felt has become a major problem in modern papermaking processes due to increased use of recycled water and increased use of recycled paper, as well as a desire to reduce pore size to minimize felt marking.
Forurensninger som tetter filt består primært av uorganiske tetningsstoffer, såsom leire, utfelt kalsiumkarbonat, kalsiumkarbonat fra grunn, og titaniumdioksider. I tillegg danner ionisk ladete, vannløselige polymerer med relativt høy molekylvekt, som anvendes for å forbedre retensjon av cellulosefibre, støv, og uorganiske fyllmasser, flokkulerte partikkelmaterialer som kan overføres fra overflaten av arket til pressfilten. De flokkulerte partikler kan ikke passere gjennom den fine, porøse struk-tur i moderne pressers filt og blir derfor inkorporert deri. Contaminants that seal felt primarily consist of inorganic sealing substances, such as clay, precipitated calcium carbonate, calcium carbonate from the ground, and titanium dioxides. In addition, ionically charged, water-soluble polymers with a relatively high molecular weight, which are used to improve the retention of cellulose fibers, dust, and inorganic fillers, form flocculated particulate materials that can be transferred from the surface of the sheet to the press felt. The flocculated particles cannot pass through the fine, porous structure of modern presses' felt and are therefore incorporated therein.
Partikler fra lateksbeleggingsbindemiddel, såsom polyvinylacetat eller gummi av styren-butadien finnes også ofte i tilstoppet pressfilt. Andre typer av forurensninger kan inkludere stivelse, naturlig bek fra trevirke (fettestere, fett- og harpikssyrer/salter) , finfordelte cellulosefibre, mikrobiologiske forurensninger og absorbanter, såsom talk eller bentonitt, oljebaserte skumnedsettere, klebremidler og uløselige metall-hydroksider. Alle disse forurensninger kan foreligge i noen grad basert på en rekke forskjellige faktorer, såsom temperaturen i papirmaskinsystemet, trefibrene og vann-kildene, årstid, graden/kvaliteten på det fremstilte materiale, type og kvantitet av tilsetningsstoffene i systemet, produksjonsfremgangsmåter for massen, hvordan utstyret er konstruert og dets kapasitet. Dersom ikke filtene kontrolleres ved anvendelse av adekvate filt-forbedringsmetoder, så vil de uorganiske tetnings-materialer og agglomererte partikkelsubstanser sterkt for-verre pressfiltens evne til å absorbere vann, og dermed redusere produksjonshastigheter og korte ned levetiden for filtene. Particles from latex coating binders such as polyvinyl acetate or styrene-butadiene rubber are also often found in clogged press felt. Other types of contaminants may include starch, natural pitch from wood (fat esters, fatty and resin acids/salts), finely divided cellulose fibers, microbiological contaminants and absorbents, such as talc or bentonite, oil-based defoamers, adhesives and insoluble metal hydroxides. All of these contaminants can be present to some extent based on a number of different factors, such as the temperature of the paper machine system, the wood fibers and water sources, the season, the grade/quality of the manufactured material, the type and quantity of the additives in the system, the production methods of the pulp, how the equipment is constructed and its capacity. If the felts are not controlled using adequate felt improvement methods, then the inorganic sealing materials and agglomerated particulate substances will greatly worsen the pressed felt's ability to absorb water, thereby reducing production rates and shortening the life of the felts.
Fremgangsmåter for å nedsette avleiringen av forurensninger i papirmaskinfilt er kjent innen fagfeltet. US-patent 4.715.931 beskriver en fremgangsmåte for å inhibere avleiring av aluminiumhydroksid i papirfremstillings-systemer omfattende å tilsette til filtene en hydroksylert karboksylsyre. Anvendelse av karboksylsyren sammen med surfaktanter, såsom oktylfenoletoksylater, nonylfenoletoksylater og andre som er listet deri, inhiberer avleiring av aluminiumhydroksid og assosierte organiske forurensninger. Procedures for reducing the deposition of contaminants in paper machine felt are known in the field. US patent 4,715,931 describes a method for inhibiting the deposition of aluminum hydroxide in papermaking systems comprising adding to the felts a hydroxylated carboxylic acid. Use of the carboxylic acid with surfactants such as octylphenol ethoxylates, nonylphenol ethoxylates and others listed therein inhibits deposition of aluminum hydroxide and associated organic contaminants.
US-patent 4.861.429 beskriver en fremgangsmåte for å inhibere avleiringer av hvit bek i filt ved å behandle filtene med en organisk, anionisk polyelektrolytt. US Patent 4,861,429 describes a method for inhibiting deposits of white pitch in felt by treating the felts with an organic, anionic polyelectrolyte.
Et formål med foreliggende oppfinnelse er å frembringe en fremgangsmåte for å behandle papirmaskinfilt for å inhibere avleiringen av partikkel-forurensninger deri, og dermed opprettholde porøsiteten i filten. An object of the present invention is to produce a method for treating paper machine felt to inhibit the deposition of particle contaminants therein, and thus maintain the porosity of the felt.
Et annet formål med foreliggende oppfinnelse er å eliminere eller redusere "off-line" rensing av filt (utkoking) med ødeleggende kaustiske eller sure løsninger. Another purpose of the present invention is to eliminate or reduce "off-line" cleaning of felt (boiling) with destructive caustic or acid solutions.
Et annet formål med foreliggende oppfinnelse er å frembringe en fremgangsmåte for behandling av papirmaskinfilt for å inhibere avleiringen av uorganiske partikler som stammer fra fyllmateriale anvendt i fremstillingen av fin-papir og/eller skrivepapir. Another object of the present invention is to produce a method for treating paper machine felt to inhibit the deposition of inorganic particles originating from filler material used in the production of fine paper and/or writing paper.
Et ytterligere formål ifølge oppfinnelsen er å frembringe en fremgangsmåte for å redusere eller eliminere avleiringen av uorganiske partikler som stammer fra av-fallspapir inneholdende fyllmassepartikler. A further object according to the invention is to produce a method for reducing or eliminating the deposition of inorganic particles originating from waste paper containing filler particles.
I samsvar med foreliggende oppfinnelse er der til-veiebrakt en fremgangsmåte som omfatter å behandle filtene i løpet av papirfremstillingsoperasjonen med et vandig filt-bearbeidingspreparat som i det vesentlige består av et pH-kontrollerende middel og en ikke-ionisk eller anionisk surfaktant, hvor pH-kontrollmidlet foreligger i en mengde som er tilstrekkelig til å frembringe en pH i området 9 til 13, og hvor surfaktanten foreligger i et konsentrasjonsområde fra 30 ppm til 2.000 ppm på vektbasis, og hvor filtene settes i kontakt med filt-bearbeidingspreparatet ved et punkt etter at filtene ikke lenger er i kontakt med papirark og ved et punkt før filtene går inn i suge-bokstrinnet. In accordance with the present invention, there is provided a method which comprises treating the felts during the papermaking operation with an aqueous felt processing preparation which essentially consists of a pH-controlling agent and a non-ionic or anionic surfactant, where pH- the control agent is present in an amount sufficient to produce a pH in the range of 9 to 13, and wherein the surfactant is present in a concentration range of from 30 ppm to 2,000 ppm on a weight basis, and wherein the felts are contacted with the felt processing composition at a point after the felts are no longer in contact with the paper sheet and at a point before the felts enter the suction book stage.
Foreliggende oppfinnelse vedrører således en forbedret fremgangsmåte for behandling av pressfilt som ned-setter eller hindrer avleiringen av partikkelsubstanser på pressfilt. Pressfilt-behandlingene ifølge foreliggende oppfinnelse opprettholder filt-porøsitet, dvs. de hindrer at filtene blir mer kompakte, de reduserer tap av tykkelse i filtene som ellers forårsakes av slitasje og sammen-pressing, og dermed reduseres frekvensen for rensemetoder som krever nedstenging. The present invention thus relates to an improved method for treating press felt which reduces or prevents the deposition of particulate substances on press felt. The pressed felt treatments according to the present invention maintain felt porosity, i.e. they prevent the felts from becoming more compact, they reduce loss of thickness in the felts that is otherwise caused by wear and compression, and thus the frequency of cleaning methods that require shutdown is reduced.
Surfaktantene ifølge foreliggende oppfinnelse som har blitt vist å frembringe uventet effektivitet idet de kombineres med pH-kontrollmidler ifølge oppfinnelsen inkluderer dodecylbenzensulfonater, lauryletersulfonater, natriumxylensulfonat, lineære olefinsulfonater, fett-aminoksider, fosfatestere, samt blandinger derav. Andre egnede surfaktanter inkluderer, men er ikke begrenset til, oktylfenoletoksylater, nonylfenoletoksylater, dodecylfenoletoksylater, primære alkoholetoksylater, sekundære alkoholetoksylater, etoksylerte polyoksypropylenglykoler, dialkylfenoletoksylater, polyoksyetylensorbitanmonoester og lineære alkybenzensulfonsyrer. Disse er nærmere beskrevet i US-patent 4.861.429. Egnede surfaktanter inkluderer også amfoteriske surfaktanter, såsom fettimidazoler og deres karboksylerte og sulfonerte derivater, fettamidobetaner, fettsulfoamidobetaner. Idet disse surfaktanter er kationiske under sure pH-betingelser, er de anioniske under normale betingelser i forbindelse med papirfremstilling. The surfactants of the present invention which have been shown to produce unexpected effectiveness when combined with pH control agents of the invention include dodecylbenzene sulfonates, lauryl ether sulfonates, sodium xylene sulfonate, linear olefin sulfonates, fatty amine oxides, phosphate esters, and mixtures thereof. Other suitable surfactants include, but are not limited to, octylphenol ethoxylates, nonylphenol ethoxylates, dodecylphenol ethoxylates, primary alcohol ethoxylates, secondary alcohol ethoxylates, ethoxylated polyoxypropylene glycols, dialkylphenol ethoxylates, polyoxyethylene sorbitan monoesters, and linear alkylbenzene sulfonic acids. These are described in more detail in US patent 4,861,429. Suitable surfactants also include amphoteric surfactants, such as fatty imidazoles and their carboxylated and sulfonated derivatives, fatty amidobetanes, fatty sulfoamidobetanes. As these surfactants are cationic under acidic pH conditions, they are anionic under normal conditions in connection with papermaking.
Egnede pH-kontrollmidler inkluderer, men er ikke begrenset til, meta-silikater, fosfater, karbonater og lignende, og blandinger derav. Foretrukne pH-kontrollmidler inkluderer natriummeta-silikat, natriumfosfat og natriumkarbonat, og mest foretrukket er natriummeta-silikat . Suitable pH control agents include, but are not limited to, meta-silicates, phosphates, carbonates and the like, and mixtures thereof. Preferred pH control agents include sodium metasilicate, sodium phosphate and sodium carbonate, and most preferred is sodium metasilicate.
Den vandige filt-behandlingsløsning fremstilles ved å fortynne surfaktantene i vann til en sluttkonsentrasjon i området 100 til 2.000 ppm, og deretter tilsette pH-kontrollmidlene i en mengde som er effektiv til å frembringe en pH i området 9 til 13, fortrinnsvis 10 til 12, og mest fortrinnsvis 11 til 12. Alternativt kan surfaktanten og pH-kontrollmidlet blandes på forhånd i et forholdstall som gir den ønskete pH og surfaktant-konsentrasjon ved fortynning med vann. Ferskt vann kan anvendes for å fremstille den vandige filt-behandlings-løsning, eller valgfritt kan resirkulert bakvann anvendes. Den vandige filt-behandlingsløsning inneholder generelt mellom 30 ppm og 2.000 ppm surfaktant, fortrinnsvis fra 50 ppm til 1.500 ppm. The aqueous felt treatment solution is prepared by diluting the surfactants in water to a final concentration in the range of 100 to 2,000 ppm, and then adding the pH control agents in an amount effective to produce a pH in the range of 9 to 13, preferably 10 to 12, and most preferably 11 to 12. Alternatively, the surfactant and the pH control agent can be mixed in advance in a ratio which gives the desired pH and surfactant concentration when diluted with water. Fresh water can be used to prepare the aqueous felt treatment solution, or optionally recycled tailwater can be used. The aqueous felt treatment solution generally contains between 30 ppm and 2,000 ppm surfactant, preferably from 50 ppm to 1,500 ppm.
Filt-behandlingspreparatene kan valgfritt inkludere et solubiliserende middel for å øke fuktighet, og/eller ett eller flere chelater for å forbedre anvendelse i vann med høy hardhetsgrad. Egnede solubiliserende midler inkluderer glykoler, såsom f.eks. heksylenglykol eller dietylenglykol, glykoletere, såsom f.eks. etylenglykolmono-butyleter. Egnede chelater er de som er i stand til å stabilisere kalsiumioner under høye pH-betingelser og inkluderer, men er ikke begrenset til, etylen-diamintetraeddiksyre (EDTA), nitrilotrieddiksyre (NTA), dietylentriaminpentaeddiksyre (DTPA) og lignende. The felt treatment compositions may optionally include a solubilizing agent to increase moisture, and/or one or more chelates to improve application in hard water. Suitable solubilizing agents include glycols, such as e.g. hexylene glycol or diethylene glycol, glycol ethers, such as e.g. ethylene glycol mono-butyl ether. Suitable chelates are those capable of stabilizing calcium ions under high pH conditions and include, but are not limited to, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA) and the like.
Det beskrives også en fremgangsmåte for å inhibere avleiringen av forskjellige organiske og uorganiske forurensninger i en filt i en presseseksjon i et papir-fremstillingssystem hvori filten lett rammes av slike avleiringer. I samsvar med foreliggende oppfinnelse, påføres filt-behandlingspreparatene ifølge oppfinnelsen ved "metering" eller spraying av pressfiltene i fersk-vannsdusjsystemet, fortrinnsvis en dusj med lavt trykk. Disse filt-behandlingspreparater påføres generelt til arksiden av filtene, fortrinnsvis ved en vifte-dusj. Filt-behandlingspreparatene sprayes fortrinnsvis på ved lavt trykk, dvs. i området 2 til 7 kg/cm<2>, fortrinnsvis 3 til 5 kg/cm<2>. A method is also described for inhibiting the deposition of various organic and inorganic contaminants in a felt in a press section in a paper-making system in which the felt is easily affected by such deposits. In accordance with the present invention, the felt treatment preparations according to the invention are applied by "metering" or spraying the pressure felts in the fresh water shower system, preferably a shower with low pressure. These felt treatment preparations are generally applied to the sheet side of the felts, preferably by a fan shower. The felt treatment preparations are preferably sprayed on at low pressure, i.e. in the range 2 to 7 kg/cm<2>, preferably 3 to 5 kg/cm<2>.
Det vurderes som et viktig trekk ifølge foreliggende oppfinnelse at filt-behandlingspreparatene ifølge oppfinnelsen påføres ved metering i én eller flere fersk-vannsdusjer som dirigeres til pressfilt i et område der filten ikke lenger er i kontakt med papirarket eller sugeboksen, fortrinnsvis mellom presseklemmen og sugeboksen (Uhle) som utnyttes for å fjerne vann fra filten. Påføring av en vandig løsning av et pH-kontrollmiddel og én eller flere ikke-ioniske eller anioniske surfaktanter på pressfilt i dette område har blitt funnet å produsere en uventet effektiv filt-behandling basert på behandlings-effekten til disse filt-behandlingspreparater i andre om-råder eller på de enkelte komponenter. It is considered an important feature according to the present invention that the felt treatment preparations according to the invention are applied by metering in one or more fresh water showers which are directed to the press felt in an area where the felt is no longer in contact with the paper sheet or the suction box, preferably between the press clamp and the suction box ( Uhle) which is used to remove water from the felt. Application of an aqueous solution of a pH control agent and one or more nonionic or anionic surfactants to press felt in this area has been found to produce an unexpectedly effective felt treatment based on the treatment effect of these felt treatment compositions in other om- prevails or on the individual components.
For typiske papirfremstillingsprosesser, kan filt-behandlingspreparater ifølge oppfinnelsen sprayes eller meteres periodisk i løpet av papirfremstillingsoperasjonen, typisk 2 til 3 ganger per dag, med en aktiv konsentrasjon på fra 1 til 5 vekt%. Alternativt kan filt-behandlingspreparater sprayes eller meteres kontinuerlig med en aktiv konsentrasjon på 0,01 til 0,2 vekt%, fortrinnsvis med en aktiv konsentrasjon på 0,1 vekt%. For typical papermaking processes, felt treatment compositions of the invention may be sprayed or metered periodically during the papermaking operation, typically 2 to 3 times per day, at an active concentration of from 1 to 5% by weight. Alternatively, felt treatment preparations can be sprayed or metered continuously with an active concentration of 0.01 to 0.2% by weight, preferably with an active concentration of 0.1% by weight.
Den totale doseringsmengde av vandig filt-behand-lingsmiddel påført filtene er også vurdert som et viktig trekk av foreliggende oppfinnelse. Generelt har de beste resultater blitt oppnådd når minst 6 liter filt-behand-lingsmiddel påføres per kvadratmeter filt per minutt (l/m<2>/min.), fortrinnsvis mellom 6 til 10 l/m^/min. The total dosage amount of aqueous felt treatment agent applied to the felts is also considered an important feature of the present invention. In general, the best results have been obtained when at least 6 liters of felt treatment agent is applied per square meter of felt per minute (l/m<2>/min.), preferably between 6 to 10 l/m^/min.
Filt-behandlingspreparatene ifølge oppfinnelsen er spesielt anvendelig for behandling av filt anvendt i fremstillingen av papirkvaliteter som har inkorporert fyllmasse-materialer, såsom f.eks. finpapir eller skrivepapir. Disse papirkvaliteter inneholder typisk store mengder av uorganiske fyllmasser, såsom leire, kalsiumkarbonat, titaniumdioksid og lignende. Filt-bearbeidingspreparatene som er beskrevet er også effektive i papirfremstillings-systemer som anvender termomekanisk masse (TMP) som typisk har et høyt nivå av finfordelt støv som er kjent å tette til pressfilt. The felt treatment preparations according to the invention are particularly applicable for the treatment of felt used in the production of paper grades which have incorporated filler materials, such as e.g. fine paper or writing paper. These paper qualities typically contain large amounts of inorganic fillers, such as clay, calcium carbonate, titanium dioxide and the like. The felt processing compositions described are also effective in papermaking systems using thermomechanical pulp (TMP) which typically have a high level of fine dust known to clog press felt.
De påfølgende eksempler er inkludert for å illustrere foreliggende oppfinnelse i samsvar med prinsippene i oppfinnelsen, men skal ikke på noen måte oppfattes som begrensende for oppfinnelsen. Alle deler og prosenter er oppgitt på vektbasis dersom ikke annet er indikert. The following examples are included to illustrate the present invention in accordance with the principles of the invention, but should not be construed as limiting the invention in any way. All parts and percentages are given on a weight basis unless otherwise indicated.
Eksempel 1 Example 1
Dette eksempel viser effektiviteten til behandlinger med filt-bearbeidingspreparatet ifølge oppfinnelsen for å opprettholde porøsiteten i filtene i den presseseksjon i papirfremstillingsmaskinen som fremstiller papir av trykkvalitet. Papirmaskinen ifølge eksempelet anvendte 100% kraftmassemateriale. Materialet inneholdt en relativt høy doseringsmengde av leire som fyllmasse. Før kontakt med papiret, ble åpenheten i papirmaskinfilt målt ved å passere filten over en vakuumboks for å fjerne overskudd av vann. Vakumm-avlesningene, som er nødvendig for å trekke luft gjennom filten, er representative for åpenheten i papirmaskinfilt. Typiske vakuum-avlesninger for ren filt er normalt ca. 12 tommer Hg. Vakuum-avlesninger større enn 12 tommer Hg indikerer generelt at kaustisk rensing av filten er nødvendig. En vandig filt-bearbeid-ingsløsning ble fremstilt inneholdende 4,5% natrium-meta-silikat, 14,5% av en blanding anioniske surfaktanter (natriumdodecylbenzensulfonsyre og lauryletersulfat), 55 chelatmiddel (EDTA) og 4% fuktemiddel (dietylenglykol). Filt-behandlingspreparatet ble oppmålt og fylt i en trykk-sprøyte før den første Uhle-boks med et trykk på 2 til 4 kg/cm<2> og en vannstrøm på 40 liter/min. This example shows the effectiveness of treatments with the felt processing preparation according to the invention to maintain the porosity of the felts in the press section of the papermaking machine which produces printing quality paper. The paper machine according to the example used 100% kraft pulp material. The material contained a relatively high dosage amount of clay as filler. Before contact with the paper, the transparency of paper machine felt was measured by passing the felt over a vacuum box to remove excess water. The vacuum readings, which are necessary to draw air through the felt, are representative of the openness of the paper machine felt. Typical vacuum readings for clean felt are normally approx. 12 inches Hg. Vacuum readings greater than 12 inches Hg generally indicate that caustic cleaning of the felt is necessary. An aqueous felt processing solution was prepared containing 4.5% sodium metasilicate, 14.5% of a mixture of anionic surfactants (sodium dodecylbenzenesulfonic acid and lauryl ether sulfate), 55% chelating agent (EDTA) and 4% wetting agent (diethylene glycol). The felt treatment preparation was measured and filled in a pressure syringe before the first Uhle box with a pressure of 2 to 4 kg/cm<2> and a water flow of 40 liters/min.
Tilstander før behandlingsprogrammet Conditions before the treatment program
Før behandling med filt-bearbeidingspreparatet, ble papirmaskinen avstengt i gjennomsnitt hver andre eller tredje dag for kaustisk rengjøring av filten for fjerning av leire. De gjennomsnittlige produksjonstap per avstenging for kaustisk rensing var 12 tonn. Prior to treatment with the felt processing composition, the paper machine was shut down on average every two or three days for caustic cleaning of the felt to remove clay. The average production loss per shutdown for caustic cleaning was 12 tonnes.
Tilstander etter behandlingsprogrammet Conditions after the treatment program
Den innledende prøveperiode var 20 dager, og i løpet av denne periode var det påkrevd med tre nedstenginger for kaustisk rensing. To av disse nedstenginger var et direkte resultat av avbrytelsen av spraypåføringen av filt-behandlingspreparatet ifølge oppfinnelsen. En 18-dagers periode ble gjennomført uten nedstenging med en kontinuerlig spray-påføring av filt-bearbeidingspreparatet. Uhle-boks-vakuum ble holdt under 16 tommer Hg gjennom hele 18-dagers perioden. Alle andre papirmaskin- og ark-standarder ble holdt konstant. The initial trial period was 20 days, during which three shutdowns were required for caustic cleaning. Two of these shutdowns were a direct result of the discontinuation of the spray application of the felt treatment composition of the invention. An 18-day period was carried out without shutdown with a continuous spray application of the felt processing preparation. Uhle box vacuum was maintained below 16 in. Hg throughout the 18-day period. All other paper machine and sheet standards were held constant.
Scanpro-testing involverer bestemming av vanninnholdet i filtene i gram H20/m<2> i filten. Et høyere mål på vanninnhold i filten indikerer en høyere filt-porøsitet. I tillegg er Scanpro-testingen et mål på uniformiteten av vanninnholdet over hele tverrsnittet av filten. Det er vurdert som viktig at pressfilt har en uniform vanninn-holdsprofil over filten. Scanpro-testing ble utført på de behandlede filt og ble sammenlignet med tidligere resultater på andre ubehandlete filt, og indikerer at de behandlede filt ikke bare hadde et høyere vanninnhold, dvs. en signifikant forbedring av porøsiteten over de tidligere ubehandlete filt, men indikerte også en mer uniform vann-innholdsprofil over filten enn de tidligere ubehandlete filt. På det tidspunkt filten ble skiftet ble den rappor-tert å være i god stand. Scanpro testing involves determining the water content of the felts in grams H20/m<2> in the felt. A higher measure of water content in the felt indicates a higher felt porosity. In addition, the Scanpro testing is a measure of the uniformity of the water content across the entire cross-section of the felt. It is considered important that pressed felt has a uniform water content profile across the felt. Scanpro testing was carried out on the treated felts and was compared to previous results on other untreated felts, indicating that the treated felts not only had a higher water content, i.e. a significant improvement in porosity over the previously untreated felts, but also indicated a more uniform water content profile across the felt than the previously untreated felts. At the time the felt was replaced, it was reported to be in good condition.
Eksempel 2 Example 2
Dette eksempel viser effektiviteten av filt-bearbeid-ingspreparatløsninger ifølge foreliggende oppfinnelse for å opprettholde filt-porøsitet i pressfilt i papirmaskiner anvendt for å fremstille forskriftsmessig klassifisert papir. Materialet omfattet 40% stenslipmasse, 50% termomekanisk masse (TMP) og 10% Kraft-masse. Papir-tilset-ningsstoffer inkluderte talk og stivelse. This example shows the effectiveness of felt processing preparation solutions according to the present invention to maintain felt porosity in press felt in paper machines used to produce legally classified paper. The material comprised 40% stone grinding mass, 50% thermomechanical mass (TMP) and 10% Kraft mass. Paper additives included talc and starch.
Fremgangsmåten i eksempel 1 ble gjentatt i dette eksempel. The procedure in example 1 was repeated in this example.
Tilstander før behandlingsprogrammet Conditions before the treatment program
Denne papirmaskin var i gjennomsnitt avstengt 4 37 timer per år for kaustisk vasking av filtene for å fjerne støv, noe som krevde et forbruk på ca. 10.000 kg kaustiske kjemikalier per år. Ved en gjennomsnittlig produksjons-hastighet på 125 tonn per dag (TPD), fører denne avstengte tid til et betydelig tap i produksjonen. I tillegg til produksjonstap på grunn av at maskinen er ute av drift, så skyldtes et produksjonstap på ca. 250 tonn per år (TPY) uregelmessige fuktighetsprofiler over filtene. Høytrykks-dusjer (8 til 12 kg/cm<2>) var påkrevd for å fjerne støv fra filtene. Den gjennomsnittlige levetid for de 13 filtene var 36,5 dager. This paper machine was shut down on average 4 37 hours per year for caustic washing of the felts to remove dust, which required a consumption of approx. 10,000 kg of caustic chemicals per year. At an average production rate of 125 tonnes per day (TPD), this shut-down time leads to a significant loss in production. In addition to production losses due to the machine being out of service, a production loss of approx. 250 tonnes per year (TPY) irregular moisture profiles across the felts. High-pressure showers (8 to 12 kg/cm<2>) were required to remove dust from the felts. The average lifespan of the 13 blankets was 36.5 days.
Tilstander etter behandlingsprogrammet Conditions after the treatment program
Behandling av papirmaskinfiltene resulterte i en fullstendig eliminering av behovet for avstenging utenom programmet for kaustisk rensing. Den kaustiske rensing av filtene ved den andre presseksjon ble redusert med 50%. Avlesningene i vakuum-boksen forble konstant gjennom hele prøveperioden, og Scanpro-resultatene indikerte uniforme vanninnholdsprofiler, noe som førte til at det ikke ble noe tap i papirproduksjonen. Trykket i høytrykksdusjene ble redusert til 8 kg/cm<2>. Levetiden for filtene økte til 57 dager. Treatment of the paper machine felts resulted in a complete elimination of the need for shutdown outside of the caustic cleaning program. The caustic cleaning of the felts at the second press section was reduced by 50%. The readings in the vacuum box remained constant throughout the trial period and the Scanpro results indicated uniform water content profiles, resulting in no loss in paper production. The pressure in the high-pressure showers was reduced to 8 kg/cm<2>. The life of the felts increased to 57 days.
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US23098594A | 1994-04-21 | 1994-04-21 | |
| PCT/US1995/004334 WO1995029292A1 (en) | 1994-04-21 | 1995-04-06 | Felt treatment - inorganic deposit prevention by spray treatment |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO964374D0 NO964374D0 (en) | 1996-10-15 |
| NO964374L NO964374L (en) | 1996-12-20 |
| NO309012B1 true NO309012B1 (en) | 2000-11-27 |
Family
ID=22867348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO964374A NO309012B1 (en) | 1994-04-21 | 1996-10-15 | Procedure for preventing the deposition of inorganic material on paper machine felt |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0764227A4 (en) |
| AU (1) | AU691275B2 (en) |
| CA (1) | CA2188466A1 (en) |
| FI (1) | FI964219A0 (en) |
| NO (1) | NO309012B1 (en) |
| NZ (1) | NZ283964A (en) |
| TW (1) | TW268064B (en) |
| WO (1) | WO1995029292A1 (en) |
| ZA (1) | ZA953243B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112017009594A2 (en) | 2014-11-25 | 2018-04-03 | Buckman Laboratories Int Inc | method for cleaning or conditioning a cloth, belt, felt or screen used in a papermaking or pulp making process, method for cleaning or conditioning a papermaking press used in a papermaking process and method for cleaning or conditioning a substrate |
| DE102017115447B4 (en) | 2017-07-10 | 2019-05-16 | SARATECH GmbH | Method and device for paper production |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3459633A (en) * | 1967-05-04 | 1969-08-05 | Shannon V West | Felt conditioner control system |
| US4895622A (en) * | 1988-11-09 | 1990-01-23 | Betz Laboratories, Inc. | Press felt conditioner for neutral and alkaline papermaking systems |
| US5167767A (en) * | 1991-03-25 | 1992-12-01 | Betz Paperchem, Inc. | Paper mill press felt conditioner |
-
1995
- 1995-04-06 CA CA002188466A patent/CA2188466A1/en not_active Abandoned
- 1995-04-06 EP EP95915606A patent/EP0764227A4/en not_active Withdrawn
- 1995-04-06 NZ NZ283964A patent/NZ283964A/en unknown
- 1995-04-06 WO PCT/US1995/004334 patent/WO1995029292A1/en not_active Application Discontinuation
- 1995-04-06 AU AU22436/95A patent/AU691275B2/en not_active Ceased
- 1995-04-19 TW TW084103858A patent/TW268064B/zh active
- 1995-04-21 ZA ZA953243A patent/ZA953243B/en unknown
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1996
- 1996-10-15 NO NO964374A patent/NO309012B1/en not_active IP Right Cessation
- 1996-10-18 FI FI964219A patent/FI964219A0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NZ283964A (en) | 1998-04-27 |
| FI964219A (en) | 1996-10-18 |
| TW268064B (en) | 1996-01-11 |
| NO964374L (en) | 1996-12-20 |
| NO964374D0 (en) | 1996-10-15 |
| FI964219A0 (en) | 1996-10-18 |
| EP0764227A4 (en) | 1998-04-01 |
| ZA953243B (en) | 1996-01-03 |
| CA2188466A1 (en) | 1995-11-02 |
| EP0764227A1 (en) | 1997-03-26 |
| AU691275B2 (en) | 1998-05-14 |
| AU2243695A (en) | 1995-11-16 |
| WO1995029292A1 (en) | 1995-11-02 |
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