EP3044364A1 - Method for producing paper - Google Patents
Method for producing paperInfo
- Publication number
- EP3044364A1 EP3044364A1 EP14777538.1A EP14777538A EP3044364A1 EP 3044364 A1 EP3044364 A1 EP 3044364A1 EP 14777538 A EP14777538 A EP 14777538A EP 3044364 A1 EP3044364 A1 EP 3044364A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber material
- acrylamide copolymer
- pulp
- mol
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000292 calcium oxide Substances 0.000 claims abstract description 53
- 239000002657 fibrous material Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229920006322 acrylamide copolymer Polymers 0.000 claims abstract description 38
- 239000000725 suspension Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 28
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013543 active substance Substances 0.000 claims abstract 3
- 229920001131 Pulp (paper) Polymers 0.000 claims description 10
- 125000002091 cationic group Chemical group 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 239000010893 paper waste Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- -1 polyvinylamines Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 239000004368 Modified starch Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 229940037003 alum Drugs 0.000 claims description 2
- 229920006320 anionic starch Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 235000019426 modified starch Nutrition 0.000 claims description 2
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 claims description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940047670 sodium acrylate Drugs 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 235000012255 calcium oxide Nutrition 0.000 description 44
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 27
- 235000011941 Tilia x europaea Nutrition 0.000 description 27
- 239000004571 lime Substances 0.000 description 27
- 238000007792 addition Methods 0.000 description 24
- 235000011116 calcium hydroxide Nutrition 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- 230000009172 bursting Effects 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 13
- 238000009533 lab test Methods 0.000 description 9
- 239000000945 filler Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 238000007630 basic procedure Methods 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000013311 vegetables Nutrition 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/22—Other features of pulping processes
- D21C3/222—Use of compounds accelerating the pulping processes
-
- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/64—Alkaline compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/65—Acid compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Definitions
- the present invention relates to a process for the production of paper in which besides at least one fibrous material, polymer, water, calcium oxide and / or calcium hydroxide are used.
- a suspension is prepared from at least water and fibers, which are mostly of vegetable origin, which are then mechanically dehydrated, thermally dried and rolled up in a paper machine.
- fiber materials today are in particular recovered paper, which is offered in different qualities on the recovered paper market. Furthermore, the
- Fibrous suspension also added additives with which the manufacturing process is improved or the quality of the finished product can be influenced.
- Additives are auxiliaries and additives of natural and synthetic origin.
- the paper strength for example, measured as bursting pressure (DIN 53141 / DIN ISO 2758), the
- SCT Streak Shock Resistance
- CMT Flat Shock Resistance
- the finished product with appropriate mechanical properties a Has as high a proportion of fillers, since they are cheaper than fibers and improve the printability.
- These are added either as mineral fillers such as chalk, kaolin, talc, bentonite, titanium dioxide or gypsum or as modified mineral fillers such as cationized calcium carbonates, calcined kaolin, anhydrite and / or added in the use of waste paper on this in the pulp suspension.
- Base material through the use of chemical additives to improve. These include in particular the use of natural and synthetic
- Dry strength agents such as starch, guar, xanthan, polyacrylamides, polyvinylamines, glyoxals, etc.
- Raw materials at least one fiber material, a polymer, water and calcium oxide and / or calcium hydroxide.
- the raw materials are preferably in the following
- the first step involves the impact of the fiber material with water in a pulper to produce a pulp suspension with the subsequent Transfer of the pulp suspension into a chest, according to the invention during the impact of the fiber material in the pulper, or following thereto, calcium oxide and / or calcium hydroxide with an active ingredient content between 0.1 kg per tonne otro fiber material and 50 kg per tonne fiber material for setting a pH Value is added between 8 and 12 in the pulp suspension. Furthermore, the pulp suspension is added as polymer an acrylamide copolymer having an active ingredient content of between 0.1 kg per tonne otro fiber material and 5 kg per tonne fiber material.
- the addition of calcium oxide and / or calcium hydroxide and acrylamide copolymer may also be reversed.
- the acrylamide copolymer for example, in the pulper or a downstream chest and then calcium oxide and / or
- calcium oxide and / or calcium hydroxide is added to the water-suspended fiber material.
- calcium oxide which is also referred to as quicklime, quicklime, quicklime, lime or quicklime, a white powder that reacts with water with a strong evolution of heat.
- the reaction with water forms calcium hydroxide (slaked lime, lime water).
- calcium oxide is produced by lime burning. From a temperature of about 800 ° C limestone (calcium carbonate) is deacidified, that is, carbon dioxide is expelled and it produces calcium oxide.
- calcium oxide can be the pulp as already with water
- suspended calcium oxide (so-called milk of lime or calcium hydroxide)
- the pH of the pulp suspension in the pulper is set to a value between 8 and 12, for which purpose usually calcium oxide must be added as a commodity in an amount between 0.1 kg and 50 kg.
- the pulp suspension calcium oxide and / or calcium hydroxide is added in such a way that the active ingredient content of calcium oxide and / or calcium hydroxide between 2 kg per tonne otro fiber material and 30 kg per tonne fiber material, preferably between 5 kg per tonne otro Fiber material and 20 kg per ton of fiber material, is.
- this addition is controlled or regulated such that the pH of the pulp suspension after the addition of calcium oxide and / or calcium hydroxide is between 7 and 13, preferably between 8 and 12 and in particular between 9 and 1 1 lies.
- the impact of the fiber material in the pulper with water is further carried out according to a further preferred embodiment of the present invention at a pulp density in the pulper between 1 wt .-% and 26 wt .-%, preferably between 4 wt .-% and 7 wt .-% ( Standard pulper) or 10% by weight and 24% by weight
- Papermaking process which in particular has a pH which is between 5.5 and 7.5, preferably between 6 and 7.
- the chest in which the whipped pulp suspension is transferred from the pulper, an intermediate chest, a mixing chest, a Ableerbütte and / or a machine chest, wherein it is also within the meaning of the present invention that the Pulp suspension is transferred from the pulper in a Ableerbütte and then into an intermediate and / or mixing chest, in which, for example, the polymer, additives and / or the calcium oxide and / or calcium hydroxide is added or be.
- the addition of the acrylamide copolymer takes place in a single chest, ie a single metering point, this being, for example, both the intermediate chest, the Mischbütte, the Ableerbütte, the machine chest or even the pulper can be.
- the fibrous materials used according to the present invention are preferably selected from a group of fibrous materials, which primary and secondary fibrous materials and especially waste paper, pulp such as sulfate or sulfite pulp, wood pulp, stone pulp, refiner pulp, thermo-mechanical pulp, Chemi-mechanical pulp, chemi-thermo-mechanical pulp, combinations thereof, and the like.
- used as fibrous material is substantially waste paper.
- the polymers used according to the present invention are preferably cationic acrylamide copolymers selected from the group consisting of ADAME (N, N-dimethylaminoethyl acrylate), DIMAPA (N, N-dimethylaminopropylacrylamide), MADAME (N, N-dimethylaminoethyl methacrylate) and DADMAC ( Diallyldimethylammonium chloride) in quaternized form and / or their acids.
- ADAME N, N-dimethylaminoethyl acrylate
- DIMAPA N, N-dimethylaminopropylacrylamide
- MADAME N, N-dimethylaminoethyl methacrylate
- DADMAC Diallyldimethylammonium chloride
- an anionic acrylamide copolymer may also be used.
- Such an anionic acrylamide copolymer is, for example, sodium acrylate and acrylamide.
- the acrylamide copolymer is in the range from 10% by weight to 99% by weight, preferably 15% by weight to 90% by weight, more preferably 20% by weight. to 80 wt.%, most preferably 25 wt.% to 70 wt.%, in particular 30 wt.% to 60 wt.%, of cationic monomers, based on the total weight of the cationic acrylamide copolymer.
- the acrylamide copolymer has an average molecular weight which is between 0.5x10 6 g / mol to 10x10 7 g / mol, preferably between 2x10 6 g / mol to 5x10 7 g / mol and in particular between 7x10 6 g / mol to 8x10 7 g / mol.
- Embodiment a cation activity, which is between 5 mol .-% and 100 mol .-%, preferably between 20 mol .-% and 80 mol .-% and in particular between 30 mol .-% and 60 mol .-%.
- the metering of the acrylamide copolymer is furthermore preferably carried out as an aqueous solution which is added as a dispersion, emulsion or suspension (prepared from a powder or granules) to the pulp suspension.
- the acrylamide copolymer as the solid directly
- the fibrous suspension is additionally added at least one further additive which is selected from a group comprising starch, in particular native starch, cationically or anionically modified starch, guar, xanthan, polyvinylamine, anionic starch, CMC, polyvinyl alcohol and / or glyoxal, polyamidoamine-epichlorohydrin, melamine-formaldehyde, urea-formaldehyde, polyaluminum chloride, polyaluminum nitrate, alum, combinations thereof, and the like.
- starch in particular native starch, cationically or anionically modified starch, guar, xanthan, polyvinylamine, anionic starch, CMC, polyvinyl alcohol and / or glyoxal, polyamidoamine-epichlorohydrin, melamine-formaldehyde, urea-formaldehyde, polyaluminum chloride, polyalum
- the metering of the acrylamide copolymer is further carried out in a manner such that the reaction time of the acrylamide copolymer with the pulp suspension is between 5 minutes and 120 minutes, preferably between 10 minutes and 80 minutes and in particular between 20 minutes and 60 minutes before the
- Fiber suspension further processed and in particular the paper on the
- Paper machine is produced.
- Fiber material and 3 kg per ton of fiber material.
- Fig. 1 is a list of the corresponding specifications of the acrylamide copolymers used in the experiments;
- Figures 2a to 2d are graphs and a table for laboratory experiments
- FIG. 5a to 5d graphics and a table for further laboratory experiments
- FIG. 6a to 6e graphics and a table for further laboratory experiments
- FIGS. 7a to 7c are graphs and a table for further laboratory experiments
- Figs. 8a to 8c are graphs and a table of industrial experiments
- 10a to 10c are graphs and a table for retention experiments. The laboratory tests were carried out as follows:
- the required amount of lime in the form of CaO, Ca (OH) 2 or lime milk was added to this mixed substance mixture (STWG).
- STWG mixed substance mixture
- 500 ml STWG were placed in a blender and then mixed with lime for about 30 sec.
- the pH of the STWG is then about pH 10 - 10.5.
- the corresponding amount of polymer was then mixed into the STWG and stirred vigorously for a further 30 sec.
- the STWG was then poured into a plastic bottle and stored for about 30 to 60 minutes. Subsequently, sheets of the appropriate weight were produced on a Rapid-Köthen sheet former. The appropriate amounts of substance were removed from the bottle.
- the polymer was added first and then the amount of lime needed.
- test sheets were then conditioned in a climate room for 24 hours and then the weight determined. The basis weight was calculated. The corresponding strength tests were then carried out on the leaves.
- the ash content was determined by ashing in a muffle furnace. This is stated in% ash. Subsequently, a test protocol was created and the tests were evaluated. The strengths were fixed
- Poly 49, Poly 35 and Poly 25 are ADAME based products
- Poly M65 and M99 are MADAME based products
- the starches used here are cereal flours, which are specified below as MK21, MK01 and MK5025:
- the zero value indicates the comparative value without polymer and calcium oxide
- Poly 49 the addition of the polymer without calcium oxide
- Poly 49 lime the addition of the polymer with calcium oxide
- SFC 60 another polymer without lime SFC 60 lime the addition of the second polymer with calcium oxide.
- the strength values of the bursting pressure and of the SCT value increase continuously up to the addition amount of 3000 g / t of polymer and decrease significantly as the amount added increases further.
- the dosage is too high, a very strong flocculation of the waste paper fibers takes place, which is another
- FIGS. 4a and 4c show the development of the bursting pressure, the SCT value and the CMT value for the various polymers investigated. For the CMT value and the SCT value resulted in comparable conditions and
- FIGS. 5a and 5c show the development of the bursting pressure, the SCT value and the CMT value for the test series according to the table from FIG. 5d, starch being used as an additional additive in addition to previous attempts.
- FIGS. 5a and 5c show the development of the bursting pressure, the SCT value and the CMT value for the test series according to the table from FIG. 5d, starch being used as an additional additive in addition to previous attempts.
- Bursting pressure could be achieved, which was compared to the use of caustic soda instead of lime by 8% better and also performs significantly better in terms of the use of the polymer without alkali. Furthermore, it is clear that without the addition of a base, despite an increase in the use of the polymer, no improvement in the bursting pressure, but its reduction was effected.
- FIGS. 7a and 7b show the development of the bursting point and the SCT value for different amounts of polymer used in combination with lime
- FIGS. 8a and 8b show the results of the industrial tests for the use of "Poly 49" and “SFC 60" as polymers in combination with lime and in comparison to the blank test. Here, too, the best results are achieved in the combination of "Poly 49” with lime.
- the filler content in the paper sheet produced was also examined in the test series, which allows a conclusion on the retention behavior of the material system. This shows that when using the polymer in combination with calcium oxide, the highest filler content in the sheet was effected and still the mechanical strengths were significantly improved.
- FIG. 9 shows a variant of a flowchart according to the invention.
- the waste paper with water (H2O) pitched so that, for example, a pulp suspension is provided which has a consistency of 4%.
- the required amount of limescale in the form of CaO or Ca (OH> 2) is first added to this mixture of substances in point 2.
- the pH of the substance mixture is then about pH 10 - 10.5
- the mixed substance mixture is then mixed in position 4 for about 30 to 60 minutes
- both the order of addition of the CaO or Ca (OH> 2 or the polymer can be reversed or in particular the addition of CaO or Ca (OH) 2 or the polymer already under point 1, for example in the pulper of a stock preparation plant, respectively.
- Graphs 10a and 10b and Table 10c show test results for retention studies in which the product combination, lime and polymer were also tested as retention aids.
- As a material system a fine paper pulp was selected, which had about 70% pulp and 30% filler. The retention measurements were performed in the laboratory with a Britt Jar (Britt Dynamic
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102013109991.2A DE102013109991A1 (en) | 2013-09-11 | 2013-09-11 | Process for the production of paper |
PCT/EP2014/069062 WO2015036357A1 (en) | 2013-09-11 | 2014-09-08 | Method for producing paper |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3044364A1 true EP3044364A1 (en) | 2016-07-20 |
EP3044364B1 EP3044364B1 (en) | 2017-11-22 |
Family
ID=51655695
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14777538.1A Active EP3044364B1 (en) | 2013-09-11 | 2014-09-08 | Method for producing paper |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3044364B1 (en) |
DE (1) | DE102013109991A1 (en) |
WO (1) | WO2015036357A1 (en) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1552243A (en) * | 1975-07-17 | 1979-09-12 | Riddle M C | Manufacture of filled paper sheet |
DE3000367A1 (en) * | 1980-01-07 | 1981-07-09 | Basf Ag, 6700 Ludwigshafen | Paper prodn. with increased dry strength - on machine with closed water circulation using neutral pulp contg. waste paper |
DE10347919A1 (en) * | 2003-10-15 | 2005-05-19 | Voith Paper Patent Gmbh | Method for adjusting a pH and machine for producing a fibrous web |
CN101929104A (en) * | 2009-06-23 | 2010-12-29 | 徐敏 | Retention aid for paper making |
-
2013
- 2013-09-11 DE DE102013109991.2A patent/DE102013109991A1/en not_active Withdrawn
-
2014
- 2014-09-08 WO PCT/EP2014/069062 patent/WO2015036357A1/en active Application Filing
- 2014-09-08 EP EP14777538.1A patent/EP3044364B1/en active Active
Non-Patent Citations (1)
Title |
---|
See references of WO2015036357A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2015036357A1 (en) | 2015-03-19 |
EP3044364B1 (en) | 2017-11-22 |
DE102013109991A1 (en) | 2015-03-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE60106253T2 (en) | METHOD OF PAPER MANUFACTURE USING FIBER AND FILLER COMPLEXES | |
EP1819877B1 (en) | Method for producing high dry strength paper, paperboard or cardboard | |
EP1999314B1 (en) | Method for producing paper, paperboard and cardboard having high dry strength | |
DE2731934A1 (en) | METHOD FOR MAKING PAPER OR THE LIKE | |
DE69834035T2 (en) | Polysilicate microgels | |
DE3644072A1 (en) | WEIGHED PAPER | |
EP1926855B1 (en) | Method for the production of paper, cardboard and card | |
DE60007549T2 (en) | PRODUCTION OF PAPER AND CARDBOARD | |
DE60008919T2 (en) | Metal silicates, pulp products and related processes | |
WO2006063632A1 (en) | Method and device for loading fibers or cellulose contained in a suspension with a filler | |
DE60222164T2 (en) | MODIFIED THICKNESS AND METHOD THEREFOR | |
DE20220979U1 (en) | Preparation of paper, pasteboard, or cardboard involving cutting of the paper pulp, addition of microparticles of cationic polymer, e.g. cationic polyamide, and a finely divided inorganic component after the last cutting step | |
DE10335751A1 (en) | Method for loading a pulp suspension and arrangement for carrying out the method | |
DE69912954T3 (en) | METHOD FOR PRODUCING PAPER AND PAPER | |
DE4436317C2 (en) | Process for improving the retention of mineral fillers and cellulose fibers on a cellulose fiber sheet | |
DE69737945T2 (en) | Hydrophilic dispersion polymers for paper applications | |
WO2007070912A1 (en) | Paper sizing emulsion, process for preparing it and use thereof | |
DE69617573T3 (en) | METHOD OF PAPER MANUFACTURE | |
DE2335330A1 (en) | POLYMERISATES CONTAINING N- (ALKYLAMINO) - AND / OR N- (ALKYLAMMONIUM) -ACRYLAMIDES AS RETENTION AIDS AND DEWATERING AIDS IN PAPER PRODUCTION | |
EP3044364B1 (en) | Method for producing paper | |
DE69931343T2 (en) | MIXTURE OF SILKY ACID AND ACIDOIL TO A MICROPARTICLE SYSTEM FOR PAPER MANUFACTURE | |
DE19832241A1 (en) | Modified starch used as retention aid in paper production, obtained by digesting starch material in water in presence of a cationic polymer based on dialkylaminoalkylacrylamide and a particulate mineral additive | |
DE10236252B4 (en) | Process for the production of paper, cardboard and cardboard | |
DE1138310B (en) | Process for the production of paper with high wet and dry strength | |
DE102004063005A1 (en) | Process for the production of paper, cardboard and cardboard |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20160411 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20170704 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 948512 Country of ref document: AT Kind code of ref document: T Effective date: 20171215 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502014006342 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180222 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180222 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180223 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502014006342 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 5 |
|
26N | No opposition filed |
Effective date: 20180823 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL Ref country code: DE Ref legal event code: R082 Ref document number: 502014006342 Country of ref document: DE Representative=s name: WITHERS & ROGERS LLP, DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180908 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180908 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180930 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171122 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20140908 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171122 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180322 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20230920 Year of fee payment: 10 Ref country code: GB Payment date: 20230913 Year of fee payment: 10 Ref country code: AT Payment date: 20230921 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230928 Year of fee payment: 10 Ref country code: DE Payment date: 20230920 Year of fee payment: 10 Ref country code: BE Payment date: 20230920 Year of fee payment: 10 |