Method for increasing the advantages of starch in pulped cellulosic material in the production of paper and paperboard
The invention relates to a method for increasing the benefit from starch in pulped, preferably repulped cellulosic material at paper or paperboard manufacturing comprising the steps of (a) pulping a cellulosic material containing a starch; (b) treating the cellulosic material containing the starch with one or more biocides, preferably in the thick stock area; and (h) adding an ionic polymer and preferably, an auxiliary ionic polymer to the cellulosic material; wherein the ionic polymer and the optionally added auxiliary ionic polymer preferably have a different average molecular weight and preferably a different ionicity, wherein the ionicity is the molar content of ionic monomer units relative to the total amount of monomer units.
1. A method for manufacturing paper, paperboard or cardboard comprising the steps of
(a) pulping a cellulosic material containing a starch;
(b) treating the cellulosic material containing the starch with one or more biocides in an amount sufficient to prevent microbiological degradation of at least a portion of the starch; and
(c) adding an ionic polymer and an auxiliary ionic polymer to the cellulosic material;
wherein the ionic polymer and the auxiliary ionic polymer are cationic;
wherein the relative difference between the ionicity of the auxiliary ionic polymer and the ionicity of the ionic polymer is at least 5 mole.-%, wherein the ionicity is the molar content of ionic monomer units relative to the total amount of monomer units; and wherein the ionic polymer has a higher average molecular weight than the auxiliary ionic polymer.
2. The method according to claim 1 , wherein
(i) the ionic polymer comprises cationic monomer units derived from N,N,N-trialkylammoniumalkyl (meth)acrylate, N,N,N-trialkylammoniumalkyl (meth)acrylamide or diallyldialkyl ammonium halide; and
(ii) the auxiliary ionic polymer comprises monomer units derived from N,N,N-trialkylammoniumalkyl (meth)acrylamide.
3. The method according to claim 1 , wherein the auxiliary ionic polymer has a higher ionicity than the ionic polymer; and wherein the relative difference between the ionicity of the auxiliary ionic polymer and that of the ionic polymer is at least 30 mole.-%.
4. The method according to claim 3 , wherein
(i) the ionic polymer has an ionicity within the range of from 20 to 45 mole.-%; and
(ii) the auxiliary ionic polymer has an ionicity of at least 90 mole.-%.
5. The method according to claim 1 , wherein the ionic polymer and/or the auxiliary ionic polymer are added to the cellulosic material in a thick stock area, where the cellulosic material has a stock consistency of at least 2.0 wt.-%.
6. The method according to claim 1 , wherein the ionic polymer and/or the auxiliary ionic polymer are added to the cellulosic material in a thin stock area, where the cellulosic material has a stock consistency of less than 2.0 wt.-%.
7. The method according to claim 1 , wherein the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that
after 1 month of treatment, the pH value of the aqueous phase of the cellulosic material has been increased by at least 0.2 pH units, compared to the pH value that was measured immediately before biocide was added for the first time; and/or
after 1 month of treatment, the electrical conductivity of the aqueous phase of the cellulosic material has been decreased by at least 5%, compared to the electrical conductivity that was measured immediately before biocide was added for the first time; and/or
after 48 hours, the extinction of the starch contained in the aqueous phase of the cellulosic material has been increased by at least 5%, compared to the extinction that was measured immediately before biocide was added for the first time.
8. The method according to claim 1 , wherein the one or more biocides are dosed in an amount of at least 5.0 g/metric ton, based on the total amount of the composition containing the cellulosic material and the starch.
9. The method according to claim 1 , wherein the one or more biocides are added to the cellulosic material in the thick stock area, where the cellulosic material has a stock consistency of at least 2.0%.
10. The method according to claim 1 , wherein the one or more biocides are added in section (I) and/or (II); and optionally also in section (III) and/or (IV) of a papermaking plant comprising a papermaking machine, wherein section (I) includes measures taking place before pulping; section (II) includes measures associated with pulping; section (III) includes measures taking place after pulping but still outside the papermaking machine; and section (IV) includes measures taking place inside the papermaking machine.
11. The method according to claim 1 , wherein the one or more biocides comprise an inorganic ammonium salt in combination with a halogen source.
12. The method according to claim 1 , wherein the one or more biocides are oxidative and/or comprise two components.
13. The method according to claim 1 , wherein additionally to the one or more biocides added in step (b), a further biocide is added to the cellulosic material which differs from the one or more biocides added in step (b).
14. The method according to claim 13 , wherein the further biocide is added in section (I) and/or (II); and optionally, also in section (III) and/or (IV) of a papermaking plant comprising a papermaking machine, wherein section (I) includes measures taking place before pulping; section (II) includes measures associated with pulping; section (III) includes measures taking place after pulping but still outside the papermaking machine; and section (IV) includes measures taking place inside the papermaking machine.
15. The method according to claim 13 , wherein the further biocide is non-oxidizing.
16. The method according to claim 13 , wherein the further biocide is an organic biocide selected from the group consisting of quaternary ammonium compounds, benzyl-C 12-16 -alkyldimethyl chlorides (ADBAC), polyhexamethylenebiguanide (biguanide), 1,2-benzisothiazol-3(2H)-one (BIT), bronopol (BNPD), bis(trichloromethyl)sulfone, diiodomethyl-p-tolylsulfone, bronopol/quaternary ammonium compounds, benzyl-C 12-16 -alkyldimethyl chlorides (BNPD/ADBAC), bronopol/didecyldimethylammonium chloride (BNPD/DDAC), bronopol/5-chloro-2-methyl-2H-isothiazol-3-one/2-methyl-2H-isothiazol-3-one (BNPD/Iso), NABAM/sodium dimethyldithiocarbamate, sodiumdimethyl-dithiocarbamate-N,N-dithiocarbamate (NABAM), sodiummethyldithiocarbamate, sodium dimethyldithiocarbamate, 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2,2-dibromo-2-cyanoacetamide (DBNPA), DBNPA/bronopol/iso (DBNPA/BNPD/Iso), 4,5-dichloro-2-n-octyl-3-isothiazolin-3-one (DCOIT), didecyldimethylammonium chloride (DDAC), didecyldimethylammoniumchloride, alkyldimethylbenzylammoniumchloride (DDAC/ADBAC), dodecylguanidine monohydrochloride/quaternary ammonium compounds, benzyl-C 12-16 -alkyldimethyl chlorides (DGH/ADBAC), dodecylguanidine monohydrochloride/methylene dithiocyanate (DGH/MBT), gluteraldehyde (Glut), gluteraldehyde/quaternary ammonium compounds/benzylcoco alkyldimethyl chlorides (Glut/coco), gluteraldehyde/didecyldimethylammonium chloride (Glut/DDAC), gluteraldehyde/5-chloro-2-methyl-2H-isothiazol-3-one/2-methyl-2H-isothiazol-3-one (Glut/Iso), gluteraldehyde/methylene dithiocyanate (Glut/MBT), 5-chloro-2-methyl-2H-isothiazol-3-one/2-methyl-2H-isothiazol-3-one (Iso), methylene dithiocyanate (MBT), 2-methyl-4-isothiazolin-3-one (MIT), methamine oxirane (methamine oxirane), sodium bromide (NaBr), nitromethylidynetrimethanol, 2-n-octyl-3-isothiazolin-3-one (OIT), bis(trichloromethyl) sulphone/quaternary ammonium compounds, benzyl-C 12-16 -alkyldimethyl chlorides (sulphone/ADBAC), symclosene, terbuthylazine, dazomet (thione), tetrakis(hydroxymethyl)phosphonium sulphate(2:1) (TRPS) and p-[(diiodomethyl)-sulphonyl]toluene (tolyl sulphone), and mixtures thereof.
17. The method according to claim 1 , wherein the ionic polymer and/or the auxiliary ionic polymer is added at the machine chest, mixing chest and/or regulating box.
18. The method according to claim 1 , wherein the ionic polymer and/or the auxiliary ionic polymer has a weight average molecular weight M w of at least 100,000 g/mol.
19. The method according to claim 1 , wherein the ionic polymer and/or the auxiliary ionic polymer contains at least 5.0 mole-% of cationic monomer units.
20. The method according to claim 1 , wherein
(i) the ionic polymer is added in section (II) and/or (III) and/or (IV); and
(ii) the auxiliary ionic polymer is added in section (II) and/or (III) and/or (IV);
of a papermaking plant comprising a papermaking machine, wherein section (II) includes measures associated with pulping; section (III) includes measures taking place after pulping but still outside the papermaking machine; and section (IV) includes measures taking place inside the papermaking machine.
21. The method according to claim 1 , which is
for (re-)fixation of the starch to the cellulosic material; and/or
to increase the strength of paper, paperboard or cardboard; and/or
to increase papermaking machine drainage and/or production rate; and/or
to reduce the effluent COD in the papermaking process; and/or
to reduce the amount of nutrients for microorganisms in the cellulosic material; and/or
to reduce the consumption of fresh starch by recycling starch that is already contained in the starting material and/or the water circuit of the papermaking plant.
22. The method according to claim 1 , wherein the ionic polymer contains 2.5 to 40 mole.-% of cationic monomer units.
23. The method according to claim 1 , wherein
(i) the ionic polymer has an ionicity of at least 5 mole.-%; and
(ii) the auxiliary ionic polymer has an ionicity of at least 90 mole.-%.
24. The method according to claim 1 , wherein the cationic monomer that has been used in the manufacture of the ionic polymer and/or the auxiliary ionic polymer is selected from the group consisting of quaternized dialkylaminoalkyl(meth)acrylates with C 1 to C 6 -alkyl and C 1 to C 6 -alkylene groups, quaternized dialkylaminoalkyl(meth)acrylamides with C 1 to C 6 -alkyl and C 1 to C 6 -alkylene groups, and diallyldimethyl ammonium chloride.
25. The method according to claim 1 , wherein the ionic polymer and the auxiliary ionic polymer independently of one another comprise cationic monomer units selected from the group consisting of quaternized N,N-dimethylaminoethyl acrylate, quaternized N,N-dimethylaminopropyl acrylamide and diallyldimethyl ammonium chloride, and further comprise non-ionic monomer units selected from the group consisting of acrylamide, methacrylamide, vinylamide and vinylamine.
26. The method according to claim 1 , wherein
(i) the ionic polymer comprises cationic monomer units derived from N,N,N-trialkylammoniumalkyl (meth)acrylate, N,N,N-trialkylammoniumalkyl (meth)acrylamide or diallyldialkyl ammonium halide; and
(ii) the auxiliary ionic polymer comprises monomer units derived from diallyldialkyl ammonium halide.
27. The method according to claim 1 , wherein
(i) the ionic polymer comprises cationic monomer units derived from quaternized N,N-dimethylaminoethyl acrylate; and
(ii) the auxiliary ionic polymer comprises monomer units derived from diallyldialkyl ammonium halide.
28. The method according to claim 1 , wherein
(i) the ionic polymer comprises cationic monomer units derived from diallyldimethyl ammonium chloride; and
(ii) the auxiliary ionic polymer comprises monomer units derived from diallyldimethyl ammonium chloride.
29. The method according to claim 1 , wherein
(i) the ionic polymer comprises cationic monomer units derived from N,N,N-trialkylammoniumalkyl(meth)acrylamide; and
(ii) the auxiliary ionic polymer comprises monomer units derived from diallyldimethyl ammonium chloride.
30. The method according to claim 1 , wherein
(i) the ionic polymer comprises cationic monomer units derived from N,N,N-trialkylammoniumalkyl(meth)acrylamide; and
(ii) the auxiliary ionic polymer comprises monomer units derived from N,N,N-trialkylammoniumalkyl (meth)acrylamide.
31. The method according to claim 1 , wherein
(i) the ionic polymer comprises cationic monomer units derived from diallyldimethyl ammonium chloride; and
(ii) the auxiliary ionic polymer comprises monomer units derived from N,N,N-trialkylammoniumalkyl (meth)acrylamide.