EP1090185B1 - Flocculation method for making a paper sheet - Google Patents
Flocculation method for making a paper sheet Download PDFInfo
- Publication number
- EP1090185B1 EP1090185B1 EP99920905A EP99920905A EP1090185B1 EP 1090185 B1 EP1090185 B1 EP 1090185B1 EP 99920905 A EP99920905 A EP 99920905A EP 99920905 A EP99920905 A EP 99920905A EP 1090185 B1 EP1090185 B1 EP 1090185B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- paper
- sheet
- paperboard
- cross
- manufacturing
- 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.)
- Revoked
Links
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000005189 flocculation Methods 0.000 title description 8
- 230000016615 flocculation Effects 0.000 title description 8
- 239000000178 monomer Substances 0.000 claims abstract description 48
- 239000000123 paper Substances 0.000 claims abstract description 37
- 238000010008 shearing Methods 0.000 claims abstract description 33
- 230000014759 maintenance of location Effects 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 29
- 239000011087 paperboard Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000002347 injection Methods 0.000 claims abstract description 10
- 239000007924 injection Substances 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 56
- 239000000839 emulsion Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 31
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 26
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- 229940048053 acrylate Drugs 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000008394 flocculating agent Substances 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- YHXPFHSXEZJGEZ-UHFFFAOYSA-L [Cl-].[O-]C(=O)C=C.CC[N+](C)(C)C.CC[N+](C)(C)C Chemical compound [Cl-].[O-]C(=O)C=C.CC[N+](C)(C)C.CC[N+](C)(C)C YHXPFHSXEZJGEZ-UHFFFAOYSA-L 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
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 claims description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- -1 dialkylaminoalkyl acrylates Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 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
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical class CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 claims description 2
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical class OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920003043 Cellulose fiber Polymers 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003926 acrylamides Chemical class 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 2
- IZZSMHVWMGGQGU-UHFFFAOYSA-L disodium;2-methylidenebutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(=C)C([O-])=O IZZSMHVWMGGQGU-UHFFFAOYSA-L 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 125000001165 hydrophobic group Chemical group 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 claims description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229940047670 sodium acrylate Drugs 0.000 claims description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000007762 w/o emulsion Substances 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- KKSNTCYLMGYFFB-UHFFFAOYSA-N (prop-2-enoylamino)methanesulfonic acid Chemical compound OS(=O)(=O)CNC(=O)C=C KKSNTCYLMGYFFB-UHFFFAOYSA-N 0.000 claims 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000011343 solid material Substances 0.000 claims 1
- 230000006872 improvement Effects 0.000 abstract description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 3
- 238000005259 measurement Methods 0.000 description 13
- 239000000440 bentonite Substances 0.000 description 10
- 229910000278 bentonite Inorganic materials 0.000 description 10
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 10
- 239000011111 cardboard Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 230000009977 dual effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 241000447437 Gerreidae Species 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 3
- 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 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920005372 Plexiglas® Polymers 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- QZVDPDGGEJKYNQ-UHFFFAOYSA-N diazanium prop-2-enoate chloride Chemical compound C(C=C)(=O)[O-].[Cl-].[NH4+].[NH4+] QZVDPDGGEJKYNQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000012726 Water-in-Oil Emulsion Polymerization Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004090 dissolution 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
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000007 metacrylic acid group Chemical group 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—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
- 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
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
- D21H17/43—Carboxyl groups or derivatives thereof
-
- 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
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
Definitions
- the present invention relates to the field of polymers synthetics obtained from water-soluble monomers, or mixtures of such monomers, and their application specific to the manufacture of a sheet of paper, cardboard or similar.
- European patent EP 0 201 237 describes a method of flocculation in which a polymeric material is added to water to form an aqueous composition, and is used to flocculate the solid matter in suspension in an aqueous suspension, said polymer consisting of a high weight polymer molecular, which is subjected to a shear, this shear being carried out before or during flocculation and the polymer in front meet certain intrinsic properties which are indicated in this patent.
- the polymer is a high polymer molecular weight, formed from monomers soluble in water or a mixture of such monomers, and the shear polymer.
- the process described in this patent is characterized in that the front shearing or during flocculation.
- Patent EP 0 201 237 also indicates that the polymer used includes a water swellable crosslinked polymer that it is possible to shear up to an intrinsic viscosity of at least minus 4 dl / g. It is also indicated that the aqueous composition containing the polymeric material can be a stable composition and homogeneous, the shearing then causing an increase in the intrinsic viscosity of at least 1 dl / g.
- stable and homogeneous designates a polymer composition which is stable when the polymer finds complete equilibrium with water, i.e. it has reached its ultimate degree of dissolution or swelling.
- the composition is also homogeneous in the sense that the polymer remains uniformly dispersed throughout the composition, without having tendency to precipitate after a few days.
- the document also states that the shear on the production line, when the suspension at flocculate approach of a centrifuge, a filter press, or a belt press, or other water removal step. It is again note that shear can be applied during a step elimination of the water which is conducted under a certain shear, preferably in a centrifuge or in a filter press or in a belt press.
- the present invention relates to a significant improvement in this process and corresponding flocculating agents, with surprising advantages in the specific application for the manufacture of a sheet of paper, cardboard or the like, and operating under specific conditions which will be described below.
- the monomers can be non-ionic, but generally at least part of the monomers used for forming the polymer is ionic.
- the monomers are usually monoethylenically unsaturated monomers, sometimes allylic monomers, but generally vinyl monomers. These are usually monomers acrylic or metacrylic.
- Suitable nonionic monomers are acrylamide, methacrylamide, N-vinylmethylacetamide or N-vinylformamide, vinyl acetate, vinylpyrrolidone, methyl methacrylate or other acrylic esters, or other ethylenically unsaturated esters, or other monomers vinyl insoluble in water such as styrene or acrylonitrile.
- Suitable anionic monomers are for example sodium acrylate, sodium methacrylate, itaconate sodium, 2-acrylamido 2-methylpropane sulfonate (AMPS), sulfopropylacrylates or sulfopropylmethacrylates, or others water-soluble forms of these sulfonic acids or polymerizable carboxyls.
- AMPS 2-acrylamido 2-methylpropane sulfonate
- sulfopropylacrylates or sulfopropylmethacrylates or others water-soluble forms of these sulfonic acids or polymerizable carboxyls.
- Suitable cationic monomers are dialkylaminoalkyl acrylates and methacrylates, in particular dialkylaminoethyl acrylate, as well as their salts acidified or quaternized by means known to those skilled in the art, such as benzyl chloride, methyl chloride, aryl, alkyl chlorides, dimethylsulfate, and also dialkylaminoalkylalkylacrylamides or -methacrylamides, as well as their acidified or quaternized salts in a known manner, for example methacrylamido-propyl trimethyl ammonium chloride (MAPTAC).
- the alkyl groups in question are generally C 1 -C 4 alkyl groups.
- the monomers can contain hydrophobic groups, as for example described in patent EP 0 172 723, and may in certain cases prefer allyl ether monomers.
- Crosslinking can be done during or after the polymerization, for example by reaction of two polymers soluble with counter ions, or by reaction on formaldehyde or a versatile metal compound. Often the crosslinking takes place during polymerization by the addition of a crosslinking agent, and this solution will be much preferred according to the invention. These crosslinking polymerization processes are known.
- Cross-linking agents which can be incorporated include ionic cross-linking agents such as salts of polyvalent metal, formaldehyde, glyoxal, or even, and preferably covalent crosslinking agents which will copolymerize with the monomers, preferably monomers diethylenically unsaturated (like the ester family of diacrylates such as polyethylene glycols PEG diacrylates) or polyethylene, of the type conventionally used for the crosslinking of water-soluble polymers, and in particular methylenebisacrylamide (MBA) or any of the other known acrylic crosslinking agents.
- ionic cross-linking agents such as salts of polyvalent metal, formaldehyde, glyoxal, or even
- covalent crosslinking agents which will copolymerize with the monomers, preferably monomers diethylenically unsaturated (like the ester family of diacrylates such as polyethylene glycols PEG diacrylates) or polyethylene, of the type conventionally used for the crosslinking of
- the amount of crosslinking agents, and in particular of methylenebisacrylamide (MBA) which can be incorporated according to the invention is generally of the order of 5 to 100, preferably 5 at 40, and according to the best mode, around 20 ppm of crosslinking / active material (polymer).
- the polymers which can be used according to the invention can be prepared by an aqueous solution polymerization method at low concentration, but the invention relates above all to a reverse phase emulsion polymerization, i.e. water-in-oil emulsion polymerization.
- the “dual” systems of the prior art were composed essentially of linear polymers with the addition of bentonite, or a branched polyacrylamide or starch, with addition of colloidal silica, the latter component being extremely expensive.
- an agent is used single retention, preferably in reverse water-in-oil emulsion, crosslinked, sheared before injection, and which leads directly to microflocs without going through the shearing of flocs more important and involving the fibrous mass.
- the Applicant considers that it is product, as a result of the strong shear carried out on the polymer itself before its injection into the fibrous mass of dough, microflocculation directly, which is therefore a process different (and unexpected) from reducing the size of large flocs (and involving the fibrous mass) in smaller and larger flocs robust, and which leads to unplanned improvements in properties of the sheet of paper or cardboard.
- microflocculation also avoids according to the invention the presence of bentonite or another second “dual” agent of retention.
- Reverse emulsion polymerization is very well known of the skilled person.
- Injection or introduction of the crosslinked polymer, and previously sheared according to the invention, is carried out in the dough paper (or fibrous mass to be flocculated) more or less diluted depending on the skilled in the art, and generally in dough diluted paper or “thin stock”, ie a pulp diluted to approximately 0.7% - 1.5% solids such as cellulose fibers, any charges, various additives customary in the manufacture of paper.
- an emulsion may be used reverse of the polymer or the powder obtained from the emulsion by a known drying technique, such as by example by spray drying or “spray-drying”, solvent precipitation or agglomeration (PEG) and grinding (cf.
- the dried product substantially comprises, according to the invention, as the emulsion, and this variant therefore provides a solution for using products dry with the benefits of an emulsion, which it is not always possible to prepare by direct polymerization in aqueous phase in gel or in solution.
- the emulsion will preferably be used reverse of the crosslinked polymer, or else the crosslinked polymer in solution as obtained by redissolving a powder, as described above, with of course shearing prior to injection in the dough.
- tests of laboratory shear at a concentration of the order of 3 - 5 to 10 - 15 g of active ingredient (ie the polymer) / liter, preferably between 5 and 10 g / l, in a material called Ultra Turrax, by example at 10,000 rpm or in a household mixer of the type Moulinex, roughly the same order of magnitude of speed of rotation, for a period between 15 - 30 seconds and 2 - 5 minutes.
- a normal dosage of the agent according to the invention will be such that it leads to approximately 100 to 500 g of active material (polymer) per ton of fibrous material to be treated.
- an ionic boost (IR as defined in the EP 0 201 237) from 40 to 50 or up to at least 60 or 70% or more, up to or above values greater than 100.
- system according to the invention is not expensive, and it therefore combines all the advantages of the systems unique linear or crosslinked products with flock shear and “dual” systems with two retention agents and also with shearing of flocs.
- Example 1, 2 or 3 The manufacturing examples of the polymer are followed by a Table (“example 1, 2 or 3”) indicating the characteristics of the polymer obtained, by a Table (numbered N ° 1, N ° 2 and N ° 3 with the reference of the produced in the preceding tables) in two parts indicating on the one hand the conditions of application test, in particular the conditions of shearing before mixing with the paste, and on the other hand the results of retention, draining and formation , and other similar characteristics.
- the histograms relating to the turbidity measurements of the water under canvas show that the turbidity is divided by a factor of three according to the invention, (Fig. 3-5). Total retention follows the same trend and therefore calls for the same comments.
- SD 448 B is 448 B which has been spray dried drying or spray drying, then dissolving the powder white obtained, shearing of the solution at approximately 5 - 10 g / l polymer and then used as emulsion 448 B.
- the paste used is diluted to a consistency of 1.5%. 2.24 g dry paste is taken, ie 149 g 15% paste and then diluted to 0.4% with clear water.
- G grammage ex.
- G80 grammage of 80 g
- the invention provides an important additional advantage with regard to a very marked improvement in the formation of the sheet.
- the formation designates as is known qualities of the sheet such as homogeneity, and the like. This advantage, which is added to the two preceding ones, is attributable to the microflocculation caused by the agents sheared according to the invention.
- Example 2 The same polymeric agent as in Example 2 is used but at a different dosage (0.1% of polymer relative to the mass fibrous to flocculate).
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Abstract
Description
La présente invention concerne le domaine des polymères synthétiques obtenus à partir de monomères solubles dans l'eau, ou de mélanges de tels monomères, et de leur application spécifique à la fabrication d'une feuille de papier, carton ou analogue.The present invention relates to the field of polymers synthetics obtained from water-soluble monomers, or mixtures of such monomers, and their application specific to the manufacture of a sheet of paper, cardboard or similar.
On a introduit ces polymères comme floculants voici une quarantaine d'années, avec des poids moléculaires qui étaient alors relativement faibles. Le brevet des Etats Unis d'Amérique US-A-3 235 490 (Goren) décrit divers polymères en gels.We introduced these polymers as flocculants here is a forties, with molecular weights that were then relatively weak. The patent of United States of America US-A-3 235,490 (Goren) describes various gel polymers.
On pouvait utiliser certains des polymères de Goren comme coagulants, et notamment pour coaguler des matières solides très fines en suspension.You could use some of Goren’s polymers like coagulants, and in particular for coagulating very solid solids fines in suspension.
On a recherché dans l'industrie depuis au moins deux décennies des floculants modernes, comme par exemple pour la floculation de matières solides en suspension dans le domaine du traitement des eaux, et notamment du traitement des eaux usées municipales, qui sont des polymères linéaires de très haut poids moléculaire. On citera par exemple dans ce domaine le brevet US-A-3,557,061.We have researched in the industry for at least two decades of modern flocculants, as for example for the flocculation of suspended solids in the field of water treatment, including wastewater treatment municipal, which are very high weight linear polymers molecular. We may cite for example in this field US-A-3,557,061.
Le brevet européen EP 0 201 237 décrit un procédé de
floculation dans lequel un matériau polymère est ajouté à de l'eau
pour former une composition aqueuse, et est utilisé pour floculer les
matières solides en suspension dans une suspension aqueuse,
ledit polymère consistant en un polymère de haut poids
moléculaire, que l'on soumet à un cisaillement, ce cisaillement
étant effectué avant ou pendant la floculation et le polymère devant
répondre à certaines propriétés intrinsèques qui sont indiquées
dans ce brevet.
Selon ce document, le polymère est un polymère de haut
poids moléculaire, formé à partir de monomères solubles dans
l'eau ou d'un mélange de tels monomères, et l'on soumet le
polymère au cisaillement. Le procédé décrit dans ce brevet est
caractérisé en ce que l'on peut effectuer le cisaillement avant ou
durant la floculation. Le brevet EP 0 201 237 indique encore que le
polymère utilisé comprend un polymère réticulé gonflable à l'eau
qu'il est possible de cisailler jusqu'à une viscosité intrinsèque d'au
moins 4 dl/g. Il est également indiqué que la composition aqueuse
contenant le matériau polymère peut être une composition stable et
homogène, le cisaillement provoquant alors une augmentation de
la viscosité intrinsèque d'au moins 1 dl/g.According to this document, the polymer is a high polymer
molecular weight, formed from monomers soluble in
water or a mixture of such monomers, and the
shear polymer. The process described in this patent is
characterized in that the front shearing or
during flocculation.
Par « stable et homogène », ce document désigne une composition de polymère qui est stable lorsque le polymère se trouve en équilibre complet avec l'eau, c'est-à-dire qu'il a atteint son degré ultime de mise en solution ou de gonflement. La composition est par ailleurs homogène en ce sens que le polymère reste uniformément dispersé dans toute la composition, sans avoir tendance à précipiter au terme de quelques jours.By "stable and homogeneous", this document designates a polymer composition which is stable when the polymer finds complete equilibrium with water, i.e. it has reached its ultimate degree of dissolution or swelling. The composition is also homogeneous in the sense that the polymer remains uniformly dispersed throughout the composition, without having tendency to precipitate after a few days.
Ce document décrit en particulier de nombreuses applications pour le traitement de l'eau , qui est manifestement l'application tout à fait principale qui est visée, et le traitement du minerai de charbon.This document describes in particular many applications for water treatment, which is clearly the very main application that is targeted, and the processing of the coal ore.
Ce brevet mentionne également, très brièvement et sans donner d'exemple de réalisation, ni même d'indications précises de mise en pratique, une application à la fabrication du papier ou d'un carton; il est seulement indiqué que le polymère peut être ajouté à un stade précoce de la ligne de circulation de pâte (masse fibreuse) avec un cisaillement le long de la ligne d'écoulement de la suspension, vers l'étape de drainage ou une autre étape d'élimination de l'eau. Le brevet indique que le cisaillement est effectué par le pompage, donc par la « fan pump » ou pompe de mélange située effectivement en ligne sur les machines à papier.This patent also mentions, very briefly and without give an example of realization, or even precise indications of put into practice, an application to the manufacture of paper or a cardboard; it is only indicated that the polymer can be added to an early stage of the pulp circulation line (fibrous mass) with a shear along the flow line of the suspension, towards the drainage stage or another stage water disposal. The patent indicates that the shear is carried out by pumping, therefore by the "fan pump" mixture actually located online on paper machines.
Pour les autres applications, et notamment le traitement des eaux, le document indique également que l'on peut effectuer le cisaillement sur la ligne de production, lorsque la suspension à floculer approche d'une centrifugeuse, un filtre presse, ou une presse à bande, ou une autre étape d'élimination de l'eau. Il est encore noté que le cisaillement peut être appliqué durant une étape d'élimination de l'eau qui est conduite sous un certain cisaillement, de préférence dans une centrifugeuse ou encore dans un filtre presse ou dans une presse à bande.For other applications, and in particular the processing of waters, the document also states that the shear on the production line, when the suspension at flocculate approach of a centrifuge, a filter press, or a belt press, or other water removal step. It is again note that shear can be applied during a step elimination of the water which is conducted under a certain shear, preferably in a centrifuge or in a filter press or in a belt press.
Ce document n'enseigne donc qu'un cisaillement dans la pompe de mélange ou « fan pump » pour l'application papier. Il enseigne par ailleurs que des taux de cisaillement très faibles peuvent convenir dans les autres applications, puisque les filtre presse et les presses à bande induisent un très faible cisaillement.This document therefore teaches only shearing in the mixing pump or "fan pump" for paper application. he also teaches that very low shear rates may be suitable for other applications, since filters press and belt presses induce very low shear.
La présente invention concerne une amélioration notable de ce procédé et des agents de floculation correspondants, avec des avantages surprenants dans l'application spécifique pour la fabrication d'une feuille de papier, carton ou analogue, et en opérant selon des conditions particulières qui seront décrites ci-dessous.The present invention relates to a significant improvement in this process and corresponding flocculating agents, with surprising advantages in the specific application for the manufacture of a sheet of paper, cardboard or the like, and operating under specific conditions which will be described below.
Selon le procédé la présente invention, on utilise comme agent unique
de floculation, destiné à améliorer nettement la rétention, la
formation, l'égouttage, et d'autres propriétés de la feuille de papier
ou carton ainsi obtenue, un polymère ou copolymère réticulé formé
par polymérisation ou
copolymérisation de
monomères
qui sont choisis parmi
des monomères à
insaturation monoéthylénique, des monomères allyliques,
et des monomères vinyliques, notamment des monomères acryliques
ou métacryliques,
solubles dans l'eau ou de
mélanges de tels monomères,
que
l'on cisaille avant l'introduction ou l'injection
dans la suspension ou masse fibreuse à floculer, et
et en ce que l'on effectue le cisaillement à une
concentration de l'ordre de 3 - 5 à 10 - 15 g de matière active ( cad
le polymère) / litre, de préférence entre 5 et 10 g/l,
à 10.000 tours/minute ou dans un mixer
ménager sensiblement au même ordre de
grandeur de vitesse de rotation, durant une durée
comprise entre 15 - 30 secondes et 2 - 5 minutes,
et on obtient par le cisaillement un regain
ionique IR de 40 à 50 ou pouvant atteindre au moins 60 ou 70 % et
même plus; jusqu'à des valeurs supérieures ou très supérieures à
100, avec:
- X :
- ionicité après cisaillement en meq/g.
- Y :
- ionicité avant cisaillement en meq/g.
- X:
- ionicity after shearing in meq / g.
- Y:
- ionicity before shearing in meq / g.
On ne procède donc pas au cisaillement de la suspension contenant le polymère.We therefore do not shear the suspension containing the polymer.
Les monomères peuvent être non ioniques, mais généralement au moins une partie des monomères utilisés pour former le polymère est ionique. Les monomères sont habituellement des monomères à insaturation monoéthylénique, quelquefois des monomères allyliques, mais généralement des monomères vinyliques. Ce sont généralement des monomères acryliques ou métacryliques.The monomers can be non-ionic, but generally at least part of the monomers used for forming the polymer is ionic. The monomers are usually monoethylenically unsaturated monomers, sometimes allylic monomers, but generally vinyl monomers. These are usually monomers acrylic or metacrylic.
Des monomères non ioniques convenables sont l'acrylamide, le methacrylamide, le N-vinylméthylacétamide ou le N-vinylformamide, l'acétate de vinyle, la vinylpyrrolidone, le methacrylate de méthyle ou d'autres esters acryliques, ou d'autres esters à insaturation éthylénique, ou encore d'autres monomères vinyliques insolubles dans l'eau comme le styrène ou l'acrylonitrile.Suitable nonionic monomers are acrylamide, methacrylamide, N-vinylmethylacetamide or N-vinylformamide, vinyl acetate, vinylpyrrolidone, methyl methacrylate or other acrylic esters, or other ethylenically unsaturated esters, or other monomers vinyl insoluble in water such as styrene or acrylonitrile.
Des monomères anioniques convenables sont par exemple l'acrylate de sodium, le methacrylate de sodium, l'itaconate de sodium, le 2-acrylamido 2-méthylpropane sulfonate (AMPS), les sulfopropylacrylates ou les sulfopropylmethacrylates, ou d'autres formes solubles dans l'eau de ces acides sulfoniques ou carboxyliques polymérisables. On pourra utiliser un vinylsulfonate de sodium, ou un allylsulfonate, ou un acrylamide sulfométhylé.Suitable anionic monomers are for example sodium acrylate, sodium methacrylate, itaconate sodium, 2-acrylamido 2-methylpropane sulfonate (AMPS), sulfopropylacrylates or sulfopropylmethacrylates, or others water-soluble forms of these sulfonic acids or polymerizable carboxyls. We can use a vinyl sulfonate sodium, or an allylsulfonate, or a sulfomethylated acrylamide.
Des monomères cationiques convenables sont les acrylates et methacrylates de dialkylaminoalkyle, en particulier l'acrylate de dialkylaminoéthyle, ainsi que leurs sels acidifiés ou quaternisés par les moyens connus de l'homme de métier, comme le chlorure de benzyle, le chlorure de méthyle, les chlorures d'aryle, d'alkyle, le diméthylsulfate, et encore les dialkylaminoalkylalkylacrylamides ou -methacrylamides, ainsi que leurs sels acidifiés ou quaternisés de manière connue, par exemple le methacrylamido-propyl triméthyl ammonium chlorure (MAPTAC). Les groupes alkyle dont il est question sont généralement des groupes alkyle en C1-C4.Suitable cationic monomers are dialkylaminoalkyl acrylates and methacrylates, in particular dialkylaminoethyl acrylate, as well as their salts acidified or quaternized by means known to those skilled in the art, such as benzyl chloride, methyl chloride, aryl, alkyl chlorides, dimethylsulfate, and also dialkylaminoalkylalkylacrylamides or -methacrylamides, as well as their acidified or quaternized salts in a known manner, for example methacrylamido-propyl trimethyl ammonium chloride (MAPTAC). The alkyl groups in question are generally C 1 -C 4 alkyl groups.
Les monomères peuvent contenir des groupes hydrophobes,
comme par exemple décrits dans le brevet EP 0 172 723, et on
pourra préférer dans certains cas des monomères d'éther allylique.The monomers can contain hydrophobic groups,
as for example described in
On pourra effectuer la réticulation durant ou après la polymérisation, par exemple par réaction de deux polymères solubles présentant des contre ions, ou par réaction sur du formaldéhyde ou un composé de métal polyvalent. Souvent, la réticulation s'effectue durant la polymérisation par addition d'un agent réticulant, et cette solution sera nettement préférée selon l'invention. Ces procédés de polymérisation avec réticulation sont connus.Crosslinking can be done during or after the polymerization, for example by reaction of two polymers soluble with counter ions, or by reaction on formaldehyde or a versatile metal compound. Often the crosslinking takes place during polymerization by the addition of a crosslinking agent, and this solution will be much preferred according to the invention. These crosslinking polymerization processes are known.
Les agents de réticulation que l'on peut incorporer comprennent des agents de réticulation ioniques comme les sels de métal polyvalent, le formaldéhyde, le glyoxal, ou encore, et de préférence, des agents de réticulation covalents qui vont copolymériser avec les monomères, de préférence des monomères à insaturation diéthylénique ( comme la famille des esters de diacrylates comme les diacrylates de polyéthylène glycols PEG) ou polyéthylénique, du type que l'on utilise classiquement pour la réticulation des polymères solubles dans l'eau, et notamment le méthylènebisacrylamide (MBA) ou encore un quelconque des autres agents de réticulation acryliques connus.Cross-linking agents which can be incorporated include ionic cross-linking agents such as salts of polyvalent metal, formaldehyde, glyoxal, or even, and preferably covalent crosslinking agents which will copolymerize with the monomers, preferably monomers diethylenically unsaturated (like the ester family of diacrylates such as polyethylene glycols PEG diacrylates) or polyethylene, of the type conventionally used for the crosslinking of water-soluble polymers, and in particular methylenebisacrylamide (MBA) or any of the other known acrylic crosslinking agents.
La quantité d'agents de réticulation, et notamment de méthylènebisacrylamide (MBA) que l'on peut incorporer selon l'invention est généralement de l'ordre de 5 à 100, de préférence 5 à 40, et selon le meilleur mode, autour de 20 ppm d'agent de réticulation / matière active (polymère).The amount of crosslinking agents, and in particular of methylenebisacrylamide (MBA) which can be incorporated according to the invention is generally of the order of 5 to 100, preferably 5 at 40, and according to the best mode, around 20 ppm of crosslinking / active material (polymer).
On se référera pour le détail de ce qui précède au contenu
du brevet EP 0 201 237, qui est incorporé ici par référence.We will refer for the detail of the above to the content
of
Les polymères utilisables selon l'invention peuvent être préparés par une méthode de polymérisation en solution aqueuse à faible concentration, mais l'invention concerne avant tout une polymérisation en émulsion en phase inverse, c'est-à-dire une polymérisation en émulsion eau-dans-huile.The polymers which can be used according to the invention can be prepared by an aqueous solution polymerization method at low concentration, but the invention relates above all to a reverse phase emulsion polymerization, i.e. water-in-oil emulsion polymerization.
On connaít également dans l'art antérieur des systèmes d'agents de rétention pour la fabrication d'une feuille de papier, carton ou analogue, qui consistent en une combinaison de deux agents de rétention, généralement un agent de rétention principal et un agent de rétention secondaire. Il s'agit alors d'un système qualifié de « dual ».We also know in the prior art systems retention agents for the manufacture of a sheet of paper, cardboard or the like, which consist of a combination of two retention officers, usually a primary retention officer and a secondary retention agent. It is then a system qualified as "dual".
Dans le brevet US-A-4,753,710, on préconise ainsi l'emploi d'un polymère acrylique linéaire de haut poids moléculaire comme agent de rétention principal, qui est ajouté à la masse fibreuse, puis un cisaillement notamment dans la pompe de mélange ou « fan pump », puis un ajout de bentonite (qui est une argile gonflante) comme agent de rétention secondaire. Ce document ne suggère et ne décrit aucun cisaillement du polymère lui-même avant l'introduction dans la suspension à floculer.In US-A-4,753,710, the use is thus recommended of a high molecular weight linear acrylic polymer such as main retention agent, which is added to the fibrous mass, and then shear in particular in the mixing pump or "fan pump ", then an addition of bentonite (which is a swelling clay) as a secondary retention agent. This document does not suggest and describes no shearing of the polymer itself before introduction into the suspension to be flocculated.
On connaít encore dans l'art antérieur des agents de
floculation réticulés tels que décrits par exemple dans le brevet
EP 0 202 780, pour le traitement des eaux, essentiellement, et
secondairement le papier. Il convient de noter qu'il emploie un
produit réticulé, qui est ajouté à la suspension à floculer, les flocs
étant ensuite cisaillés dans le processus de fabrication du papier,
c'est-à-dire cisaillés dans et en même temps que la pâte à papier.
Les flocs sont ainsi transformés en flocs plus petits et résistant au
cisaillement, donc plus robustes. Ce document ne suggère et ne
décrit donc aucun cisaillement du polymère lui-même avant
l'introduction dans la suspension à floculer.We still know in the prior art agents
crosslinked flocculation as described for example in the
Selon les techniques antérieures relatives aux applications papier, on forme ainsi, entre l'agent 'de flocculation et la masse fibreuse de pâte, des flocs d'une assez grande dimension, qui sont ensuite cisaillés afin de former des flocs dont on indique dans les documents cités qu'ils sont plus petits et plus robustes.According to prior techniques relating to applications paper, we thus form, between the agent of flocculation and the mass fibrous dough, fairly large flocks, which are then sheared to form flocs which are indicated in the cited documents they are smaller and more robust.
De plus, les systèmes de l'art antérieur du type système dual, imposent l'emploi de deux composants de rétention, et notamment l'emploi de la bentonite qui est un produit très lourd à utiliser dans l'industrie, ne serait-ce que par les problèmes d'environnement qu'il provoque. Cette bentonite est nécessaire pour provoquer le réassemblage des flocs cisaillés, sinon ceux-ci ne tiennent pas sur la toile d'égouttage ou de drainage du papier. De tels systèmes peuvent être qualifiés de «microparticulaires», et ils comprennent au moins deux agents de rétention.In addition, the prior art systems of the dual system type, require the use of two retention components, and in particular the use of bentonite which is a very heavy product to use in industry, if only for environmental reasons that it provokes. This bentonite is necessary to cause the reassembly of the sheared flocs, otherwise they do not hold on drip cloth or paper drainage. Such systems can be called "microparticles", and they include at least two retention officers.
Les systèmes « dual » de l'art antérieur étaient composés essentiellement de polymères linéaires avec adjonction de bentonite, ou d'un polyacrylamide ramifié ou d'amidon, avec adjonction de silice colloïdale, ce dernier composant étant extrêmement onéreux.The “dual” systems of the prior art were composed essentially of linear polymers with the addition of bentonite, or a branched polyacrylamide or starch, with addition of colloidal silica, the latter component being extremely expensive.
On connaít une amélioration à ces procédés, décrite dans le brevet FR 95 13 051 au nom du Demandeur, qui concerne un système dual à base d'un polymère de type polyacrylamide linéaire ou ramifié et de kaolin, le kaolin étant une argile non gonflante qui ne présente pas les lourds inconvénients de la bentonite, le kaolin étant prétraité dans un mode préféré de réalisation.There is an improvement to these processes, described in the patent FR 95 13 051 in the name of the Applicant, which relates to a dual system based on a linear polyacrylamide polymer or branched and kaolin, kaolin being a non-swelling clay which does not have the serious disadvantages of bentonite, kaolin being pretreated in a preferred embodiment.
Au contraire, selon le procédé de la présente invention, on utilise un agent de rétention unique, de préférence en émulsion inverse eau-dans-huile, réticulé, cisaillé avant son injection, et qui conduit directement à des microflocs sans passer par le cisaillement de flocs plus importants et impliquant la masse fibreuse.On the contrary, according to the process of the present invention, an agent is used single retention, preferably in reverse water-in-oil emulsion, crosslinked, sheared before injection, and which leads directly to microflocs without going through the shearing of flocs more important and involving the fibrous mass.
Selon l'invention, et sans vouloir être limité par une quelconque théorie, le Demandeur considère en effet qu'il se produit, à la suite du fort cisaillement effectué sur le polymère lui-même avant son injection dans la masse fibreuse de pâte, directement une microfloculation, ce qui est donc un processus différent (et inattendu) de la réduction de taille de flocs importants (et impliquant la masse fibreuse) en flocs plus petits et plus robustes, et qui conduit à des améliorations non prévues des propriétés de la feuille de papier ou carton.According to the invention, and without wishing to be limited by a any theory, the Applicant considers that it is product, as a result of the strong shear carried out on the polymer itself before its injection into the fibrous mass of dough, microflocculation directly, which is therefore a process different (and unexpected) from reducing the size of large flocs (and involving the fibrous mass) in smaller and larger flocs robust, and which leads to unplanned improvements in properties of the sheet of paper or cardboard.
Cette « microfloculation » évite par ailleurs selon l'invention la présence de bentonite ou d'un autre second agent « dual » de rétention.This “microflocculation” also avoids according to the invention the presence of bentonite or another second “dual” agent of retention.
On évite également selon l'invention les contraintes et les problèmes notables liés au réglage et à l'optimisation des paramètres de flocculation d'un système dual, dont le choix précis des points d'introduction respectifs des deux réactifs.The constraints and the notable issues related to tuning and optimizing flocculation parameters of a dual system, including the precise choice respective introduction points of the two reagents.
La polymérisation en émulsion inverse est très bien connue de l'homme de métier.Reverse emulsion polymerization is very well known of the skilled person.
On notera que, contrairement à certains aspects de
l'enseignement du brevet EP 0 201 237, un cisaillement dans les
conditions de lignes décrites dans ce document avec une référence
très brève à la fabrication du papier, page 6 ligne 3 - 4 , ne conduit
absolument pas aux résultats de l'invention.Note that, unlike some aspects of
the teaching of
Par exemple, un cisaillement dans une pompe du type « fan
pump » ou pompe centrifuge ne donne pas le résultat escompté.
Notamment, et encore une fois en référence avec une mention
extrêmement brève d'une « production de papier et de carton »,
l'introduction selon le brevet EP 0 201 237 de l'agent de rétention
selon la ligne de process « flow line » vers une étape de drainage
ou une autre étape d'élimination de l'eau, ne fonctionne
absolument pas.For example, shearing in a fan-type pump
pump ”or centrifugal pump does not give the expected result.
In particular, and again with reference to a mention
extremely brief of a "production of paper and cardboard",
the introduction according to
Au contraire, il a été découvert selon l'invention que, pour l'application concernant la fabrication d'une feuille de papier ou de carton ou analogue, il était essentiel d'effectuer un fort cisaillement avant l'injection du polymère réticulé dans la pâte à papier ou masse fibreuse devant être floculée.On the contrary, it has been discovered according to the invention that, for the application for making a sheet of paper or cardboard or the like, it was essential to make a strong shear before injecting the crosslinked polymer into the pulp or fibrous mass to be flocculated.
L'injection ou introduction du polymère réticulé, et préalablement cisaillé selon l'invention, est effectuée dans la pâte à papier (ou masse fibreuse à flocculer) plus ou moins diluée selon la pratique de l'homme du métier, et généralement dans la pâte à papier diluée ou « thin stock », cad une pâte diluée à environ 0,7% - 1,5% de matières solides telles que fibres de cellulose, charges éventuelles, divers additifs usuels de la fabrication du papier.Injection or introduction of the crosslinked polymer, and previously sheared according to the invention, is carried out in the dough paper (or fibrous mass to be flocculated) more or less diluted depending on the skilled in the art, and generally in dough diluted paper or “thin stock”, ie a pulp diluted to approximately 0.7% - 1.5% solids such as cellulose fibers, any charges, various additives customary in the manufacture of paper.
Selon une variante de l'invention, à introduction fractionnée, on introduira une partie du polymère réticulé, et cisaillé selon l'invention, au niveau de l'étape de préparation de la pâte épaisse ou « thick stock » à env. 5 % ou plus de matières solides , ou même au niveau de la préparation de la pâte épaisse.According to a variant of the invention, with fractional introduction, we will introduce a part of the crosslinked polymer, and sheared according to the invention, in the thick dough preparation step or "thick stock" at approx. 5% or more solids, or even in the preparation of thick dough.
Selon une variante de l'invention, on pourra utiliser une émulsion
inverse du polymère ou bien la poudre obtenue à partir de
l'émulsion par une technique de séchage connue, comme par
exemple par séchage par pulvérisation ou « spray-drying »,
précipitation au solvant ou agglomération (PEG) et broyage ( cf. à
ce sujet l'art antérieur tel que US-A-5,696,228, WO 97 / 48 755
(USSN 08/668,288) , WO 97 / 48 750, WO 97 / 48 732, WO 97 / 34
945, WO 96 / 10589, US-A-5,346,986, 5,684,107, EP 0 412 388,
EP 0 238 050, US-A-4,873,299, EP 0 742 231, WO 90 / 08789 ou
EP 0 224 923) que l'on redissous dans l'eau, cisaille puis met en
oeuvre comme une émulsion.According to a variant of the invention, an emulsion may be used
reverse of the polymer or the powder obtained from
the emulsion by a known drying technique, such as by
example by spray drying or “spray-drying”,
solvent precipitation or agglomeration (PEG) and grinding (cf.
this subject the prior art such as US-A-5,696,228, WO 97 / 48,755
(USSN 08 / 668,288), WO 97/48 750, WO 97/48 732, WO 97/34
945, WO 96/10589, US-A-5,346,986, 5,684,107,
Cette variante est très intéressante car le produit séché se comporte sensiblement, selon l'invention, comme l'émulsion, et cette variante procure donc une solution pour utiliser des produits secs ayant les avantages d'une émulsion, qu'il n'est pas toujours possible de préparer par polymérisation directe en phase aqueuse en gel ou en solution.This variant is very interesting because the dried product substantially comprises, according to the invention, as the emulsion, and this variant therefore provides a solution for using products dry with the benefits of an emulsion, which it is not always possible to prepare by direct polymerization in aqueous phase in gel or in solution.
Selon l'invention, on utilisera de préférence l'émulsion inverse du polymère réticulé, ou bien le polymère réticulé en solution tel qu'obtenu par redissolution d'une poudre, comme décrit ci-dessus, avec bien entendu cisaillement préalable à l'injection dans la pâte.According to the invention, the emulsion will preferably be used reverse of the crosslinked polymer, or else the crosslinked polymer in solution as obtained by redissolving a powder, as described above, with of course shearing prior to injection in the dough.
On trouvera ci-dessous un exemple comparatif montrant que, si l'on effectue le cisaillement de la masse fibreuse (cad après l'addition du polymère) dans une application papier, on n'obtient pas de rétention. Sans vouloir être limitée par une quelconque théorie, le Demandeur considère que cela est dû au fait qu'on ne libère pas la charge cationique.Below is a comparative example showing that, if the fibrous mass is sheared (ie after addition of the polymer) in a paper application, one does not obtain no retention. Without wishing to be limited by any theory, the Applicant considers that this is due to the fact that no not release the cationic charge.
Selon l'invention, on pourra effectuer des essais de cisaillement en laboratoire, à une concentration de l'ordre de 3 - 5 à 10 - 15 g de matière active ( cad le polymère) / litre, de préférence entre 5 et 10 g/l, dans un matériel dénommé Ultra Turrax, par exemple à 10.000 tours/minute ou dans un mixer ménager du type Moulinex, sensiblement au même ordre de grandeur de vitesse de rotation, durant une durée comprise entre 15 - 30 secondes et 2 - 5 minutes.According to the invention, tests of laboratory shear, at a concentration of the order of 3 - 5 to 10 - 15 g of active ingredient (ie the polymer) / liter, preferably between 5 and 10 g / l, in a material called Ultra Turrax, by example at 10,000 rpm or in a household mixer of the type Moulinex, roughly the same order of magnitude of speed of rotation, for a period between 15 - 30 seconds and 2 - 5 minutes.
Dans l'industrie, il existe des matériels qui conviennent à la
mise en oeuvre de l'invention, par exemple des pompes haute
pression ou des turbines, qui ne sont pas concernés par l'exemple
théorique du document EP 0 201 237.In industry, there are materials that are suitable for
implementation of the invention, for example high pumps
pressure or turbines, which are not affected by the example
theoretical of
L'homme de métier saura naturellement envisager tous les équipements possibles permettant d'effectuer un fort cisaillement de l'émulsion de polymère, diluée à une valeur appropriée comme il sera décrit ci-dessous, sans être limité aux exemples ci-dessus.A person skilled in the art will naturally be able to envisage all the possible equipment for performing high shear of the polymer emulsion, diluted to an appropriate value as it will be described below, without being limited to the above examples.
Pour les généralités de la fabrication d'une pâte à papier ou carton et analogues, ainsi que la liste des additifs, charges, etc...., qui sont bien connus, l'homme de métier pourra se référer utilement au US-A-4,753,710 dont l'enseignement est incorporé ici par référence.For the generalities of making paper pulp or cardboard and the like, as well as the list of additives, fillers, etc., which are well known, those skilled in the art can usefully refer to to US-A-4,753,710, the teaching of which is incorporated here by reference.
Un dosage normal de l'agent selon l'invention sera tel qu'il conduise à environ 100 à 500 g de matière active (polymère) par tonne de matière fibreuse à traiter.A normal dosage of the agent according to the invention will be such that it leads to approximately 100 to 500 g of active material (polymer) per ton of fibrous material to be treated.
Selon l'invention, on peut utiliser un polymère présentant une viscosité intrinsèque i.v. aussi faible que 1 à 3, qui devient une viscosité intrinsèque aussi élevée que 3 -7 ou -8 après l'application du cisaillement.According to the invention, it is possible to use a polymer having an intrinsic viscosity i.v. as low as 1 to 3, which becomes a intrinsic viscosity as high as 3 -7 or -8 after application shear.
Selon l'invention, on obtient, par une optimisation à la portée
de l'homme de métier, un regain ionique (IR tel que défini dans le
brevet EP 0 201 237) de 40 à 50 ou pouvant atteindre au moins 60
ou 70 % et même plus, jusqu'à des valeurs supérieures ou très
supérieures à 100.According to the invention, by optimization within reach,
skilled in the art, an ionic boost (IR as defined in the
On peut de plus ajuster le cisaillement de manière à favoriser, pour la première fois dans cette industrie, une propriété du papier par rapport à une autre, par exemple favoriser un peu plus la rétention que la formation et l'égouttage, ou l'inverse, ou les différentes combinaisons possibles, comme cela sera visible à la lecture des exemples qui vont suivre.It is also possible to adjust the shear so as to favor, for the first time in this industry, a property paper over another, for example favor a little more retention than formation and drainage, or vice versa, or different possible combinations, as will be visible on the reading of the examples which will follow.
De plus, le système selon l'invention n'est pas onéreux, et il combine par conséquent l'ensemble des avantages des systèmes de produits linéaires ou réticulés uniques à cisaillement de flocs et des systèmes « dual » à deux agents de rétention et également à cisaillement de flocs.In addition, the system according to the invention is not expensive, and it therefore combines all the advantages of the systems unique linear or crosslinked products with flock shear and “dual” systems with two retention agents and also with shearing of flocs.
Les exemples de fabrication du polymère sont suivis d'un Tableau (« exemple 1, 2 ou 3 ») indiquant les caractéristiques du polymère obtenu, d'un Tableau ( numéroté N°1, N°2 et N°3 avec la référence du produit dans les tableaux précédents ) en deux parties indiquant d'une part les conditions d'essai d'apptication, notamment les conditions de cisaillement avant mélange avec la pâte, et d'autre part les résultats de rétention, d'égouttage et de formation, et autres caractéristiques analogues.The manufacturing examples of the polymer are followed by a Table (“example 1, 2 or 3”) indicating the characteristics of the polymer obtained, by a Table (numbered N ° 1, N ° 2 and N ° 3 with the reference of the produced in the preceding tables) in two parts indicating on the one hand the conditions of application test, in particular the conditions of shearing before mixing with the paste, and on the other hand the results of retention, draining and formation , and other similar characteristics.
Ces tableaux en deux parties permettent de tracer les graphes d'égouttage, de rétention ou de turbidité qui sont annexés sous forme des figures 1 à 8.These two-part tables are used to draw the graphs of drainage, retention or turbidity which are annexed under form of Figures 1 to 8.
Les abbréviations ont les sens indiqués ci dessous.
Dans un réacteur A, on mélange à température ambiante les
constituants de la phase organique de l'émulsion à synthétiser.
- 266 g d'exxsol D100
- 18 g de Span 80
- 6 g d'Hypermer 2296.
- 438 g d'acrylamide à 50 %
- 186,5 g de chlorure d'acrylate d'éthyl triméthyl ammonium (80 %)
- 85 g d'eau
- 0,31 ml de méthylène bis acrylamide à 6 g/l
- 1,50 ml de bromate de sodium à 50 g/l
- 0,24 ml de Versenex à 200 g/l
- pH : 4.
- 266 g of exxsol D100
- 18 g Span 80
- 6 g of Hypermer 2296.
- 438 g of 50% acrylamide
- 186.5 g of ethyl trimethyl ammonium acrylate chloride (80%)
- 85 g water
- 0.31 ml of methylene bis acrylamide at 6 g / l
- 1.50 ml sodium bromate at 50 g / l
- 0.24 ml of Versenex at 200 g / l
- pH: 4.
On mélange le contenu de B dans A sous agitation. Après le
mélange des phases, on cisaille l'émulsion au mixer pendant 1
minute afin de créer l'émulsion inverse. L'émulsion est alors
dégazée par un bullage d'azote puis après 20 minutes, l'addition
progressive du métabisulfite entraíne l'initiation puis la
polymérisation.
La réaction terminée, on effectue un bum out afin de diminuer la
teneur en monomère libre.
L'émulsion est alors incorporée avec son tensio-actif inverseur afin
de libérer par la suite le polymère en phase aqueuse.
When the reaction is complete, a bum out is carried out in order to reduce the content of free monomer.
The emulsion is then incorporated with its inverting surfactant in order to subsequently release the polymer in the aqueous phase.
Définitions des regains ioniques et regains de viscosité intrinsèque:
- avec X :
- ionicité après cisaillement en meq/g.
- Y :
- ionicité avant cisaillement en meq/g.
- avec V1 :
- viscosité intrinsèque après cisaillement en dl/g
- V2 :
- viscosité intrinsèque avant cisaillement en dl/g
- with X:
- ionicity after shearing in meq / g.
- Y:
- ionicity before shearing in meq / g.
- with V1:
- intrinsic viscosity after shearing in dl / g
- V2:
- intrinsic viscosity before shearing in dl / g
G = grammage ex. G80 = grammage de 80 g / m2
G = grammage ex. G80 = grammage of 80 g / m2
Le volume de 560 ml est introduit dans le cylindre en plexiglas de la formette automatisée et l'on démarre la séquence.
- t = 0 s, démarrage agitation à 1500 rpm.
- t = 10 s, addition du polymère.
- t = 60 s, réduction automatique à 1000 rpm et addition si nécessaire de la bentonite.
- t = 75 s, arrêt de l'agitation, formation de la feuille avec le vide sous toile puis récupération des eaux blanches.
- mesure de la turbidité des eaux sans toile.
- dilution d'un bêcher de pâte épaisse pour une nouvelle feuille avec les eaux sous toiles recueillies.
- séchage de la feuille dite 1ère passe («X» = 1ère passe)
- démarrage d'une nouvelle séquence afin de réaliser la feuille dite 2nde passe.
- t = 0 s, stirring start at 1500 rpm.
- t = 10 s, addition of the polymer.
- t = 60 s, automatic reduction to 1000 rpm and addition, if necessary, of bentonite.
- t = 75 s, stirring stopped, formation of the sheet with the vacuum under canvas then recovery of the white water.
- measurement of the turbidity of water without canvas.
- dilution of a beaker of thick paste for a new leaf with the water under canvas collected.
- drying of the sheet called 1st pass (“X” = 1st pass)
- start of a new sequence in order to make the so-called 2nd pass sheet.
Après 3 passes, l'on change de produits à tester.
Les analyses suivantes sont alors réalisées :
- mesure des matières en suspension des eaux sous toile (Norme TAPPI: T 656 cm / 83 )
- mesure du poids des cendres des feuilles, (Norme TAPPI: T 211 om - 93 )
- mesure de la turbidité 30' après que les fibres soient déposées
afin de connaítre l'état du milieu ionique.
(MES= matières en suspension) - mesure du degré d'égouttabilité de la pâte avec un Canadian Standard Freeness ( CSF; norme TAPPI T 227 om - 94 ).
The following analyzes are then carried out:
- measurement of suspended matter in canvas (TAPPI standard: T 656 cm / 83)
- measurement of the weight of the ash from the leaves, (TAPPI standard: T 211 om - 93)
- measurement of the turbidity 30 'after the fibers are deposited in order to know the state of the ionic medium.
(MES = suspended matter) - measurement of the degree of dripability of the dough with a Canadian Standard Freeness (CSF; standard TAPPI T 227 om - 94).
Les résultats sont présentés dans le tabkeau 1 et les figures tels
que définis ci-dessous :
En ce qui concerne la rétention de charge les résultats montrent
qu'il existe peu d'intérêt à utilise une émulsion de polymère
réticulé non cisaillée (valeur 64,13%) à un dosage habituel dans
cette industrie, de 500 g/l , par rapport à une émulsion de
polyacrylamide linéaire ( 69,95 %) (Essais 2 et 3, Fig. 2).
Par contre, l'intérêt du cisaillement de l'émulsion réticulée, avant
son addition à la suspension ou masse fibreuse, apparaít très
clairement et est surprenant. En effet, ceci entraíne (Fig. 2) une
amélioration de 28 % en rétention de charge par rapport au produit
non cisaillé avant l'introduction dans la masse fibreuse, et une
amélioration de 20 % environ par rapport à une émulsion linéaire. As regards charge retention, the results show that there is little interest in using an unsheared crosslinked polymer emulsion (value 64.13%) at a dosage usual in this industry, of 500 g / l, per compared to a linear polyacrylamide emulsion (69.95%) (Tests 2 and 3, Fig. 2).
On the other hand, the interest of the shearing of the crosslinked emulsion, before its addition to the suspension or fibrous mass, appears very clearly and is surprising. Indeed, this results (Fig. 2) in a 28% improvement in charge retention compared to the product not sheared before introduction into the fibrous mass, and an improvement of about 20% compared to a linear emulsion.
De même, les histogrammes relatifs aux mesures de turbidité des
eaux sous toiles (eaux blanches récupérées sous la toile) montrent
de manière surprenante que la turbidité est divisée par un facteur
trois selon l'invention, (Fig. 3-5).
La rétention totale suit la même tendance et appelle donc les
mêmes remarques.Likewise, the histograms relating to the turbidity measurements of the water under canvas (white water recovered under the canvas) surprisingly show that the turbidity is divided by a factor of three according to the invention, (Fig. 3-5).
Total retention follows the same trend and therefore calls for the same comments.
Dans un réacteur A, on mélange à température ambiante les
constituants de la phase organique de l'émulsion à synthétiser.
- 266 g d'exxsol D100
- 18 g de Span 80
- 6 g d'Hypermer 2296.
- 565,7 g d'acrylamide à 50 %
- 107 g de chlorure d'acrylate d'éthyl triméthylammonium (80 %)
- 35,3 g d'eau
- 0,31 ml de méthylène bis acrylamide à 6 g/l
- 1,50 ml de bromate de sodium à 50 g/l
- 0,24 ml de Versenex à 200 g/l
- pH : 4.
- 266 g of exxsol D100
- 18 g Span 80
- 6 g of Hypermer 2296.
- 565.7 g of 50% acrylamide
- 107 g ethyl trimethylammonium acrylate chloride (80%)
- 35.3 g of water
- 0.31 ml of methylene bis acrylamide at 6 g / l
- 1.50 ml sodium bromate at 50 g / l
- 0.24 ml of Versenex at 200 g / l
- pH: 4.
On mélange le contenu de B dans A sous agitation. Après le
mélange des phases, on cisaille l'émulsion au mixer pendant 1
minute afin de créer l'émulsion inverse. L'émulsion est alors
dégazée par un bullage d'azote puis après 20 minutes, l'addition
progressive du métabisulfite entraíne l'initiation puis la
polymérisation.
La réaction terminée, on effectue un « burn out » (traitement au
bisulfite ou métabisulfite) afin de diminuer la teneur en monomère
libre.
L'émulsion est alors incorporée avec son tensio-actif inverseur afin
de libérer par la suite le polymère en phase aqueuse.
Once the reaction is complete, a “burn out” is carried out (bisulfite or metabisulfite treatment) in order to reduce the content of free monomer.
The emulsion is then incorporated with its inverting surfactant in order to subsequently release the polymer in the aqueous phase.
Le produit SD 448 B est le produit 448 B qui a été séché par spray
drying ou séchage par pulvérisation, puis dissolution de la poudre
blanche obtenue, cisaillement de la solution à 5 - 10 g/l environ de
polymère et ensuite mise en oeuvre comme l'émulsion 448 B.
- X :
- ionicité après cisaillement en meq/g.
- Y :
- ionicité avant cisaillement en meq/g.
- V1 :
- viscosité intrinsèque après cisaillement en dl/g
- V2 :
- viscosité intrinsèque avant cisaillement en dl/g
- X:
- ionicity after shearing in meq / g.
- Y:
- ionicity before shearing in meq / g.
- V1:
- intrinsic viscosity after shearing in dl / g
- V2:
- intrinsic viscosity before shearing in dl / g
La pâte utilisée est diluée à une consistance de 1,5 %. On prélève
2,24 g sec de pâte, soit 149 g de pâte à 15 % puis l'on dilue à 0,4
% avec des eaux claires.
G = grammage ex. G80 = grammage de 80 g The paste used is diluted to a consistency of 1.5%. 2.24 g dry paste is taken, ie 149
G = grammage ex. G80 = grammage of 80 g
Le volume de 560 ml est introduit dans le cylindre en plexiglas de la fermette automatisée et l'on démarre la séquence.
- t = 0 s, démarrage agitation à 1500 rpm.
- t = 10 s, addition du polymère.
- t = 60 s, réduction automatique à 1000 rpm et addition si nécessaire de la bentonite.
- t = 75 s, arrêt de l'agitation, formation de la feuille avec le vide sous toile puis récupération des eaux blanches.
- mesure de la turbidité des eaux sans toile.
- dilution d'un bêcher de pâte épaisse pour une nouvelle feuille avec les eaux sous toiles recueillies.
- séchage de la feuille dite 1 ère passe («X» = 1ère passe)
- démarrage d'une nouvelle séquence afin de réaliser la feuille dite 2nde passe.
- t = 0 s, stirring start at 1500 rpm.
- t = 10 s, addition of the polymer.
- t = 60 s, automatic reduction to 1000 rpm and addition, if necessary, of bentonite.
- t = 75 s, stirring stopped, formation of the sheet with the vacuum under canvas then recovery of the white water.
- measurement of the turbidity of water without canvas.
- dilution of a beaker of thick paste for a new leaf with the water under canvas collected.
- drying of the sheet known as the 1st pass (“X” = 1st pass)
- start of a new sequence in order to make the so-called 2nd pass sheet.
Après 3 passes, l'on change de produits à tester.
Les analyses suivantes sont alors réalisées :
- mesure des matières en suspension des eaux sous toile (Norme TAPPI : T 656 cm / 83)
- mesure du poids des cendres des feuilles, (Norme TAPPI : T 211 om - 93)
- mesure de la turbidité 30' après que les fibres soient déposées
afin de connaítre l'état du milieu ionique.
(MES= matières en suspension) - mesure du degré d'égouttabilité de la pâte avec un Canadian Standard Freeness ( CSF; Norme TAPPI T 227 om - 94).
The following analyzes are then carried out:
- measurement of suspended matter in canvas (TAPPI standard: T 656 cm / 83)
- measurement of the weight of the ash from the leaves, (TAPPI standard: T 211 om - 93)
- measurement of the turbidity 30 'after the fibers are deposited in order to know the state of the ionic medium.
(MES = suspended matter) - measurement of the degree of dripability of the dough with a Canadian Standard Freeness (CSF; TAPPI T 227 om - 94).
Les résultats sont présentés dans le tableau 2 et les figures ci
dessous :
Le cisaillement appliqué à l'agent de rétention standard linéaire
(EM 140 CT) provoque une dégradation de l'égouttage (-5%) (Fig.6).
Les produits réticulés mais utilisés sans cisaillement conduisent à
de meilleurs résultats que l'émulsion linéaire ( 448 A : + 7%)
Un cisaillement appliqué à ce même produit réticulé 448 A
provoque une amélioration de + 4% de l'égouttage par rapport à
l'émulsion linéaire.
On note par ailleurs que ces améliorations d'égouttage ne se font
pas, de manière surprenante, au détriment de la rétention de
charge.
Au contraire, et donc de manière encore plus surprenante, on
obtient selon l'invention une nette amélioration de la clarté des
eaux blanches, comme en témoignent les mesures de turbidité 1
ère passe (Fig. 7) (colonne X); on comparera notamment les exemples
suivants:
A shear applied to this same
It should also be noted that these drainage improvements are not, surprisingly, to the detriment of charge retention.
On the contrary, and therefore even more surprisingly, according to the invention, a clear improvement in the clarity of the white waters is obtained, as evidenced by the first pass turbidity measurements (Fig. 7) (column X); the following examples will be compared in particular:
Par ailleurs, l'invention apporte un avantage additionnel important
en ce qui concerne une très nette amélioration de la formation de la
feuille. La formation désigne comme on le sait des qualités de la
feuille telles que l'homogénéité, et analogues.
Cet avantage, qui s'ajoute aux deux précédents, est attribuable à la
microfloculation provoquée par les agents cisaillés selon
l'invention. Furthermore, the invention provides an important additional advantage with regard to a very marked improvement in the formation of the sheet. The formation designates as is known qualities of the sheet such as homogeneity, and the like.
This advantage, which is added to the two preceding ones, is attributable to the microflocculation caused by the agents sheared according to the invention.
On utilise le même agent polymère que selon l'exemple 2 mais à un dosage différent (0,1 % de polymère par rapport à la masse fibreuse à floculer).The same polymeric agent as in Example 2 is used but at a different dosage (0.1% of polymer relative to the mass fibrous to flocculate).
Les résultats sont présentés dans le tableau 3 et les figures ci
dessous :
Cet exemple montre les effets obtenus à fort dosage d'agent de
rétention.
On observe une dégradation évidente de la formation dans le cas
de surdosage d'un polymère linéaire standard de haut poids
moléculaire. Au contraire, aucun effet néfaste n'est observé dans le
cas d'un surdosage des produits réticulés et cisaillés avant
introduction, selon l'invention.
En ce qui concerne l'égouttage et la turbidité, les agents réticulés et
cisaillés, avant l'introduction dans la masse fibreuse, selon
l'invention, conservent leurs avantages surprenants décrits ci-dessus.
An obvious degradation of the formation is observed in the case of an overdose of a standard linear polymer of high molecular weight. On the contrary, no harmful effect is observed in the case of an overdose of the crosslinked and sheared products before introduction, according to the invention.
With regard to drainage and turbidity, the crosslinked and sheared agents, before introduction into the fibrous mass, according to the invention, retain their surprising advantages described above.
Claims (21)
- A process for manufacturing a sheet of paper or paperboard or the like, intended to improve distinctly the retention, formation, drainage and other properties of the sheet of paper or paperboard thus obtained, in which the fibrous mass of pulp is flocculated by at least one polymeric retention agent, characterised in that there is used as the sole flocculating agent a cross-linked polymer or copolymer formed by polymerisation or copolymerisation of monomers which are selected from among monoethylenically unsaturated monomers, allyl monomers and vinyl monomers, in particular acrylic or methacrylic monomers, which are water-soluble, or mixtures of such monomers, in that said cross-linked polymer is sheared before the introduction or injection into the suspension or fibrous mass to be flocculated,
and in that the shearing is effected at a concentration of the order of 3 - 5 to 10 - 15 g of active material (that is to say, the polymer)/litre, preferably between 5 and 10 g/l, at 10,000 rpm or in a domestic mixer substantially at the same order of magnitude of speed of rotation, for a period of between 15 - 30 seconds and 2 - 5 minutes,
and an ionic recovery IR of 40 to 50 or which may reach at least 60 or 70% and even more, up to values greater than or very much greater than 100, is obtained by the shearing, where:- X:
- ionicity after shearing in meq/g
- Y :
- ionicity before shearing in meq/g.
- A process for manufacturing a sheet of paper or paperboard or the like according to Claim 1, characterised in that monomers selected from among non-ionic monomers are used to prepare said (co)polymer.
- A process for manufacturing a sheet of paper or paperboard or the like according to Claim 1 or 2, characterised in that at least part of the monomers used to form the polymer is ionic.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 3, characterised in that non-ionic monomers selected from among acrylamide, methacrylamide, N-vinyl methylacetamide or N-vinylformamide, vinyl acetate, vinylpyrrolidone, methyl methacrylate or other acrylic esters, or other ethylenically unsaturated esters, or alternatively other vinyl monomers which are insoluble in water such as styrene or acrylonitrile, are used.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 4, characterised in that anionic monomers selected from among sodium acrylate, sodium methacrylate, sodium itaconate, 2-acrylamido-2-methylpropanesulphonate (AMPS), sulphopropyl acrylates or sulphopropyl methacrylates, or other water-soluble forms of these polymerisable sulphonic or carboxylic acids, a sodium vinylsulphonate, or an alkylsulphonate, or a sulphomethyl acrylamide, are used.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 and 3 to 5, characterised in that cationic monomers selected from among dialkylaminoalkyl acrylates and methacrylates, in particular dialkylaminoethyl acrylate, and their salts which are acidified or quaternised for example by benzyl, methyl, aryl or alkyl chlorides, dimethyl sulphate, or dialkylaminoalkylalkyl acrylamides or methacrylamides, and also their acidified or quaternised salts, for example methacrylamidopropyl trimethylammonium chloride (MAPTAC), in which the alkyl groups are C1-C4 alkyl groups, are used.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 6, characterised in that the monomers may contain hydrophobic groups.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 7, characterised in that the cross-linking is effected during or after the polymerisation, for example by reaction of two soluble polymers having counter-ions, or by reaction on formaldehyde or a polyvalent metal compound.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 8, characterised in that the cross-linking is effected during the polymerisation by addition of a cross-linking agent.
- A process for manufacturing a sheet of paper or paperboard or the like according to Claim 9, characterised in that the cross-linking agents which can be incorporated comprise ionic cross-linking agents such as polyvalent metal salts, formaldehyde, glyoxal, or alternatively, and preferably, covalent cross-linking agents which will copolymerise with the monomers, preferably diethylenically unsaturated monomers (such as the family of diacrylate esters such as diacrylates of polyethylene glycols PEG) or polyethylenically unsaturated monomers, of the type conventionally used for cross-linking water-soluble polymers, and in particular methylenebisacrylamide (MBA) or alternatively any one of the other known acrylic cross-linking agents.
- A process for manufacturing a sheet of paper or paperboard or the like according to Claim 9 or 10, characterised in that the quantity of cross-linking agents, and in particular of methylenebisacrylamide (MBA) which can be incorporated is from 5 to 100 ppm of cross-linking agent / active material (polymer).
- A process for manufacturing a sheet of paper or paperboard or the like according to Claim 11, characterised in that the quantity of cross-linking agents, and in particular of methylenebisacrylamide (MBA) which can be incorporated is from 5 to 40 ppm of cross-linking agent / active material (polymer).
- A process for manufacturing a sheet of paper or paperboard or the like according to Claim 11 or 12, characterised in that the quantity of cross-linking agents, and in particular of methylenebisacrylamide (MBA) which can be incorporated is 20 ppm of cross-linking agent / active material (polymer).
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 13, characterised in that the polymers are prepared by a reversed-phase (water-in-oil) emulsion polymerisation method.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 14, characterised in that the injection or introduction of the cross-linked polymer which is sheared according to the invention is effected in the diluted papermaking pulp (or fibrous mass to be flocculated) or "thin stock", that is to say a pulp diluted to approximately 0.7 - 5% of solid material such as cellulose fibres, any fillers and various conventional papermaking additives.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 15, characterised in that part of the cross-linked polymer which is sheared according to the invention is introduced at the level of the preparation stage for the thick pulp or "thick stock", or even at the level of the preparation of the thick stock at 5% or more.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 16, characterised in that the shearing is effected in high-pressure pumps or turbines.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 17, characterised in that a polymer having an intrinsic viscosity i.v. as low as 1 to 3, which becomes an intrinsic viscosity as high as 3 -7 or 8 after the application of the shearing, is used.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 18, characterised in that the polymer is prepared from acrylamide monomers and ethyl trimethylammonium acrylate chloride, and is cross-linked by methylenebisacrylamide.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 19, characterised in that the polymer is prepared from acrylamide monomers and ethyl trimethylammonium acrylate chloride, in an amount of preferably 20 or 10 mole-% of acrylate, and is cross-linked by methylenebisacrylamide.
- A process for manufacturing a sheet of paper or paperboard or the like according to any one of Claims 1 to 19, characterised in that the polymer is used in the form of an invert water-in-oil emulsion of the cross-linked polymer, or alternatively of a solution of the polymer, obtained by redissolving in water a powder of the cross-linked polymer, obtained itself by drying of the emulsion by spray drying, or by solvent precipitation, or agglomeration and grinding.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9806876A FR2779159B1 (en) | 1998-05-28 | 1998-05-28 | FLOCCULATING PROCESS FOR THE MANUFACTURE OF A SHEET OF PAPER, CARDBOARD OR THE LIKE, CROSSLINKED EMULSIONS AS NEW FLOCCULATING AGENTS OF THIS PREPARATION, AND THE ARTICLES THUS OBTAINED |
| FR9806876 | 1998-05-28 | ||
| PCT/FR1999/001209 WO1999061702A1 (en) | 1998-05-28 | 1999-05-21 | Flocculation method for making a paper sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1090185A1 EP1090185A1 (en) | 2001-04-11 |
| EP1090185B1 true EP1090185B1 (en) | 2004-08-11 |
Family
ID=9526916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99920905A Revoked EP1090185B1 (en) | 1998-05-28 | 1999-05-21 | Flocculation method for making a paper sheet |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6579417B1 (en) |
| EP (1) | EP1090185B1 (en) |
| AT (1) | ATE273417T1 (en) |
| AU (1) | AU3830999A (en) |
| CA (1) | CA2333508C (en) |
| DE (1) | DE69919356T2 (en) |
| FR (1) | FR2779159B1 (en) |
| WO (1) | WO1999061702A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030150575A1 (en) * | 1998-06-04 | 2003-08-14 | Snf Sa | Paper and paperboard production process and corresponding novel retention and drainage aids, and papers and paperboards thus obtained |
| DE10059828A1 (en) * | 2000-12-01 | 2002-06-13 | Clariant Gmbh | Comb-shaped copolymers based on acryloyldimethyltauric acid |
| US20040087717A1 (en) * | 2002-11-04 | 2004-05-06 | Ge Betz, Inc. | Modified polymeric flocculants with improved performance characteristics |
| FR2869626A3 (en) * | 2004-04-29 | 2005-11-04 | Snf Sas Soc Par Actions Simpli | METHOD FOR MANUFACTURING PAPER AND CARDBOARD, NEW CORRESPONDING RETENTION AND DRAINING AGENTS, AND PAPERS AND CARTONS THUS OBTAINED |
| GB0518059D0 (en) * | 2005-09-06 | 2005-10-12 | Dow Corning | Delivery system for releasing active ingredients |
| CA2701317C (en) | 2009-09-15 | 2016-08-23 | Suncor Energy Inc. | Process for flocculating and dewatering oil sand mature fine tailings |
| EP2477707B8 (en) | 2009-09-15 | 2017-07-26 | Suncor Energy Inc. | Process for drying fine tailings |
| AU2009354586A1 (en) | 2009-10-30 | 2012-05-24 | Suncor Energy Inc. | Depositing and farming methods for drying oil sand mature fine tailings |
| US9404223B2 (en) * | 2012-02-01 | 2016-08-02 | Basf Se | Process for the manufacture of paper and paperboard |
| CN113248651B (en) * | 2021-07-12 | 2021-10-01 | 山东诺尔生物科技有限公司 | Papermaking retention aid and preparation method and application thereof |
| CN113354773B (en) * | 2021-08-09 | 2021-10-29 | 山东诺尔生物科技有限公司 | Amphoteric polyacrylamide papermaking retention aid and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4759856A (en) * | 1984-04-30 | 1988-07-26 | Allied Colloids, Ltd. | Flocculation processes |
| DE202780T1 (en) * | 1985-04-25 | 1988-01-14 | Allied Colloids Group Ltd., Bradford, Yorkshire | FLOCKING PROCEDURE. |
| US5180473A (en) * | 1987-03-20 | 1993-01-19 | Mitsui-Cyanamid, Ltd. | Paper-making process |
| US5254221A (en) * | 1988-04-22 | 1993-10-19 | Allied Colloids Limited | Processes for the production of paper and paper board |
| US5571380A (en) * | 1992-01-08 | 1996-11-05 | Nalco Chemical Company | Papermaking process with improved retention and maintained formation |
| US5630907A (en) * | 1992-12-07 | 1997-05-20 | Basf Aktiengesellschaft | Use of hydrolyzed copolymers of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids in papermaking |
| US5431783A (en) * | 1993-07-19 | 1995-07-11 | Cytec Technology Corp. | Compositions and methods for improving performance during separation of solids from liquid particulate dispersions |
| DE4406624A1 (en) * | 1994-03-01 | 1995-09-07 | Roehm Gmbh | Crosslinked water-soluble polymer dispersions |
-
1998
- 1998-05-28 FR FR9806876A patent/FR2779159B1/en not_active Expired - Fee Related
-
1999
- 1999-05-21 CA CA2333508A patent/CA2333508C/en not_active Expired - Lifetime
- 1999-05-21 AT AT99920905T patent/ATE273417T1/en not_active IP Right Cessation
- 1999-05-21 AU AU38309/99A patent/AU3830999A/en not_active Abandoned
- 1999-05-21 DE DE69919356T patent/DE69919356T2/en not_active Revoked
- 1999-05-21 EP EP99920905A patent/EP1090185B1/en not_active Revoked
- 1999-05-21 US US09/700,719 patent/US6579417B1/en not_active Expired - Lifetime
- 1999-05-21 WO PCT/FR1999/001209 patent/WO1999061702A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE69919356T2 (en) | 2005-09-08 |
| CA2333508A1 (en) | 1999-12-02 |
| AU3830999A (en) | 1999-12-13 |
| FR2779159A1 (en) | 1999-12-03 |
| US6579417B1 (en) | 2003-06-17 |
| CA2333508C (en) | 2010-05-18 |
| EP1090185A1 (en) | 2001-04-11 |
| DE69919356D1 (en) | 2004-09-16 |
| WO1999061702A1 (en) | 1999-12-02 |
| FR2779159B1 (en) | 2000-08-11 |
| ATE273417T1 (en) | 2004-08-15 |
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