EP3568519A1 - Ablagerungsverhinderung in der zellstoff-herstellung nach dem sulfatverfahren (kraft-aufschluss) - Google Patents
Ablagerungsverhinderung in der zellstoff-herstellung nach dem sulfatverfahren (kraft-aufschluss)Info
- Publication number
- EP3568519A1 EP3568519A1 EP18701117.6A EP18701117A EP3568519A1 EP 3568519 A1 EP3568519 A1 EP 3568519A1 EP 18701117 A EP18701117 A EP 18701117A EP 3568519 A1 EP3568519 A1 EP 3568519A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- monoethylenically unsaturated
- acids
- group
- comb polymers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000008569 process Effects 0.000 title claims abstract description 33
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229910021653 sulphate ion Inorganic materials 0.000 title claims abstract description 12
- 239000002655 kraft paper Substances 0.000 title claims abstract description 10
- 230000002265 prevention Effects 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 150000007513 acids Chemical class 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 238000010411 cooking Methods 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000003784 tall oil Substances 0.000 claims description 13
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000002455 scale inhibitor Substances 0.000 claims description 8
- 238000010526 radical polymerization reaction Methods 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 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 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000004537 pulping Methods 0.000 claims description 5
- 239000000344 soap Substances 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 4
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 4
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 claims description 3
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 150000003009 phosphonic acids Chemical class 0.000 claims description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 claims 1
- COJBCAMFZDFGFK-VCSGLWQLSA-N 2-O-sulfo-alpha-L-idopyranuronic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1OS(O)(=O)=O COJBCAMFZDFGFK-VCSGLWQLSA-N 0.000 claims 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 claims 1
- 101100345345 Arabidopsis thaliana MGD1 gene Proteins 0.000 claims 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 239000003945 anionic surfactant Substances 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000174 gluconic acid Substances 0.000 claims 1
- 235000012208 gluconic acid Nutrition 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 claims 1
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 claims 1
- OHOTVSOGTVKXEL-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C(C)N(CC([O-])=O)CC([O-])=O OHOTVSOGTVKXEL-UHFFFAOYSA-K 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 5
- 229920005610 lignin Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002266 Pluriol® Polymers 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- RSNDTPFSMDVWCS-UHFFFAOYSA-N 2-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCC(=C)C(N)=O RSNDTPFSMDVWCS-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 244000089654 Betula populifolia Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- -1 sulfide anion Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/22—Other features of pulping processes
- D21C3/226—Use of compounds avoiding scale formation
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/02—Washing ; Displacing cooking or pulp-treating liquors contained in the pulp by fluids, e.g. wash water or other pulp-treating agents
Definitions
- the present invention relates to the use of comb polymers as scale inhibitors in pulp production by the sulfate process (Kraft pulping).
- the most important and most frequently used process for the production of pulp is the sulphate or kraft process.
- C.F. Dahl patented a process using sodium sulfide or sodium sulfate, respectively.
- the resulting sulphate pulp is preferred because of its high strength, especially for mechanically stressed paper "kraft papers” and therefore also kraft pulp.
- the basis of the method is the partial solubility of lignin in hot solutions.
- the alkaline process uses cooking liquors containing sodium hydroxide, sodium sulfide, sodium sulfate and sodium carbonate.
- the chips are treated in pressure vessels for three to six hours at elevated pressure (7 to 10 bar) and at a temperature of 140 to 170 ° C.
- sodium sulfide increases the delignification, in which the lignin is split by a nucleophilic attack of the sulfide anion and turns into the so-called black liquor (soluble alkali lignin), and on the other hand, the fiber lengths are increased.
- carbohydrates are also degraded in the more alkaline range.
- Polysulfide-containing lyes stabilize the polyoses. Paper made of Kraftpulp is tear-resistant, unbreakable and tensile. Advantages of the sulphate process are a good impregnation of the chips in alkaline solution and thus shorter cooking times, it can be used virtually all woods.
- Sulfate pulps contain even larger amounts of polyoses and are darker than sulfite pulps. They do not have a sufficiently high content of ⁇ -cellulose for the production of cellulose derivatives.
- the lignin-containing waste liquors arising from the sulphate process are concentrated and incinerated so that the energy requirement of the entire process can be met.
- turpentine oil and about 30 to 35 kg of tall oil per 1,000 kg of pulp are produced.
- JPH 1025684 (A) describes a terpolymer based on maleic acid, acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) having a molecular weight of 500 to 20,000 g / mol.
- AMPS 2-acrylamido-2-methylpropanesulfonic acid
- No. 5,409,571 A discloses a copolymer based on maleic acid and acrylic acid which has been polymerized with the addition of hypophosphite.
- the molecular weight is 500 to 10,000 g / mol.
- polyitaconic acid in a mixture with phosphonic acids is known from JP 2011-052358 (A).
- Scale inhibitor-1 polyitaconic acid and l-hydroxyethylidene-l, l-diphosphonic acid (HEDP) are mixed.
- JP 2014-147911 discloses a mixture of two polyitaconic acid polymers having different molecular weights.
- Polymer A has a molecular weight of 500 to 15,000 g / mol and Polymer B has a molecular weight of 15,000 to 40,000 g / mol.
- WO 00/12436 A claims a copolymer of l, 2-dihydroxy-3-butene, and another monomer from the group of maleic acid, acrylic acid, acrylamide, methacrylic acid, itaconic acid, vinylsulfonic acid, styrenesulfonic acid, N-tert-butylacrylamide, butoxymethylacrylamide , N, N-dimethylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid and salts thereof.
- the publications listed are exclusively concerned with the inhibition of deposits of inorganic calcium carbonate.
- WO 2010/019425 AI gives in the cited prior art a good overview of which substances can be used as a resin dispersant.
- the application itself claims a mixture of triglyceride oil or triglyceride alkyl esters with polyalkylene glycol based surfactants and / or resin, rosin soaps, tall oil, tall oil soaps and derivatives thereof.
- WO 2008/057492 A2 describes a copolymer of vinyl alcohol and vinyl acetate and hydrophobically modified hydroxyethyl cellulose as a detackifier. Also mentioned are enzymes which catalyze the hydrolysis of resin.
- WO 2004/057101 A1 discloses a mixture of fatty acids and resin acids as an effective dispersant with respect to extractable substances.
- the publications listed are exclusively concerned with the inhibition of organic resin deposits.
- the object of the present invention is the ne gative ⁇ influencing the CaC0 3 -Ablagerungsinhibitoren by resin dispersant during the kraft cooking process effectively underbin ⁇ .
- polymers are to be provided which effectively inhibit the deposits of CaCO 3 during the cooking process. when working with the addition of resin dispersants based on organic carboxylic acids.
- the comb polymers used according to the invention can be obtained by a free radical polymerization of monoethylenically unsaturated monomers of the group AI) monoethylenically unsaturated acids and their salts and the group A2) monoethylenically unsaturated polyethers.
- the invention therefore provides the use of comb polymers obtainable by a free-radical polymerization of monoethylenically unsaturated monomers
- Examples of the monomers of group AI, the monoethylenically unsaturated acids and their salts are acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylphosphonic.
- the monomers of group AI can be used individually or as a mixture of different monomers.
- acrylic acid, methacrylic acid or maleic acid in an amount of from 5 to 95% by weight, based on the polymer, acrylic acid or maleic acid being particularly preferably used in an amount of from 10 to 90% by weight, based on the polymer.
- the monoethylenically unsaturated polyethers are polyethylene glycol monoallyl ether, polypropyleneglycol monoallyl ether and polyethylene-polypropylene monoallyl ether; these are, for example, by the company. Clariant under the product number polyglycol ® A, from Fa. BASF ® under the product number Pluriol A ... R or by the company. NOF Corporation under the product rows Uniox ® 'Unisafe ® and Unilube ® commercially available. Further examples are Polyethylenglycolmonovinylether (range from Clariant. Polyglycol ® R) Isoprenylethoxilate (product series from BASF. Pluriol ® A ... I) and Vinyloxybutylethoxilate (product series from BASF. Pluriol ® A ... V).
- the monomers of group A2 can be OH-terminated or have an end-group bond.
- the monomers may be used singly or as mixtures of different monomers. Preference is given to using polyalkyl glycol monoallyl ethers in an amount of from 2 to 25% by weight, based on the polymer, more preferably using polyethylene glycol monoallyl ether and polyethylene-polypropylene monoallyl ether with an amount of from 5 to 20% by weight, based on the polymer.
- the use according to the invention can be carried out as part of pulp production by the sulphate process in a continuous or discontinuous process such that the comb polymer is added separately to a cooking liquor, or the comb polymer is introduced into the cooking liquor as a constituent of the CaC0 3 deposition inhibitor or the resin dispersant.
- Another object of the invention is therefore a CaC0 3 deposition inhibitor containing a comb polymer according to the invention.
- CaC0 3 deposition inhibitors and resin dispersants containing the comb polymer to be used in the present invention may contain any of the usual ingredients of such agents which do not undesirably interact therewith.
- such a CaC0 3 deposition inhibitor contains polymers as mono-, co- and terpolymers based on monoethylenically unsaturated acids and their salts, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, allylsulfonic acid, Methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylphosphonic acid, acrylamide, N-tert-butylacrylamide, butoxymethylacrylamide and N, N-dimethylacrylamide.
- the solution was made with demineralized water.
- the 140 ° C was maintained for a further 30 minutes.
- the contents of the cup were then cooled to 80 ° C, the cups were opened and the hot solution filtered through black filter.
- ⁇ 5 amorphous and crystalline deposits
- Standard polymer acrylic acid / maleic acid copolymer, which is used as a deposit inhibitor in pulp boiling in the sulfate process in practice.
- Experiment No. 1 clearly shows what massive crystalline deposits can be formed under pulp cooking conditions when no scale inhibitor is used.
- the coarse-crystalline structure leads to a complete and rapid filtration of the deposits, the filtrate is clear.
- different levels of scale inhibitors were added.
- the test parameters are only insignificantly influenced.
- Mainly coarse-crystalline structures are formed, which lead to rapid and complete filtration. From a concentration of 40 mg, the results change abruptly.
- the crystal structure changes from coarse-crystalline to fine-amorphous.
- the pores of the filter material are added quickly and there is a significant reduction in the filtration rate. From experience, the mechanism of crystal modification is necessary to practice effective to prevent CaC0 3 deposits during pulp cooking.
- Experiment No. 5 shows the effect of tall oil on the resulting deposits. Compared to experiment # 1, the deposits on the filter have obviously increased.
- Experiment No. 6 now discloses the whole problem known from practice that the standard polymers fail by the use of tall oil and are no longer sufficiently effective. If the standard polymer in Experiment No. 4 could still effectively modify the resulting deposits, it completely fails in Experiment No. 6. An increase in the amount used (experiments Nos. 7 and 8) does improve the situation, but it is far from having sufficient effect.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyethers (AREA)
Abstract
Description
Claims
Priority Applications (1)
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PL18701117T PL3568519T3 (pl) | 2017-01-12 | 2018-01-09 | Zapobieganie tworzeniu się osadu w produkcji pulpy w procesie siarczanowym (roztwarzanie kraft) |
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DE102017200430.4A DE102017200430A1 (de) | 2017-01-12 | 2017-01-12 | Ablagerungsverhinderung in der Zellstoff-Herstellung nach dem Sulfatverfahren (Kraft-Aufschluss) |
PCT/EP2018/050472 WO2018130528A1 (de) | 2017-01-12 | 2018-01-09 | Ablagerungsverhinderung in der zellstoff-herstellung nach dem sulfatverfahren (kraft-aufschluss) |
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EP3568519A1 true EP3568519A1 (de) | 2019-11-20 |
EP3568519B1 EP3568519B1 (de) | 2020-11-18 |
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EP (1) | EP3568519B1 (de) |
AU (1) | AU2018207866B2 (de) |
BR (1) | BR112019013116A2 (de) |
CA (1) | CA3043462A1 (de) |
CL (1) | CL2019001599A1 (de) |
DE (1) | DE102017200430A1 (de) |
ES (1) | ES2845552T3 (de) |
PL (1) | PL3568519T3 (de) |
PT (1) | PT3568519T (de) |
RU (1) | RU2746828C2 (de) |
WO (1) | WO2018130528A1 (de) |
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CN109665634A (zh) * | 2019-01-30 | 2019-04-23 | 上海电力学院 | 一种高分子阻垢缓蚀剂及其制备方法和应用 |
IT202200003134A1 (it) | 2022-02-21 | 2023-08-21 | Alter Eco Pulp S R L | Metodo di estrazione della cellulosa da biomasse di scarto |
Family Cites Families (18)
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US4500693A (en) * | 1981-07-07 | 1985-02-19 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Water soluble copolymer method for manufacture therefore and use thereof |
EP0537870A1 (de) | 1991-10-18 | 1993-04-21 | W.R. Grace & Co.-Conn. | Copolymere von äthylenisch ungesättigten Ethern verwendbar als hydraulischer Zementsuperweichmacher |
JPH0699879B2 (ja) | 1992-08-27 | 1994-12-07 | 伯東株式会社 | パルプ蒸解釜のスケール付着防止剤およびスケール付着防止方法 |
US5534157A (en) * | 1994-11-10 | 1996-07-09 | Calgon Corporation | Polyether polyamino methylene phosphonates for high pH scale control |
JP3088085B2 (ja) * | 1996-12-27 | 2000-09-18 | 株式会社日本触媒 | スケール防止剤 |
US6146495A (en) | 1998-08-31 | 2000-11-14 | Nalco Chemical Company | Kraft process for the production of wood pulp by adding a copolymer of 1,2-dihydroxy-3-butene antiscalant |
MY129053A (en) | 2001-06-06 | 2007-03-30 | Thermphos Trading Gmbh | Composition for inhibiting calcium salt scale |
MY138251A (en) | 2001-06-06 | 2009-05-29 | Thermphos Trading Gmbh | Method for inhibiting calcium salt scale |
FI121382B (fi) | 2002-12-23 | 2010-10-29 | Arizona Chemical B V | Puunkeiton apuaine, sen valmistus ja käyttö |
FR2894998A1 (fr) * | 2005-12-16 | 2007-06-22 | Coatex Sas | Procede de fabrication de sauces de couchage a la retention d'eau et a la viscosite brookfield ameliorees mettant en oeuvre un polymere peigne avec au moins une fonction greffee oxyde de polyalkylene. |
BRPI0718537B1 (pt) | 2006-11-06 | 2017-07-18 | Solenis Technologies Cayman, L.P. | A method and composition for inhibiting the deposition of one or more organic contaminants in pulp production and paper production systems |
EP2020422A1 (de) * | 2007-07-31 | 2009-02-04 | Sika Technology AG | Emulgierende Polymere und deren Verwendung |
WO2009093615A1 (ja) * | 2008-01-22 | 2009-07-30 | Lion Corporation | クラフトパルプ用洗浄剤及びそれを用いたクラフトパルプの製造方法 |
US8052840B2 (en) | 2008-08-15 | 2011-11-08 | Hercules Incorporated | Pulping additives for a reduction of resin from Kraft pulp |
JP2011052358A (ja) | 2009-09-04 | 2011-03-17 | Hakuto Co Ltd | スケール防止剤およびスケール防止方法 |
JP2014147911A (ja) | 2013-02-04 | 2014-08-21 | Hakuto Co Ltd | スケール防止剤及びスケール防止方法 |
DE102013207778A1 (de) * | 2013-04-29 | 2014-10-30 | Cht R. Beitlich Gmbh | Kammpolymere als Waschkraftverstärker für Wasch- und Reinigungsmittel |
US10173925B2 (en) * | 2014-03-31 | 2019-01-08 | Dow Global Technologies Llc | Synthetic polymer rheology modifier and water retention agent replacement for cellulose ether in cement compositions |
-
2017
- 2017-01-12 DE DE102017200430.4A patent/DE102017200430A1/de not_active Withdrawn
-
2018
- 2018-01-09 EP EP18701117.6A patent/EP3568519B1/de active Active
- 2018-01-09 PT PT187011176T patent/PT3568519T/pt unknown
- 2018-01-09 CA CA3043462A patent/CA3043462A1/en not_active Abandoned
- 2018-01-09 WO PCT/EP2018/050472 patent/WO2018130528A1/de active Application Filing
- 2018-01-09 BR BR112019013116A patent/BR112019013116A2/pt active Search and Examination
- 2018-01-09 ES ES18701117T patent/ES2845552T3/es active Active
- 2018-01-09 RU RU2019121787A patent/RU2746828C2/ru active
- 2018-01-09 PL PL18701117T patent/PL3568519T3/pl unknown
- 2018-01-09 AU AU2018207866A patent/AU2018207866B2/en active Active
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Publication number | Publication date |
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CA3043462A1 (en) | 2018-07-19 |
WO2018130528A1 (de) | 2018-07-19 |
PL3568519T3 (pl) | 2021-05-31 |
EP3568519B1 (de) | 2020-11-18 |
BR112019013116A2 (pt) | 2019-12-17 |
DE102017200430A1 (de) | 2018-07-12 |
PT3568519T (pt) | 2021-02-10 |
RU2746828C2 (ru) | 2021-04-21 |
AU2018207866B2 (en) | 2022-04-14 |
RU2019121787A (ru) | 2021-02-12 |
AU2018207866A1 (en) | 2019-05-23 |
ES2845552T3 (es) | 2021-07-27 |
CL2019001599A1 (es) | 2019-08-23 |
RU2019121787A3 (de) | 2021-02-12 |
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