EP1467017A1 - Verfahren zur Kontrolle von Mikroorganismen in Wasserstoffperoxydbleichen einer Zellstoffsuspension - Google Patents
Verfahren zur Kontrolle von Mikroorganismen in Wasserstoffperoxydbleichen einer Zellstoffsuspension Download PDFInfo
- Publication number
- EP1467017A1 EP1467017A1 EP03255848A EP03255848A EP1467017A1 EP 1467017 A1 EP1467017 A1 EP 1467017A1 EP 03255848 A EP03255848 A EP 03255848A EP 03255848 A EP03255848 A EP 03255848A EP 1467017 A1 EP1467017 A1 EP 1467017A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- hydroxylamine
- aqueous
- pulp
- solution
- 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.)
- Withdrawn
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 244000005700 microbiome Species 0.000 title claims abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title description 28
- 238000004076 pulp bleaching Methods 0.000 title description 4
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000003139 biocide Substances 0.000 claims abstract description 21
- 230000003115 biocidal effect Effects 0.000 claims abstract description 17
- 239000002738 chelating agent Substances 0.000 claims abstract description 15
- 150000004967 organic peroxy acids Chemical class 0.000 claims abstract description 14
- 238000004061 bleaching Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 229920002678 cellulose Polymers 0.000 claims abstract description 5
- 239000001913 cellulose Substances 0.000 claims abstract description 5
- 150000002978 peroxides Chemical class 0.000 claims abstract description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 8
- -1 hydroxylamine compound Chemical class 0.000 claims description 8
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000002443 hydroxylamines Chemical class 0.000 claims description 7
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229960003330 pentetic acid Drugs 0.000 claims description 6
- 150000003009 phosphonic acids Chemical class 0.000 claims description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 3
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 3
- 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 description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 229960004585 etidronic acid Drugs 0.000 claims description 3
- VPRHJIQBWBXGNE-UHFFFAOYSA-N 3-(1,1-diphosphonoethylamino)propanoic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(C)NCCC(O)=O VPRHJIQBWBXGNE-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- CBCFMBJMEVBDRZ-UHFFFAOYSA-N 3-[amino(diphosphono)methyl]pentanedioic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(N)C(CC(O)=O)CC(O)=O CBCFMBJMEVBDRZ-UHFFFAOYSA-N 0.000 claims 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- QXVJRDMNUOAUNI-UHFFFAOYSA-N [1-[bis(hydroxymethyl)amino]-1-phosphonoethyl]phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(C)N(CO)CO QXVJRDMNUOAUNI-UHFFFAOYSA-N 0.000 claims 1
- 229940116254 phosphonic acid Drugs 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 231100000419 toxicity Toxicity 0.000 description 8
- 230000001988 toxicity Effects 0.000 description 8
- 230000002906 microbiologic effect Effects 0.000 description 7
- 102000016938 Catalase Human genes 0.000 description 5
- 108010053835 Catalase Proteins 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ZKHQWZAMYRWXGA-KQYNXXCUSA-N Adenosine triphosphate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)[C@@H](O)[C@H]1O ZKHQWZAMYRWXGA-KQYNXXCUSA-N 0.000 description 3
- ZKHQWZAMYRWXGA-UHFFFAOYSA-N Adenosine triphosphate Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(=O)OP(O)(=O)OP(O)(O)=O)C(O)C1O ZKHQWZAMYRWXGA-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- 229960001456 adenosine triphosphate Drugs 0.000 description 3
- 238000005282 brightening Methods 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 238000011284 combination treatment Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- PJXKZTFOBRSZOY-UHFFFAOYSA-N 2-[carboxymethyl(1,1-diphosphonoethyl)amino]acetic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(C)N(CC(O)=O)CC(O)=O PJXKZTFOBRSZOY-UHFFFAOYSA-N 0.000 description 1
- KONBRAAEGUYPQV-UHFFFAOYSA-N 2-phosphonobutane-1,1,2-tricarboxylic acid Chemical compound CCC(P(O)(O)=O)(C(O)=O)C(C(O)=O)C(O)=O KONBRAAEGUYPQV-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- TTWYZDPBDWHJOR-IDIVVRGQSA-L adenosine triphosphate disodium Chemical compound [Na+].[Na+].C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OP(O)(=O)OP([O-])([O-])=O)[C@@H](O)[C@H]1O TTWYZDPBDWHJOR-IDIVVRGQSA-L 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical class [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940013688 formic acid Drugs 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- AAJBNRZDTJPMTJ-UHFFFAOYSA-L magnesium;dinitrite Chemical compound [Mg+2].[O-]N=O.[O-]N=O AAJBNRZDTJPMTJ-UHFFFAOYSA-L 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical group CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 231100000916 relative toxicity Toxicity 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000003643 water by type 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
- 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
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
-
- 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
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1026—Other features in bleaching 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
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1026—Other features in bleaching processes
- D21C9/1042—Use of chelating agents
-
- 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
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/166—Bleaching ; Apparatus therefor with per compounds with peracids
Definitions
- This invention relates to a method of controlling microorganisms responsible for degrading hydrogen peroxide in hydrogen peroxide pulp bleaching processes using a synergistic combination of one or more organic peracid biocides and one or more chelating agents.
- hydroxylamine an established product known for its brightening effects and degradation of enzymes that can affect the brightening process. See, for example, GB-A-2 269 191 and GB-A-846 079, EP 686 216 and U.S. Patent No. 4,752,354.
- hydroxylamine alone does not reduce bacteria populations.
- Peracetic acid based biocides are known to be effective for controlling microbiological populations in industrial water systems, including papermaking process water. See GB 2,269,191 and U.S. Patent No. 5,494,588. Furthermore, a process for bleaching cellulose by means of an organic peracid in the acid region followed by peroxide in the alkaline region is disclosed in U.S. Patent Nos. 4,400,237. None of these references, however, disclose a dual treatment program comprising hydroxylamine and an organic peracid biocide.
- this invention is a method of controlling micro-organisms during peroxide bleaching of cellulose pulp comprising adding to the pulp an effective micro-organism controlling amount of
- the method of this invention is suitable for controlling microbiological populations in programs for bleaching all manner of cellulose pulps, including pulp made from recycled paper, pulps from sulfite or sulfate cooking, mechanical pulp, thermomechanical pulp and chemothermomechanical pulp.
- the method is especially suitable for controlling microbiological populations responsible for degrading hydrogen peroxide during the bleaching process in de-inking plants.
- controlling encompasses both reducing microbiological populations and inhibiting the growth of microbiological populations.
- the aqueous biocide solution of this invention typically comprises about 5 to about 60 percent by weight of one or more organic peracids, about 5 to about 60 percent by weight of the corresponding organic carboxylic acids and about 10 to about 20 percent by weight hydrogen peroxide.
- the aqueous biocides solution may also contain stabilizers to prolong the storage stability of the peracid.
- Representative stabilizers include ethyleneaminopolymethylenephosphonic acids, hydroxyethylidene diphosphonic acid or salts thereof, and heterocyclic carboxylic acids such as dipicolinic acid, quinolinic acid, and the like.
- Organic peracid means a compound of formula RC(O)OOH where R is straight or branched C 1 -C 6 alkyl or phenyl.
- Representative organic peracids include peracetic acid, perpropionic acid, perbenzoic acid, and the like.
- the organic peracid is peracetic acid.
- corresponding organic carboxylic acid means an acid of formula RCO 2 H where R is a defined above and the same as the R group of the percarboxylic acid.
- acetic acid is the corresponding carboxylic acid of peracetic acid.
- the aqueous biocide solution may be prepared by mixing the corresponding carboxylic acid and hydrogen peroxide in aqueous solution in the presence of any desired stabilizers.
- Suitable aqueous biocide solutions are available commercially from several sources including Ondeo Nalco Company, Naperville, IL.
- a preferred aqueous biocide solution comprises about 5 to about 15 percent by weight of peracetic acid, about 10 to about 20 percent by weight hydrogen peroxide and about 8 to about 35 percent by weight of acetic acid.
- the aqueous biocide solution is used in conjunction with an aqueous solution comprising about 10 to about 50 weight percent of one or more chelating agents in order to control microbiological populations.
- Chelant and "chelating agent” mean an agent capable of complexing metals such as iron and manganese.
- Preferred chelants include hydroxylamine compounds, phosphonic acids and polyhydroxycarboxylic acids.
- Representative phosphonic acids include N,N -bis-(carboxymethyl)-1-aminoethane-1,1-diphosphonic acid, N -2-carboxyethyl-1-aminoethane-1,1-diphosphonic acid, N,N-bis -(hydroxymethly)-1-aminoethane-1,1-diphosphonic acid, 1,2,1-tricarboxybutane-2-phosphonic acid, diethylenetriamine-pentamethylenephosphonic acid (DTPMP), hydroxyethanediphosphonic acid (HEDP) and aminotrismethylenephosphonic acid (ATMP), and the like and salts thereof.
- DTPMP diethylenetriamine-pentamethylenephosphonic acid
- HEDP hydroxyethanediphosphonic acid
- ATMP aminotrismethylenephosphonic acid
- polyhydroxycarboxylic acids include gluconic acid, citric acid, N,N -dihydroxyethyleneglycine, diethylenetriamine-pentaacetic acid (DTPA), ethylenediamine-tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and the like and salts thereof.
- DTPA diethylenetriamine-pentaacetic acid
- EDTA ethylenediamine-tetraacetic acid
- NTA nitrilotriacetic acid
- Hydroxylamine compound means hydroxylamine and alkyl hydroxylamine and salts thereof.
- Alkyl groups are straight chain or branched C 1 -C 10 alkyl.
- a representative alkyl hydroxylamine is N -methylhydroxylamine.
- Representative hydroxylamine salts include hydroxylamine hydrochloride, hydroxylamine sulfate and hydroxylamine salts of ammonium thiocyanate, salts of organic acids such as formic acid, ascorbic acid, salicylic acid, and the like and salts of nitrites such as sodium nitrite, potassium nitrite, calcium nitrite, magnesium nitrite, and the like.
- the hydroxylamine compound is hydroxylamine sulfate.
- the chelating agent is a mixture of one or more hydroxylamine compounds and one or more phosphonic acids or polyhydroxycarboxylic acids.
- the chelating agent is a mixture of hydroxylamine sulfate and one or more phosphonic acids or polyhydroxycarboxylic acids.
- the chelating agent is a mixture of hydroxylamine sulfate and diethylenetriamine-pentaacetic acid.
- the organic peracid is peracetic acid and the chelating agent is a mixture of hydroxylamine sulfate and diethylenetriamine-pentaacetic acid.
- the aqueous biocide solution and the aqueous hydroxylamine solution can be added anywhere in the pulp bleaching process including to the pulp prior the bleaching step.
- the aqueous biocide solution and aqueous hydroxylamine solution may be added at the mixing screw before the bleaching tower, at the flotation, at the pulper and in the incoming white water from the press and in the white water tanks.
- the solutions are added to pulper fill water.
- the amount of aqueous biocide solution and aqueous hydroxylamine solution are determined by measuring residual hydrogen peroxide in the process water and pulp and with regard to the brightness of the pulp.
- the brightness depends on the pH, temperature, to what extent the process water is recirculated and the used pulp, especially when recycled paper is used, because the pulp can contain varying amounts of microorganisms depending on the conditions under which it is stored.
- Typical doses of aqueous biocide solution and aqueous hydroxylamine solution are about 50 ppm to about 200 ppm based on active organic peracid and hydroxylamine compound. Both solutions may be added continuously or intermittantly, preferably at the same point of addition.
- the aqueous hydroxylamine solution is added continuously to the pulper fill water at a dose of about 50 ppm and the aqueous biocide solution is added to the pulper fill water at 4-hour intervals at a dose of about 75 ppm.
- Pulper Fill Tank water from a de-inking plant is allowed to stand overnight to allow any residual hydrogen peroxide to be degraded and allow the existing microbiological populations to proliferate.
- the pH of the water is 8.5 and the ORP (Oxidative-Reductive Potential) is around +100mV (slightly oxidative conditions).
- composition A aqueous biocide solution
- Composition B aqueous hydroxylamine solution
- Composition A is 12% active by weight peracetic acid blended with hydrogen peroxide and acetic acid.
- Composition B is a mixture of hydroxylamine sulphate (12 % by weight) and inorganic salts with aminocarboxylic acids. Both compositions are available from Ondeo Nalco Company, Naperville, IL.
- Toxicity is measured using the Ondeo-Nalco Tra-cide TM system, a diagnostic tool, which measures TOX (toxicity) and ATP (adenosine-tri-phosphate).
- Toxicity is a test based on the response of luminescent bacteria to toxic compounds and is measured in RTU (Relative Toxicity Units). As the toxic compounds kill or inhibit the luminescent bacteria, the light output decreases. Therefore, a high RTU reading indicates high toxicity.
- Total viable count is measured by diluting the sample and plating out onto Total Aerobic Petrifilms TM (available from 3M, 3M House, Loughborough, Leicestershire, UK). The resulting count is multiplied by the dilution factor applied.
- Tables 2 and 3 show the synergy achieved for defined endpoints, 3-log 10 reduction in total viable count and reduction in ATP to less than 2000 RLU, respectively, for the combination treatment of this invention.
- Synergy where the Endpoint is a 3-log 10 Reduction in Total Viable Count Ac A a A c /A a B c B a B c /B a Synergy 100ppm "A” + 100ppm "B” 100 200 0.50 100 1000 0.10 0.60 50ppm "A” + 200ppm “B” 50 200 0.25 200 1000 0.20 0.45 100ppm "A” + 200ppm “B” 100 200 0.50 200 1000 0.20 0.70
- Synergy where the Endpoint is a Reduction in ATP to less than 2000 RLU A c A a A c /A a B c B a B c /B a Synergy 100ppm "A” + 50ppm "B” 100 200 0.50 50 1000 0.05 0.55 100ppm "
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US410753 | 2003-04-10 | ||
US10/410,753 US20040200588A1 (en) | 2003-04-10 | 2003-04-10 | Method of controlling microorganisms in hydrogen peroxide pulp bleaching processes |
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Publication Number | Publication Date |
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EP1467017A1 true EP1467017A1 (de) | 2004-10-13 |
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Application Number | Title | Priority Date | Filing Date |
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EP03255848A Withdrawn EP1467017A1 (de) | 2003-04-10 | 2003-09-18 | Verfahren zur Kontrolle von Mikroorganismen in Wasserstoffperoxydbleichen einer Zellstoffsuspension |
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US (1) | US20040200588A1 (de) |
EP (1) | EP1467017A1 (de) |
Cited By (3)
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WO2021040956A1 (en) * | 2019-08-30 | 2021-03-04 | Ecolab Usa Inc. | Volatile fatty acid control |
WO2021123504A1 (en) * | 2019-12-19 | 2021-06-24 | Kemira Oyj | Process for manufacturing a fibre web |
US12065367B2 (en) | 2021-04-23 | 2024-08-20 | Ecolab Usa Inc. | Volatile fatty acid control |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0001417D0 (en) * | 2000-01-22 | 2000-03-08 | Albright & Wilson Uk Ltd | Bleaching pulp |
ES2415831T3 (es) * | 2010-05-31 | 2013-07-29 | Kemira Oyj | Control de enzimas en la producción de pasta |
WO2012166997A2 (en) | 2011-05-31 | 2012-12-06 | Clean Chemistry, Llc | Electrochemical reactor and process |
EP2892854A4 (de) | 2012-09-07 | 2016-11-02 | Clean Chemistry Llc | Systeme und verfahren zur erzeugung von reaktiven sauerstoffspezies und anwendungen davon |
CA2960104C (en) | 2014-09-04 | 2023-05-02 | Clean Chemistry, Inc. | Method of water treatment utilizing a peracetate oxidant solution |
WO2016154531A1 (en) | 2015-03-26 | 2016-09-29 | Clean Chemistry, Inc. | Systems and methods of reducing a bacteria population in high hydrogen sulfide water |
US10883224B2 (en) | 2015-12-07 | 2021-01-05 | Clean Chemistry, Inc. | Methods of pulp fiber treatment |
US10611656B2 (en) | 2015-12-07 | 2020-04-07 | Clean Chemistry, Inc. | Methods of microbial control |
US11136714B2 (en) | 2016-07-25 | 2021-10-05 | Clean Chemistry, Inc. | Methods of optical brightening agent removal |
US11001864B1 (en) | 2017-09-07 | 2021-05-11 | Clean Chemistry, Inc. | Bacterial control in fermentation systems |
US11311012B1 (en) | 2017-09-07 | 2022-04-26 | Clean Chemistry, Inc. | Bacterial control in fermentation systems |
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DE3005947B1 (de) * | 1980-02-16 | 1981-01-29 | Degussa | Verfahren zur Bleiche von Zellstoffen mittels organischer Persaeure |
CA2129489C (en) * | 1993-08-05 | 2000-10-10 | Judy G. Lazonby | Method and composition for inhibiting growth of microorganisms including peracetic acid and a non-oxidizing biocide |
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- 2003-04-10 US US10/410,753 patent/US20040200588A1/en not_active Abandoned
- 2003-09-18 EP EP03255848A patent/EP1467017A1/de not_active Withdrawn
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US3645840A (en) * | 1971-01-19 | 1972-02-29 | Atlantic Richfield Co | Method for peroxide bleaching of pulp |
US4548674A (en) * | 1983-08-08 | 1985-10-22 | Interox (Societe Anonyme) | Process for the regeneration of waste paper |
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WO2021040956A1 (en) * | 2019-08-30 | 2021-03-04 | Ecolab Usa Inc. | Volatile fatty acid control |
CN114206786A (zh) * | 2019-08-30 | 2022-03-18 | 埃科莱布美国股份有限公司 | 挥发性脂肪酸控制 |
WO2021123504A1 (en) * | 2019-12-19 | 2021-06-24 | Kemira Oyj | Process for manufacturing a fibre web |
CN114765998A (zh) * | 2019-12-19 | 2022-07-19 | 凯米拉公司 | 纤维网的制造方法 |
CN114765998B (zh) * | 2019-12-19 | 2024-05-10 | 凯米拉公司 | 纤维网的制造方法 |
US12065367B2 (en) | 2021-04-23 | 2024-08-20 | Ecolab Usa Inc. | Volatile fatty acid control |
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