EP1862591A1 - Pre-dispersion - Google Patents
Pre-dispersion Download PDFInfo
- Publication number
- EP1862591A1 EP1862591A1 EP06011536A EP06011536A EP1862591A1 EP 1862591 A1 EP1862591 A1 EP 1862591A1 EP 06011536 A EP06011536 A EP 06011536A EP 06011536 A EP06011536 A EP 06011536A EP 1862591 A1 EP1862591 A1 EP 1862591A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dispersion
- water
- substance
- oils
- maximum
- 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- Withdrawn
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 121
- 239000002245 particle Substances 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000013530 defoamer Substances 0.000 claims abstract description 5
- 239000003112 inhibitor Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 72
- 239000000126 substance Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 32
- 235000007586 terpenes Nutrition 0.000 claims description 25
- 150000003505 terpenes Chemical class 0.000 claims description 25
- 239000003921 oil Substances 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 15
- -1 aliphatic alcohols Chemical class 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 14
- 239000000194 fatty acid Substances 0.000 claims description 14
- 229930195729 fatty acid Natural products 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 13
- 239000001993 wax Chemical class 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 239000013505 freshwater Substances 0.000 claims description 9
- 239000012188 paraffin wax Substances 0.000 claims description 8
- 239000002480 mineral oil Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 230000036541 health Effects 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000003209 petroleum derivative Substances 0.000 claims description 6
- 238000013112 stability test Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008157 edible vegetable oil Substances 0.000 claims description 5
- 239000003925 fat Substances 0.000 claims description 5
- 235000019271 petrolatum Nutrition 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 235000019809 paraffin wax Nutrition 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000341 volatile oil Substances 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005276 aerator Methods 0.000 claims description 2
- 238000010009 beating Methods 0.000 claims description 2
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 244000005700 microbiome Species 0.000 claims description 2
- 229920005615 natural polymer Polymers 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 230000000284 resting effect Effects 0.000 claims description 2
- 229920002994 synthetic fiber Polymers 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 description 21
- 235000019198 oils Nutrition 0.000 description 20
- 239000011521 glass Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 230000003068 static effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 235000019484 Rapeseed oil Nutrition 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000003225 biodiesel Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000003784 tall oil Substances 0.000 description 3
- 235000019871 vegetable fat Nutrition 0.000 description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- 239000001593 sorbitan monooleate Substances 0.000 description 2
- 229940035049 sorbitan monooleate Drugs 0.000 description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004165 Methyl ester of fatty acids Substances 0.000 description 1
- 206010033546 Pallor Diseases 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000037358 bacterial metabolism Effects 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 235000019508 mustard seed Nutrition 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
-
- 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
- D21H17/60—Waxes
-
- 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
- D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
-
- 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
Definitions
- Paper, board and such products are invariably made by dispersing fibres in much water and dewatering the resulting low-consistency slurry through a sieve.
- the sieve is a continuous length of plastic woven sieve, known as a formation wire, revolving over guide-rolls.
- the pre-dispersed fibres and possibly fillers are fed onto the moving wire through a slotted gap or whereby the water drains away leaving a continuous sheet of wet paper.
- the slurry could contain starch and sizing substances to improve the final paper characteristics.
- Such process chemicals could be added continuously or as shock-dose directly to the water circuits of the plant or could be applied to various parts of the plant such as formation wires, press-felts, drying-fabrics etc. via spray-bar systems to achieve the required treatment effects.
- any process chemicals added should at least initially be able to be dispersed throughout the system to reach the various parts to be treated.
- de-foamers can comprise natural or mineral oils or alternatively, cleaner compositions to reduce problems caused by sticky contamination can consist of organic solvents.
- oils or solvents if not correctly dispersed, collect as large globules on the water surface and adversely affect the paper being produced by creating visible oil flecks in the paper or actually disturb the process.
- the additive comprises tenside and solvent whereby the most preferred additive comprises 50-90% surfactant and 10-50% solvent.
- Some of the so far known cleaning or deposit control compositions comprise a significant level of emulsifier as well as water so the product can be supplied and stored as a long-term stable emulsion or if comprising only tenside and solvent, some comprise enough tenside to form an emulsion in the water-containing system.
- the tenside or emulsifier component of an additive can be contra-productive in that it can lead to foaming or even that it impedes the fast release of the actual active component from the emulsified state.
- anionic tensides it can be that these will be seen as so called “anionic disturbing substances” or “anionic trash” in that some important papermaking chemicals such as flocculating agents are of a cationic charge nature and can be negatively influenced by such anionic substances.
- pre-emulsified process chemicals are oil-in-water emulsions with say only 20% active content also means that significant amounts of water are being stored and transported. Additionally the emulsions including the tensides are not always stable particularly when being diluted in water-containing systems.
- the present invention provides a method of dispersion at least one substance in a water-containing system without the use of tensides. Further the method according to the present invention does not involve the presence of long-term stable microemulsions but involves the presence of metastable pre-dispersions having an average particle size of from 1 ⁇ m to 1 mm.
- the method and the pre-dispersion according to the present invention show several advantages. Firstly cleaning can be carried out in a more environmental friendly way. Further it can be avoided that oily products float up and agglomerate into unwanted lakes and large globules when dilution occurs in places not having permanent disturbance by the technical facilities in industrial plants. Additionally the pre-dispersions according to the present invention show defoaming activity which enables the reduction or even abdication of additional defoaming agents.
- an active process chemical such as a defoamer oil based on an edible oil
- an emulsifying tenside may not be exactly fitting as although it may carry legal approval, it may impart an undesired taste or other undesirable characteristic.
- Further defoamer activity is desired in applications such as pre-cooking or blanching vegetables prior to freezing.
- the method according to the present invention comprising the pre-dispersion avoids an unwanted influence on the bacterial metabolism caused by tensides.
- the present invention relates to a method for dispersing at least one substance in a water-containing system including the following steps of
- a solubility in deionised water at 20°C of maximum 0.05 mol/1 each refers to the creation of standard solutions. Standard solutions have particle diameters of below 5 nm.
- the pre-dispersion may decompose by the mean particle size exceeding 1mm and/or by creaming and/or oiling and/or sediment formation.
- the present invention relates a pre-dispersion having a mean particle size of from 1 ⁇ m to 1 mm, preferably 2 ⁇ m to 500 ⁇ m and most preferably 5 ⁇ m to 100 ⁇ m.
- the present invention further relates to pre-dispersion comprising at least one substance having a solubility in deionised water at 20 °C of maximum 0.05 mol/1 each and water, whereby the mean particle size of the pre-dispersion is from 1 ⁇ m to 1 mm, and whereby the pre-dispersion is stable for a minimum of 3 minutes and a maximum of 60 minutes, and wherein the pre-dispersion does not contain a tenside.
- the mean particle size is measured according to the following method.
- a so-called particle counting chamber is used together with a microscope fitted with a digital camera to examine a given volume of the pre-dispersion.
- the apparatus comprises a precision glass base with engraved lines spaced 50 microns ( ⁇ m) apart, crossing each other thus providing ruled squared areas of 50 x 50 ⁇ m.
- Each side of the flat area generally has two raised parts where a glass slide is placed creating a depth of 100 ⁇ m.
- a suitable counting chamber is for example model Reference 0640710 supplied by Paul Marienfeld GmbH&Co.KG of Lauda-Konigshofen, Germany.
- a drop of the dispersion is placed on the counting-chamber.
- a glass cover slide is placed on the chamber to trap a 100 ⁇ m thick film of dispersion over the ruled 50 ⁇ m calibration lines.
- the counting-chamber is placed under an optical microscope. As an example a 40 x objective lens can be used together with digital camera. Using the same setting, photos of the ruled calibrations of the empty counting chamber are taken as calibration reference. The mean particle size is then determined on the basis of the photos taken. Computer assisted analysis is possible.
- the supply of energy according to present invention is controlled such that a metastable pre-dispersion is produced.
- Metastability means that the pre-dispersion is only stable for a particular time range.
- the supply of energy is adjusted that the pre-dispersion has a minimum stability of 3 minutes and a maximum stability of 60 minutes.
- the pre-dispersion should have a minimum stability of 3 minutes and a maximum stability of 45 minutes.
- the pre-dispersion should have a minimum stability of 4 minutes and a maximum stability of 30 minutes.
- the pre-dispersion can decompose by agglomeration of particles whereby the particle size is increased over the limit of 1mm. Additionally, or as an alternative, the pre-dispersion may decompose by creaming and/or oiling and/or sediment formation.
- the supply of energy in step b) of the method according to the present invention is selected such that the pre-dispersion has a stability of at least 5 minutes according to the World Health Organisation Emulsion Stability Test Specification WHO/M/13.R4 revised 10 th December 1999.
- the water used should have a hardness of 342 mg/l calcium carbonate according to WHO method WHO/M/29 version approved 25 th September 1989.
- Creaming and/or oiling and/or sediment formation can easily be measured by using a Turbiscan instrument supplied by the company Formulaction of L'Union, France.
- the Turbiscan principal is that a pulsed laser light source at 850 nm wavelength is applied to a cylindrical glass tube in which a sample of the original dispersion is held.
- a detector measures the directly transmitted light energy and a second synchronised detector measures the light that is back-scattered from the dispersion.
- the light source and detector are programmed to repeatedly scan down the glass cylinder and measure the transmitted and scattered light at intervals of 40 ⁇ m. This procedure is conducted over the time frame of the stability requirement.
- the mean particle size can be measured from 0.05 ⁇ m up to 1 mm with this technique. Particle migration (creaming), particle size variations (agglomeration), phase separation can all be measured.
- each pass down the cylinder creates a curve of a function of transmitted light and back-scattered light over the height distance measured. Over the time of the test, the repeated measurement produces a series of overlayed curves which show either no change or gradual changes depending on the position of measurements down the cylinder.
- the method according to the present invention involves applying energy to the mixture of the at least one substance having a solubility in deionized water at 20°C of maximum 0.05 mol/l each, whereby the energy may be added through at least of one of the following provisions:
- the at least one substance having the above mentioned low solubility is selected from, hydrogen-treated petroleum distillate fraction, white spirit, including high-flash dearomatized white spirit, paraffin oils, edible fats and edible oils, silicone oils, aliphatic alcohols with 8 to 26 carbon atoms, fatty acid esters and derivatives thereof, ethylene oxide and/or propylene oxide oxylated derivatives of fatty acid esters, waxes derived from mineral oils including paraffin waxes, natural waxes, etheric oils and terpenes of natural origin including orange terpene.
- the substance is selected from white spirits and more preferably from high-flash, dearomatized white spirit.
- Preferable substances also include rapeseed oil methylester (biodiesel) and mixtures of white spirit with terpenes. Particularly preferred are mixtures of high-flash, dearomatized white spirit with orange terpene. Further substances are listed in Table 2.
- the total amount of the substance or the substances having low solubility according to the definition given above is generally below 33 vol% in the pre-dispersion.
- the amount is below 12 vol% and even more preferably the amount is below 6 vol% in the pre-dispersion. Most preferably the amount is below 3 vol%.
- the pre-dispersion may optionally be diluted by water after preparation of the pre-dispersion according to step b) and before addition of the pre-dispersion to the water-containing system keeping up the metastability properties. Upon dilution the total amount of substance / substances may be reduced to below 2 vol% and preferentially to below 1.5 vol%. This embodiment may be combined with all other options mentioned in the specification and the claims.
- the water-containing system comprises water and optionally at least one substance selected from natural and/or synthetic fibres and fines thereof, natural and/or synthetic fillers and/or pigments and/or solids, natural and/or synthetic polymers and resins, inorganic salts, suspended or surface-adhering micro-organisms, substances used in paper and pulp manufacture.
- the water-containing system may alternatively comprise compounds as generally present in waste water facilities.
- the water-containing system as used in the method according to the present invention includes may be for example a paper machine circuit, a circuit in a fibrous-pulp producing plant, a waste water circuit, or an industrial fresh water preparation plant. All vessels and pipe-work used in any of these systems shall be included.
- step c) should be carried out prior to decomposition of the pre-dispersion.
- a time limit of a maximum of 15 minutes is appropriate.
- step c) is carried out up to 10 minutes after preparation of the pre-dispersion and more preferably 5 minutes after preparation of the pre-dispersion. In the pre-dispersion the time limits are the same. Therefore the additional step has to be carried out within the time limits.
- the present invention further relates to a pre-dispersion comprising at least one substance having a solubility in deionised water at 20 °C of maximum 0.05 mol/l each as a first component and water as a second component, wherein the mean particle size of the pre-dispersion is in the range of from 1 ⁇ m to 1 mm, and wherein the pre-dispersion is stable for a minimum of 3 minutes and a maximum of 60 minutes, and wherein the pre-dispersion does not contain a tenside.
- "Not containing a tenside” means that the total amount of tenside components is below 2 wt.%, preferable below 1 wt.% and most preferable below 0.5 wt.%.
- pre-dispersion according to the present invention preferably has a stability of at least 5 minutes according to the World Health Organisation Emulsion Stability Test Specification WHO/M/13.R4 revised 10 th December 1999 in water having a hardness of 34.2 mg/l calcium carbonate according to WHO method WHO/M/29 version approved 25 th September 1989.
- the pre-dispersion according to the present invention preferably has a mean particle size within the range of 2 ⁇ m and 500 ⁇ m and more preferably within the range of 5 ⁇ m and 500 ⁇ m.
- the pre-dispersion according to the present invention comprises at least one substance having a solubility in deionised water at 20°C of maximum 0.05 mol/l each as a first component, wherein this first component is selected from hydrogen-treated petroleum distillate fraction, white spirit, including high-flash dearomatized white spirit, paraffin oils, edible fats and edible oils, silicone oils, aliphatic alcohols with 8 to 26 carbon atoms, fatty acid esters and oxylated derivatives thereof, ethylene oxide and/or propylene oxide oxylated derivatives of fatty acid esters, waxes derived from mineral oils including paraffin waxes, natural waxes, etheric oils and terpenes of natural origin including orange terpene, biodiesel.
- this first component is selected from hydrogen-treated petroleum distillate fraction, white spirit, including high-flash dearomatized white spirit, paraffin oils, edible fats and edible oils, silicone oils, aliphatic alcohols with 8 to 26 carbon atoms, fatty acid
- mixtures of the aforementioned substances are also possible. This includes double and triple mixtures as well as mixtures of more than 3 substances.
- Preferred mixtures include mixtures of white spirit with terpenes including high-flash dearomatized white spirit with orange terpene.
- Particularly preferred are mixtures of high-flash dearomatized white spirit with orange terpene in a ratio of from 50/50 to 90/10 (white spirit / orange terpene) whereby the amounts of the substances refer to wt%. Even more preferred is a ratio in the range of 70/30 to 90/10 high-flash dearomatized white spirit with orange terpene (wt% ratio).
- Further substances are listed in Table 2.
- the pre-dispersion according to the present invention preferably has a total amount of the substance or substances having a solubility in deionised water at 20°C maximum 0.05 mol/1 each below 12 vol%. More preferably the total amount of the substance or substances having a solubility in deionised water at 20°C maximum 0.05 mol/l each below 6 vol% and most preferably below 3 vol%.
- the pre-dispersion according to the present invention may be obtained by a process as described above.
- the pre-dispersion according to the present invention can be used as a cleaning agent in industrial plants. Additionally the pre-dispersion according to the present invention can be used as de-foamer, de-aerator, adhesion inhibitor against stickies and/or cleaner in the paper and pulp industry, including re-cycle pulp production, the foodstuffs industry or in waste-water treatment.
- Example 1 Pre-dispersion based on white spirit / mechanical dispersion
- a dispersion of a solvent in water was produced by pumping certain proportions of both the solvent and water under pressure firstly through a static mixer to premix the two immiscible liquids and then through a variable orifice into an area of lower pressure.
- a variable speed progressive cavity pump (Supplied by Gebrüder Netzsch Maschinenfabrik GmbH & Co. KG, Austria) with a maximum capacity of 19 1/h was used to pump a solvent comprising of a high-flash, de-aromatized white spirit.
- the high-flash, de-aromatized white spirit used was a hydrogen-treated petroleum distillate fraction with an initial boiling point of 180°C.
- the pump could be adjusted using a built-in variable-speed gearbox to deliver from 2 1/h up to 20 1/h of liquid and depending on the back-pressure in the system up to a maximum permitted working pressure of approximately 15 bars.
- a similar pump was used to pump normal fresh water.
- the water used was industrial fresh water with a hardness measured as equivalent to 214 mg CaCO 3 /l (12° German Hardness).
- the outputs of both pumps were fed into the entry of a static mixer comprising a 20 cm long, 19 mm internal diameter stainless-steel pipe packed tightly with stainless-steel wool.
- the entry end of the static-mixer was equipped with T-piece fitted with a manometer to measure the input pressure.
- an adjustable stainless-steel needle-valve On the outlet of the static-mixer was fitted an adjustable stainless-steel needle-valve, the outlet of which was fitted with a 30 cm long, open-ended plastic pipe with an internal diameter of 5 mm which acted as a collector to prevent aerosols spraying into the surrounding.
- the pump for water was started and adjusted to a flow of 16 1/h.
- the needle valve was closed down until a back pressure of 10 bars was showing on the manometer.
- the flow was measured with a measuring cylinder and stop-watch and corrected to 16 1/h.
- the needle valve was now opened slightly to drop the back pressure.
- the pump for solvent was started and adjusted to an approximate flow of 8 1/h measured as a total of 24 1/h total with the water.
- the needle-valve was progressively closed down until the manometer showed a back-pressure of 10 bars and the solvent pump was readjusted to maintain 24 1/h total flow.
- Example 1 was repeated whereby the output of the both pumps were adjusted such that the final pre-dispersion comprises a total amount of white spirit of 30 vol%.
- Example 2 Pre-dispersion based on a mixture of white spirit and orange terpene / mechanical dispersion
- Example 4 Pre-dispersion based on white spirit / microemulsifier
- a manometer was fitted to the pipe feeding the water to the entry side of the mixer.
- the outlet of the mixer was fed via a plastic pipe into a collecting vessel.
- the liquid mixture was forced through the caterpillar mixer causing highly turbulent mixing of the components.
- the pressure drop over the mixer with a total flow of 24 1/h was 15 bars given by an inlet pressure of 15 bars on the manometer and that the outlet flowed directly into a vessel at atmospheric pressure.
- the liquid flowing out of the outlet of the caterpillar mixer was milky-white and was fed directly into a receiving vessel.
- a so-called particle counting chamber was used together with a microscope fitted with a digital camera to examine a given volume of mechanically dispersed solvent in water.
- the counting chamber was a model Reference 0640710 supplied by Paul Marienfeld GmbH&Co.KG of Lauda-Königshofen, Germany. This unit could be used for counting bacteria cells in suspension but was ideal for judging any particle in suspension of a suitable size.
- the unit consisted of a precision glass base with engraved lines spaced 50 microns ( ⁇ m) apart, crossing each other thus providing ruled squared areas of 50 x 50 ⁇ m. each side of the flat area were two raised parts where a glass slide is placed creating a depth of 100 ⁇ m.
- a mechanical dispersion of high-flash, de-aromatized white spirit was produced as described in example 1 but with the component amounts adjusted to give 10% by volume of solvent in the dispersion, the rest being fresh water.
- the water used was industrial fresh water with a hardness measured as equivalent to 214 mg CaCO 3 /1 (12° German Hardness).
- the dispersion was tested for stability according to the WHO (World Health Organization) Emulsion Stability Test Specification WHO/M/13.R4 Revised 10th December 1999 in standard "soft" water (a hardness of 34.2 mg/1 expressed as calcium carbonate hardness) prepared according to the WHO (World Health Organisation) Method WHO/M/29 (version approved 25.09.1989).
- the diluted dispersion prepared thus was immediately poured into a clean 100 ml measuring cylinder as part of test WHO/M/13.R4 whereby the appearance of the dispersion was observed over time.
- Creaming is defined according to WHO/M/13.R4 as the formation, at the top or bottom of the dispersion, of a layer containing a proportion of the dispersed phase, namely solvent, higher than in the remainder of the emulsion.
- a layer of creaming would show as a denser white layer than the normal dispersion as it would absorb or scatter more light. This may be detected by using a Turbiscan instrument supplied by the company Formulaction of L'Union, France.
- the Turbiscan principal is that a pulsed laser light source at 850 nm wavelength is applied to a cylindrical glass tube in which a sample of the original dispersion is held.
- a detector measures the directly transmitted light energy and a second synchronised detector measures the light that is back-scattered from the dispersion.
- the light source and detector are programmed to repeatedly scan down the glass cylinder and measure the transmitted and scattered light at intervals of 40 ⁇ m. This procedure is conducted over the time frame of the stability requirement.
- the mean particle size can be measured from 0.05 ⁇ m up to 1 mm with this technique. Particle migration (creaming), particle size variations (agglomeration), phase separation can all be measured.
- Oiling is defined as formation at the top or the bottom of the dispersion of a liquid phase that is not miscible with water. In practice, an oiling layer would show as a clear liquid. Using the Turbiscan analyser, oiling would show as more transmitted light and less back-scattered light when the light beam is applied to that phase.
- Sediment formation refers to any solids separation out and sinking to the bottom, which is detectable by the Turbiscan analyser as changes in the light scattering.
- the particle size and distribution were detected. It was seen that the particles of solvent were still evenly dispersed and within a size range where no particles bigger than 200 ⁇ m whereby the majority of the particles were smaller than 50 ⁇ m.
- a pre-dispersion in water based on a mixture of 80% by volume of a hydrogen-treated petroleum distillate with an initial boiling point of 180°C plus 20% by volume of an orange-terpene oil derived from citrus fruit was prepared continuously using the basic procedure and equipment as described in example 1. The equipment was installed near the white-water circuit of a paper machine.
- the water used was industrial fresh water from the paper mill supply measured to have a total hardness equivalent to 240 mg CaCO 3 /l.
- the pre-dispersion produced was fed continuously into the white-water I circuit of the paper machine into the white-water channel leading to the white-water silo.
- the amount of solvent thus added to the circuit in the form of a mechanical dispersion was 1.7 1/h (litres/hour).
- the normal amount of de-foaming product used in the circuits of this paper machine was approximately 4 1/h. It was found that the de-foamer quantity used could be reduced down to a level of 2.1 1/h while remaining within the acceptable air content levels in the thin-stock and white-water system.
- a felt in a paper machine press-section regularly became contaminated with hydrophobic, sticky contamination meaning that it had to be off-line chemically washed with an alkaline cleaner every 3 or 4 days.
- the washing cycle lasted about 1 hour meaning that paper production was stopped for about 1.5 hours each time the felt had to be washed.
- An on-line cleaning composition comprising 3% tensides and 77% high flash, dearomatized white spirit and 20 % orange terpene thus containing essentially no water was used whereby the product was applied continually over the felt width.
- a spray-bar with fanned spray-pattern nozzles was fitted on the inside of a press-felt in the press-section of a paper machine. The spray-bar was fitted with fanned-spray pattern nozzles every 20 cm. The designed throughput of each nozzle was 0.5 litres per minute at 3 bar water pressure. The spray-bar was placed so that the nozzles were approximately 20 cm from the surface of the felt to give an overlap in the individual spray pattern of 60% so that the coverage of the sprayed medium was uniform. Water was fed to the spray-bar at 3 bar pressure giving an amount of 2.5 litres per metre felt width per minute.
- the tenside containing product was added using a small diaphragm pump at a rate of 5 ml per minute per metre width of felt meaning for the felt of 4.7 m wide a total volume of product of 23.5 ml/minute (or 23.0 ml/min as pure solvent).
- a pre-dispersion according to example 2 was produced.
- the concentration of solvent was adjusted to be the same as in the comparative test described above.
- the total amount of active ingredient applied was 5 ml/min per metre felt width but in a form finely mechanically dispersed in water.
- Wax No. 71965-38-3) Wax, petroleum, Type I and Type II. Wax, petroleum (oxidized). Wax (montan) Cyclohexane Dimers and trimers of unsaturated C 18 fatty acids derived from animal and vegetable fats and oils. Tall oil. Fats and oils derived from animal,marine, or vegetable sources:Fatty acids derived from animal,marine, or vegetable fats andoils, and salts of such acids,single or mixed, as follows: Aluminum,Calcium,Magnesium,Zinc. Methyl esters of fatty acids derived from animal, marine, or vegetable fats and oils. Methyl oleate Methyl palmitate Mineral oil Odorless light petroleum hydrocarbons Tall oil fatty acids...................
- the pre-dispersion according to experiment 5d was compared with the mixture according to comparative experiment 5.
- the pre-dispersion and the mixture were added (in equal amounts) to a pilot plant, which simulated the turbulences present in paper machines.
- the amount of bubbles was significantly lower than in the case of the mixture according to comparative example 5. Additionally the necessary amount of defoamer agent for a reliable cleaning could be reduced by a factor of 1.7.
Landscapes
- Paper (AREA)
- Colloid Chemistry (AREA)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06011536A EP1862591A1 (fr) | 2006-06-02 | 2006-06-02 | Pre-dispersion |
| RU2007120349/15A RU2007120349A (ru) | 2006-06-02 | 2007-05-31 | Предварительная дисперсия |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06011536A EP1862591A1 (fr) | 2006-06-02 | 2006-06-02 | Pre-dispersion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1862591A1 true EP1862591A1 (fr) | 2007-12-05 |
Family
ID=37499747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP06011536A Withdrawn EP1862591A1 (fr) | 2006-06-02 | 2006-06-02 | Pre-dispersion |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP1862591A1 (fr) |
| RU (1) | RU2007120349A (fr) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5800677A (en) * | 1995-03-30 | 1998-09-01 | Nissin Kagaku Kenkyusho Co., Ltd. | Method for preventing pitch trouble |
| WO2000020499A1 (fr) * | 1998-10-02 | 2000-04-13 | The Dow Chemical Company | Resines epoxides et leurs dispersions aqueuses stables |
| DE19851024A1 (de) * | 1998-11-05 | 2000-05-11 | Basf Ag | Wäßrige Dispersionen von wasserlöslichen Polymerisaten von N-Vinylcarbonsäureamiden, Verfahren zu ihrer Herstellung und ihre Verwendung |
| WO2001085846A1 (fr) * | 2000-05-08 | 2001-11-15 | Ondeo Nalco Company | Procede et composition permettant de disperser des particules hydrophobes dans des suspensions aqueuses |
| EP1176254A1 (fr) * | 2000-07-24 | 2002-01-30 | The Dow Chemical Company | Utilisation de dispersions d'amidon reticulé dans la fabrication du papier |
| US6380299B1 (en) * | 1998-01-26 | 2002-04-30 | Krems Chemis Aktiengesellschaft | Stable aqueous dispersions for sizing paper |
| EP1314822A1 (fr) * | 2001-11-19 | 2003-05-28 | Akzo Nobel N.V. | Procédé de collage de papier et composition de collage |
| US20030127205A1 (en) * | 2001-11-19 | 2003-07-10 | Lars Odberg | Process for sizing paper and sizing composition |
| EP1522556A1 (fr) * | 2002-06-21 | 2005-04-13 | Hymo Corporation | Dispersion polymere hydrosoluble, son procede de production et d'utilisation |
-
2006
- 2006-06-02 EP EP06011536A patent/EP1862591A1/fr not_active Withdrawn
-
2007
- 2007-05-31 RU RU2007120349/15A patent/RU2007120349A/ru not_active Application Discontinuation
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5800677A (en) * | 1995-03-30 | 1998-09-01 | Nissin Kagaku Kenkyusho Co., Ltd. | Method for preventing pitch trouble |
| US6380299B1 (en) * | 1998-01-26 | 2002-04-30 | Krems Chemis Aktiengesellschaft | Stable aqueous dispersions for sizing paper |
| WO2000020499A1 (fr) * | 1998-10-02 | 2000-04-13 | The Dow Chemical Company | Resines epoxides et leurs dispersions aqueuses stables |
| DE19851024A1 (de) * | 1998-11-05 | 2000-05-11 | Basf Ag | Wäßrige Dispersionen von wasserlöslichen Polymerisaten von N-Vinylcarbonsäureamiden, Verfahren zu ihrer Herstellung und ihre Verwendung |
| WO2001085846A1 (fr) * | 2000-05-08 | 2001-11-15 | Ondeo Nalco Company | Procede et composition permettant de disperser des particules hydrophobes dans des suspensions aqueuses |
| EP1176254A1 (fr) * | 2000-07-24 | 2002-01-30 | The Dow Chemical Company | Utilisation de dispersions d'amidon reticulé dans la fabrication du papier |
| EP1314822A1 (fr) * | 2001-11-19 | 2003-05-28 | Akzo Nobel N.V. | Procédé de collage de papier et composition de collage |
| US20030127205A1 (en) * | 2001-11-19 | 2003-07-10 | Lars Odberg | Process for sizing paper and sizing composition |
| EP1522556A1 (fr) * | 2002-06-21 | 2005-04-13 | Hymo Corporation | Dispersion polymere hydrosoluble, son procede de production et d'utilisation |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2007120349A (ru) | 2008-12-10 |
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