WO1991003599A1 - Collector chemical for deinking of waste paper - Google Patents
Collector chemical for deinking of waste paper Download PDFInfo
- Publication number
- WO1991003599A1 WO1991003599A1 PCT/SE1990/000554 SE9000554W WO9103599A1 WO 1991003599 A1 WO1991003599 A1 WO 1991003599A1 SE 9000554 W SE9000554 W SE 9000554W WO 9103599 A1 WO9103599 A1 WO 9103599A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- collector
- acid
- tall oil
- flotation
- deinking
- Prior art date
Links
- 239000000126 substance Substances 0.000 title claims abstract description 23
- 239000002761 deinking Substances 0.000 title claims abstract description 15
- 239000010893 paper waste Substances 0.000 title claims abstract description 11
- 238000005188 flotation Methods 0.000 claims abstract description 32
- 239000003784 tall oil Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 16
- 229920000728 polyester Polymers 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 5
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 23
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 23
- 239000011976 maleic acid Substances 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229920001451 polypropylene glycol Polymers 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- -1 aliphatic alcohols Chemical class 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 235000011087 fumaric acid Nutrition 0.000 claims 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- 239000002253 acid Substances 0.000 description 18
- 239000000835 fiber Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000344 soap Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 235000019353 potassium silicate Nutrition 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- VUYXVWGKCKTUMF-UHFFFAOYSA-N tetratriacontaethylene glycol monomethyl ether Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO VUYXVWGKCKTUMF-UHFFFAOYSA-N 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- XDXHAEQXIBQUEZ-UHFFFAOYSA-N Ropinirole hydrochloride Chemical compound Cl.CCCN(CCC)CCC1=CC=CC2=C1CC(=O)N2 XDXHAEQXIBQUEZ-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 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
- 150000002894 organic compounds Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Chemical class 0.000 description 1
- 229920005989 resin Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 125000003198 secondary alcohol group Chemical group 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
-
- 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
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/02—Working-up waste paper
- D21C5/025—De-inking
- D21C5/027—Chemicals therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Definitions
- Waste paper has in later years become more and more important as raw material for paper pulp manufacture.
- One reason is that the supply of cellulose does not correspond to the demand of the paper industry, i.e. one compensates the shortage of pulp fibers by using waste paper.
- Another important reason is that the energy cost has become increasingly higher.
- Besides the collecting of waste paper has increased, since people are more conscious about environmental aspects today. The increased use of more complex printing ink and the increasing energy costs makes it necessary to develop more cost efficient deinking chemicals.
- the flotation process is most common in Europe and in South-east Asia. It gives a high yield of fibers and filler. Other advantages are environmental aspects, such as a closed water system, a low water consumption and that contaminants are obtained in concentrated form. Disadvantages with this process are the relatively high capital - and chemical costs. These costs are however compensated by the high yield, so that as a whole an economically advantegeous system is achieved.
- the flotation process requires a careful supervision, i.e. depending on that it is sensitive to variations in the composition of the waste paper pulp. The method is mainly used when the recovered fiber mass is to be used for manufacture of newsprint paper.
- the washing process is dominating in the United States and Canada. In this process filler and fine material are also removed besides the printing ink. This is a drawback in the manufacture of newsprint paper, since the yield is bad. However it is an advantage when soft paper for sanitary purposes is to be produced. An advantage with this method is its insensitiveness for differences in the composition of the waste paper pulp. Besides the capital- and chemical costs are lower than for the flotation process. In the washing process it is important that the printing ink is kept as dispersed and stable as possible, which is provided by high admixture of non-ionactive tensides. Washing is performed by diluting the pulp mixture to low concentrations and then watering it down to higher concentrations in a water extractor, a washing filter.
- the flotation process comprises several steps, the most important of which are:
- the ink is removed from the fibers.
- the waste paper is here mixed with water and chemicals.
- the paper is disintegrated into separate fibers with adhering printing ink.
- the added caustic liquid gives a saponification of the surface layer of the binding agent of the printing ink, which contributes to an electrostatic repulsion between the carboxylic groups in the printing ink and on the surfaces of the fibers. This together with the softening provided by the ink components, facilitates the release of the printing ink. At the same time mechanical energy is supplied.
- the caustic liquid also helps to disperse the ink to small ink particles, but a good wetting of the ink is also requi red.
- a wetting agent which can be a non-ionic tenside, which helps the liquid to penetrate the paper.
- the tenside is also absorbed on the ink particles and stabilizes these so that reprecipitation is avoided.
- dispersion and stabilization may not occur to well, since in such case flotation can be made difficult. This is the next step in the process.
- a collector agent In order to enable separation of dispersed ink particles their surface properties must be changed, which is made by a collector agent.
- the collector increases the hydrophobic character and creates an electro - chemical attraction to the air bubbles.
- the flotation is made in a flotation cell. Air is blown into the pulp and the ink particles then collide with and stick to the air bubbles, which, flow to the surface. A foam layer is created there, which is then separated.
- Sodium hydroxide is one of the most important deinking chemicals.
- the caustic liquid contributes to break hydrogen bonds, swell the fibers and release the printing ink.
- the NaOH saponifies the surface layer of the binding agent of the printing ink, i.e. an alkaline hydrolysis takes place. This involves electrostatic repulsion between the carboxylic groups in the printing ink and on the fiber surface. The printing ink is released and dispersed.
- At the flotation pH is raised to 10 - 11 by adding the caustic liquid.
- Hydrogen peroxide is used both for bleaching the fibers and for oxidizing possible organic contaminants. It has a great importance for the deinking process, since it contributes to breaking the strong bonds in the printing ink. At high temperatures the instable hydrogen peroxide decomposes .
- Water glass effects the flotation process in many different ways. It acts as a wetting agent, printing ink dissolver, pH buffer, corrosion inhibitor and complex former which bonds different metals.
- water glass When adding water glass the collecting effect of the fatty acids are considerably increased and the reprecipitation of the printing ink on the fibers are reduced.
- the instable hydrogen peroxide is stabilized by water glass.
- the surfactants have different functions:
- the collector agglomerates and hydrophobizes the printing ink. Surfactants thus contribute to release the printing ink from the fibers and then prevent that the printing ink is reprecipitated thereon.
- the collector shall destabilize the effect of the dispersant on the printing ink, before flotation of the pulp.
- the added collector increases the hydrophobic character of the ink particles and creates electro - chemical attraction to the air bubbles.
- the function of the collector is thus to agglomerate and hydrophobize the printing ink effectively.
- soap When soap is used as collector there is one requirement.
- the fatty acids must be treated with calcium - and magnesium ions in order to function effectively. These ions can later in the process cause problem in the process.
- soap is the collector that has caused the best brightness, i.e. the best deinking result. Soap is relatively cheap and there are many distributors.
- Both synthetic and semisynthetic collectors have the advantage of being independent on the water hardness, i.e. calcium ions is no requirement. Therefore a better runuability can be provided.
- the collector gives a lower brightness and are more expensive than soap, but they often give effective deinking at a lower dose.
- the msot common synthetic collectors consist of strongly hydrophobic non-ionic tensides, e.g. etoxylated fatty acids.
- the mechanism of the collector could be explained in two ways. Synthetic collectors can function as a small wetting and in this way catch the printing ink, but there is then a risk that also fibers are catched. The collector can also due to there hydrophobic properties collect the printing ink to aggregates. The are a number of factors which influence the effect of the.
- the molecular weight is an important parameter, which probably should be between 3000 - 10000. This can be controlled in e.g. a GPC (gel permeation chromatography), after finished synthesis.
- the hydrophobity is important for enabling the collector to selectively collect the ink particles, i.e. without bringing the fibers along.
- the length of the carbon chain can be varied.
- the object of the present invention is to provide a collector, which fulfils the following requirements.
- the collector should function without admixture of calcium ions. It should not detoriate the backwater purity with time, and thus permit recirculation of the water without detoriating the brightness of the pulp.
- the collector should function selectively without negatively influencing the other chemicals. The dosing requirement must not be so exact that small variations influence the deinking process.
- the collector should be simple to handle and cheap to manufacture. Besides it should not give any side effects on the environment, i.e. at least partly be based on naturally occuring substances and be decomposeable.
- polyester produced by reaction between 1 ) polyalkylene glycol, 2) di - and/or tricarboxylic acid and/or anhydrides thereof and 3) tall oil, said polyester having a molecular weight between 3000-10000.
- Figure 1 is a block diagram showing the increase of bright ness at flotation tests with the collector according to the invention, a commercial collector and soap.
- Figure 2 shows flotation graphs for the collector according to figure 1.
- FIG. 3 shows flotation graphs for the collector according to the invention in different additive amounts.
- a polyester is an organic compound formed through reaction between alcohols and acids.
- the polyester is defined as a polymer with ester bond in the main chain:
- polyesters There are different polyesters available: linear saturated or unsaturated polyesters, branched saturated or unsaturated polyesters and saturated and unsaturated network polyesters.
- step polymerisation is used, so called condensation polymerisation.
- step polymerisation is characterized by the following:
- MPD molecular weight distribution
- acids are maleic acid, fumaric acid and adipic acid.
- Common diols are ethylene glycol, propylene glycol and 1,4 - butane diol. By varying the acids and diols polyesters with different properties are obtained.
- multifunctional monomers i.e. trifunctional
- no linear polymers are obtained.
- the multifunctional monomers contain more reactive groups, and thus give branching points, which can contribute to branching and netting at the polymerisation.
- the final product is then a network polymer. Ex .
- the polymer becomes sparingly soluble and forms a gel. This occurs at the so called gel point, which can be determined when the functionality is known.
- the network consists of one single polymer molecule.
- Polyethylene glycol PEG HO-(CH 2 -CH 2 O) n -H PEG occurs in many different molecular weights. We have used the mean molecular weight 300, 400 and 600, which all are liquids and PEG 1500, which is a solid compound. Polypropylene glycol, PPG HO-CCH 2 -CH 2 -CH 2 O) n -H.
- PPG 400, 600, 1200, 2000 and 4000 have been used. All are liquids.
- Tall oil which contains i.a. varying amounts of fatty acids and resin acids.
- the final product is a polymer (polyester) with a mean molecular weight of 3000-10000, preferably 5000-10000.
- a member of different collectors were prepared having the following composition of raw material:
- Collector 1A Collector 1B
- the solid and liquid initial chemicals were mixed together with the catalyst in a flange falsk. Nitrogen gas was introduced into the mixture in order to provide stirring and avoid oxidation. The vacuum suction device was then started in order to reduce the pressure.
- the flask When the pressure was sufficiently reduced the flask was heated from room temperature to 150 - 200°C. The synthesis was continued for about 3 hours, and was controlled at regular intervals. This was made for measuring the acid value, which showed how far the reaction had proceeded. When the acid value was sufficiently low the synthesis was interrupted.
- the collector (0,73 g) was added. Full dosis is 0,5% of the dry weight of paper pulp. In cases where soap was used as collector 3,6 g CaCl 2 had to be added.
- Ink sludge is collected between the times 0-4, 4-8, 8-16 minutes of flotation. The volume was measured on the respective fraction.
- the filter paper was dried and weighed on a balance scale. From a fraction was taken 250 ml of well mixed sludge, which was sucked off in a B ⁇ chner funnel on a filter paper that was weighed beforehand. The content in the Buchner funnel was removed and transferred to the sheet, air-dried with a lattice weight on top and weighed.
- the test results prove that a collector based on maleic acid, polyethylene glycol with a mean molecular weight of 400, and tall oil gave the best deinking result.
- the increase of brightness after 16 min. flotation was 7,4 units (according to Hunter Lab.).
- Corresponding values for soap was 5, 6 and for commercial collector (KAO) 6,7.
- the increase of brightness for the collector according to the invention was thus 10% higher for the commercial collector.
- the flotation was functioning better with the collector according to the invention as compared to soap and commercial collector.
- fig. 1 is shown in the form of block diagram the brightness increase after 16 minutes flotation for the collector according to the invention based on maleic acid, polyethylene glycol and tall oil and for soap and commercial collector resp.
- the backwater purity with the collector according to the invention was besides higher. Tests for determining the influence of different dosing amounts on the deinking result have also been performed. To every flotation there has been used 2 kg Bimex 400/ton and varying amounts of collector 1 A according to above. The added amounts were 1, 2, 3, 4 and 5 kg collector resp. /ton pulp. In fig. 3 is shown flotation graphs (brightness as a function of time) for the different admixture amounts. An admixture amount of 5 kg collector/ton pulp gave about: 5% better brightness than an admixture amount of 1 kg collector /ton pulp.
- the polyester according to the invention provides a collector which is very effective and gives improved deinking results as compared to soap and commercial synthetic collectors. It is besides harmless to the environment due to its composition.
Abstract
Collector chemical for deinking of waste paper according to the flotation process and which consists of a polyester obtained through reaction between 1) polyalkylene glycol, 2) di- and/or tricarboxylic acid and/or anhydrides thereof and 3) tall oil, said polyester having a molecular weight between 3000 - 10000.
Description
COLLECTOR CHEMICAL FOR DEINKING OF WASTE PAPER
Background of the invention
Waste paper has in later years become more and more important as raw material for paper pulp manufacture. One reason is that the supply of cellulose does not correspond to the demand of the paper industry, i.e. one compensates the shortage of pulp fibers by using waste paper. Another important reason is that the energy cost has become increasingly higher. Besides the collecting of waste paper has increased, since people are more conscious about environmental aspects today. The increased use of more complex printing ink and the increasing energy costs makes it necessary to develop more cost efficient deinking chemicals.
In order to remove printing ink from waste paper there are mainly two methods that are used, viz. the washing process and the flotation process. These two methods differ mainly in the separation of the ink.
The flotation process is most common in Europe and in South-east Asia. It gives a high yield of fibers and filler. Other advantages are environmental aspects, such as a closed water system, a low water consumption and that contaminants are obtained in concentrated form. Disadvantages with this process are the relatively high capital - and chemical costs. These costs are however compensated by the high yield, so that as a whole an economically advantegeous system is achieved. The flotation process requires a careful supervision, i.e. depending on that it is sensitive to variations in the composition of the waste paper pulp. The method is mainly used when the recovered fiber mass is to be used for manufacture of newsprint paper.
The washing process is dominating in the United States and
Canada. In this process filler and fine material are also removed besides the printing ink. This is a drawback in the manufacture of newsprint paper, since the yield is bad. However it is an advantage when soft paper for sanitary purposes is to be produced. An advantage with this method is its insensitiveness for differences in the composition of the waste paper pulp. Besides the capital- and chemical costs are lower than for the flotation process. In the washing process it is important that the printing ink is kept as dispersed and stable as possible, which is provided by high admixture of non-ionactive tensides. Washing is performed by diluting the pulp mixture to low concentrations and then watering it down to higher concentrations in a water extractor, a washing filter.
The flotation process comprises several steps, the most important of which are:
1. release of ink from the fibers.
2. dispersion of the ink particles.
3. separation of ink from the fiber - ink - suspension, i.e. flotation.
In the dissolver the ink is removed from the fibers. The waste paper is here mixed with water and chemicals. The paper is disintegrated into separate fibers with adhering printing ink. The added caustic liquid gives a saponification of the surface layer of the binding agent of the printing ink, which contributes to an electrostatic repulsion between the carboxylic groups in the printing ink and on the surfaces of the fibers. This together with the softening provided by the ink components, facilitates the release of the printing ink. At the same time mechanical energy is supplied.
The caustic liquid also helps to disperse the ink to small ink particles, but a good wetting of the ink is also requi
red. This is achieved by a wetting agent, which can be a non-ionic tenside, which helps the liquid to penetrate the paper. The tenside is also absorbed on the ink particles and stabilizes these so that reprecipitation is avoided. However dispersion and stabilization may not occur to well, since in such case flotation can be made difficult. This is the next step in the process.
In order to enable separation of dispersed ink particles their surface properties must be changed, which is made by a collector agent. The collector increases the hydrophobic character and creates an electro - chemical attraction to the air bubbles. The flotation is made in a flotation cell. Air is blown into the pulp and the ink particles then collide with and stick to the air bubbles, which, flow to the surface. A foam layer is created there, which is then separated.
The following chemicals are used in the deinking:
Sodium hydroxide (NaOH) .
Sodium hydroxide is one of the most important deinking chemicals. In high concentration the caustic liquid contributes to break hydrogen bonds, swell the fibers and release the printing ink. The NaOH saponifies the surface layer of the binding agent of the printing ink, i.e. an alkaline hydrolysis takes place. This involves electrostatic repulsion between the carboxylic groups in the printing ink and on the fiber surface. The printing ink is released and dispersed. At the flotation pH is raised to 10 - 11 by adding the caustic liquid.
Hydrogen peroxide (H2O2)
Hydrogen peroxide is used both for bleaching the fibers and for oxidizing possible organic contaminants. It has a great importance for the deinking process, since it contributes to breaking the strong bonds in the printing ink. At high
temperatures the instable hydrogen peroxide decomposes .
Water glass (Sodium silicate Na2SiO3)
Water glass effects the flotation process in many different ways. It acts as a wetting agent, printing ink dissolver, pH buffer, corrosion inhibitor and complex former which bonds different metals. When adding water glass the collecting effect of the fatty acids are considerably increased and the reprecipitation of the printing ink on the fibers are reduced. The instable hydrogen peroxide is stabilized by water glass.
Surfactants
The surfactants have different functions:
* the wetting agent; reduces the surface tension
* the frothing agent; stabilized the air bubbles
* the collector; agglomerates and hydrophobizes the printing ink. Surfactants thus contribute to release the printing ink from the fibers and then prevent that the printing ink is reprecipitated thereon.
The collector shall destabilize the effect of the dispersant on the printing ink, before flotation of the pulp. The added collector increases the hydrophobic character of the ink particles and creates electro - chemical attraction to the air bubbles. The function of the collector is thus to agglomerate and hydrophobize the printing ink effectively.
There are different types of :
* Soap
* Synthetic collectors (advanced synthesis technique)
* Semisynthetic collectors ( further refinement of fatty acids).
The border - line between synthetic and semisynthetic col
lectors is however diffuse.
When soap is used as collector there is one requirement. The fatty acids must be treated with calcium - and magnesium ions in order to function effectively. These ions can later in the process cause problem in the process. Up to now soap is the collector that has caused the best brightness, i.e. the best deinking result. Soap is relatively cheap and there are many distributors.
One of the disadvantages is that at least 30% of the added soap goes along with the paper, which gives poor runnability and coatings. Soap is besides difficult to handle. Use of soap causes high fiber losses, which means that the amount of raw material to the process has to be increased.
Both synthetic and semisynthetic collectors have the advantage of being independent on the water hardness, i.e. calcium ions is no requirement. Therefore a better runuability can be provided. The collector gives a lower brightness and are more expensive than soap, but they often give effective deinking at a lower dose. The msot common synthetic collectors consist of strongly hydrophobic non-ionic tensides, e.g. etoxylated fatty acids.
The mechanism of the collector could be explained in two ways. Synthetic collectors can function as a small wetting and in this way catch the printing ink, but there is then a risk that also fibers are catched. The collector can also due to there hydrophobic properties collect the printing ink to aggregates. The are a number of factors which influence the effect of the.
The molecular weight is an important parameter, which probably should be between 3000 - 10000. This can be controlled in e.g. a GPC (gel permeation chromatography), after finished synthesis.
The acid value is a measure of the number of carboxylic groups in the product ( =mg potassium hydroxide per g sample). The acid value is reduced during the progress of the reaction. A low acid value indicates that most carboxylic groups have reacted which involves a hydrophobic product, which is desireable.
The hydrophobity is important for enabling the collector to selectively collect the ink particles, i.e. without bringing the fibers along. In order to regulate the hydrophobity the length of the carbon chain can be varied.
Object: and most important features of the invention The object of the present invention is to provide a collector, which fulfils the following requirements.
The collector should function without admixture of calcium ions. It should not detoriate the backwater purity with time, and thus permit recirculation of the water without detoriating the brightness of the pulp. The collector should function selectively without negatively influencing the other chemicals. The dosing requirement must not be so exact that small variations influence the deinking process. The collector should be simple to handle and cheap to manufacture. Besides it should not give any side effects on the environment, i.e. at least partly be based on naturally occuring substances and be decomposeable.
This has according to the invention been provided by a polyester produced by reaction between 1 ) polyalkylene glycol, 2) di - and/or tricarboxylic acid and/or anhydrides thereof and 3) tall oil, said polyester having a molecular weight between 3000-10000. Description of the drawings
Figure 1 is a block diagram showing the increase of bright
ness at flotation tests with the collector according to the invention, a commercial collector and soap.
Figure 2 shows flotation graphs for the collector according to figure 1.
Figure 3 shows flotation graphs for the collector according to the invention in different additive amounts.
Theoretical background A polyester is an organic compound formed through reaction between alcohols and acids. The polyester is defined as a polymer with ester bond in the main chain:
-R-COO-R'-OOC-R-COO-R'- or
-RCOO-RCOO-RCOO-
There are different polyesters available: linear saturated or unsaturated polyesters, branched saturated or unsaturated polyesters and saturated and unsaturated network polyesters.
There are two types of polymerisation reactions, namely chain - and step polymerisation. For producing polyesters step polymerisation is used, so called condensation polymerisation. The step polymerisation is characterized by the following:
* all molecules, irrespective of size, can react with each other.
* during the whole reaction there are all molecular sizes present, i.e. there is a broad molecular weight distribution (MPD).
* the monomers disappear early from the reaction mixture.
* the molecular weight increases continuously during the progress of the polymerisation.
* long reaction time and high transformation are required for achieving high molecular weight and degree of polymerisation ( and by that a low acid value) .
In order to obtain a polymer the monomers have to be at least bifunctional, i.e. they should contain two functional groups per molecule. Direct esterification with such raonomers gives:
n HO-R-OH-n HOOC-R'-COOH
H0-(R-OCO-R'-COO)n-H + H2O
Examples of acids are maleic acid, fumaric acid and adipic acid. Common diols are ethylene glycol, propylene glycol and 1,4 - butane diol. By varying the acids and diols polyesters with different properties are obtained.
At technical production of polyesters, which often takes place at temperatures between 150°C and 200ºC,.one usually directly esterifies the acids with a certain excess of diol. At the same time water is removed through distillation. This is made in order to prevent a return reaction and for obtaining high polymerisation degrees. Excess of one of the monomers gives a stoicheiometric unbalance, which involves a limited molecular growth, i.e. control of chain length and molecular weight is obtained. Other ways of controlling this is by means of monofunctional compounds, monovalent acid or monovalic alcohol, which stops the reaction (so called chain stopper). In all esterification reactions H2SO4 can be used as catalyzer.
If instead of bifunctional monomers multifunctional monomers are used, i.e. trifunctional, no linear polymers are obtained. The multifunctional monomers contain more reactive groups, and thus give branching points, which can contribute to branching and netting at the polymerisation. The final product is then a network polymer.
Ex .
One here speaks of a certain functionality f , e. g . f = 3 .
At a certain yield (transformation) the polymer becomes sparingly soluble and forms a gel. This occurs at the so called gel point, which can be determined when the functionality is known. When 100% transformation is achieved the network consists of one single polymer molecule.
Under conditions that functional groups of the same kind are equally reactive and that the reactivity is independent of the molecular size, one can calculate in the same way as for bifunctional monomers. There are however exceptions, i.a. glycerol, where the secondary alcohol group is less reactive than the two primary groups.
The following chemicals have been used at the preparation of the collector according to the invention.
1) Polyalkylene glycol, e.g.
Polyethylene glycol PEG HO-(CH2-CH2O)n-H
PEG occurs in many different molecular weights. We have used the mean molecular weight 300, 400 and 600, which all are liquids and PEG 1500, which is a solid compound. Polypropylene glycol, PPG HO-CCH2-CH2-CH2O)n-H.
This also occurs in different molecular weights. PPG 400, 600, 1200, 2000 and 4000 have been used. All are liquids. 2) Di- and tricarboxylic acid or its anhydrides in e.g. Maleic acid (cis-form)
Fumaric acid (trans-form)
Adipic acid HOOC-(CH2)4-COOH
Citric acid
Oxalic acid HOOC-COOH Sebacic acid HOOC-(CH2)8-COOH
3) Tall oil which contains i.a. varying amounts of fatty acids and resin acids.
The final product is a polymer (polyester) with a mean molecular weight of 3000-10000, preferably 5000-10000.
By using bifunctional alcohols and acid the molar ratio should be close to 1. Tall oil is used for controlling the chain length of the final polymer.
Since we have used a simple one-stop synthesis no residual products are obtained, which should be taken care of in the manufacturing process. Only aliphatic carboxylic acids have been used, which are more easily decomposeable and less toxic (cancerogenic) as compared to aromatic compounds.
Description of embodiments
A member of different collectors were prepared having the following composition of raw material:
Collector 1A Collector 1B
Maleic acid 102 g Maleic acid 51 g
PEG 400 461 g PEG 400 230 g
Tall oil 35 g Tall oil 35 g Collector 2 Collector 3
Maleic acid 97 g Maleic acid 70 g
PEG 400 486 g PEG 300 223 g
Tall oil 47 g Tall oil 28 g Collector 4 Collector 5
Maleic acid 53 g Maleic acid 8 g
PEG 600 365 g PEG 1500 238 g
Tall oil 26 g Tall oil 9g Collector 6 Collector 7
Maleic acid (90%) 46 g Maleic acid (50%) 26 g
Citric acid (10%) 5 g Citric acid (50%) 42 g
PEG 400 231 g PEG 400 379 g
Tall oil 17 g Tall oil 152 g
Collector 8 Collector 9
Citric acid 92 g Oxalic acid 80 g
PEG 400 576 g PEG 400 456 g
Tall oil 293 g Tall oil 66 g
Collector 10 Collector 11
Fumaric acid 102 g Adipic acid 127 g
PEG 400 461 g PEG 400 464 g
Tall oil 35 g Tall oil 36 g
Collector 12 Collector 13
Sebacic acid 94 g Maleic acid 102 g
PEG 400 235 g PPG 400 461 g
Tall oil 22 g Tall oil 35 g
Collector 14 Collector 15A
Maleic acid 53 g Maleic acid 11 g PPG 600 365 g PPG 1200 218 g Tall oil 26 g Tall oil 10 g
Collector 15B Collector 16A
Maleic acid 49 g Maleic acid 9 g PPG 1200 480 g PPG 2000 370 g Tall oil 11 g Tall oil 13 g
Collector 16B Collector 17A
Maleic acid 28 g Maleic acid 4g PPG 2000 455 g PPG 4000 758 g Tall oil 7 g Tall oil 11 g
Collector 17B Collector 18
Maleic acid 10 g Maleic acid 102 g PPG 4000 322 g PEG 400 461 g Tall oil 2 g Unitol (Tall oil) 35 g
At the manufacture of all the above collectors 1 ml sulphuric acid has been used as catalyst.
Synthesis of the collector
The solid and liquid initial chemicals were mixed together with the catalyst in a flange falsk. Nitrogen gas was introduced into the mixture in order to provide stirring and avoid oxidation. The vacuum suction device was then started in order to reduce the pressure.
When the pressure was sufficiently reduced the flask was heated from room temperature to 150 - 200°C. The synthesis was continued for about 3 hours, and was controlled at regular intervals. This was made for measuring the acid value, which showed how far the reaction had proceeded. When the acid value was sufficiently low the synthesis was interrupted.
Another way of controlling how far the reaction has proceeded was to measure the amount of water given off, as it is a condensation reaction. Flotation tests with the collector
Magazine papers and daily papers were cut in pieces of about 3,5 cm. We used the same numbers of both journal papers and daily papers in all tests.
Correct amounts were weighed and put in a beater together with a part of the deinking chemicals.
After a period of rest the paper pieces were refined to a pulp in the beater. More chemicals were mixed in and the pulp was allowed to rest for about 1 hour. The pulp was further disintegrated in another beater. The collector was
added and the slurry was brought to the cell, after which the flotation was started. Samples were taken at regular intervals from the flotation cell, said samples were later used for analysis. We controlled pH before and after the flotation.
At the tests were used 100 g daily paper, 45 g magazine paper, 4 1 water (40°C), 13 ml water glass, 30 ml NaOH (6,8%) and 2 ml 2% Bimex (R) (nonion tenside). The pulp was allowed to rest for 10 min and was beaten in a beater for 20 min.
Then 2 ml 2% Bimex(R) and 25 ml water glass was added. The pulp was stirred and was allowed to rest 1 hour. 6 1 water (40°C) was added and the pulp was disintegrated during 2 minutes.
The collector (0,73 g) was added. Full dosis is 0,5% of the dry weight of paper pulp. In cases where soap was used as collector 3,6 g CaCl2 had to be added.
About 4 1 water was further added when the cell is filled up. Hand-sheet for optical tests
From the flotation cell was taken 500 ml mass and pH was adjusted to pH 5 with diluted sulphuric acid. The pulp is sucked off in a Buchner funnel with filter paper of 11 cm diameter. Then the sheets are rolled 10 times with a stainless roller (3 clean blotting papers below and above resp.) and are allowed to dry in room temperature with a lattice weight on top. The hand sheet are made from pulp from 0, 4, 4, 8 and 16 minutes flotation time. These are used for optical tests.
Ink sludge
Ink sludge is collected between the times 0-4, 4-8, 8-16 minutes of flotation. The volume was measured on the respective fraction. The filter paper was dried and weighed on a balance scale. From a fraction was taken 250 ml of well mixed sludge, which was sucked off in a Bϋchner funnel on a filter paper that was weighed beforehand. The content in the Buchner funnel was removed and transferred to the sheet, air-dried with a lattice weight on top and weighed.
Backwater purity
Settled filtrate from the following dewaterings:
50 ml filtrate from 0 min. flotation (handsheet for optical tests)
50 ml filtrate from 16 min. flotation (handsheet for optical tests).
These were micro-filtrated (1,2 μm) with a membrane filter device (with water suction device). Optical tests were then performed on these microfliters. The results of these optical tests (absolute values) are given in table 1.
Table 1
Hand sheet for optical test Millipore paper
Time (min)
Collector 0 4 8 16 0 16
00 66,2 68,3 69,2 71,2 55,2 58,6
0 a 66,7 69,2 70,6 72,5 54,8 59,9
0 b 66,7 69,3 70,6 72,4 56,5 59,2
Tvål a 68,6 70,8 72,4 74,2 - -
Tvål b 66,9 68,7 69,6 71,7 62,1 60,6
Tvål c 66,5 68,3 69,7 72,1 55,9 63,8
Tvål d 66,6 68,4 69,4 72,2 60,3 63,6
1Aa 67,0 71,5 72,4 74,4 55,8 63,5
1Ab 66,2 69,8 70,8 72,6 54,2 59,6
1Ac 66,5 71,7 72,9 74,5 57,8 62,8
1Ad 67,1 70,1 72,1 73,5 54,4 62,5
1Ae 67,5 70,3 71,2 73,6 54,6 62,0
1Af 66,9 69,8 70,8 71,5 58,3 60,1
1Ag 67,5 69,7 70,2 72,1 55,1 61,0
1Ba 67,3 70,4 72,0 74,0 54,5 58,7
1Bb 67,4 70,7 71,7 73,0 54,4 62,0
1Bc 66,7 69,6 71,2 72,7 54,4 63,0
1Bd 66,7 68,7 72,0 72,7 57,6 65,4
Mixed a 66,8 69,7 71,7 74,1 54,9 61,4
Mixed b 67,1 70,5 72,2 73,6 54,1 59,7
2 a 66,0 67,9 68,0 69,8 56,1 60,0
2 b 67,1 69,6 71,1 72,8 54,6 60,4
2 c 66,6 69,8 70,7 72,8 58,3 60,6
2 d 67,2 69,2 70,4 72,3 58,2 64,2
3 a 67,8 70,7 72,0 73,5 54,0 59,3
3 b 66,0 68,8 70,5 72,1 59,6 61,8
4 a 67,1 70,1 71,7 72,8 58,3 60,5
4 b 67,1 70,1 72,0 73,6 56,3 62,5
5 a 65,8 70,0 71,2 73,0 56,9 59,9
5 b 67,8 69,9 71,2 73,7 54,6 59,8
6 a 67,0 70,9 72,1 73,3 54,5 65,7
6 b 66,6 69,7 71,1 73,2 55,2 62,9
6 c 67,7 70,5 71,1 73,0 56,9 63 , 5
Hand sheet for optical test Millipore paper
Time (min)
Collector 0 4 8 16 0 16
6 d 66,4 69,6 70,7 72,4 55,7 62,0
7 a 67,0 70,3 71,2 73,5 56,3 62,6
7 b 67,5 71,2 72,5 74,4 54,7 60,4
7 c 66,9 70,3 71,6 73,3 54,9 63,1
8 68,5 72,2 73,3 74,7 55,5 59,8
9 a 66,6 67,8 70,0 73,0 54,9 60,4
9 b 67,5 70,0 71,5 73,2 55,4 60,1
10 a 67,8 70,6 72,3 73,3 57,3 60,8
10 b 66,4 69,6 70,8 72,8 56,0 60,6
10 b 66,4 69,6 70,8 72,8 56,0 60,0
11 a 67,3 69,7 71,0 72,8 54,3 65,2
11 b 68,6 72,7 74,0 75,8 60,4 64,4
12 a 67,1 69,4 70,3 72,0 55,9 63,4
12 b 67,2 69,7 71,4 74,0 59,5 -
12 c 66,7 69,8 71,2 73,2 55,9 63,0
14 66,8 67,8 70,0 71,2 55,3 58,7
15B 66,9 67,8 69,0 70,8 59,8 65,7
18 a 67,3 70,8 72,0 73,1 56,7 63,2
18 b 67,1 69,8 71,1 72,5 56,4 61,8
19 a 67,3 70,4 72,1 74,0 56,8 61,1
19 b 66,8 70,7 71,4 73,7 53,8 59,1
19 c 67,5 71,0 72,4 73,7 57,0 60,8
20 a 66,3 66,8 69,8 70,9 56,9 60,2
20 b 66,3 68,1 68,2 71,0 55,0 61,4
The increase of brightness (A-brightness) for the different collectors is given in table 2.
Table 2
Δ-brightness
Collector Acid value Hand sheet Backwater
00 - 5,0 3,4
0 a - 5,8 5,1
0 b - 5,7 2,7
Tvål a - 5,6 -
Tvål b - 5,8 -
Tvål c - 5,6 7,9
Tvål d - 5,6 3,3
1Aa 9 7,4 7,7
1Ab 9 6,4 5,4
1Ac 20 8,0 5,0
1Ad 20 6,4 8,1
1Ae 14 6,1 7,4
1Af 9 4,6 ϊ",8
1Ag 9 4,6 5,9
1Ba 13 6,7 4,2
1Bb 9 5,6 7,9
1Bc 9 6,0 8,6
1Bd 9 6,0 7,8
Mixed a - 7,3 6,5
Mixed b - 6,5 5,6
2 a 8 3,8 3,9
2 b 8 5,7 5,8
2 c 11 6,2 2,3
2 d 11 5,1 6,0
3 a 13 5,7 5,3
3 b 8 6,1 2,2
4 a 10 5,7 2,2
4 b 10 6,5 6,2
5 a 8 7,2 3,0
5 b 8 5,9 5,2
Δ -brightness
Collector Acid value Hand sheet Backwater
6 a 18 6,3 11,2
6 b 9 6,6 7,7
6 c 9 5,3 6,6
6 d 9 6,0 6,3
7 a 16 6,5 6,3
7 b 11 6,9 5,7
7 c 11 6,4 8,2
8 18 6,2 4,3
9 a 59 6,4 5,5
9 b 59 5,7 4,7
10 a 7 5,5 3,5
10 b 9 6,4 4,6
11 a 11 5,5 10,9
11 b 11 7,2 4,0
12 a 9 4,9 7,5
12 b 9 6,8 7,5
12 c 9 6,5 7,1
14 10 4,4 3,4
15B 12 3,9 5,9
18 a 12 5,8 6,5
18 b 12 5,4 5,4
19 a - 6,7 4,3
19 b - 6,9 5,3
19 c - 6,2 3,8
20 a - 4,6 6,4
20 b - 4,7 6,4
Determination of acid value
About 2 g sample was weighed in a 300 ml E-flask. 100 ml ethanol (denaturated) was added to a E-flask and 15-20 drops of phenolphtalein solution was added. The ethanol was titrated to light rose colour change by means of 0,1 M KOH (only one or a few drops). The ethanol was added to the sample and the flask was shaken until the sample was dissolved. The sample solution was filtered to rose-red colour change with 0,1 M KOH and the amount of KOH needed for the change was determined. The titration must take place quickly, since CO2 in the air consumes KOH. A long lasting titration gives the result of a higher acid value. In the formula below the determined values of volume and mass are inserted:
Acid value = (M·K·ml)/m mg KOH/g solution
M = molecular. weight
k = concentration KOH (0,1M)
ml = ml KOH required for the titration
m = mass of sample (g)
Result
The test results prove that a collector based on maleic acid, polyethylene glycol with a mean molecular weight of 400, and tall oil gave the best deinking result. The increase of brightness after 16 min. flotation was 7,4 units (according to Hunter Lab.). Corresponding values for soap was 5, 6 and for commercial collector (KAO) 6,7. The increase of brightness for the collector according to the invention was thus 10% higher for the commercial collector. Besides the flotation was functioning better with the collector according to the invention as compared to soap and commercial collector.
In fig. 1 is shown in the form of block diagram the brightness increase after 16 minutes flotation for the collector according to the invention based on maleic acid, polyethylene glycol and tall oil and for soap and commercial collector resp.
In fig. 2 is shown flotation graphs showing the brightness as a function of time for the collector according to the invention, soap and commercial collector.
The backwater purity with the collector according to the invention was besides higher. Tests for determining the influence of different dosing amounts on the deinking result have also been performed. To every flotation there has been used 2 kg Bimex 400/ton and varying amounts of collector 1 A according to above. The added amounts were 1, 2, 3, 4 and 5 kg collector resp. /ton pulp. In fig. 3 is shown flotation graphs (brightness as a function of time) for the different admixture amounts. An admixture amount of 5 kg collector/ton pulp gave about: 5% better brightness than an admixture amount of 1 kg collector /ton pulp.
As a summary it can be stated that the polyester according to the invention provides a collector which is very effective and gives improved deinking results as compared to soap and commercial synthetic collectors. It is besides harmless to the environment due to its composition.
Claims
1. Collector chemical for use in deinking of waste paper according to the flotation process,
c h a r a c t e r i z e d i n,
that it comprises a polyester obtained through reaction between 1) polyalkylene glycol, 2) di- and/or tricarboxylic acid and/or anhydrides thereof and 3) tall oil, said polyester having a molecular weight between 3000 - 10000.
2. Collector chemical according to claim 1,
c h a r a c t e r i z e d i n,
that only aliphatic alcohols and carboxylic acids are used as monomors .
3. Collector chemical according to claim 1,
c h a r a c t e r i z e d i n,
that the polyalkylene glycol is polyethylene glycol, polypropylene glycol or mixtures thereof.
4. Collector chemical according to claim 1,
c h a r a c t e r i z e d i n,
that the di- and tricarboxylic acid preferably is chosen from the group consisting of maleic acid, fumaric acid, adipic acid, citric acid, oxalic acid and sebacic acid.
5. Collector chemical according to any of the preceding claims,
c h a r a c t e r i z e d i n,
that it has a molecular weight between between 5000 and 10000.
6. Collector chemical according to any of the preceding claims,
c h a r a c t e r i z e d i n,
that is produced by reaction between polyethylene glycol, maleic acid and tall oil.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE8902871-6 | 1989-08-30 | ||
SE8902871A SE464639B (en) | 1989-08-30 | 1989-08-30 | COLLECTOR INTENDED TO BE USED IN THE EVALUATION OF RETURN PAPER BASED ON A POLYESTER INCLUDING INCLUDING TALL OIL AND APPLICATION OF THIS POLYESTER AS A COLLECTOR |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991003599A1 true WO1991003599A1 (en) | 1991-03-21 |
Family
ID=20376770
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/SE1990/000554 WO1991003599A1 (en) | 1989-08-30 | 1990-08-30 | Collector chemical for deinking of waste paper |
Country Status (2)
Country | Link |
---|---|
SE (1) | SE464639B (en) |
WO (1) | WO1991003599A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992001109A1 (en) * | 1990-07-04 | 1992-01-23 | Basf Aktiengesellschaft | Process for de-inking printed papers |
US5258376A (en) * | 1989-11-22 | 1993-11-02 | Bernstein Lawrence R | Pharmaceutical compositions of gallium complexes of 3-hydroxy-4-pyrones |
WO1995000699A1 (en) * | 1993-06-23 | 1995-01-05 | Bim Kemi Ab | Collector intended to be used in deinking of waste paper according to the flotation process |
US5574027A (en) * | 1989-11-22 | 1996-11-12 | Bernstein; Lawrence R. | Pharmaceutical compositions of gallium complexes of 3-hydroxy-4-pyrones |
US8007754B2 (en) | 2005-02-04 | 2011-08-30 | Mineral And Coal Technologies, Inc. | Separation of diamond from gangue minerals |
-
1989
- 1989-08-30 SE SE8902871A patent/SE464639B/en not_active IP Right Cessation
-
1990
- 1990-08-30 WO PCT/SE1990/000554 patent/WO1991003599A1/en unknown
Non-Patent Citations (3)
Title |
---|
CHEMICAL ABSTRACTS, Volume 103, No. 18, abstract 144359s, 4 November 1985, (Columbus, Ohio, US), KACHAN, V. et al., "Resistance of Emulsion Cutting Fluids to Microbial Degradation"; & KHIM. TEKHNOL. TOPL. MASEL 1985, 8, 25-8. * |
DIALOG INFORMATION SERVICES, File 350, World Patent Index 63-80, Dialog accession no. 78-91970A/51, MIYOSHI YUSHI KK: "Ink Removing Agent Used in Waste Paper Recycling Process - is prepd. from Mixed Carboxylic Acids and Alkylene Oxide Deriv."; & JP,A,53 130 309, 14-11-78, 7851 (Basic). * |
DIALOG INFORMATION SERVICES, File 351, World Patent Index 81-90, Dialog accession no. 82-73041E/35, HONSHU PAPER MFG KK: TOHO CHEM IND LTD: "Removing Ink from Waste Printed Paper in Flotation Process Using cpd. obtd. by addn. Polymerising Alkylene Oxide with Mono or Polyfunctional Alcohol and Reacting the prod. with Dicarboxylic * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5258376A (en) * | 1989-11-22 | 1993-11-02 | Bernstein Lawrence R | Pharmaceutical compositions of gallium complexes of 3-hydroxy-4-pyrones |
US5574027A (en) * | 1989-11-22 | 1996-11-12 | Bernstein; Lawrence R. | Pharmaceutical compositions of gallium complexes of 3-hydroxy-4-pyrones |
WO1992001109A1 (en) * | 1990-07-04 | 1992-01-23 | Basf Aktiengesellschaft | Process for de-inking printed papers |
WO1995000699A1 (en) * | 1993-06-23 | 1995-01-05 | Bim Kemi Ab | Collector intended to be used in deinking of waste paper according to the flotation process |
US8007754B2 (en) | 2005-02-04 | 2011-08-30 | Mineral And Coal Technologies, Inc. | Separation of diamond from gangue minerals |
Also Published As
Publication number | Publication date |
---|---|
SE8902871L (en) | 1991-03-01 |
SE8902871D0 (en) | 1989-08-30 |
SE464639B (en) | 1991-05-27 |
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