WO2000050147A1 - Hydrocarbon oil free defoamer - Google Patents
Hydrocarbon oil free defoamer Download PDFInfo
- Publication number
- WO2000050147A1 WO2000050147A1 PCT/US2000/003975 US0003975W WO0050147A1 WO 2000050147 A1 WO2000050147 A1 WO 2000050147A1 US 0003975 W US0003975 W US 0003975W WO 0050147 A1 WO0050147 A1 WO 0050147A1
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- WO
- WIPO (PCT)
- Prior art keywords
- composition
- recited
- ester
- fatty
- water
- Prior art date
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- 239000004215 Carbon black (E152) Substances 0.000 title claims description 13
- 229930195733 hydrocarbon Natural products 0.000 title claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 13
- 239000013530 defoamer Substances 0.000 title description 5
- 239000000203 mixture Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002518 antifoaming agent Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 14
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical group C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 150000002195 fatty ethers Chemical class 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002193 fatty amides Chemical class 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical group CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical group N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- -1 e.g. Substances 0.000 description 5
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 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
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- RKZXQQPEDGMHBJ-LIGJGSPWSA-N [(2s,3r,4r,5r)-2,3,4,5,6-pentakis[[(z)-octadec-9-enoyl]oxy]hexyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC RKZXQQPEDGMHBJ-LIGJGSPWSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940116335 lauramide Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- WNCFYFLYHFIWIL-UHFFFAOYSA-N n-[2-(docosanoylamino)ethyl]docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCCCCCC WNCFYFLYHFIWIL-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/12—Defoamers
Definitions
- the present invention relates to foam control compositions, their preparation and use in aqueous systems.
- the foam control compositions are particularly useful in the processing of pulp and paper and the treatment of effluent water.
- Foam can present serious problems in the manufacture of pulp and paper. Lack of adequate foam control in the paper slurry can limit or halt production, as well as affect finished product quality.
- Defoamers when added to a foaming liquid, can prevent bubble formation or cause coalescence of smaller bubbles into larger ones, leading to rupture.
- Most conventional defoamers include a hydrophobic material having a melting point greater than 40° C, such as a diamide and/or a hydrophobically modified insoluble particle, e.g., silica, dispersed in a hydrocarbon oil phase.
- Many of these compositions also contain silicone oil.
- a problem with these types of compositions is that they quickly become unstable, and a settling of individual components, such as silica, occurs. Hydrophobic materials with melting points above 40° C will precipitate rapidly after the processing temperatures fall below their melting point when dispersed in a hydrocarbon oil phase.
- Pure organic-based defoamers are not highly effective and require large amounts of material to defoam systems, while silica-based defoamers are expensive because large amounts of the silica particles are required to perform effectively.
- the present invention relates to a water-based defoaming agent containing (1) an ester of a dicarboxylic acid and a monohydric alcohol, (2) at least one predominantly hydrophobic material having a melting point greater than 40° C selected from the group consisting of hydrocarbon waxes, fatty amides, fatty acids and fatty alcohols, (3) a surfactant selected from the group consisting of polyethylene glycol esters, sorbitan/sorbitol esters, ethoxylated fatty alcohols, fatty acids and fatty ethers, and (4) water.
- the defoaming agent further includes a polyether modified silicone copolymer, an aqueous polyacrylate and an alkali material.
- the present invention provides a defoaming agent with improved efficacy in aqueous systems that is particularly effective at controlling foam in the paper making process.
- the present invention provides a water-based defoamer composition with improved stability and no particle precipitation over a temperature range of about 10° C to 50° C.
- the invention provides an "environmentally friendly" defoamer composition comprising low or no volatile organic carbon (VOC) content and no dioxin precursor containing hydrocarbon oils.
- VOC volatile organic carbon
- the dicarboxylic acid ester is formed from the reaction of a dicarboxylic acid with a monohydric alcohol.
- the dicarboxylic acid is selected from the group consisting of adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid and isomers thereof. These acids are then reacted with alcohols selected from the group consisting of hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl alcohol, and isomers thereof.
- the hydrophobic material with a melting point greater than 40° C includes fatty acid amides with the general formula:
- n is an integer from 2 to 6
- R is a saturated or unsaturated, straight or branched aliphatic group having from 5 to 22 carbons.
- the fatty amides are formed from the reaction of polyamine containing at least one alkylene group having from 2 to 6 carbon atoms and a fatty acid having from 5 to 22 carbon atoms not including the carboxyl group carbon.
- suitable hydrophobic amides formed from this reaction include but are not limited to methylene bis acrylamide, methylene bis lauramide, ethylene bis stearamide, ethylene bis behenamide, and ethylene bis oleoamide.
- the aliphatic fatty alcohols and fatty acids are saturated, linear or branched and contain at least 12 carbon atoms, while the hydrocarbon wax has a melting point of from about 40° C to 120° C.
- the emulsifying surfactants are preferably nonionic surfactants and include polyethylene glycol esters such as PEG 400 dioleate and PEG 600 dioleate, sorbitan/sorbital esters such as sorbitan monooleate, POE (20) sorbitan monooleate and POE (40) sorbitol hexaoleate, ethoxylated fatty acids, ethoxylated fatty alcohols, and ethoxylated fatty ethers such as POE (40) stearate, POE (20) stearyl alcohol and POE (10) oleyl ether.
- polyethylene glycol esters such as PEG 400 dioleate and PEG 600 dioleate
- sorbitan/sorbital esters such as sorbitan monooleate
- POE (20) sorbitan monooleate and POE (40) sorbitol hexaoleate ethoxylated fatty acids, ethoxyl
- the polyether-modified silicone copolymer is a silicone copolymer modified with ethylene oxide and propylene oxide which results in a copolymer with a cloud point of from about 40° C to less than about 25° C, and a molecular weight range of from about 10,000 to 40,000.
- the polyacrylates that are encompassed by the present invention are aqueous, acidic, acrylic emulsion copolymers that thicken by an uncoiling action of the polymer chain upon neutralization with an alkali material.
- the preferred polyacrylate is a copolymer of ethylacrylate and methacrylic acid.
- the alkali material can be sodium hydroxide, potassium hydroxide, ammonium hydroxide, or triethanolamine.
- the present invention relates to the use of a dicarboxylic acid ester, without organic solvent or hydrocarbon oil, as a carrier for the high melting point hydrophobic material and a surfactant selected from the group consisting of polyethylene glycol esters, sorbitol/sorbitan esters, ethoxylated fatty acids, ethoxylated fatty alcohols and ethoxylated fatty ethers, emulsified in water to form a stable dispersion of particles that does not precipitate upon cooling below the melting point of the hydrophobic material.
- the dispersions are stable at temperatures of from about 10° C to 50° C for about 6 weeks.
- Preferred amounts of the components of the defoamer composition of the present invention are as follows:
- Hydrophobic material 0.5 - 20 1 - 10
- the defoamers are prepared by charging all the material excluding the water to a vessel, heating to about 120° C, and holding at this temperature for about 30 minutes. The mixture is added to a vessel that has been charged with the water phase maintained under constant agitation. The dispersion is then cooled to below 45° C, at which time the polyacrylate is added and then neutralized with the alkali material.
- various defoamers were tested in a recirculation test cell.
- the foaming medium is circulated from the bottom of a calibrated graduated column via a pump and returned down through the top of the column. This action agitates the medium and causes foam which flows up the calibrated tube and allows determination of foam height at different time intervals.
- the calibrated column is wrapped with heat tape and kept at a constant temperature (+/-2° F) via a probe and temperature controller.
- the foam test cell holds approximately 1200 ml of medium.
- the column is filled with medium and recirculated briefly to evacuate all the air from the loop.
- the defoamers noted below were tested using the synthetic medium at a temperature of 130° F and a pH of 7.5.
- the conductivity of the medium was 2400 umhos.
- Control time was 6.5 seconds to top.
- An emulsion antifoam of the present invention containing diisononyl adipate, wax, surfactants, silicon copolymer, ethylene bis stearamide, polyacrylate, water and sodium hydroxide.
- An emulsion antifoam of the present invention containing dioctyl sebacate, ethylene bis stearamide, wax, surfactants, silicone copolymer, polyacrylate, water, and sodium hydroxide.
- An emulsion antifoam of the present invention containing diisoctyl phthalate, ethylene bis stearamide, surfactants, and water.
- An emulsion antifoam of the present invention containing diisononyl adipate, ethylene bis stearamide, surfactants, and water.
- an amide particulate antifoam emulsion containing hydrocarbon oil (No. 1 ) is not as effective as the other examples which are variations of the present invention and contain various dicarboxylic acid esters. All formulations were run at a dosage of 10 ul.
- the defoamers listed below were tested using the synthetic medium at a temperature of 125° F and a pH of 7.0.
- the conductivity of the medium was 4600 umhos.
- Control time was 8 seconds to top.
- An emulsion antifoam of the present invention containing diisononyl adipate, ethylene bis stearamide, surfactants, and water.
- An emulsion antifoam of the present invention containing diisoctyl phthalate, ethylene bis stearamide, surfactants, and water.
- tests 7, 8 and 10 provide superior performance when compared to the hydrocarbon oil/amide emulsion and the polybutene/amide based product. All products were tested at a dosage of 12 ul.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention is directed to foam control compositions and their use in aqueous systems. The foam control compositions are particularly useful in the processing of pulp and paper and the treatment of effluent water.
Description
HYDROCARBON OIL FREE DEFOAMER
FIELD OF THE INVENTION
The present invention relates to foam control compositions, their preparation and use in aqueous systems. The foam control compositions are particularly useful in the processing of pulp and paper and the treatment of effluent water.
BACKGROUND OF THE INVENTION
Foam can present serious problems in the manufacture of pulp and paper. Lack of adequate foam control in the paper slurry can limit or halt production, as well as affect finished product quality.
Defoamers, when added to a foaming liquid, can prevent bubble formation or cause coalescence of smaller bubbles into larger ones, leading to rupture. Most conventional defoamers include a hydrophobic material having a melting point greater than 40° C, such as a diamide and/or a hydrophobically modified insoluble particle, e.g., silica, dispersed in a hydrocarbon oil phase. Many of these compositions also
contain silicone oil. A problem with these types of compositions is that they quickly become unstable, and a settling of individual components, such as silica, occurs. Hydrophobic materials with melting points above 40° C will precipitate rapidly after the processing temperatures fall below their melting point when dispersed in a hydrocarbon oil phase. Pure organic-based defoamers are not highly effective and require large amounts of material to defoam systems, while silica-based defoamers are expensive because large amounts of the silica particles are required to perform effectively.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a water-based defoaming agent containing (1) an ester of a dicarboxylic acid and a monohydric alcohol, (2) at least one predominantly hydrophobic material having a melting point greater than 40° C selected from the group consisting of hydrocarbon waxes, fatty amides, fatty acids and fatty alcohols, (3) a surfactant selected from the group consisting of polyethylene glycol esters, sorbitan/sorbitol esters, ethoxylated fatty alcohols, fatty acids and fatty ethers, and (4) water. In a preferred embodiment, the defoaming agent further includes a polyether modified silicone copolymer, an aqueous polyacrylate and an alkali material.
The present invention provides a defoaming agent with improved efficacy in aqueous systems that is particularly effective at controlling foam in the paper making process. The present invention provides a water-based defoamer composition with improved stability and no particle precipitation over a temperature range of about 10° C to 50° C. Furthermore, the invention provides an "environmentally friendly"
defoamer composition comprising low or no volatile organic carbon (VOC) content and no dioxin precursor containing hydrocarbon oils.
The dicarboxylic acid ester is formed from the reaction of a dicarboxylic acid with a monohydric alcohol. The dicarboxylic acid is selected from the group consisting of adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid and isomers thereof. These acids are then reacted with alcohols selected from the group consisting of hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl alcohol, and isomers thereof.
The hydrophobic material with a melting point greater than 40° C includes fatty acid amides with the general formula:
The fatty amides are formed from the reaction of polyamine containing at least one alkylene group having from 2 to 6 carbon atoms and a fatty acid having from 5 to 22 carbon atoms not including the carboxyl group carbon. Examples of suitable hydrophobic amides formed from this reaction include but are not limited to methylene bis acrylamide, methylene bis lauramide, ethylene bis stearamide, ethylene bis behenamide, and ethylene bis oleoamide. The aliphatic fatty alcohols
and fatty acids are saturated, linear or branched and contain at least 12 carbon atoms, while the hydrocarbon wax has a melting point of from about 40° C to 120° C.
The emulsifying surfactants are preferably nonionic surfactants and include polyethylene glycol esters such as PEG 400 dioleate and PEG 600 dioleate, sorbitan/sorbital esters such as sorbitan monooleate, POE (20) sorbitan monooleate and POE (40) sorbitol hexaoleate, ethoxylated fatty acids, ethoxylated fatty alcohols, and ethoxylated fatty ethers such as POE (40) stearate, POE (20) stearyl alcohol and POE (10) oleyl ether. The polyether-modified silicone copolymer is a silicone copolymer modified with ethylene oxide and propylene oxide which results in a copolymer with a cloud point of from about 40° C to less than about 25° C, and a molecular weight range of from about 10,000 to 40,000.
The polyacrylates that are encompassed by the present invention are aqueous, acidic, acrylic emulsion copolymers that thicken by an uncoiling action of the polymer chain upon neutralization with an alkali material. The preferred polyacrylate is a copolymer of ethylacrylate and methacrylic acid. The alkali material can be sodium hydroxide, potassium hydroxide, ammonium hydroxide, or triethanolamine.
In a preferred embodiment, the present invention relates to the use of a dicarboxylic acid ester, without organic solvent or hydrocarbon oil, as a carrier for the high melting point hydrophobic material and a surfactant selected from the group consisting of polyethylene glycol esters, sorbitol/sorbitan esters, ethoxylated fatty acids, ethoxylated fatty alcohols and ethoxylated fatty ethers, emulsified in water to form a stable
dispersion of particles that does not precipitate upon cooling below the melting point of the hydrophobic material. The dispersions are stable at temperatures of from about 10° C to 50° C for about 6 weeks.
Preferred amounts of the components of the defoamer composition of the present invention are as follows:
(Values in percent by weight)
Particularly
Component Preferred % Preferred %
Dicarboxylic Acid Ester 5 - 60 10 - 40
Hydrophobic material 0.5 - 20 1 - 10
Surfactants 0.5 - 30 5 - 20
Modified silicone copolymer 0.1 - 5 0.1 - 5
Water 40 - 95 40 - 80
Polyacrylate 0.5 - 5 0.5 - 5
Alkali material 0.1 - 5 0.5 - 5
The defoamers are prepared by charging all the material excluding the water to a vessel, heating to about 120° C, and holding at this temperature for about 30 minutes. The mixture is added to a vessel that has been charged with the water phase maintained under constant agitation. The dispersion is then cooled to below 45° C, at which time the polyacrylate is added and then neutralized with the alkali material.
In the testing of the present invention, various defoamers were tested in a recirculation test cell. The foaming medium is circulated from the bottom of a calibrated graduated column via a pump and returned
down through the top of the column. This action agitates the medium and causes foam which flows up the calibrated tube and allows determination of foam height at different time intervals. The calibrated column is wrapped with heat tape and kept at a constant temperature (+/-2° F) via a probe and temperature controller. The foam test cell holds approximately 1200 ml of medium. The column is filled with medium and recirculated briefly to evacuate all the air from the loop.
Examples
The defoamers noted below were tested using the synthetic medium at a temperature of 130° F and a pH of 7.5. The conductivity of the medium was 2400 umhos. Control time was 6.5 seconds to top.
Example 1 (Numbers below correspond to entries in Figure 1)
1) An emulsion antifoam containing hydrocarbon oil, ethylene bis stearamide, surfactants and water.
2) An emulsion antifoam of the present invention containing diisononyl adipate, wax, surfactants, silicon copolymer, ethylene bis stearamide, polyacrylate, water and sodium hydroxide.
3) An emulsion antifoam of the present invention containing dioctyl sebacate, ethylene bis stearamide, wax, surfactants, silicone copolymer, polyacrylate, water, and sodium hydroxide.
4) An emulsion antifoam of the present invention containing diisoctyl phthalate, ethylene bis stearamide, surfactants, and water.
5) An emulsion antifoam of the present invention containing diisononyl adipate, ethylene bis stearamide, surfactants, and water.
As shown in Figure 1 , an amide particulate antifoam emulsion containing hydrocarbon oil (No. 1 ) is not as effective as the other examples which are variations of the present invention and contain various dicarboxylic acid esters. All formulations were run at a dosage of 10 ul.
Example 2 (Numbers below correspond to entries in Figure 2)
The defoamers listed below were tested using the synthetic medium at a temperature of 125° F and a pH of 7.0. The conductivity of the medium was 4600 umhos. Control time was 8 seconds to top.
6) An emulsion antifoam containing hydrocarbon oil, ethylene bis stearamide, surfactants and water.
7) An emulsion antifoam of the present invention containing diisononyl adipate, ethylene bis stearamide, surfactants, and water.
8) An emulsion antifoam of the present invention containing diisoctyl phthalate, ethylene bis stearamide, surfactants, and water.
9) An antifoam from U.S. Patent 3,959,175 containing polybutene and ethylene bis stearamide.
10) An emulsion antifoam of the present invention containing diisononyl adipate, wax, surfactants, silicon copolymer, ethylene bis stearamide, polyacrylate, water and sodium hydroxide.
As shown in Figure 2, tests 7, 8 and 10 provide superior performance when compared to the hydrocarbon oil/amide emulsion and the polybutene/amide based product. All products were tested at a dosage of 12 ul.
While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
Claims
1. A water-based defoaming agent composition comprising:
(a) an ester of dicarboxylic acid and a monohydric alcohol;
(b) a hydrophobic material having a melting point greater than 40° C selected from the group consisting of hydrocarbon waxes, fatty amides, fatty acids and fatty alcohols; and
(c) a surfactant selected from the group consisting of polyethylene glycol esters, sorbitan/sorbitol esters, ethoxylated fatty alcohols, fatty acids and fatty ethers.
2. The composition as recited in claim 1 further comprising a polyether modified silicone copolymer.
3. The composition as recited in claim 1 further comprising an aqueous polyacrylate.
4. The composition as recited in claim 1 wherein said defoaming agent forms a stable dispersion at from about 10° - 50° C.
5. The composition as recited in claim 1 wherein said ester is a diisononyl adipate.
6. The composition as recited in claim 1 wherein said ester is a dioctyl sebacate.
7. The composition as recited in claim 1 wherein said ester is a diisooctyl phthalate.
8. The composition as recited in claim 1 wherein said amide is ethylene bis stearamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU34926/00A AU3492600A (en) | 1999-02-24 | 2000-02-17 | Hydrocarbon oil free defoamer |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25605999A | 1999-02-24 | 1999-02-24 | |
| US09/256,05919990224 | 1999-02-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2000050147A1 true WO2000050147A1 (en) | 2000-08-31 |
Family
ID=22970953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2000/003975 WO2000050147A1 (en) | 1999-02-24 | 2000-02-17 | Hydrocarbon oil free defoamer |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU3492600A (en) |
| WO (1) | WO2000050147A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110248213A1 (en) * | 2010-04-12 | 2011-10-13 | Cognis Ip Management Gmbh | Defoaming Agents and Articles and Methods Using Same |
| CN103866609A (en) * | 2014-02-25 | 2014-06-18 | 苏州恒康新材料有限公司 | Papermaking defoamer and preparation method thereof |
| CN111437632A (en) * | 2020-04-17 | 2020-07-24 | 五色石新材料(杭州)有限公司 | Method for preparing emulsion type defoaming agent by utilizing polyether modified silicone oil |
| JP2025026278A (en) * | 2023-08-08 | 2025-02-21 | ヒンドゥスタン ペトロリアム コーポレーション リミテッド | Defoamers/Defoamers |
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|---|---|---|---|---|
| US4341656A (en) * | 1978-11-03 | 1982-07-27 | Ciba-Geigy Corporation | Foam inhibitors and their use for defoaming aqueous systems |
| DE3242202A1 (en) * | 1981-11-25 | 1983-06-01 | Sandoz-Patent-GmbH, 7850 Lörrach | Foam prevention agents, production and use thereof |
| US4559162A (en) * | 1981-03-10 | 1985-12-17 | Ciba-Geigy Corporation | Compositions of polymers based on acrylic acid, solvents, surfactants and, if appropriate, silicone oils, their preparation and their use as anti-foams and deaerating agents |
| US4880564A (en) * | 1986-09-29 | 1989-11-14 | Ciba-Geigy Corporation | Antifoams for aqueous systems and their use |
| US4988463A (en) * | 1988-03-26 | 1991-01-29 | Bayer Aktiengesellschaft | Foam suppressants |
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2000
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| US4341656A (en) * | 1978-11-03 | 1982-07-27 | Ciba-Geigy Corporation | Foam inhibitors and their use for defoaming aqueous systems |
| US4559162A (en) * | 1981-03-10 | 1985-12-17 | Ciba-Geigy Corporation | Compositions of polymers based on acrylic acid, solvents, surfactants and, if appropriate, silicone oils, their preparation and their use as anti-foams and deaerating agents |
| DE3242202A1 (en) * | 1981-11-25 | 1983-06-01 | Sandoz-Patent-GmbH, 7850 Lörrach | Foam prevention agents, production and use thereof |
| US4880564A (en) * | 1986-09-29 | 1989-11-14 | Ciba-Geigy Corporation | Antifoams for aqueous systems and their use |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110248213A1 (en) * | 2010-04-12 | 2011-10-13 | Cognis Ip Management Gmbh | Defoaming Agents and Articles and Methods Using Same |
| US8802739B2 (en) * | 2010-04-12 | 2014-08-12 | Cognis Ip Management Gmbh | Defoaming agents and articles and methods using same |
| CN103866609A (en) * | 2014-02-25 | 2014-06-18 | 苏州恒康新材料有限公司 | Papermaking defoamer and preparation method thereof |
| CN103866609B (en) * | 2014-02-25 | 2016-03-30 | 新昌县鸿裕工业产品设计有限公司 | A kind of foam-killing agent in paper-making and preparation method thereof |
| CN111437632A (en) * | 2020-04-17 | 2020-07-24 | 五色石新材料(杭州)有限公司 | Method for preparing emulsion type defoaming agent by utilizing polyether modified silicone oil |
| JP2025026278A (en) * | 2023-08-08 | 2025-02-21 | ヒンドゥスタン ペトロリアム コーポレーション リミテッド | Defoamers/Defoamers |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3492600A (en) | 2000-09-14 |
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