WO1997035067A1 - Compositions antimousses contenant des polymeres et leurs procedes d'utilisation - Google Patents

Compositions antimousses contenant des polymeres et leurs procedes d'utilisation Download PDF

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Publication number
WO1997035067A1
WO1997035067A1 PCT/US1997/003902 US9703902W WO9735067A1 WO 1997035067 A1 WO1997035067 A1 WO 1997035067A1 US 9703902 W US9703902 W US 9703902W WO 9735067 A1 WO9735067 A1 WO 9735067A1
Authority
WO
WIPO (PCT)
Prior art keywords
plus
epichlorohydrin
group
dimethylamine
black liquor
Prior art date
Application number
PCT/US1997/003902
Other languages
English (en)
Inventor
Duy T. Nguyen
William A. Hendricks
Original Assignee
Betzdearborn Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Betzdearborn Inc. filed Critical Betzdearborn Inc.
Publication of WO1997035067A1 publication Critical patent/WO1997035067A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/28—Prevention of foam
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • C08G73/022—Preparatory process from polyamines and epihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/12—Prevention of foaming

Definitions

  • This invention relates to the control of foam generated during papermaking operations.
  • foam found in black liquor residual containing process streams.
  • Foam can cause a serious problem in pulp mills, paper mills and in effluent treatment. Lack of adequate foam control may result in curtail ⁇ ment of production or diminished product quality.
  • Foam is a colloidal system in which a gas is dispersed in a liquid. Foam can exist either as bubbles of entrained air in bulk or as a combination of entrained gases and surface foam. Foams are thermodynamicaliy unstable and are stabi ⁇ lized by two basic mechanisms in pulp and paper process stream: 1 The adso ⁇ tion at the air/water interface of surface active materials such as salts of rosin acids, fatty acids and lignin;
  • Foam caused by the presence of residual black pulping liquor is believed to be stabilized primarily by the first mechanism whereas foam in paper machine white water is stabilized primarily by the second mechanism
  • defoamers/antifoams which, when added to a foaming liquid, prevent the formation of bubbles or cause small bubbles to coalesce are well known to those skilled in the art
  • defoamers/antifoams are usually comprised of either high melting point hydrophobic materials such as stearic acid, ethyl ⁇ ne-bistearamide, saturated fatty alcohols or concen ⁇ trates of various low HLB surfactants such as propoxylated and/or ethoxylated esters of various fatty acids and/or polyhydric alcohol fatty acid esters.
  • foam stabilizers adsorb at the air/liquid interface and defoamers disperse in the medium. Before the film starts to burst, its surface usually will be indent ⁇ ed, which will cause weak spots to form. Indentation causes a local in- crease of surface area, which disturbs the equilibrium distribution of sur ⁇ factant (i.e., concentration of surfactant in the stretched area is lower than that in the undisturbed areas) and produces a surface tension gradient. Thermodynamicaliy, a new equilibrium must be established. This can be done in two ways. First, the foam stabilizers from the areas of lower surface tension are pushed toward the weak spot until the sur ⁇ face tension is uniform.
  • the antifoam must have a high surface area per molecule.
  • surfac- tant-based antifoams begin to spread onto the surface and eventually rupture the film.
  • the surface viscosity also affects the defoaming performance. A high surface viscosity tends to retard the drainage rate and spreading rate which, in turn, decreases the antifoam effectiveness.
  • the above mechanism is applicable for mediums which have a low surface density (i.e., fine paper white water systems).
  • the anti ⁇ foam which was found to be quite effective in low surface charge density, loses its effectiveness.
  • foam is caused by lignin, resin and fatty acids from the wood.
  • Sulfate soaps derived from pitch may also act as foaming agents.
  • Kraft lignins have been shown to be surface active and good foam stabi- lizing agents. Lignin residues stabilize the foam via steric stabilization.
  • black liquor the zeta potential is much more negative than is found in fine paper white water due to sulfate soap and lignin residue.
  • Figures I - VIII are plots which show the defoaming capabilities of numerous defoaming compositions under simulated paper processing conditions.
  • conventional antifoaming compounds include, among others, polyether surfactants, polyhydric alcohol fatty acid esters and polybutene.
  • the polymers useful in the practice of the present invention are certain homopolymers and condensate polymers.
  • the desired homopolymer is polyethyleneimine
  • the desired condensation polymers are the products of dimethylamine plus epichlorohydrin, and a terpolymer of epichlorohydrin plus dimethylamine plus ethylene diamine (EPI/ DMA/EDA).
  • the number average molecular weights of the above identified polymers should be between 5,000 and 2,000,000.
  • the defoamer treatment composition according to the present invention comprises at least one conventional defoamer plus at least one polymer as defined above.
  • the amount of polymer present in the de- foamer composition is from 0.1 % to 20%, by weight, of the total compo ⁇ sition with the remainder consisting of conventional defoamer compounds as defined above.
  • the chemical components may be diluted or dissolved in water.
  • the defoamer composition of the present invention should be added in a sufficient amount to maintain a concentration in the black liquor of from 0.1 to 100 ppm, by weight.
  • concentration range would be, however, from 1.0 to 50 ppm, by weight.
  • diluted pulp mill black liquor is used as the foaming medium.
  • the medium is circulated from a calibrated reservoir (in centimeters) via a pump and is returned back to the reservoir. This action agitates the medium which, in turn, causes foam.
  • a known amount of the defoamer is introduced into the test cell before the pump is turned on.
  • the calibration of the test cell ranges from 0 to 295 cm; the medium usually occupies the first 135 cm.
  • a longer time required for the foam to reach a certain level indicates a better defoamer. The time is recorded when the foam reaches the 290 cm level.
  • the sources of the compounds tested are disclosed in the legend following Example 8.
  • a 100% active blend of a polyglycol ester and a polyether surfactant 1.
  • Poly-N-vinyl pyrrolidone (M.W. approximately 360,000), 2.2% of 33% solids Polyethyleneimine (M.W. approximately 20,000) 8
  • the defoaming compositions for these four samples are listed below:
  • Ethoxylated fatty triglyceride and 4.9% (active) EPI/DMA/EDA polymer (M.W. approximately 400,000)
  • EPI/DMA/EDA polymer (50% active solids) (M.W. approximately 500,000)
  • FIG 6 schematically illustrates the results. It can be seen that the defoamer of the present invention (defoamer 20) is superior to all of the conventional, prior-art defoamers.
  • EPI/DMA/EDA polymer (M.W. approximately 600,000)
  • Ethoxylated fatty triglyceride and 5.0% (active) EPI/DMA/EDA polymer (M.W. approximately 600,000)
  • Figure 8 shows the results. This example compared the effect of various molecular weights on defoaming performance. It can be seen that increasing the active amount of high molecular weight (approximately 600,000) dimethylamine epichlorohydrin condensation polymer decreas ⁇ es the defoaming performance (36, 37, 41), presumably the high molecu ⁇ lar weight polymer is so bulky and thus has a difficult time to orient or adsorb at the air/liquid interface. At the same amount of active (1.3%), the condensation polymers (36, 38) are much more efficacious than the copolymer (40).
  • LEGEND The sources of the compounds used in the above examples are disclosed below:
  • polyethyleneimine Cordova Chemical polybutene L14: Amoco poly-N-vinyl pyrrolidone: GAF dimethylamine epichlorohydrin condensate polymer: Betz Laboratories epichlorohydrin plus dimethylamine plus ethylene diamine terpolymer (EPI/DMA/EDA): Betz Laboratories ethoxylated fatty triglyceride: Buckman 454c
  • AM/AETAC Betz Laboratories HMDA/EDC: Betz Laboratories DMAPA/EPI: Betz Laboratories DETA/EPI: Betz Laboratories AM/Sipomer: Betz Laboratories polydimethyl diallyl ammonium chloride: Betz Laboratories

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)

Abstract

La présente invention concerne une composition et un procédé de régulation du phénomène de formation de mousse dans la liqueur noire d'une opération de fabrication de pâte à papier. Ladite composition comprenant au moins un produit antimousse classique et au moins un polymère sélectionné dans un groupe composé d'un polyéthyléneimine, d'un condensât de diméthylamine auquel on ajoute de l'épichlorohydrine et un terpolymère constitué d'épichlorohydrine à laquelle on ajoute du diméthylamine et de l'éthylénediamine.
PCT/US1997/003902 1996-03-21 1997-03-13 Compositions antimousses contenant des polymeres et leurs procedes d'utilisation WO1997035067A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62173596A 1996-03-21 1996-03-21
US08/621,735 1996-03-21

Publications (1)

Publication Number Publication Date
WO1997035067A1 true WO1997035067A1 (fr) 1997-09-25

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Family Applications (1)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000047524A1 (fr) * 1999-02-11 2000-08-17 Huntsman Petrochemical Corporation Procede de traitement des eaux usees
US6559116B1 (en) 1999-09-27 2003-05-06 The Procter & Gamble Company Antimicrobial compositions for hard surfaces
WO2006107603A1 (fr) * 2005-04-04 2006-10-12 Ge Betz, Inc. Regulation de la mousse dans des milieux aqueux
WO2008137195A1 (fr) * 2007-05-01 2008-11-13 General Electric Company Procédé d'élimination de microbes de surfaces
WO2011018279A1 (fr) * 2009-08-13 2011-02-17 Huntsman Advanced Materials (Switzerland) Gmbh Agents d’après-nettoyage

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3894946A (en) * 1973-04-02 1975-07-15 American Cyanamid Co Process for treating industrial wastes
US4021365A (en) * 1973-01-24 1977-05-03 Diamond Shamrock Corporation Silica base defoamer compositions with improved stability
WO1991000764A1 (fr) * 1989-07-12 1991-01-24 Rhone-Poulenc Surfactants And Specialties, L.P. Formulations desemulsifiantes/antiemulsifiantes a faible viscosite
US5178770A (en) * 1991-07-12 1993-01-12 Nalco Canada Inc. Method of treating bctmp/ctmp wastewater
US5229033A (en) * 1991-02-06 1993-07-20 Betz Paperchem, Inc. Polybutene based foam control compositions for aqueous systems

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021365A (en) * 1973-01-24 1977-05-03 Diamond Shamrock Corporation Silica base defoamer compositions with improved stability
US3894946A (en) * 1973-04-02 1975-07-15 American Cyanamid Co Process for treating industrial wastes
WO1991000764A1 (fr) * 1989-07-12 1991-01-24 Rhone-Poulenc Surfactants And Specialties, L.P. Formulations desemulsifiantes/antiemulsifiantes a faible viscosite
US5229033A (en) * 1991-02-06 1993-07-20 Betz Paperchem, Inc. Polybutene based foam control compositions for aqueous systems
US5178770A (en) * 1991-07-12 1993-01-12 Nalco Canada Inc. Method of treating bctmp/ctmp wastewater

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000047524A1 (fr) * 1999-02-11 2000-08-17 Huntsman Petrochemical Corporation Procede de traitement des eaux usees
US6315908B1 (en) 1999-02-11 2001-11-13 Huntsman Petrochemical Corporation Method for treatment of waste water
US6559116B1 (en) 1999-09-27 2003-05-06 The Procter & Gamble Company Antimicrobial compositions for hard surfaces
US6730654B2 (en) 1999-09-27 2004-05-04 The Procter & Gamble Company Antimicrobial compositions for hard surfaces containing biguanide compounds
WO2006107603A1 (fr) * 2005-04-04 2006-10-12 Ge Betz, Inc. Regulation de la mousse dans des milieux aqueux
US7442722B2 (en) 2005-04-04 2008-10-28 Ge Betz, Inc. Foam control in aqueous media
AU2006232906B2 (en) * 2005-04-04 2010-12-23 Ge Betz, Inc. Foam control in aqueous media
WO2008137195A1 (fr) * 2007-05-01 2008-11-13 General Electric Company Procédé d'élimination de microbes de surfaces
WO2011018279A1 (fr) * 2009-08-13 2011-02-17 Huntsman Advanced Materials (Switzerland) Gmbh Agents d’après-nettoyage
US8740992B2 (en) 2009-08-13 2014-06-03 Huntsman International Llc Afterclearing agents

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