EP2461898B1 - Appareil, systeme et procede pour emulsifier de l'huile et de l'eau - Google Patents

Appareil, systeme et procede pour emulsifier de l'huile et de l'eau Download PDF

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EP2461898B1
EP2461898B1 EP09784330.4A EP09784330A EP2461898B1 EP 2461898 B1 EP2461898 B1 EP 2461898B1 EP 09784330 A EP09784330 A EP 09784330A EP 2461898 B1 EP2461898 B1 EP 2461898B1
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Prior art keywords
continuous phase
emulsion
phase
nozzle
diameter
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German (de)
English (en)
French (fr)
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EP2461898A1 (fr
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Olivier Maniere
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Solenis Technologies Cayman LP
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Solenis Technologies Cayman LP
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
    • B01F25/3124—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof characterised by the place of introduction of the main flow
    • B01F25/31243—Eductor or eductor-type venturi, i.e. the main flow being injected through the venturi with high speed in the form of a jet
    • 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
    • D21H21/14—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 characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • D21H17/16—Addition products thereof with hydrocarbons
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/17—Ketenes, e.g. ketene dimers

Definitions

  • the present invention relates to an apparatus, system and method for emulsifying oil and water which are particularly useful in the preparation of aqueous emulsions of sizing agents for internal or surface sizing. paper and paperboard or for the reversal of inverse emulsion polymer products used in paper and paperboard processing.
  • Additives used in the paper industry for the purpose of rendering aqueous penetrants resistant are generally referred to as sizing agents.
  • US 1,540,592 published in 1925 , describes an apparatus with an ejector and a turbine pump in series.
  • WO 99/25466 A1 relates to a polymer supply system and its method of use. The disclosure of this document forms the basis for the preamble of claims 1, 7, and 15.
  • alkyl ketene dimer (AKD) and alkenyl succinic anhydride (ASA).
  • ASA alkenyl succinic anhydride
  • ASA and AKD are hydrophobic materials, not soluble in water. These materials can be added to the liquid paste before forming the sheet, which is called internal sizing, or can be applied to the surface of the formed coil, which is called surface sizing. For both applications, to be effective, the sizing agent must be well distributed in the aqueous system. For this reason, these insoluble additives in water are generally added in the form of aqueous oil emulsions.
  • aqueous emulsions of the sizing agents can be provided to the paper mill in this form, or be prepared on site. Indeed, it is more advantageous for some synthetic sizing agents reactive with cellulose to emulsify them on site.
  • ASA for example, is emulsified on site because of the instability of the anhydride functionality after emulsification with water.
  • Pawlowska, et al. disclose "an improved process for wet paper sizing which uses simpler and less expensive low shear equipment for ASA emulsification.”
  • Pawlowska et al. disclose a sizing process comprising "forming, in the absence of high shear forces, an aqueous sizing emulsion comprising an alkenyl succinic anhydride component" which is subsequently diluted using a cationic component.
  • the main difference between Pawlowska and Mazzarella lies in the post-dilution of the emulsion with a cationic component in order to improve retention.
  • Low shear systems consist of: “simply stirring, passing through a mixing valve or a conventional vacuum cleaner or through the usual agitation present in a dough preparation system" (Mazzarella) or, the shear conditions "created by a selected device from the group consisting of centrifugal pumps, static line mixers, peristaltic pumps, and combinations thereof” (Pawlowska). But these definitions merge into lists of commercial emulsification equipment that include low and high pressure industrial units such as Cytec's low-pressure turbine emulsifiers from Cytec Industries, Inc., Nalco high-pressure foam systems, and Venturi emulsifiers and turbines from National Starch “suggesting that there are turbine pumps that fall into the category of low shear.
  • Waring mixers are used to produce high and low energy ASA emulsions ( Chen and Woodward, Tappi J. Aug 1986, pg 95 ) by varying the voltage.
  • “low shear” and “high shear” systems can not be defined solely by the type of equipment.
  • Dilts et al. defines low shear as the ability to pump liquid through a pump with a backpressure of 3.4 bar (50 psi) or less, while high shear is defined as the need for backpressure from 10.3 to 20.7 bar (150 to 300 psi) for pumping a liquid.
  • WO 01/88262 A2 discloses commercial emulsification equipment comprising industrial low and high pressure units, and refers to a turbine and venturi emulsification device.
  • a system for emulsifying oil in water or water in oil comprises a venturi device.
  • a continuous phase is introduced under pressure into the venturi device and through a continuous phase nozzle having a first diameter in a mixing section.
  • a dispersed phase is introduced into the mixing section of the venturi device to form an emulsion of the dispersed phase in the continuous phase.
  • the emulsion is conducted through a mixed phase nozzle which has a second diameter and to an outlet of the venturi device.
  • the diameter of the mixed phase nozzle is larger than the diameter of the continuous phase nozzle with a ratio greater than 1: 1 and less than 4: 1.
  • Venturi devices were known.
  • WO 98/45034 A1 describes a venturi device used in the field of support in size.
  • the venturi device was intended to mix oil soluble in water.
  • the continuous phase comprises water, which is introduced at a pressure of about 10 bar to about 50 bar.
  • the dispersed phase comprises one or more sizing agents.
  • the emulsion may be discharged into a discharge chamber, where optional additives may be mixed therein.
  • the emulsion can be stored for later use, or diluted with water or other aqueous solution before being added to the wet portion, or a sizing press or coater for a paper making system. or cardboard.
  • the emulsion can be added directly to the wet portion, or to a sizing press or coater for a papermaking or paperboard manufacturing system.
  • the dispersed phase may contain a sizing component of the cellulose-reactive paper or a mixture of such components or a sizing component of the non-cellulose-reacting paper or a mixture of such components.
  • exemplary cellulose-reactive paper sizing components include alkenyl succinic anhydride (ASA), ketene dimers and multimers, such as alkyl ketene dimer (AKD), organic epoxies containing about 12 to 22 carbon atoms, acyl halides containing from about 12 to 22 carbon atoms, fatty acid anhydrides from about 12 to 22 carbon atoms fatty acids, and organic isocyanates containing from about 12 to about 22 carbon atoms. about 12 to 22 carbon atoms.
  • ASA alkenyl succinic anhydride
  • ketene dimers and multimers such as alkyl ketene dimer (AKD)
  • organic epoxies containing about 12 to 22 carbon atoms
  • the dispersed phase can be introduced only by suction at the suction inlet of the venturi device, or possibly pumped with a pump in the mixing section.
  • the dispersed phase is filtered before it is introduced into the mixing section.
  • the continuous phase may be water and the dispersed phase may be an inverse emulsion polymer generally used in papermaking.
  • an oil-in-water emulsion containing a polymer in the aqueous phase can be introduced into the venturi device through the suction inlet. The presence of a large volume of dilution water and the mixing in the mixing section which breaks the emulsion will "activate" the polymer, producing a dilute polymer-based mixture containing oil droplets.
  • An example of an inverse emulsion polymer generally used in papermaking is a retention and drainage aid, such as PERFORM SP7200 or PERFORM PC8179 retention and drainage assistants (Ashland). Inc., Covington, KY).
  • a method of emulsifying a sizing agent to be used for processing paper or board comprises the following steps.
  • a continuous phase is introduced under pressure into a venturi device and into a continuous phase nozzle which has a first diameter which directs said continuous phase into a mixing section of the device.
  • a dispersed phase is introduced into the mixing section of the venturi device to form an emulsion of the dispersed phase in the continuous phase.
  • the emulsion is passed through a mixed phase nozzle which has a second diameter d2 which is larger than the diameter of the continuous phase nozzle d1 with a ratio greater than 1: 1 and less than 4: 1.
  • the continuous phase is introduced at a pressure of about 10 bar to about 50 bar and with a continuous phase nozzle flow rate of from about 10 to about 100 m / sec.
  • the dispersed phase may contain a sizing component of the cellulose-reactive paper or a mixture of such components or a sizing component of the paper not reacting with the cellulose or a mixture of such components.
  • exemplary cellulose-reactive paper sizing components include alkenyl succinic anhydride (ASA), ketene dimers and multimers, organic epoxides containing from about 12 to 22 carbon atoms, acyl halides. containing from about 12 to 22 carbon atoms, fatty acid anhydrides from about 12 to 22 carbon atoms and organic isocyanates containing from about 12 to about 22 carbon atoms.
  • the dispersed phase can be introduced solely by suction at the suction inlet of the venturi device, or possibly pumped by means of a pump into the mixing section.
  • the dispersed phase is filtered before it is introduced into the mixing section.
  • the resulting emulsion of sizing agent has an average particle diameter of less than about 2 microns, preferably 0.5 to 1.5 microns, and most preferably less than about 1 micron as measured. by means of a light diffusion technique on a control emulsion for about one to about ten minutes after emulsion exit of the venturi device.
  • the emulsion is added to either a wet part or a sizing or coater for a paper or board making system. If the continuous phase is water, the emulsion is preferably post-diluted with water to produce a solids content in the range of about 1 to about 5% by weight. Subsequently, the post-dilution emulsion is preferably mixed with an aqueous solution of a synthetic or natural cationic polymer before being added to the wet portion, sizing press or coater.
  • a venturi device has a continuous phase nozzle that has a first diameter that conducts a first liquid under pressure to a mixing section, and an inlet for directing a second liquid to the mixing section so as to form an emulsion.
  • the venturi device further has a mixed phase nozzle which has a second diameter through which the emulsion is directed to an outlet of the venturi device.
  • the diameter of the mixed phase nozzle is larger than the diameter of the continuous phase nozzle with a ratio greater than 1: 1 and less than 4: 1.
  • the mixing section is tapered and tapered with a larger diameter at which the inlet meets the narrower diameter mixing section at which the mixed phase nozzle rejoins the mixing section.
  • the venturi device comprises a discharge diffuser in fluid communication with the nozzle for mixed phase and at the outlet of the venturi device.
  • an “emulsion” is a mixture of particles of a liquid in a second liquid.
  • Two common types of emulsions are oil-in-water and water-in-oil emulsions.
  • oil is generally meant a liquid that is insoluble or almost insoluble in water.
  • water is the “continuous phase” and the oil is the discontinuous phase.
  • discontinuous phase the liquid that forms the continuous phase of the final emulsion
  • disperse phase the other liquid that forms the discontinuous phase of the final emulsion.
  • the water is the continuous phase and the oil is the dispersed phase.
  • FIG. figure 1 A scheme of a system for oil and water emulsification is shown in FIG. figure 1 .
  • System 10 will be described with reference to the emulsification of a sizing agent, such as alkyl ketene dimer (AKD) or alkenyl succinic anhydride (ASA), in water.
  • a sizing agent such as alkyl ketene dimer (AKD) or alkenyl succinic anhydride (ASA)
  • ASA alkenyl succinic anhydride
  • the flow rate of the water which may alternatively be called “continuous phase” with respect to this embodiment, is controlled at a specific flow rate. using a control loop with the flow meter 20 and the control valve 18.
  • Other flow control means are conceivable as is known to those skilled in the art.
  • the pump 22 can be of any type, including a multi-stage centrifugal pump or a regenerative pump, which can provide a supply pressure of about 30 bar, or supply pressures in the range of about 10 to 50 bar, more preferably about 18 to 35 bar.
  • Pressure gauges 40a, 40b, 40c are provided for the purpose of monitoring, respectively, the pressures of the continuous phase, the dispersed phase and the emulsion.
  • the continuous phase is sent to a first entry 48 (refer to the figure 3 ) of a venturi device 50.
  • the filter 36 is designed to prevent clogging of a nozzle 60 for mixed phase of the venturi device 50. Referring to Figures 2-4 for details regarding the Venturi 50 device.
  • the optional pump 38 may be of any type that can provide a supply pressure of up to about 5 bar, preferably about 3 bar, for example.
  • the flow rate of the sizing agent which may also be referred to as the "disperse phase" in this embodiment, can be controlled using the pump 38 or using a control loop. It is also conceivable to provide alternative commands to adjust the ratio of the continuous phase by the dispersed phase fed to the venturi device 50. Since the continuous phase fed to the venturi device 50 produces a vacuum at the inlet of suction 52 of the dispersed phase, it is not necessarily necessary for the pump 38 to provide the dispersed phase to the venturi device 50. Nevertheless, using the pump 38 to provide the dispersed phase to the venturi device 50 is obtained a pressure of more sustained feeding and better control of the emulsion formation process.
  • the continuous and dispersed phases mix in the venturi device 50 and are evacuated to a chamber 70.
  • the diameter of the chamber 70 must be sufficient to reduce the velocity of the emulsified product from the venturi device 50.
  • Additives may be mixed with the emulsified product in the chamber 70 or downstream of the chamber 70.
  • the mixed phase or the emulsified product may be directed to the paper machine or to a storage tank 76 or delivery container (not shown) via a pressure control valve 74.
  • the continuous phase is water
  • the emulsion is preferably post-diluted with water to produce a solids content in the range of about 1 to about 5% by weight.
  • the post-dilution emulsion is preferably mixed with an aqueous solution of a natural or synthetic cationic polymer before being added to the wet portion, the sizing press or the coater of a coating machine. manufacture of paper or cardboard.
  • FIGS. Figures 2 to 4 One embodiment of a venturi device 50 for the emulsification of oil and water is shown in FIGS. Figures 2 to 4 .
  • the figure 3 is a longitudinal section of the venturi device 50.
  • the venturi device 50 has a first inlet 48 into which the continuous phase, such as water, is introduced.
  • the continuous phase flows through the venturi device 50 in the direction of the arrow 54.
  • the flow rate of the continuous phase increases from the first inlet 48 to a smaller diameter channel 56 and then through a conical section 58 before to enter a nozzle with the smallest diameter or nozzle 66 for continuous phase.
  • the shape and dimensions of the flow channel of the continuous phase can be varied.
  • the venturi device 50 has a suction inlet 52 through which the dispersed phase, such as a sizing agent, but not limited thereto, enters the venturi device 50 in the direction of the arrow 62. Vacuum is produced at the suction inlet 52 by the flow of the continuous phase through the continuous phase nozzle 66.
  • the dispersed phase such as a sizing agent, but not limited thereto
  • the continuous phase (for example water) and the dispersed phase (for example a sizing agent) mix in a generally conical chamber 80 and return through the nozzle 60 for mixed phase.
  • the diameter d2 of the mixed phase nozzle is larger than the diameter d1 of the continuous phase nozzle at a ratio greater than 1: 1 and less than 4: 1.
  • the nozzle 60 for mixed phase has a diameter d2 which is twice the diameter d1 of the nozzle 66 for continuous phase.
  • the continuous phase and the dispersed phase are mixed due to the turbulence within the tapered mixing chamber 80 between the continuous phase nozzle 66 and the mixed phase nozzle 60 to form the emulsion or mixed phase.
  • the emulsion leaves the mixed phase nozzle 60 through a discharge diffuser 82 and leaves the venturi device in the direction of arrow 84.
  • the emulsion thus formed is discharged into chamber 70 (refer to FIG. figure 1 ).
  • the emulsions are formed by feeding the continuous phase of an emulsion via the high-pressure continuous phase nozzle 66.
  • the flow of the continuous phase via the continuous phase nozzle 66 creates a low pressure region at the dispersed phase inlet 52 to the venturi device 50.
  • the continuous and dispersed phases are mixed in a generally conical mixing chamber 80. inside the venturi device 50 and supplied to a nozzle 60 for mixed phase which has a diameter d2 greater than the diameter d1 of the nozzle 66 for continuous phase.
  • the two distinct dimensions d2 and d1 of the diameters create two layers of jets at high speed.
  • the emulsified product from the venturi device 50 is discharged into a chamber 70 where the pressure and the fluid velocity are reduced.
  • FIG. 1 further shows an optional reservoir 76 into which the emulsion can be deposited.
  • a representative venturi device 50 has the following dimensions.
  • the mixed phase nozzle 60 has a circular diameter d2 of about 1.2 mm and the continuous phase nozzle 66 has a circular diameter d1 of about 0.7 mm.
  • the mixed phase nozzle 60 has a circular diameter d2 of about 1.8 mm and the continuous phase nozzle 66 has a circular diameter d1 of about 1 mm.
  • the representative venturi device 50 has a total length of about 90 mm.
  • the first inlet 48 is formed with a tapped female circular opening of about 12.7 mm (0.5 inches) to receive a feed tube or fitting (not shown) for the introduction of the continuous phase into the first
  • the first inlet 48 has a length of about 20 mm, and the smaller diameter channel 56 has a length of about 35 mm, the distal end forming a tapering to direct the liquid from the continuous phase to the continuous phase nozzle 66.
  • the continuous phase nozzle 66 has a length of approximately 4 mm.
  • Mixed phase nozzle 60 has a length of about 15 mm.
  • the suction inlet 52 in the representative venturi device 50 has a circular diameter of about 10 mm and a length of about 10 mm.
  • the suction inlet 52 tapers at a conical distal end which directs the material of the dispersed phase to a tubing which leads to a conical chamber 80 for mixing the continuous phase and the dispersed phase together to form a mixed phase or emulsion.
  • the conical chamber 80 has a circular proximal diameter of about 10 mm and tapers toward the mixed phase nozzle 60 at its distal end.
  • the discharge diffuser 82 at the distal end of the representative venturi device 50, is formed with an externally threaded outer portion of about 12.7 mm (0.5 inch) which will be connected to a threaded discharge tube or fitting (not shown) so that the mixed phase (emulsion) leaves the venturi device 50.
  • the discharge diffuser has a length of about 18 mm, and an outer circular opening with a diameter of about 15 mm.
  • An end elevational view of the venturi device 50 from the discharge diffuser 82 in the figure 2 shows that the venturi device 50 has a generally hexagonal or six-sided exterior appearance, and its height and width is about 36 mm.
  • the representative venturi device 50 is shown in FIG. figure 3 formed of two machined parts, the first part, in which is formed the first inlet 48 leading to the nozzle 66 of the venturi, and the second part, in which is formed the suction inlet 52, the conical chamber 80, the nozzle
  • the first portion engages with the second portion and is threadably threaded through threads 77 formed on the outside of the first portion and the interior of the second portion.
  • a sealing ring 78 is provided for fluid sealing of the first and second parts.
  • the continuous phase of the emulsion can be based on water or oil.
  • the dispersed phase of the emulsion may be oil-based.
  • the dispersed phase of the emulsion may be water-based.
  • water-based continuous phases include, but are not limited to, water, solutions aqueous starches and polymer solutions. Additional ingredients customarily used in emulsions of sizing agents, such as, but not limited to, biocides, alums, cationic resins, surfactants, etc. may be contained in the phase addition. keep on going.
  • the oil-based dispersed phase include, but are not limited to, ASA, AKD, and polymers. Additives such as surfactants may optionally be present in the oily phase.
  • the pressure of the continuous phase feed is between about 10 bar and 50 bar, preferably between about 18 bar and 35 bar.
  • the ratio of the dimensions of the mixed phase nozzle and the continuous phase nozzle is greater than 1: 1 and less than 4: 1, preferably between 1.5: 1 and 2.5: 1.
  • the diameter of the continuous phase nozzle (for example the nozzle 66 in the figure 3 ) is set in order to obtain a flow rate of about 10 to 100 m / s, preferably about 40 to 60 m / s. high speed creates instant emulsion creation conditions.
  • the ratio of the continuous phase to the dispersed phase is varied to meet the requirements of the emulsion in terms of viscosity, stability and homogeneity.
  • the concentration of the dispersed phase in the continuous phase ranges from about 2 to 50% by weight, preferably from about 4 to 35% by weight.
  • the diameter of the chamber at the outlet of the venturi device (for example, the chamber 70 in the figure 1 ) is about 5 to 100 times the diameter of the continuous phase nozzle of the venturi device (for example the nozzle 66 in the figure 2 ), preferably about 40 to 80 times the diameter of the nozzle 66 for continuous phase.
  • the pressure that prevails in the chamber is about 1 to 6.7 bar, preferably about 1.3 to 5 bar.
  • the pressure of the dispersed phase input is about 1.3 to 6.7 bar, preferably about 3 to 4.3 bar.
  • the preferred paper sizing components are selected from the group consisting of cellulose reactive paper sizing components and paper sizing components not reactive with cellulose.
  • cellulose-reactive adhesives are defined as adhesives capable of forming covalent chemical bonds by reaction with hydroxyl groups of the cellulose, and non-reactive adhesives are defined as the adhesives that do not form these covalent bonds with cellulose.
  • Preferred cellulose-reactive adhesives for use in the invention include alkenyl succinic anhydrides (ASA), ketene dimers and multimers, organic epoxides containing from about 12 to 22 carbon atoms, acyl halides, and the like. containing about 12 to 22 carbon atoms, fatty acid anhydrides from about 12 to 22 carbon atoms and organic isocyanates containing from about 12 to about 22 carbon atoms. It is also possible to envisage the use of mixtures of reactive sizing agents.
  • ASA alkenyl succinic anhydrides
  • ketene dimers and multimers organic epoxides containing from about 12 to 22 carbon atoms
  • acyl halides containing about 12 to 22 carbon atoms
  • organic isocyanates containing from about 12 to about 22 carbon atoms. It is also possible to envisage the use of mixtures of reactive sizing agents.
  • ASAs Alkenyl succinic anhydrides
  • ASAs are composed of unsaturated hydrocarbon chains containing pendant succinic anhydride groups. They are usually made through a two-step process starting with an alpha olefin. The olefin is first isomerized by randomly shifting the double bond from the alpha position. In the second step, the isomerized olefin is reacted with a maleic anhydride to yield the final ASA having the standard formula (1) (see below).
  • Typical olefins used for the reaction with maleic anhydride include alkenyl, cycloalkenyl and aralkenyl components containing from about 8 to about 22 carbon atoms.
  • n-decenyl succinic anhydride isooctadecenyl succinic anhydride, n-octadecenyl succinic anhydride, n-hexadecenyl succinic anhydride, n-dodecyl succinic anhydride, i-dodecenyl succinic anhydride, and the like.
  • n-decenyl succinic anhydride and n-octenyl succinic anhydride are examples.
  • Succinic alkenyl anhydrides are disclosed in the patent US. No. 4,040,900 and by CE Farley and RB Wasser in The Sizing of Paper, Second Edition, edited by WF Reynolds, Tappi Press, 1989, pages 51-62 .
  • Various alkenyl succinic anhydrides are commercially available from Bercen Inc., Denham Springs, LA.
  • the alkenyl succinic anhydrides to be used in the invention are preferably liquid at 25 ° C. More preferably, they are liquid at 20 ° C.
  • the preferred ketene dimers and multimers are materials of the formula (2) (see below), wherein n is an integer from 0 to about 20, R and R ", which may be the same or different, are groups saturated or unsaturated straight chain or branched alkyl or alkenyl groups having 6 to 24 carbon atoms, and R 'is a straight chain or branched alkenyl group, saturated or unsaturated having from about 2 to about 40 carbon atoms.
  • the groups R and R " are straight-chain or branched alkyl or alkenyl groups having 6 to 24 carbon atoms, cycloalkyl groups having at least 6 carbon atoms, aryl groups having at least 6 carbon atoms, aralkyl groups having at least 7 carbon atoms, alkaryl groups having at least 7 carbon atoms, and mixtures thereof.
  • the ketene dimer is selected from the group consisting of (a) octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, beta-naphthyl, and ketene dimers.
  • ketene dimers prepared from organic acids selected from the group consisting of montanic acid, naphthenic acid, 9,10-decylenic acid, 9,10-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic, of eleostearic acid, natural mixtures of fatty acids found in coconut oil, babassu oil, palm kernel oil, palm oil, olive oil , peanut oil, rapeseed oil, beef tallow, lard, whale blubber, and mixtures of any of the aforementioned fatty acids.
  • the ketene dimer is selected from the group consisting of octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-, octadecyl-, eicosyl-, docosyl-, tetracosyl-, phenyl-, benzyl-, ⁇ - -naphthyl-, and cyclohexyl-ketenes.
  • Alkyl ketene dimers have been used commercially for many years and are prepared by dimerization of alkylketenes obtained from straight-chain saturated fatty acid chlorides; those that are most widely used are obtained from palmitic and / or stearic acid.
  • the pure alkyl ketene dimer is provided by Ashland Hercules Water Technologies, Ashland Inc, Wilmington, Del., As a sizing agent with the designation AQUAPEL 364.
  • the preferred ketene multimers for use as the dispersed phase in the process of this invention have the formula (2) where n is an integer equal to at least 1, R and R ", which may be the same or different, are alkyl groups or saturated or non-saturated straight chain or branched alkenyls having 6 to 24 carbon atoms, preferably 10 to 20 carbon atoms, and still more preferably 14 to 16 carbon atoms, and R 'is a saturated straight or branched chain alkylene group or not having 2 to 40 carbon atoms, preferably 4 to 8 carbon atoms or 28 to 40 carbon atoms.
  • ketene dimers and multimers for use as the disperse phase in the invention are those which are not in solid form at 25 ° C (non-substantially crystalline, semi-crystalline or waxy solids; that they flow by heating without heat of fusion). Dimers and multimers of ketene which are not in the solid state at 25 ° C. are disclosed in US Pat. US. No. 5,685,815 , 5846663 , 5725731 , 5766417 and 5879814 . Ketene dimers that are not in a solid state at 25 ° C are provided by Ashland Hercules Water
  • cellulose reactive adhesives for use as the disperse phase in the invention are mixtures of ketene dimers or multimers with alkenyl succinic anhydrides as described in US Pat. US. No. 5,766,417 .
  • the adhesives which do not react with the cellulose to be used in the form of dispersed phase in the invention preferably include hydrophobic materials which flow freely at temperatures below 95 ° C., preferably below 70 ° C., of the wax. Esterified rosins, hydrocarbon or terpene resins, and polymeric sizing agents.
  • the sizing emulsions of this invention may conveniently contain at least one surfactant to facilitate their emulsification in water, such materials are well known in the art.
  • the surfactant component facilitates the emulsification of the sizing agent with a water component when the emulsion is made.
  • the surfactants are anionic or nonionic or may be cationic and may have a wide range of HLB values.
  • Suitable surfactants include, but are not limited to, phosphate ethoxylates which may contain hydrocarbon substituents of alkyl, aryl, aralkyl or alkenyl, sulfonated products such as those obtained by sulfonating fatty alcohols or aromatic fatty alcohols, ethoxylated alkyl phenols such as nonyl phenoxy polyethoxy ethanols, octyl phenoxy polyethoxy ethanols, polyethylene glycols such as PEG 400 monooleate and PEG 600 dilaurate, ethoxylated phosphate esters, dialkyl sulfosuccinates such as dioctyl sodium sulphosuccinate, polyoxyalkylenealkyl or polyoxyalkylene alkylaryl esters or the corresponding mono or diesters, and trialkyl amines and their quaternary acids and salts as well as amine hydrates such as oleyl dimethylamine and
  • Preferred surfactants are those that emulsify the bonding agent to result in the average droplet size of the emulsion or the smallest particle size.
  • Such emulsions may have a mean droplet size or particle size about 2 microns or less, preferably between 0.5 and 1.5 microns, and most preferably about 1 micron or less.
  • the size of the droplets can be conveniently measured by any well-known particle size measurement technique, for example, microscope, conventional or quasi-elastic light scattering, sedimentation, disk centrifugation, sensing electrozone, chromatographic and fractionation of the flow in an equilibrium sedimentation field.
  • the droplet sizes can be estimated by a light scattering method using an instrument such as the HORIBA LA-300 Particle Size Analyzer.
  • the amount of surfactant may vary depending on the specific surfactant, or surfactant mixture used, as is well known to those skilled in the art.
  • the amount of surfactant present in a sizing composition of the invention should not exceed the minimum required to have an average particle size of about 2 microns or less, preferably between 0.5 and 1.5 microns and most preferably about 1 micron or less in the resulting emulsion. Higher amounts can result in particle size degradation and machine behavior problems that are a consequence of low quality emulsion. From about 0.01% to about 10% surfactant by weight may be used based on the total weight of sizing agent. Preferably, the quality of surfactant present in a sizing composition is from about 0.1% to about 5% by weight.
  • the amount of surfactant present in a sizing composition is less than about 1.0% by weight.
  • Commercially available blends comprising at least one sizing agent and at least one surfactant, such as PREQUEL 20F sizing agents or PREQUEL 90F supplied by Ashland Inc., Wilmington, Del., May be suitably used for forming the sizing emulsions of the invention.
  • the continuous phase may be water or an aqueous solution of a natural or synthetic polymer. Water is preferred. If the continuous phase is water, post-dilution of the emulsion with water to obtain a desired solids content, followed by further dilution with an aqueous solution based on natural or synthetic polymer is recommended.
  • Cationic polymers that can be used for the formation of oil emulsions in water of sizing agents include any cationic polymer containing water-soluble nitrogen which imparts a positive surface charge to particles of the dispersed phase of the emulsion.
  • such cationic polymers are quaternary ammonium compounds; homopolymers or copolymers of unsaturated amines to ethylene; resinous reaction products of epihalohydrins and polyaminopolyamides; alkylenepolyamines; poly (diallylamines), bis-aminopropylpiperazine, dicyandiamide (or cyanamide) -polyalkylene polyamine condensates, dicyandiamide (or cyanamide) -formaldehyde condensates, and dicyandiamide (or cyanamide) -bis-aminopropylpiperazine condensates; and cationic starches.
  • the cationic starches are water-soluble starches containing amino groups, quaternary ammonium or other cationic groups in an amount sufficient for the starch as a whole to have a pronounced cellulose affinity.
  • Cationic starch is preferred.
  • Non-cationic polymers can also be used.
  • cationic polymers in sizing compositions is generally described in the Patents US 4,240,935 , 4243481 , 4279794 , 4295931 , 4317756 , 4522686 , all delivered to Dumas, in the Patent US 2,961,366 issued Weisgerber, and in the Patent No. 5,853,542 (delivered to Bottorff). Atmospheric polymers, like those disclosed in the patent US 7,270,727 (Varnell ), can also be used.
  • the minimum amount of cationic polymer used must be sufficient for the dispersion to become cationic.
  • the amount used will vary depending on the solubility in water and the cationic strength of the particular polymer employed, as well as other variables, such as water quality.
  • the amount of natural or synthetic polymer can be expressed as a percentage of the weight of the cellulose-reactive glue used.
  • the amount of polymer is from about 0.1% to about 400% by weight based on the weight of the cellulose-reactive glue, more preferably from about 2 to about 100% by weight relative to the weight of the cellulose-reactive glue, and most preferably from about 10 to about 30% by weight based on the weight of the cellulose-reactive glue. This amount will depend on the requirements of a specific paper production application.
  • the temperature of the aqueous solution used for the post-dilution is generally less than about 50 ° C, but may be higher depending on the application.
  • the pH of the aqueous solution varies, depending on the application. The pH may be in the range of about 4 to about 8.
  • Post dilution is generally performed under low shear conditions, for example, under shear conditions created by a device such as a centrifugal pump, static in-line mixer, peristaltic pump, rod stirrer, or combinations. of these devices.
  • the emulsions of sizing agents prepared by this invention can be used in the context of internal sizing of paper or board where the sizing emulsions are added to the liquid paste at the wet end of the sizing. papermaking process, or surface sizing of paper or board in which the sizing dispersions are applied at the sizing press or coater.
  • This invention can also be used in one or both parts of a two-part gluing system. For example, a portion may be mixed internally with the wood pulp and a second portion applied at the sizing press, a common practice in papermaking.
  • the amount of sizing agent added to the paste or applied as surface adhesive ranges from about 0.005 to 5% by weight, based on the dryness of the dough, i.e. and optional fillers, and preferably from 0.01 to 1% by weight, where the dosage depends primarily on the quality of the paste or paper to be bonded, the sizing compound used and the desired sizing level.
  • Chemical elements conventionally added to the pulp during the production of paper or board such as treatment assistants (for example, retention aids, drainage assistants, additives) contaminant control, etc.) or other functional additives (eg, wet or dry strength additives, colorants, optical brighteners, etc.) can be used combined with the sizing agents of this invention.
  • treatment assistants for example, retention aids, drainage assistants, additives
  • contaminant control etc.
  • other functional additives eg, wet or dry strength additives, colorants, optical brighteners, etc.
  • the venturi device 50 of this invention can also be used for the preparation of the inverse emulsion polymers usually used in the papermaking process.
  • the polymers of the inverse emulsion are prepared and stabilized using active surfactants, more commonly referred to as surfactants.
  • the surfactants used will allow emulsification of the water-soluble monomer in the oil phase prior to polymerization, and provide stability to the resulting emulsion polymer. Stability that includes sedimentation resistance, minor changes in viscosity over time and premature inversion, not to mention the need for a stable emulsion during the polymerization process, requires a robust set of stabilization of the viscosity. 'emulsion.
  • Emulsion inversion refers to the process before use, in which the phases are reversed, and the polymer is released from the discontinuous phase.
  • a large volume of aqueous solution is added to create a continuous aqueous (water) phase in which the coalescence of the previously dispersed aqueous phase results in the dispersion of the polymer in the solution, making the solution viscous.
  • Surfactants called “disintegrating surfactants”, are added to the emulsion to promote inversion, to disrupt the stabilization system of the original emulsion when the relatively large volume of water is combined, having use a certain level of agitation where shearing, with the emulsion of water in the oil.
  • the polymer can now interact with other aqueous phase materials.
  • the relatively small amount of oil (20-40% by weight of the original emulsion) is dispersed in the aqueous phase, where due to the addition of the large volume of aqueous solution, the oil is a minor component.
  • the polymer is inverted to an aqueous solution, so that the resulting concentration of the active polymer is typically in the range of about 0.1% to about 1.5% by weight.
  • concentration used depends on several factors, including, but not limited to, water temperature and chemistry, solution viscosity, feed rate, and equipment dimensions and flow rates.
  • the emulsion polymer can be inverted into an aqueous solution by directing convergent streams of water and pure emulsion to the desired concentrations through the device. venturi 50.
  • the continuous phase is water, which is introduced by the first inlet 48 of the venturi device 50
  • the dispersed phase is the emulsion based on polymer or crude emulsion, which is introduced by the suction inlet 52 of the venturi device 50.
  • the pressure of the continuous phase is in the range of about 10 to 40 bar, preferably about 15 to 25 bar, and the flow rate of the continuous phase of about 10 to 50 m / s, preferably about 25 to 35 m / s.
  • the resulting mixture undergoes a mixing step, in a static mixer or mechanical pump, in which the mixing action improves the inversion process.
  • a mixing step in a static mixer or mechanical pump, in which the mixing action improves the inversion process.
  • the aqueous solution is then transferred to a reservoir, where it is mixed until homogeneous.
  • the transfer step to a tank is eliminated.
  • the water supply pressure is 30 bar.
  • the diameter of the continuous phase nozzle (for example, the diameter of the nozzle 66 in the figure 3 ) is 1 mm.
  • a dispersed phase based on PREQUEL 20F sizing agent (ASA) was supplied under vacuum to the suction inlet of the venturi device at 15 kg / h.
  • the diameter of the mixed phase nozzle (for example, the diameter of the nozzle 60 in the figure 3 ) is 2 mm.
  • the venturi velocity is 53 m / s in the continuous phase nozzle.
  • the median particle size of the emulsion is 0.67 microns.
  • 170 l / h of water were fed as a continuous phase into a first inlet of a venturi device as shown in FIGS. Figures 2-4 .
  • the water supply pressure is 30 bar.
  • the diameter of the continuous phase nozzle (for example, the diameter of the nozzle 66 in the figure 3 ) is 1 mm.
  • a dispersed phase based on PREQUEL 20F sizing agent (ASA) was supplied under vacuum to the suction inlet of the venturi device at 27 kg / h.
  • the diameter of the mixed phase nozzle (for example, the diameter of the nozzle 60 in the figure 3 ) is 2 mm.
  • the venturi velocity is 60 m / s in the continuous phase nozzle.
  • the median particle size of the emulsion is 0.67 microns.
  • the water supply pressure is 31 bar.
  • the diameter of the continuous phase nozzle (for example, the diameter of the nozzle 66 in the figure 3 ) is 0.8 mm.
  • a dispersed phase based on PREQUEL 20F sizing agent (ASA) was supplied under vacuum to the suction inlet of the venturi device at 8 kg / h.
  • the diameter of the mixed phase nozzle (for example, the diameter of the nozzle 60 in the figure 3 ) is 1.6 mm.
  • the venturi velocity is 44 m / s in the continuous phase nozzle.
  • the median particle size of the emulsion is 0.82 microns.
  • a venturi device 180 l / h of water was fed as a continuous phase into a first inlet of a venturi device as shown in FIGS. Figures 2-4 .
  • the water supply pressure is 32 bar.
  • the diameter of the continuous phase nozzle (for example, the diameter of the nozzle 66 in the figure 3 ) is 1 mm.
  • a dispersed phase based on PREQUEL 20F sizing agent (ASA) was supplied under vacuum to the suction inlet of the venturi device at 15 kg / h.
  • the diameter of the mixed phase nozzle (for example, the diameter of the nozzle 60 in the figure 3 ) is 1 mm (same diameter for the continuous phase and mixed phase nozzle).
  • the venturi velocity is 63 m / s in the mixed phase nozzle.
  • the emulsion was almost immediately dispersed in separate phases: water and drops of ASA. It was impossible to measure the particle size distribution.
  • the water supply pressure is 30 bar.
  • the diameter of the continuous phase nozzle (for example, the diameter of the nozzle 66 in the figure 3 ) is 1 mm.
  • a dispersed phase based on PREQUEL 90F sizing agent (one AnKD provided by Ashland Hercules Water Technologies, Wilmington, Del.) was supplied under vacuum to the suction inlet of the venturi device at 30 kg / h.
  • the diameter of the mixed phase nozzle (for example, the diameter of the nozzle 60 in the figure 3 ) is 2 mm.
  • the venturi velocity is 53 m / s in the continuous phase nozzle.
  • the emulsion was stable with a median particle size of 0.8 microns.
  • the water supply pressure is 30 bar.
  • the diameter of the continuous phase nozzle (for example, the diameter of the nozzle 66 in the figure 3 ) is 0.8 mm.
  • a dispersed phase based on PREQUEL 20F sizing agent (ASA) was supplied under vacuum to the suction inlet of the venturi device at 30 kg / h.
  • the diameter of the mixed phase nozzle (for example, the diameter of the nozzle 60 in the figure 3 ) is 2.4 mm.
  • the venturi velocity is 44 m / s in the continuous phase nozzle.
  • the emulsion was stable with a median particle size of 1.15 microns.
  • the water supply pressure is 30 bar.
  • the diameter of the continuous phase nozzle (for example, the diameter of the nozzle 66 in the figure 3 ) is 1.2 mm.
  • a dispersed phase based on PREQUEL 20F sizing agent (ASA) was supplied under vacuum to the suction inlet of the venturi device at 30 kg / h.
  • the diameter of the mixed phase nozzle (for example, the diameter of the nozzle 60 in the figure 3 ) is 1.6 mm.
  • the venturi velocity is 53 m / s in the continuous phase nozzle.
  • the emulsion was stable with a median particle size of 0.8 microns.
EP09784330.4A 2009-08-04 2009-08-04 Appareil, systeme et procede pour emulsifier de l'huile et de l'eau Active EP2461898B1 (fr)

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MX2012001551A (es) 2012-05-23
PL2461898T3 (pl) 2016-01-29
CA2770942A1 (en) 2011-02-10
RU2538578C2 (ru) 2015-01-10
JP2013501164A (ja) 2013-01-10
US11554353B2 (en) 2023-01-17
BR112012002642B1 (pt) 2021-05-25
CA2770942C (en) 2016-11-01
CN102639219B (zh) 2016-03-09
JP5740548B2 (ja) 2015-06-24
PT2461898E (pt) 2015-11-30
AU2009350832A1 (en) 2012-03-08
KR101644212B1 (ko) 2016-07-29
BR112012002642A2 (pt) 2020-12-15
AU2009350832B2 (en) 2016-06-09
EP2461898A1 (fr) 2012-06-13
KR20120041242A (ko) 2012-04-30
US20120103546A1 (en) 2012-05-03
ZA201201603B (en) 2013-10-28
ES2550620T3 (es) 2015-11-11
RU2012108162A (ru) 2013-09-10
WO2011015715A1 (fr) 2011-02-10

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