EP2929929A1 - Herstellungsverfahren einer emulsion aus alkenylbernsteinsäureanhydrid - Google Patents

Herstellungsverfahren einer emulsion aus alkenylbernsteinsäureanhydrid Download PDF

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Publication number
EP2929929A1
EP2929929A1 EP15163102.5A EP15163102A EP2929929A1 EP 2929929 A1 EP2929929 A1 EP 2929929A1 EP 15163102 A EP15163102 A EP 15163102A EP 2929929 A1 EP2929929 A1 EP 2929929A1
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EP
European Patent Office
Prior art keywords
emulsification
asa
rotor
emulsion
aqueous solution
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Granted
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EP15163102.5A
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English (en)
French (fr)
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EP2929929B1 (de
Inventor
Nicolas Leroy
Jean-Charles Vieren
Sébastien Monnel
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Roquette Freres SA
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Roquette Freres SA
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    • 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
    • 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
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/27—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices
    • B01F27/271—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed radially between the surfaces of the rotor and the stator
    • B01F27/2711—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed radially between the surfaces of the rotor and the stator provided with intermeshing elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/81—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
    • B01F33/813—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles mixing simultaneously in two or more mixing receptacles
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • 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

Definitions

  • the present invention relates to a process for producing an alkenyl succinic anhydride (ASA) emulsion in an aqueous solution of cationic starchy material, it being understood that the oily phase is constituted by ASA, the starchy solution acting as a carrier of said emulsion.
  • aqueous solution of cationic starchy material is meant a composition containing at least one cationic starch in aqueous solution.
  • the method described in the present application does not implement a recirculation loop of the product at the emulsification unit, and carries out a dilution of the emulsion once it is manufactured: a product with granulometry both fine, monodisperse, stable for a while, and which limits the fouling in the pipes carrying the emulsion from the emulsion manufacturing facility to the paper machine.
  • This provides an efficient method, simple to implement, on a papermaking production site, suitable for production rates compatible with the needs of paper machines.
  • the invention also relates to an installation for manufacturing an emulsion suitable for implementing the method.
  • ASA alkenyl succinic anhydride
  • This chemical species which is not miscible in water must be emulsified in order to be advantageously used in the form of a liquid product: this allows a good contact between the ASA and the cellulose fibers.
  • the emulsion in question is an ASA emulsion in an aqueous solution of cationic starchy material; in the rest of the application, it may also be referred to simply as an emulsion.
  • aqueous solutions of cationic starchy materials of different natures the starchy material being optionally modified; the function of such compositions is to prevent the coalescence of the ASA particles by positive ionization of the surface of the particles, and to bring the ASA particles closer to the fibers by an ionic mechanism.
  • a dry weight ratio of cationic starchy material / ASA of between 0.2 and 4 is used.
  • the ASA emulsion in the aqueous solution of cationic starchy material must have a number of characteristics. In particular, it must have a great fineness of particle sizes, as well as a narrow spectrum of distribution of these sizes ("monodisperse" product). As explained in the document WO97 / 35068 A1 these parameters condition the effectiveness of the bonding composition vis-à-vis the hydrophobicity properties it is supposed to confer.
  • the Applicant has recently developed a method of manufacturing an ASA emulsion in a composition of cationic starchy material, leading to a narrow particle size distribution and centered on an interval of between 1 ⁇ m and 1.5 ⁇ m and this, without temperature rise of the emulsion, a phenomenon that accelerates the hydrolysis of ASA.
  • the resulting emulsions indeed confer excellent hydrophobizing properties on the papers in which they are intended to be used.
  • the key to this process is based on a step of emulsifying an ASA / aqueous cationic amylaceous material in a single pass (that is to say without recirculation loop as in the prior art), while by adjusting the dry matter content of the initial aqueous solution of cationic starch material to between about 7% and 12% of its total weight.
  • a step of emulsifying an ASA / aqueous cationic amylaceous material in a single pass that is to say without recirculation loop as in the prior art
  • dry matter content of the initial aqueous solution of cationic starch material to between about 7% and 12% of its total weight.
  • the emulsions thus manufactured do not exhibit a stable particle size distribution. It has thus been found that the average diameter of said particles is rapidly changing over time, sometimes to values of greater than 4 ⁇ m: it therefore deviates substantially from the optimum value sought by the paper manufacturer and as defined above, with a view to get an effective collage of the sheet of paper. However, it is not unusual for the paper machine to be stopped for several minutes, or even several hours, due to technical problems, for cleaning or maintenance operations. In this respect, it is essential that the particle size distribution of the particle size of the emulsion does not vary.
  • the device of the document FR1259423 further comprises a dilution unit of the emulsion connected to the emulsification unit 3) and which makes it possible to dilute the emulsion, and thus to stabilize the particle size of the emulsion.
  • the Applicant has identified two devices (“emulsification unit") for producing the emulsion from the mixture of ASA and the aqueous solution of cationic starchy material, preferably without recirculation of the emulsion to the device.
  • emulsification unit Two devices
  • Process Pilot DR 2000/4 IKA ®
  • Ytron Z YTRON ®
  • ASA alkenyl succinic anhydride
  • the Applicant has used Ytron Z material (YTRON ®), the only emulsifier device among the two identified suitable for this industrial application, online.
  • ASA which is the Chemsize® A180 product marketed by CHEMEC®, is also used.
  • the water supply is from an existing distribution network. Transfers and dosing of the ASA and the aqueous solution of cationic starchy material to the emulsification unit, are made from their container, by means of pipe and positive displacement pumps, whose rotation speeds are controlled by the instructions desired flow rate and the target cationic starch content (dry) / ASA.
  • the dry weight ratio cationic starchy material / ASA is 0.3.
  • ASA / aqueous solution of cationic starchy material Prior to the mixing of "ASA / aqueous solution of cationic starchy material", the aqueous solution marketed under the name VECTOR® SCA 2015 is diluted in line so as to obtain an aqueous solution of starchy material whose dry matter content is 8% of its total weight.
  • This aqueous solution of starchy material is mixed in line with the ASA at the mixing unit 2).
  • This mixture " aqueous solution of starchy material / ASA” is then conveyed via a pipe to the emulsification unit 3).
  • This device comprises a housing, whose internal volume forms a substantially cylindrical emulsification chamber, and a single rotor / stator torque.
  • Each rotor and each stator have three rows of concentric toothed rings: the stator and rotor rings are mutually entangled in order to allow shearing of the toothed rings during rotation of the rotor.
  • the rotational speed of the rotor is set to obtain a peripheral speed of the rotor, at the toothed crowns, of the order of 31 m / s.
  • the fluid flow rate to the emulsification unit is about 50 l / h.
  • the casing of the emulsification unit comprises a single inlet, with a diameter of the order of 2-3 cm for the "aqueous starch solution / ASA" mixture to be homogenized, and located substantially in the axis of the rotor, and a single outlet for the directional emulsion substantially tangential to the cylindrical chamber.
  • an emulsion is obtained, the particle size distribution of which is centered on a gap between 1 ⁇ m and 1.5 ⁇ m.
  • the peak of the curve is measured at 1.25 microns analyzed from a laser granulometer marketed by MALVERN® under the name Mastersizer® and under the conditions specified below for the examples.
  • the emulsion is then diluted in line by a factor of 2, ie a diluted emulsion flow rate of about 90-100 l / h.
  • a diluted emulsion is obtained, the particle size distribution of which is narrow and centered over a range of between 1 ⁇ m and 1.5 ⁇ m.
  • We speak of "narrow" particle size distribution when at least 80% by volume of said particles will have a diameter of less than 2 ⁇ m, and when the average diameter is comprised in 1 ⁇ m and 1.5 ⁇ m.
  • the stability of the particle size of the emulsion is improved compared to an undiluted emulsion.
  • the results are thus satisfactory with regard to the quality of the emulsion and in particular the distribution of the particle size distribution.
  • the use of the emulsion as a sizing composition gives satisfactory performance in terms of hydrophobicity of the paper.
  • the method of manufacturing an emulsion aims to overcome the fouling problems identified above.
  • This method makes it possible to produce an emulsion whose particle size distribution is narrow and centered over an interval of between 1 ⁇ m and 1.5 ⁇ m, without substantial rise in temperature of the emulsion, a phenomenon which accelerates hydrolysis of ASA.
  • the manufacturing method according to the invention optionally allows, according to one embodiment, obtaining such an emulsion whose particle size is stabilized compared to an undiluted emulsion.
  • the invention also relates to an assembly comprising a paper machine and an installation for continuously manufacturing an ASA emulsion in an aqueous solution of cationic starchy material according to the invention and connected to the paper machine.
  • the invention also relates to the use of a gluing composition containing an emulsion obtained according to the process according to the invention in a gluing operation of a sheet of paper or cardboard.
  • the invention arose from the finding by the inventors that one of the causes of fouling results, according to the state of the art known from the document WO2013 / 186491 , prior mixing, upstream of the emulsification unit, of the ASA with the aqueous solution of cationic starchy material.
  • the ASA and the aqueous solution of cationic starchy material are not mixed before being introduced into the emulsification chamber 2.
  • the mixing of these two components is carried out directly in the emulsification chamber 2, and not in an upstream mixer, distinct from the emulsification unit as taught by the document. WO 2013/186491 .
  • the emulsification unit 1 has two separate inputs E1, E2 for the ASA and the aqueous solution of cationic starchy material and separate pipes for conveying these two fluids.
  • these two inputs E1, E2 may advantageously be axes inclined relative to the axis A of the rotor 3 in such a way that their jets intersect in the emulsification chamber 2.
  • Step a) of producing the aqueous solution of cationic starchy material either consists in providing an aqueous solution of cationic starchy material, as commercially available, or else in diluting it with water, in order to obtain the desired dry matter content.
  • This dilution can be performed online, in the installation, for example by means of a static mixer.
  • the dilution water is preferably between 5 ° C and 40 ° C, and more preferably between 5 ° C and 25 ° C.
  • cationic starchy material designates a starchy material obtained by any of the known methods of cationisation in aqueous medium, in a solvent medium or in a dry phase, since this process allows one or more a plurality of nitrogen group (s) of electropositive nature to be attached to said starchy material.
  • s nitrogen group
  • aqueous solution of cationic starchy materials that can be used according to the present invention, mention may be made of the products marketed under the range VECTOR® SC and IC (ROQUETTE®), Raisabond® 15 (CHEMIGATE), Licocat® P (SUEDSTAERKE®), Lyckeby® LP 2145 and LP 1140 (LYCKEBY®), Redisize® 205 and Redibond® 4000 (NATIONAL STARCH®) and Raifix® 25035 and 01035 (CIBA RAISIO®).
  • ROQUETTE® range VECTOR® SC and IC
  • Raisabond® 15 CHEMIGATE
  • Licocat® P SUVEDSTAERKE®
  • Lyckeby® LP 2145 and LP 1140 LYCKEBY®
  • Redisize® 205 and Redibond® 4000 NATIONAL STARCH®
  • Raifix® 25035 and 01035 CIBA RAISIO®
  • Step c) consists, directly in the emulsification chamber 2, of mixing between the aqueous solution of cationic starchy material from step a) and the ASA.
  • the dry weight ratio cationic starchy material / ASA is less than 1, preferably between 0.2 and 0.6, and very preferably between 0.25 and 0.5.
  • the manufacturing plant comprises volumetric pumps (not shown) and pipes, intended respectively to conduct the ASA and an aqueous solution of cationic starchy material in a ratio of flow rates determined in order to obtain the ratio by weight dry cationic starchy material / ASA.
  • Step d) consists of circulating in a single pass the mixture which has been obtained in stage c), in the emulsification unit 1.
  • This unit comprises the emulsification chamber 2 receiving the rotor torque 3 / stator 4.
  • the rotor 3 and the stator 4 preferably each have concentric toothed rings, the stator and rotor rings being mutually entangled.
  • each rotor and each stator have several rows of concentric toothed rings, for example three in number, as illustrated in the examples of the figures.
  • the emulsification unit preferably comprises a single rotor / stator torque 4.
  • the emulsification unit may comprise several successive stages (ie 3 stages) each having a rotor / stator torque.
  • the rotor 3 of the emulsification unit is preferably rotated in order to obtain a peripheral speed of the rotor, in particular at the toothed crowns, of between 30 m / s and 40 m / s.
  • the dilution step e) is preferably carried out in the immediate vicinity of the outlet So of the emulsification unit 1, and not just upstream of the paper machine.
  • the emulsion is preferably diluted with water.
  • This dilution step firstly makes it possible to cool the emulsion at the outlet of the emulsification unit 1, and thus to avoid the hydrolysis of the ASA.
  • This dilution further reduces the deposits in the pipe downstream of the dilution device, carrying the diluted emulsion from the manufacturing facility to the paper machine, substantially increasing the flow of fluid in the pipe.
  • a minimum fluid velocity in this downstream pipe is sought, greater than 0.2 m / s, preferably greater than 0.8 m / s, or even greater than or equal to 1 m / s.
  • a dilution of a factor strictly greater than 3.5 may be necessary, in particular when the fluid flow rate is between 45 l / h and 300 l / h in the emulsification unit 1, in order to achieve such fluid velocities in the pipes.
  • This dilution factor is greater than that taught in the application FR1259423 , of the Applicant. If necessary and for high dilutions, close to the upper limit (ie dilution factor of 21), this high dilution can be to the detriment of the stability over time of the emulsion. A dilution factor of between 4 and 11 may be a good compromise between the stability of the emulsion and the objective of limiting the fouling.
  • the fluid outlet So of the emulsification chamber 2 may be of reduced diameter, between 10 mm and 3 mm, such as for example 4 mm, 6 mm or 8 mm: an output diameter of less than or equal to 10 mm is chosen, much smaller than the output diameter of the commercial version Ytron Z (YTRON ®)., To limit deposits on this area.
  • the emulsification unit may comprise a set of tips 7, removable, to allow the diameter change of the So output.
  • Each tip 7 has a clean internal diameter (i.e. 4 mm, 6 mm or 8 mm).
  • the change in diameter of the output So is obtained simply by the removal of a nozzle 7 and its replacement, for example in a housing of the cylindrical wall 6 of the housing, by another endpiece of more suitable diameter.
  • the emulsification unit 1 may comprise a set of rotor / stator pairs, distinct, and differentiated by the length of the teeth of the concentric ring gear.
  • stator 4 and a rotor 3 For example, and for a fluid flow rate of between 45 l / h and 150 l / h at the emulsification unit 1, it is possible to choose a stator 4 and a rotor 3, the length of the teeth of the toothed crowns being between 4 mm and 6 mm and the difference between teeth is between 1 mm and 2 mm.
  • This rotor / stator torque is hereinafter referred to as short-rotor rotor / stator torque.
  • stator 4 and a rotor 3 whose length of the teeth of the ring gear is between 9 mm and 12 mm. and whose gap between teeth is between 1 mm and 2 mm.
  • This rotor / stator torque is hereinafter referred to as rotor / long-tooth stator torque.
  • dilution downstream of the outlet So of the emulsification unit 1 is carried out by means of a control device.
  • dilution 8 preferably comprising a straight section 80 of hose whose proximal end is connected to the outlet So of the emulsification unit 1 and whose distal end opens into a bend 81 of a larger diameter pipe, channeling the dilution liquid.
  • the undiluted emulsion is thus conveyed in a rectilinear path, from the outlet So of the emulsification unit 1 and up to the place of dilution, without change of direction and thus without elbow likely to promote deposits.
  • a dilution device 8 operates by venturi effect.
  • Figures 7a, 7b and 7c illustrate a rotor / stator torque, as known from the state of the art, as such.
  • the free internal volume of the emulsification chamber 2, upstream of the shear work (in the direction of flow) is defined between the walls of the cover and the rotor / stator assembly.
  • the free volume of the emulsification chamber 2 is defined between the rotor 3, the inner surface of the cylindrical wall 6 of the housing, and a cover 5 'of the housing (opposite the cover 5 carrying the inputs E1, E2).
  • the new rotor / stator torque illustrated in Figures 8a, 8b and 8c is intended to significantly reduce this free volume of the emulsification chamber, upstream shear work between the toothed crowns.
  • the stator 4 is always positioned between the rotor 3 and said fluid inlets E1, E2 in said emulsification chamber 2.
  • the geometry of the stator thus modified comprises a reduced central opening 40, of diameter smaller than the average diameter of the toothed crowns and a wall 41 extending from the central opening 40 and up to crowns of the stator 4, flaring out.
  • This reduced central opening 40 is intended to be traversed by the jets of the fluid inlets E1, E2.
  • this new geometry of the stator 4 substantially reduces the free internal volume of the emulsification chamber 2, upstream of shear work, and thus the deposition surfaces.
  • this free internal volume, upstream is defined between the flared wall 41 and the rotor 3, and is thus contained with a diameter smaller than the diameter of the toothed rings of the stator 4.
  • the emulsification unit 1 may comprise a third fluid inlet, marked En, distinct from the inputs E1 and E2, and allowing the implementation of a cleaning cycle of the emulsification unit 1, or even the device 8 located downstream of the emulsification unit.
  • the cleaning is carried out by feeding the inlet En of a cleaning fluid such as water, with or without adjuvant, and preferably by rotating the rotor.
  • a cleaning fluid such as water
  • the emulsion manufacturing plant can advantageously comprise, as illustrated in FIG. figure 10 , two emulsification units 1, 1 ", the emulsion being produced from the same source of ASA and the same solution of cationic starch material, to one of the two emulsification units 1.1 while the other emulsification unit implements a cleaning cycle, or undergoes maintenance.
  • the electrovalve marked 9 is a three-way solenoid valve which makes it possible to conduct the cationic solution of starchy material, either at the inlet E2 of the first emulsification unit 1, or at the inlet E2 "of the second emulsification unit 1 ".
  • the solenoid valve marked 10 is a three-way solenoid valve for driving the ASA, either at the inlet E1 of the first emulsification unit 1, or at the inlet E1 "of the second emulsification unit 1" .
  • these two solenoid valves 9 and 10 conduct the ASA and the cationic starch solution either at the inputs of the first emulsification unit 1, or at the inputs of the second emulsification unit 1 ".
  • the electrovalve marked 11 is a three-way solenoid valve which makes it possible to drive the diluted emulsion resulting from step e) to the paper machine via a pipe, or from the outlet of the dilution device 8 associated with the first emulsification unit 1, or from the output of the dilution device 8 "associated with the second emulsification unit 1".
  • An automaton makes it possible to control these three solenoid valves 9, 10 and 11 and to synchronize them in order to connect either the first emulsification unit 1 or the second emulsification unit 1 ".
  • the process according to the present invention is also characterized in that the ASA is a product preferably of synthetic origin; these are modified oils that result from C16-C18 cuts.
  • ASA is a product preferably of synthetic origin; these are modified oils that result from C16-C18 cuts.
  • Chemsize® A 180 (CHEMEC®) or the product PENTASIZE® 8A by the company PENTAGON® which is an equivalent product.
  • This process is also characterized in that the aqueous solution of cationic starchy material has a fixed nitrogen content of less than 3.5%, preferably between 0.3% and 3.5%, very preferably between 0.7% and 2% by dry weight of nitrogen relative to the total weight of cationic starchy material.
  • This cationic starchy material may optionally be modified from an operation chosen from hydrolysis, chemical and physical, mechanical, thermomechanical or even thermal transformations.
  • a hydrolysis operation very directly aimed at reducing the molecular weight and, in most cases, reducing the viscosity, can be conducted by various means such as chemical, commonly by the action of an acid, a base or an oxidizing agent or by an enzymatic action, most commonly by amylase.
  • the common chemical modifications are of different natures such as oxidation, especially with hypochlorite, esterification, such as acetylation, etherification, for example, by cationization, carboxymethylation or hydroxypropylation.
  • Physical treatments may be practiced by thermomechanical means, such as extrusion or pre-gelatinization, or thermal, such as those known to those skilled in the art as Hot Moisture Treatment (HMT) or Annealing .
  • HMT Hot Moisture Treatment
  • the first test is that which made it possible to note the problem of fouling, already here described in the introduction, and illustrated schematically in the figure 1 .
  • ASA which is the Chemsize® A180 product marketed by CHEMEC®, is also used.
  • the water supply is from an existing distribution network.
  • the transfers and dosing of the ASA and the aqueous solution of cationic starchy material to the emulsification unit are, from their container, by means of pipe and pumps volumetric, whose rotational speeds are slaved to the desired flow rates and the target ratio cationic starchy material (dry) / ASA.
  • the dry weight ratio cationic starchy material / ASA is 0.3.
  • ASA / aqueous solution of cationic starchy material Prior to the mixing of "ASA / aqueous solution of cationic starchy material", the aqueous solution marketed under the name VECTOR® SCA 2015 is diluted in line so as to obtain an aqueous solution of starchy material whose dry matter content is 8% of its total weight.
  • This aqueous solution of starchy material is mixed in line with the ASA in a mixing unit.
  • This mixture " aqueous solution of starchy material / ASA” is then conveyed via a pipe to the emulsification unit.
  • This device comprises a housing, whose internal volume forms a substantially cylindrical emulsification chamber, and a single rotor / stator torque.
  • Each rotor and stator have three rows of concentric ring gear: the stator and rotor rings are mutually entangled to allow shearing.
  • the speed of rotation of the rotor is adjusted so as to obtain a peripheral speed of the rotor, at the level of the toothed crowns, of the order of 31 m / s.
  • the fluid flow rate to the emulsification unit is about 50 l / h.
  • the casing of the emulsification unit comprises a single inlet of diameter of the order of 3-4 cm for the mixture "aqueous solution of starchy material / ASA" to be homogenized, located substantially in the axis of the rotor, and a single outlet for the directional emulsion substantially tangential to the cylindrical chamber and of diameter of the order of 2-3 cm.
  • the emulsion is then diluted in line by a factor of 2, ie a diluted emulsion flow rate of approximately 100 l / h.
  • the temperature of the diluted water is 38 ° C.
  • an emulsion is obtained, the particle size distribution of which is narrow and centered on a gap between 1 ⁇ m and 1.5 ⁇ m.
  • the peak of the curve (particle volume in% / diameter in ⁇ m) measured by the granulometer is 1.25 ⁇ m.
  • a first substantial modification consists, according to steps b) and c) of the process according to the invention, to mix the ASA and the amylaceous cationic solution resulting from step a) directly in the emulsification chamber of the unit emulsification, and not in an upstream mixing unit.
  • the modified plant thus comprises separate pipes and separate entrances for the ASA and the starch cationic material solution.
  • step e A second substantial change is, according to step e) of the process to further dilute the emulsion, in order to increase the velocity of fluid in the pipe downstream of the dilution device.
  • the dilution factor goes from 2 to 6.
  • an outlet is used for the emulsification unit of smaller diameter (8 mm) and a dilution device 8 as previously described.
  • a rotor / stator torque with short teeth as defined above is used.
  • test n ° 1 an aqueous solution of cationic starchy material marketed by ROQUETTE® under the name VECTOR® SCA 2015 is used.
  • ASA is also used. which is the Chemsize® A180 product marketed by CHEMEC®.
  • a diluted emulsion sample is taken: the peak of the particle distribution curve (volume of particles in% / diameter in ⁇ m) measured by the particle size analyzer is 1.30 ⁇ m.
  • Test No. 3 differ from those of Test No. 2 by the discharge at the emulsion unit of 190 l / h, as well as by the dry weight ratio of cationic starchy material / ASA. which is slightly different, equal to 0.3.
  • the installation is the modified one of test n ° 2: one replaces the rotor / stator torque with "short teeth” by a rotor / stator with "long teeth”.
  • a diluted emulsion sample is taken: the peak of the particle distribution curve (volume of particles in% / diameter in ⁇ m) measured by the particle size analyzer is 1.38 ⁇ m.
  • Test No. 4 differ from those of Test No. 3 only by the flow rate at the emulsification unit which is 300 l / h.
  • a diluted emulsion sample is taken: the peak of the particle size distribution curve (in terms of volume of particles in% / diameter in ⁇ m) measured by the particle size analyzer is 1.49 ⁇ m.
  • Test No. 5 differ from those of Test No. 4 only by the rotor speed of the emulsification unit which is 5700 rpm.
  • a diluted emulsion sample is taken: the peak of the particle size distribution curve (in terms of volume of particles in% / diameter in ⁇ m) measured by the particle size analyzer is 1.39 ⁇ m.
  • step a) 8 8 8 8 8 8 8 Ratio of step c) 0.3 0.25 0.3 0.3 0.3 Flow rate at the emulsification unit (1 / h) 50 49.5 190 300 300 Dilution factor of step e) 2 6 6 6 6 Rotor speed (rpm) 4600 4600 4600 4600 5700 Rotor peripheral speed (m / s) 31 31 31 31 38 Peak distribution curve ( ⁇ m) 1.25 1.30 1.38 1.49 1.39 Clogging (at 24 hours) Yes no no no no no no no no no no no no no no
  • an ASA emulsion is made in an aqueous solution of cationic starchy material in the laboratory and the emulsion is diluted according to three different dilution factors, namely 6, 11 and 21, in order to obtain three diluted emulsions. referred to as “emulsion 1 ", "emulsion 2 " and " emulsion 3".
  • ASA which is the Chemsize® A180 product marketed by CHEMEC®, is also used.
  • the aqueous solution marketed under the name VECTOR® SCA 2015 is diluted so as to obtain an aqueous solution of starchy material whose solids content is 8% of its total weight.
  • This aqueous solution is mixed with ASA.
  • the dry weight ratio cationic starchy material / ASA is 0.3.
  • This mixture is then transferred to a device for obtaining an emulsion.
  • emulsion 1 The diluted emulsion of a ratio 1/5 (of a dilution factor 6) is called " emulsion 1 ".
  • the diluted 1: 10 emulsion (with a dilution factor of 11) is referred to as “ emulsion 2 ".
  • the diluted emulsion of a 1/20 ratio (of a dilution factor 21) is called " emulsion 3".
  • these sheets of laboratory paper are manufactured from a FRET device (retention plates) marketed by TECHPAP.
  • FRET device retention plates
  • Such forms have characteristics close to the industrial customer paper, especially with regard to flocculation and retentions.
  • the method of manufacturing the formette uses a pulp which is a pulp of virgin fibers (50% resinous, 50% hardwood) with a refining level of 35 ° Schopper (° SR). 35% (by dry weight relative to the total weight of the dough) of natural calcium carbonate marketed by OMYA® under the name of Omyalite®50 is added. The fibrous suspension is loaded at a concentration of 2.5 g / l. 0.3% (dry equivalent / paper) of a HICAT® 5163AM (ROQUETTE®) glue is then added. Three samples of dough are thus taken.
  • a third form is thus produced having a grammage of 70 g / m 2 .
  • the sheets After manufacturing the sheets, they are placed between 2 blotters and the set is passed twice in a TECHPAP® brand roller press. Each formette is then separated from the blotters and is placed on a TECHPAP® brand dryer, for 5 min at 100 ° C. A ripening of the forms is then carried out, by placing them for 30 minutes in an oven at 110 ° C, to allow the bonding agent to fully give the paper its hydrophobic character. The forms are then placed for a minimum of 24 hours in a room conditioned at 23 ° C (+/- 1 ° C) and 50% relative humidity (+ / 2%) (ISO 187: 1990 and Tappi T402 sp-08 standards). ).
  • Table 2 summarizes the Cobb 60 (g / m 2 ) values measured on the forms prepared with these three emulsions. ⁇ b> Table 2 ⁇ / b> Emulsion N ° Dilution factor Cobb 60 (g / m2) 1 6 20 2 11 20 3 21 18.5
  • E1, E2, E1 ", E2”. Separate Inputs (Emulsification Unit), In, In. Inputs for Cleaning Fluid (Emulsification Unit), So. Output (Emulsification Chamber 2).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Colloid Chemistry (AREA)
  • Paper (AREA)
EP15163102.5A 2014-04-11 2015-04-10 Herstellungsverfahren einer emulsion aus alkenylbernsteinsäureanhydrid Active EP2929929B1 (de)

Applications Claiming Priority (1)

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FR1453239A FR3019823B1 (fr) 2014-04-11 2014-04-11 Procede de fabrication d'une emulsion d'anhydride alkenyle succinique

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EP2929929B1 EP2929929B1 (de) 2017-07-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112538780A (zh) * 2020-12-22 2021-03-23 浙江凯丰新材料股份有限公司 一种asa施胶剂在线乳化装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1259423A (fr) 1960-03-14 1961-04-28 Boîte à outils
WO1997035068A1 (en) 1996-03-21 1997-09-25 Betzdearborn Inc. Paper size and paper sizing process
WO2008077116A2 (en) * 2006-12-19 2008-06-26 Dow Global Technologies Inc. A device for producing dispersions and method of producing dispersions
WO2013186491A1 (fr) 2012-06-12 2013-12-19 Roquette Freres Procede de fabrication d'une emulsion d'anhydride alkenyle succinique (asa) dans une solution aqueuse de matiere amylacee cationique, emulsion obtenue et son utilisation
WO2014053788A1 (fr) * 2012-10-04 2014-04-10 Roquette Freres Procede de fabrication d'une emulsion stable d'anhydride alkenyle succinique (asa) dans une solution aqueuse de matiere amylacee cationique, emulsion obtenue et son utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1259423A (fr) 1960-03-14 1961-04-28 Boîte à outils
WO1997035068A1 (en) 1996-03-21 1997-09-25 Betzdearborn Inc. Paper size and paper sizing process
WO2008077116A2 (en) * 2006-12-19 2008-06-26 Dow Global Technologies Inc. A device for producing dispersions and method of producing dispersions
WO2013186491A1 (fr) 2012-06-12 2013-12-19 Roquette Freres Procede de fabrication d'une emulsion d'anhydride alkenyle succinique (asa) dans une solution aqueuse de matiere amylacee cationique, emulsion obtenue et son utilisation
WO2014053788A1 (fr) * 2012-10-04 2014-04-10 Roquette Freres Procede de fabrication d'une emulsion stable d'anhydride alkenyle succinique (asa) dans une solution aqueuse de matiere amylacee cationique, emulsion obtenue et son utilisation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112538780A (zh) * 2020-12-22 2021-03-23 浙江凯丰新材料股份有限公司 一种asa施胶剂在线乳化装置

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ES2641882T3 (es) 2017-11-14
PT2929929T (pt) 2017-10-03
FR3019823B1 (fr) 2017-10-27
EP2929929B1 (de) 2017-07-12
FR3019823A1 (fr) 2015-10-16

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