EP1534416A1 - Reacteur et procede destines a la production et/ou au sechage de polymeres hydrosolubles ou de leurs derives - Google Patents

Reacteur et procede destines a la production et/ou au sechage de polymeres hydrosolubles ou de leurs derives

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Publication number
EP1534416A1
EP1534416A1 EP03792089A EP03792089A EP1534416A1 EP 1534416 A1 EP1534416 A1 EP 1534416A1 EP 03792089 A EP03792089 A EP 03792089A EP 03792089 A EP03792089 A EP 03792089A EP 1534416 A1 EP1534416 A1 EP 1534416A1
Authority
EP
European Patent Office
Prior art keywords
dryer
continuous
reactor
wsps
closed
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP03792089A
Other languages
German (de)
English (en)
Inventor
Sahbi Belkhiria
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP1534416A1 publication Critical patent/EP1534416A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/006—Processes utilising sub-atmospheric pressure; Apparatus therefor
    • 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
    • B01F27/60—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
    • B01F27/72—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with helices or sections of helices
    • B01F27/721—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with helices or sections of helices with two or more helices in the same receptacle
    • B01F27/722—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with helices or sections of helices with two or more helices in the same receptacle the helices closely surrounded by a casing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/90—Heating or cooling systems
    • B01F35/92—Heating or cooling systems for heating the outside of the receptacle, e.g. heated jackets or burners
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/90—Heating or cooling systems
    • B01F35/93—Heating or cooling systems arranged inside the receptacle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00029—Batch processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00033—Continuous processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B01J2219/00128—Controlling the temperature by direct heating or cooling by evaporation of reactants

Definitions

  • WSPs Water- Soluble Polymers
  • This Invention relates to an improved batch or continuous process for the production or modification of Hydrosoluble Polymers, referred hereafter, as WSPs. More particularly, this invention relates to a continuous kneader reactor, having at least one shaft, for the production or modification of WSPs and a process in which such continuous closed reactor could be combined with a continuous moved bed and closed dryer, avoiding the needs of intermediate maturity tank(s) and allowing the condensing then recycling of solvents and/or unreacted components.
  • WSPs Water and sewage treatment, mining, oil well drilling, oil production, coatings, paints, adhesives, detergents, cosmetics, papermaking, ceramics, textiles, etc.
  • the (co)polymerization reaction to produce WSPs can be carried out either in aqueous and initially homogenous phase (bulk solutions polymerization, precipitation polymerization) or in water-in-oil and therefore heterogeneous phase (reverse emulsion or reverse suspension polymerizations). In this latter case, usually, the presence of at least one surfactant and/or other emulsion stabilizer(s) is necessary.
  • Bulk solution polymerization An homogenous solution of the monomeric reactant(s) mixture is initially prepared. Generally, water is the only solvent present in the mixture. But the reaction can also be carried out in the presence of other solvents or a combination thereof.
  • reaction mixture becomes more and more viscous and a gelly WSP is progressively formed.
  • the monomer(s) are reacted in a medium, which is a solvent for them but a non-solvent for the polymer. As the polymer forms, it precipitates from the monomer phase.
  • Suspension Polymerization for commodity: In these cases, two phases are present in the reaction mixture: An organic continuous phase and an aqueous discontinuous phase (droplets), in which the (co)monomers and other reactants and additives are dissolved.
  • At least one suspending agent such as surfactants is usually used to stabilize the heterogeneous mixture.
  • the suspension polymerization leads to less viscous reaction media and better heat transfer.
  • the polymerization is generally carried out under inert condition, i.e. in the presence of inert gas.
  • WSPs are generally obtained by two ways:
  • WSPs are usually produced by (co)polymerization of at least one water-soluble monoethylenically unsaturated monomer and/or at least one water-insoluble monoethylenically unsaturated monomer that can be totally or partly transformed to a water-soluble one by chemical modification(s), in the presence of at least one initiator, and usually other additives such as surfactant(s).
  • the obtained WSP is generally composed of a high molecular weight linear polymer chains.
  • Linear poly(meth)acrylic acids and partially or totally neutralized poly(meth)acryIic acids, poly(meth)acrylamides and partial or total hydrolyzates of poly(meth)acrylamides, poly(meth)acrylonitriles and partial or total hydrolyzates of poly(meth)acrylonitriles, polyethylene or polypropylene glycols, polyvinyl alcohol or poly(allylamines) are some examples of WSPs.
  • WSPs Another way to prepare WSPs is to carry on at least one modification on one or more already available natural or synthetic polymer chains such as polysaccharides, poly(meth)acrylic acids, poly(meth)acrylate esters, poly(meth)acrylamides, poly(meth)acrylonitriles, polyanhydrides, etc.
  • modifications include thermal treatment, partial or total neutralization, hydrolysis, saponification, dehydration, addition or substitution of chemical ionic and/or non-ionic functional groups, etc.
  • WSPs are generally sold either in a powder form or in "dried" emulsion form, depending on the process and finishing operations (finishing step).
  • finishing step one or more reactants or additives such as solvent(s), initiator(s), surfactant(s), or a combination thereof, are removed from (ex.: during drying) and/or added to (ex.: in reaction completion phase) the WSP gel.
  • the process efficiency can be improved through, for example, increasing temperature, maximizing conversion, and/or recycling of solvents and unreacted components.
  • the product properties (ex.: higher solubility rate in water) may also be improved during this step by, for example, additives addition.
  • the finishing step may be carried out in atmospheric, vacuum, or inert conditions and in the presence or absence of heating.
  • Example of water-soluble monoethylenically unsaturated monomers used for preparing WSPs include ⁇ , ⁇ - ethylenically unsaturated carboxylic acid such as (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, citraconic acid, their esters (ex. (meth)acrylates of Methyl, ethyl, N- butyl, 2- hydroxyethyl, etc.), their N-substituted (alkyl)amides (ex.
  • water-soluble monoethylenically unsaturated monomers used for preparing WSPs include monomers containing nitrile group (ex. (meth)acrylonitrile, etc.), sulfo group (vinyl sulfonic acid, etc.), esters obtained by reaction of organic oxides (ethylene oxide, propylene oxide, etc.) or carboxylic acids with alcohols and there derivates.
  • water-soluble monoethylenically unsaturated monomers used for preparing WSPs include (meth)acroleine, vinyl acetate, vinyl propionate, N-vinylpirrolidone, N-vinylformamide, N-vinycaprolactame and their derivatives.
  • water-soluble monoethylenically unsaturated monomers used for preparing WSPs include cationic monomers such as diallyldialkylammonium chloride, methacryloyloxyethyltrimethyl-ammonium chloride, methacryloyloxyethyltrimethyl-ammonium sulfate, 3-
  • a combination of two or more of the above-mention water-soluble monoethylenically unsaturated monomers and their derivatives can also be used.
  • Any natural or synthetic polymer or a combination thereof that is water-soluble or becomes partly or totally water-soluble after neutralisation, hydrolysis, and/or other modification(s) of their functional groups are polysaccharides, alginates, poly(meth)acrylic acids, poly(meth)acrylate esters, poly(meth)acrylamides, poly(meth)acrylonitriles, polyanhydrides, etc.
  • modifications include partial or total neutralization, hydrolysis, saponification, dehydration, addition of chemical ionic and/or non-ionic functional groups,, etc.
  • Additives, and/or Surfactants This includes any type of initiator(s),
  • WSPs Derivatives WSPs can be thermally and/or chemically modified by at least one modification of its functional group(s) yielding to an increase or a decrease of the hydrophilic property of the resulting polymer. Examples of such modifications include curing, compounding, esterification, amidation, partial or total neutralization, hydrolysis, saponification, dehydration. More generally, it consists mainly on the addition or substitution of chemical ionic and/or non-ionic functional groups. II. WSPs Production (Reaction and/or Drying)
  • a method for the continuous production of WSPs as described in part I which method comprises the continuous production of the polymer in a kneader reactor having at least one shaft, the eventual (but not necessary) continuous mixing of additive(s) with that polymer, and/or its continuous drying, wherein said dryer is characterized by a moved product-bed.
  • this method will allow higher monomer concentrations and, for example, replace the conventional moving belt reactors and dryers, wherein the product remains motionless on a moveable surface.
  • suspension polymerization the method allows the use of higher monomer concentrations while controlling efficiently the reaction and mixing parameters and yielding a high product quality.
  • Any kneader having at least one shaft and that can work continuously can be employed as a reactor to produce WSPs.
  • Some Examples of such kneaders are those commercialized by List AG (ex. DTB, ORP, CRP or CKR) or SMS GmbH (ex. Reactotherm, Reasol, Reavisc, Reacom, or Reaflow). Due to their higher self-cleaning and mixing efficiency, twin-shaft kneader reactors are preferred.
  • any continuous moved-bed dryer e.g. rotary dryer, drum dryer, Discotherm dryer
  • Examples of such dryers are those commercialized by List AG (ex. DT) or SMS GmbH (ex. Reactotherm, Rovactor).
  • the polymeric mixture exiting the continuous kneader reactor having at least one shaft be directly dried through any conventional continuous but not moved-bed dryer (ex. belt dryer) already employed in WSPs drying.
  • kneaders reactors having at least one shaft and working in a batch way can also be employed to produce WSPs or their derivatives.
  • WSPs can for example, be ideally and safely carried out in one of the continuous single or twin-shaft kneader reactors of the companies List AG (ex. DTB, ORP, CRP or CKR), SMS GmbH (ex. Reactotherm, Reasol, Reavisc, Reacom, or Reaflow), or other companies that manufacture analogous equipment.
  • the viscosity of the reaction mixture increases as a gel is formed.
  • the intermeshing of the kneading elements assures a uniform mixture over time and cuts the gelly mass into small, uniform gel particles, which are discharged at a conversion up to 90% or even more.
  • Orientation angle of the kneading elements assures the axial conveying of the pasty polymer.
  • the shape of kneading elements is an additional parameter to adjust the compression or shear between the intermeshing zones. Due to its capacity to mix efficiently very viscous media, the kneader is also very suitable to produce WSPs by functional groups modification(s) of polymeric mixtures.
  • the reaction can be carried out at any pressure.
  • evaporative cooling can be used to remove the heat of reaction, especially when the autoacceleration of the reaction rate occurs (gel or Trommsdorff - Norrish effect).
  • approximately 0.1 % to 50% or more of the water and/or other solvent(s) is evaporated to remove the high reaction heat of the monomers (ex.: ⁇ 70KJ/mol for the acrylates monomers).
  • the condensed phase may contain traces or low concentrations of monomer(s) additives and/or surfactants.
  • the evaporated water or liquid mixture can be condensed, eventually separated, then totally (reflux) or partly recycled in the reaction mixture (evaporative cooling). Alternatively, it can also be totally removed to dry partially the produced WSP. Continuous Kneader Reactors
  • the Kneader Reactors are particularly very suitable to produce WSPs since they are designed to improve the radial/axial self-cleaning and axial conveying of viscous polymers, in addition to a good mixing during the reaction. Therefore, the system allows avoiding the complete filling/plugging of the reactor and the dead zones whilst working continuously. Torque is very important to the compression zones, especially with regard to solid or gel particles. Particularly, the twin-shaft kneaders are optimized in order to avoid compression zones between the barrel and the kneading elements, and the intermeshing zones of the kneading elements. At these conditions, no significant presence of squeezed or destroyed gels was observed, but a good and uniform quality of WSPs.
  • Reactants and catalysts are continuously fed in a twin-shaft kneading reactor 1 by arrow A together with vapor and/or inert gas by arrow B.
  • the bulk solution polymerization is conducted in the twin-shaft kneading reactor 1 equipped with a vacuum and condensing systems and in which the axial conveying is optimal and the gel free flowing particles can be formed.
  • the gel particle size can be adjusted at the end of the twin-shaft kneading reactor 1 and after discharge means 3 with a twin-screw 4 by means of adjustable knives 5.
  • the cutting of the gel should be done at this wet stage (in vapour environment) in order to keep the cut particles free flowing.
  • the particle size at this stage of the continuous process is very important because of the drying efficiency, which is improved while processing small particles (diffusion controlled).
  • Vapor and/or inert gas may be removed from the discharge means 3 after the knives.
  • the WSP particles coming out of the twin-shaft kneading reactor 1 are already free-flowing particles because of the humidity and eventually the presence of other component(s) or a combination thereof acting as lubricant(s) on the surface of the particles.
  • a continuous moved-bed dryer 2 e.g. rotary dryer, drum dryer, Discotherm dryer
  • the mixing shown through arrow C of one or more appropriate additives or a combination thereof with the flow of hydrated gel particles coming out of the twin-shaft kneading reactor within a rotary mixer-tube 6 avoids the stickiness of the hydrated gel particles between each other while being separated from the superficial liquid film.
  • These additives act as a free-flowing agent in the continuous dryer 2 wherein the product-bed is moved.
  • the additive(s) could be in a powder or a liquid form, preferably as a powder and more preferably the powder consisting on dried WSP fines D, which can be recycled at the end of the process and may be milled before being mixed as a free-flowing agent.
  • any material or a combination of materials that are used in WSP finishing, as described in paragraph I may also be employed as a free flowing agent while improving the polymer properties, i.e. improved polymer dissolution rate, reduced residual monomers, reduced dust, etc.
  • the dried WSP could be transferred to a not shown mill and sieve.
  • the foregoing pre-drying mixing process can be carried out at atmospheric pressure or in the presence of air, inert gas and/or vacuum.
  • the presence of vacuum is preferred.
  • the process may operate under vacuum by using any commercial periphery systems.
  • the new method of drying is innovative compared to the usual continuous belt convective dryer. Based on the dryer only, the financial impact is a considerable reduction of the drying investments when a moved-bed dryer is compared to a moving belt dryer wherein the product rests motionless on a movable surface. Moreover, by employing the moved-bed dryer 2, the use of maturity tanks to complete reaction can be avoided since this completion reaction can be carried out into the dryer.
  • Each of the kneading reactor 1 and the dryer 2 can be used independently or in combination with the other (cf. Fig.1). Combining of the two equipment to carry on the whole process is preferred, however.
  • Each of the reactor 1 and the dryer 2 can be equipped with a condensing system.
  • the discharge 3 includes a discharge twin-screw 4 and adjustable knives system 5, and is inserted between the twin-shaft kneading reactor 1 and the dryer 2.
  • a pressure lock chamber 7 may also be inserted between the reactor and the dryer. The pressure lock chamber is particularly important when the reactor 1 and the dryer 2 are functioning at different pressures. Any pressure lock chamber present on the market can be used.
  • the process described above and consisting on using either the reactor 1 or the dryer 2 or the combination thereof has the advantages to be more efficient economically and environmentally and gives an improved product's quality since it has the benefits of being more compact (lower space occupation), controlling better the reaction and drying parameters, avoiding the use of maturity tank(s), and giving the possibility to condense the evaporated solvents, and/or unreacted components then recycle them with larger recycling rate, which allows less residuals and gas wastes to be treated.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un procédé de production en continu ou en discontinu de polymères hydrosolubles dans des réacteurs-malaxeurs fermés.
EP03792089A 2002-08-20 2003-08-20 Reacteur et procede destines a la production et/ou au sechage de polymeres hydrosolubles ou de leurs derives Withdrawn EP1534416A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US40469602P 2002-08-20 2002-08-20
US404696P 2002-08-20
PCT/CH2003/000564 WO2004018087A1 (fr) 2002-08-20 2003-08-20 Reacteur et procede destines a la production et/ou au sechage de polymeres hydrosolubles ou de leurs derives

Publications (1)

Publication Number Publication Date
EP1534416A1 true EP1534416A1 (fr) 2005-06-01

Family

ID=31946745

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03792089A Withdrawn EP1534416A1 (fr) 2002-08-20 2003-08-20 Reacteur et procede destines a la production et/ou au sechage de polymeres hydrosolubles ou de leurs derives

Country Status (3)

Country Link
EP (1) EP1534416A1 (fr)
AU (1) AU2003249838A1 (fr)
WO (1) WO2004018087A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005027221A1 (de) 2005-06-13 2007-01-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung von pulverförmigen hochmolekularen wasserlöslichen Polymeren für die Anwendung in fest/flüssig-Trennprozessen
DE102006015541A1 (de) † 2006-03-31 2007-10-04 List Holding Ag Verfahren und Vorrichtung zur Behandlung von zähviskosen Produkten

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
CN1173228A (zh) * 1995-02-03 1998-02-11 诺瓦提斯公司 含光引发剂的交联聚合物
US6149842A (en) * 1998-11-12 2000-11-21 Novartis Ag Methods and compositions for manufacturing tinted ophthalmic lenses
WO2001005365A1 (fr) * 1999-07-16 2001-01-25 Calgon Corporation Composition polymere soluble dans l'eau et methode d'utilisation
US6180754B1 (en) * 1999-09-03 2001-01-30 The Dow Chemical Company Process for producing cross-linked polyallylamine polymer
DE19955861A1 (de) * 1999-11-20 2001-05-23 Basf Ag Verfahren zur kontinuierlichen Herstellung von vernetzten feinteiligen gelförmigen Polymerisaten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004018087A1 *

Also Published As

Publication number Publication date
AU2003249838A1 (en) 2004-03-11
WO2004018087A1 (fr) 2004-03-04

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