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WO2020079124A1 - Procédé de production de compositions de polyacrylamide aqueuses - Google Patents

Procédé de production de compositions de polyacrylamide aqueuses Download PDF

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Publication number
WO2020079124A1
WO2020079124A1 PCT/EP2019/078166 EP2019078166W WO2020079124A1 WO 2020079124 A1 WO2020079124 A1 WO 2020079124A1 EP 2019078166 W EP2019078166 W EP 2019078166W WO 2020079124 A1 WO2020079124 A1 WO 2020079124A1
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WO
WIPO (PCT)
Prior art keywords
aqueous
reactor device
location
water
aqueous polyacrylamide
Prior art date
Application number
PCT/EP2019/078166
Other languages
English (en)
Inventor
Anna-Corina SCHMIDT
Alexander KRONAST
Dennis Loesch
Faissal-Ali El-Toufaili
Original Assignee
Basf Se
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 Basf Se filed Critical Basf Se
Publication of WO2020079124A1 publication Critical patent/WO2020079124A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y402/00—Carbon-oxygen lyases (4.2)
    • C12Y402/01—Hydro-lyases (4.2.1)
    • C12Y402/01084—Nitrile hydratase (4.2.1.84)

Definitions

  • the invention relates to a process for producing aqueous polyacrylamide
  • compositions by polymerizing an aqueous solution comprising at least acrylamide thereby obtaining an aqueous polyacrylamide gel, comminuting said aqueous polyacrylamide gel and mixing it with an aqueous liquid, wherein the polymerization is a continuous process comprising partially polymerizing said aqueous monomer solution in a first reactor device comprising a positive displacement pump and continuing the polymerization in a second reactor device.
  • the invention furthermore relates to a modular, relocatable plant for carrying out the described process.
  • Water-soluble, high molecular weight homo- and copolymers of acrylamide may be used for various applications such as mining and oilfield applications, water treatment, sewage treatment, papermaking, and agriculture. Examples include its use in the exploration and production of mineral oil, in particular as thickener in aqueous injection fluids for enhanced oil recovery or as rheology modifier for aqueous drilling fluids. Further examples include its use as flocculating agent for tailings and slurries in mining activities.
  • a common polymerization technology for manufacturing such high molecular weight polyacrylamides is the so called“gel polymerization”.
  • gel polymerization an aqueous monomer solution having a relatively high concentration of monomers, for example from 15 % by weight to 50 % by weight is polymerized by means of suitable polymerization initiators under essentially adiabatic conditions in an unstirred reactor thereby forming a polymer gel.
  • the polymer gels formed are converted to polymer powders by comminuting the gel into smaller pieces by one or more size reduction steps, drying such gel pieces for example in a fluid bed dryer followed by sieving, grinding and packaging.
  • the obtained polyacrylamide powders are thereafter packaged and shipped to customers.
  • the aqueous polyacrylamide gel obtained from gel polymerization typically comprises from 65 % to 80 % of water.
  • polyacrylamide powders typically is from about 4 to 12 % by weight. So,“drying” such polyacrylamide gels does not mean to remove only some residual moisture in course of drying but rather about 0.55 to 0.75 kg of water need to be removed per kg of polymer gel, or -with other words- per kg of polymer powder produced also 1.5 to 2.5 kg of water are“produced”.
  • High-molecular weight polyacrylamides are usually used as dilute aqueous solutions. Typical concentrations of polyacrylamides for oilfield and mining applications range from 0.05 wt. % to 0.5 wt. %. Consequently, the polyacrylamide powders manufactured as mentioned above need to be dissolved in aqueous fluids before use. Dissolving high molecular weight polymers in aqueous fluids is time consuming and it is difficult to do so without degrading the polymers and without forming lumps. Suitable equipment for dissolving polyacrylamide powders is necessary on-site.
  • DE 2 059 241 discloses a process for preparing water-soluble polymers, including acrylamide containing polymers, in which an aqueous solution comprising water- soluble monomers and polymerization initiators is filled into transportable containers for polymerization. In the transportable containers, the aqueous solution polymerizes thereby forming polymer gel. The gel may be transported to the end users who can remove the polymer gels and dissolve them in water.
  • transportable containers may be -for instance- bags, cans, drums, or boxes having a volume from 2 I to 200 I.
  • US 4,248,304 discloses a process for recovering oil from subterranean formations wherein a water-in-oil-emulsion of an acrylamide polymer in the presence of an inverting agent is injected into the formation.
  • the water-in-oil emulsion is manufactured in a small chemical plant located near the wells and the manufacturing procedure comprises the steps of forming a water-in-oil emulsion of acrylonitrile, converting a substantially portion of the acrylonitrile to acrylamide using a suitable catalyst, and polymerizing the water-in-oil emulsion of acrylamide in the presence of a free radical polymerization catalyst.
  • the catalyst may be a copper catalyst.
  • ZA 8303812 discloses a process for preparing polyacrylamides comprising polymerizing acrylamide and optionally suitable comonomers on-site and transferring the polymer formed to its desired place of use on site without drying or concentrating.
  • the polymerization can be carried out as an emulsion
  • polymerization bead polymerization, or as solution / dispersion polymerization.
  • the polymer may be pumped from the polymerization reactor to the position on site where it is used.
  • WO 84/00967 A1 discloses an apparatus and method for the continuous production of aqueous polymer solutions, in particular of partially hydrolyzed polyacrylamides.
  • the apparatus comprises a polymerization reactor, a hydrolysis reactor and a diluter.
  • the polymerization may be performed on-site and the solutions may be used in secondary or tertiary oil recovery.
  • US 4,605,689 discloses a method for on-site production of aqueous polyacrylamide solutions for enhanced oil recovery.
  • aqueous polyacrylamide gel is provided by polymerizing acrylamide and preferably acrylic acid as comonomer.
  • the polyacrylamide gel obtained is conveyed together with a minor amount of aqueous solvent through at least one static cutting device thereby obtaining a slurry of small gel particles in water, the gel particles are dissolved in the aqueous solvent which forms a homogeneous solution composition which is then readily diluted with aqueous solvent thereby obtaining a diluted aqueous polyacrylamide solution.
  • US 4,845,192 discloses a method of rapidly dissolving particles of gels of water- soluble polymers comprising forming a suspension of such gel particles in water and subjecting said suspension to instantaneous and momentary conditions of high shearing effective to finely slice said particles.
  • WO 2017/186567 A1 relates to a process for producing an aqueous polymer solution comprising the steps of providing an aqueous polyacrylamide gel comprising at least 10 % by weight of active polymer, cutting the aqueous polyacrylamide gel by means of an aqueous liquid at a pressure of at least 150 bar to reduce the size of the aqueous polyacrylamide gel, and dissolving the aqueous polyacrylamide gel in an aqueous liquid.
  • WO 2017/186697 A1 relates to a method of preparing an aqueous polyacrylamide solution, comprising hydrolyzing acrylonitrile in water in presence of a biocatalyst thereby obtaining an acrylamide solution, directly polymerizing the acrylamide solution thereby obtaining a polyacrylamide gel, and directly dissolving the polyacrylamide gel by addition of water thereby obtaining an aqueous
  • polyacrylamide solution which may have a concentration from 0.03 % to 5 % by weight.
  • the method may be carried out on-site.
  • WO 2017/186685 A1 relates to a method of preparing an aqueous polyacrylamide solution, comprising hydrolyzing acrylonitrile in water in presence of a biocatalyst thereby obtaining an acrylamide solution, directly polymerizing the acrylamide solution thereby obtaining a polyacrylamide gel, and directly dissolving the polyacrylamide gel by addition of water by means of a mixer comprising a rotatable impeller thereby obtaining an aqueous polyacrylamide solution, which may have a concentration from 0.03 % to 5 % by weight.
  • the method may be carried out on site.
  • WO 2017/186698 A1 relates to a method of preparing an aqueous polyacrylamide solution, comprising hydrolyzing acrylonitrile in water in presence of a biocatalyst thereby obtaining an acrylamide solution, directly polymerizing the acrylamide solution thereby obtaining a polyacrylamide gel, and directly dissolving the polyacrylamide gel by addition of water by means of water-jet cutting, thereby obtaining an aqueous polyacrylamide solution, which may have a concentration from 0.03 % to 5 % by weight.
  • the method may be carried out on-site.
  • WO 2016/006556 A1 describes a method for producing a compound using a continuous tank reactor which is provided with two or more reaction tanks for producing the compound and with a reaction liquid feeding pipe that feeds a reaction liquid from an upstream reaction tank to a downstream reaction tank, said method being characterized in that the Reynold's number of the reaction liquid that flows in the reaction liquid feeding pipe is configured to be 1800-22000.
  • the tank reactor may be mounted in a portable container.
  • the compound may be acrylamide produced by conversion from acrylonitrile by means of a biocatalyst.
  • WO 84/00967 A1 describes a method for the continuous preparation of dilute solutions of water-soluble polymers.
  • a first reactor which preferably is tubular, an aqueous monomer solution is polymerized at a predetermined flow rate.
  • the resulting aqueous polymer solution is continuously modified in a second reactor and then diluted by means of a diluter.
  • the aqueous polymer solution is continuously modified in a second reactor and then diluted by means of a diluter.
  • the manufactured in the first step may be an aqueous polyacrylamide solution (the example discloses that the polymer concentration is 6 % by wt.) which is partially hydrolyzed in the second step.
  • the polymerization can be carried out on-site.
  • WO 2014/049513 A1 describes a continuous process for producing polymers by partially polymerizing an aqueous solution comprising monoethylenically unsaturated monomers in a first reactor comprising a positive displacement pump, preferably a progressive cavity pump, transferring the partially polymerized product to a second reactor and continuing the polymerization in the second reactor.
  • WO 2017/167803 A1 discloses a method for producing a polyacrylamide solution having an increased viscosity by preparing an aqueous acrylamide solution by converting acrylonitrile to acrylamide using a biocatalyst, separating the biocatalyst from the aqueous acrylamide solution such that the OD 600 of the aqueous acrylamide solution is equal or less than 0.6, and polymerizing the aqueous acrylamide solution thus obtained to polyacrylamide.
  • WO 97/21827 A1 discloses a process for making a solution of ammonium acrylate by enzymatic hydrolysis of acrylonitrile.
  • WO 2019/081318 Al discloses the manufacture of aqueous polyacrylamide solutions on site in modular plants.
  • aqueous solutions comprising acrylamide and optionally further monoethylenically unsaturated comonomers are polymerized by adiabatic gel polymerization in a polymerization unit which preferably has a volume of 20 m 3 to 30 m 3 .
  • Such a polymerization may be performed at a location A and thereafter the relocatable polymerization unit filled with the aqueous polyacrylamide gel is transported to another location B where the gel is removed from the polymerization unit, comminuted and dissolved in water thereby yielding an aqueous polyacrylamide solution.
  • Location B typically is a location where the aqueous polyacrylamide solutions are used, e.g. at an oil well or in mining area.
  • Location A typically is a central hub comprising units for monomer storage, monomer make-up and polymerization which serves a number of different locations B with aqueous polyacrylamide gel. Locations A and B may be apart from each other significantly, for example the distance may be up to 3000 km and the transport of the gel form location A to location B may last several days.
  • the present invention relates to a process for producing aqueous polyacrylamide compositions by polymerizing an aqueous solution comprising at least acrylamide thereby obtaining an aqueous
  • aqueous monomer solution comprising at least water and 15 % to 50 % by weight -relating to the total of all components of the aqueous monomer solution- of water-soluble, monoethylenically unsaturated monomers, wherein said water-soluble, monoethylenically unsaturated monomers comprise at least acrylamide, [2] radically polymerizing said aqueous monomer solution at the location B in a relocatable polymerization unit, comprising at least
  • a first reactor device comprising an inlet, an outlet and a positive
  • a second reactor device for continuing polymerization of the partially polymerized product mounted substantially vertical comprising at least one tubular or at least one conical section or combinations thereof and furthermore comprising an inlet at the upper end and an outlet at the lower end,
  • polymerization is a continuous process comprising at least the following steps
  • aqueous polyacrylamide composition having a concentration from 0.05 to 14.9 % by weight of polyacrylamides, relating to the total of all components of the aqueous polyacrylamide composition.
  • aqueous polyacrylamide compositions having a concentration from 0.05 to 14.9 % by weight of polyacrylamides, relating to the total of all components of the aqueous polyacrylamide composition.
  • the composition may be a solution or a (soft) solid.
  • polyacrylamides as used herein means water-soluble homopolymers of acrylamide, or water-soluble copolymers comprising at least 10 %, preferably at least 20 %, and more preferably at least 30 % by weight of acrylamide and at least one additional water-soluble, monoethylenically unsaturated monomer different from acrylamide, wherein the amounts relate to the total amount of all monomers in the polymer. Copolymers are preferred.
  • water-soluble monomers in the context of this invention means that the monomers are to be soluble in the aqueous monomer solution to be used for polymerization in the desired use concentration.
  • the monomers to be used are miscible with water without any gap; instead, it is sufficient if they meet the minimum requirement mentioned.
  • the presence of acrylamide in the monomer solution might enhance the solubility of other monomers as compared to water only.
  • the solubility of the water- soluble monomers in water at room temperature should be at least 50 g/l, preferably at least 100 g/l.
  • the kind and amount of water-soluble, monoethylenically unsaturated comonomers to be used besides acrylamide is not limited and depends on the desired properties and the desired use of the aqueous solutions of polyacrylamides to be manufactured.
  • comonomers may be selected from uncharged water-soluble, monoethylenically unsaturated monomers.
  • examples comprise methacrylamide, N-methyl(meth)acrylamide, N,N’-dimethyl(meth)acrylamide, N- methylol(meth)acrylamide or N-vinylpyrrolidone. Further examples have been mentioned in WO 2015/158517 A1 page 7, lines 9 to 14.
  • comonomers may be selected from water-soluble, monoethylenically unsaturated monomers comprising at least one acidic group, or salts thereof.
  • the acidic groups are preferably selected from the group of -COOH, -S0 3 H and -P0 3 H 2 or salts thereof. Preference is given to monomers comprising COOH groups and/or -S0 3 H groups or salts thereof.
  • Suitable counterions include especially alkaline earth metal ions such as Ca 2+ , alkali metal ions such as Li + , Na + or K + , and also ammonium ions such as NH 4 + or ammonium ions having organic radicals.
  • ammonium ions having organic radicals include [N H(CH 3 ) 3 ] + , [NH 2 (CH 3 ) 2 ] + , [NH 3 (CH 3 )] + , [NH(C 2 H 5 ) 3 ] + , [NH 2 (C 2 H 5 ) 2 ] + , [N H 3 (C 2 H 5 )] + , [N H 3 (CH 2 CH 2 0H)] + , [H 3 N-CH 2 CH 2 -N H 3 ] 2+ or [H (H 3 C) 2 N- CH 2 CH 2 CH 2 N H 3 ] 2+ .
  • Exam ples of monomers com prising -COOH grou ps include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid or fu maric acid or salts thereof. Preference is given to acrylic acid or salts thereof.
  • Exam ples of monomers com prising -S0 3 H groups or salts thereof include vinylsu lfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), 2-methacrylamido-2-methylpropanesu lfonic acid, 2- acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesu lfonic acid or 2- acrylamido-2,4,4-trimethylpentanesu lfonic acid.
  • Preference is given to 2- acrylamido-2-methylpropanesulfonic acid (ATBS) or salts thereof.
  • Exam ples of monomers com prising -P0 3 H 2 grou ps or salts thereof include vi nylphosphonic acid, allylphosphonic acid, N-(meth)acrylamidoalkylphosphonic acids or (meth)acryloyloxyalkylphosphonic acids, preferably vinylphosphonic acid.
  • Preferred monomers comprising acidic grou ps com prise acrylic acid and/or ATBS or salts thereof.
  • comonomers may be selected from water-soluble, monoethylenically u nsatu rated monomers comprising cationic grou ps.
  • Suitable cationic monomers include especially monomers having ammoniu m grou ps, especially am moniu m derivatives of N-(w- aminoalkyl) (meth)acrylamides or w-aminoal kyl (meth)acrylates such as
  • comonomers may be selected from associative monomers.
  • Associative monomers to be used in the context of this invention are water-soluble, monoethylenically u nsaturated monomers having at least one hyd rophilic group and at least one, preferably terminal, hyd rophobic grou p.
  • associative monomers have been described for example in WO 2010/133527, WO 2012/069478, WO 2015/086468 or WO 2015/158517.
  • “Hydrophobically associating copolymers” are understood by a person skilled in the art to mean water-soluble copolymers which, as well as hydrophilic units (in a sufficient amount to assure water solubility), have hydrophobic groups in lateral or terminal positions. I n aqueous solution, the hydrophobic groups can associate with one another. Because of this associative interaction, there is an increase in the viscosity of the aqueous polymer solution compared to a polymer of the same kind that merely does not have any associative groups.
  • the hydrophilic linking group R 2 may be a group comprising quaternary ammonium groups.
  • R 3a is an aliphatic and/or aromatic, straight-chain or branched hydrocarbyl radical having 8 to 40 carbon atoms, preferably 12 to 32 carbon atoms.
  • the groups include n-octyl, n-decyl, n-dodecyl, n- tetradecyl, n-hexadecyl or n-octadecyl groups.
  • the groups are aromatic groups, especially substituted phenyl radicals, especially
  • distyrylphenyl groups and/or tristyrylphenyl groups are distyrylphenyl groups and/or tristyrylphenyl groups.
  • the associative monomers are monomers of the general formula
  • R 1 is defined as above and the R 5 radicals are each independently selected from hydrocarbyl radicals comprising at least 2 carbon atoms, preferably from ethyl or propyl groups.
  • n is a natural number from 2 to 6, for example 4
  • x is a number from 10 to 50, preferably from 12 to 40, and for example, from 20 to 30 and y is a number from 5 to 30, preferably 8 to 25.
  • z is a number from 0 to 5, for example 1 to 4, i.e. the terminal block of ethylene oxide units is thus merely optionally present.
  • the associative monomers are cationic monomers.
  • water-soluble monoethylenically unsaturated monomers also water-soluble, ethylenically unsaturated monomers having more than one ethylenic group may be used.
  • Monomers of this kind can be used in special cases in order to achieve easy crosslinking of the acrylamide polymers.
  • the amount thereof should generally not exceed 2% by weight, preferably 1% by weight and especially 0.5% by weight, based on the sum total of all the monomers. More preferably, the monomers to be used in the present invention are only monoethylenically unsaturated monomers.
  • composition of the polyacrylamides to be manufactured according the process of the present invention may be selected according to the desired use of the polyacrylamides.
  • Preferred polyacrylamides comprise, besides at least 10 % by weight of acrylamide, at least one water-soluble, monoethylenically unsaturated comonomer, preferably at least one comonomer selected from the group of acrylic acid or salts thereof, ATBS or salts thereof, associative monomers, in particular those of formula (V) or DMA3Q, more preferably at least one comonomer selected from acrylic acid or salts thereof, ATBS or salts thereof, associative monomers, in particular those of formula (V).
  • the polyacrylamides comprise 20 % to 90 % by weight of acrylamide and 10 % to 80 % by weight of acrylic acid and/or salts thereof, wherein the amounts of the monomers relate to the total of all monomers in the polymer.
  • the polyacrylamides comprise 20 % to 40 % by weight of acrylamide and 60 % to 80 % by weight of acrylic acid and/or salts thereof.
  • the polyacrylamides comprise 55 % to 75 % by weight of acrylamide and 25 % to 45 % by weight of acrylic acid and/or salts thereof. In one embodiment, the polyacrylamides comprise 45 % to 75 % by weight of acrylamide and 25 % to 55 % by weight of ATBS and/or salts thereof.
  • the polyacrylamides comprise 30 % to 80 % by weight of acrylamide, 10 % to 40 % by weight of acrylic acid and/or salts thereof, and 10 % to 40 % by weight of ATBS and/or salts thereof.
  • the polyacrylamides comprise 45 % to 75 % by weight of acrylamide, 0.1 to 5 %, preferably 0.1 to 2 % by weight of at least one associative monomer of the general formulas (I) or (I I) mentioned above and 10 to 54.9 % by weight of acrylic acid and/or ATBS and/or salts thereof.
  • the associative monomer(s) have the general formula (V) including the preferred embodiments mentioned above.
  • the polyacrylamides comprise 60 % to 75 % by weight of acrylamide, 0.1 to 5 %, preferably 0.1 to 2 % by weight of at least one associative monomer of the general formula (V) mentioned above, including the preferred embodiments, and 20 to 39.9 % by weight of acrylic acid or salts thereof.
  • the polyacrylamides comprise 45 % to 55 % by weight of acrylamide, 0.1 to 5 %, preferably 0.1 to 2 % by weight of at least one associative monomer of the general formula (V) mentioned above, including the preferred embodiments, and 40 to 54.9 % by weight of acrylic acid or salts thereof.
  • the polyacrylamides comprise 60 % to 99 % by weight of acrylamide and 1 % to 40 % by weight of DMA3Q.
  • the polyacrylamides comprise 10 % to 50 % by weight of acrylamide and 50 % to 90 % by weight of DMA3Q.
  • the polyacrylamides comprise 90 to 99.5 % by weight of acrylamide, 0.5 to 2 % by weight of at least one associative monomer, and 0 % to 9.5 % by weight of and anionic monomer, for example ATBS or a cationic monomer, for example DM3AQ.
  • the associative monomer(s) have the general formula (V) including the preferred embodiments mentioned above.
  • the amount of the monomers relates to the total of all monomers in the polyacrylamide. Further water-soluble,
  • monoethylenically unsaturated monomers may be present besides those specifically mentioned, however, the embodiments each include also one embodiment in which besides the monomers specifically mentioned no further monomers are present, i.e. in these embodiments the total amount of the monomers specifically mentioned is 100 % by weight.
  • a high molecular weight corresponds to a high intrinsic viscosity (IV) of the
  • the intrinsic viscosity may be at least 15 deciliter/gram (dL/g). In one embodiment of the invention, the intrinsic viscosity is from 30 to 45 dl/g.
  • the numbers mentioned relate to the measurement with an automatic Lauda iVisc ® LMV830 equipped with an Ubbelohde capillary tube and automatic injection.
  • an aqueous solution of the polymers to be analyzed was prepared having a concentration of 250 ppm.
  • the pH was adjusted at 7 by means of a buffer and the solution comprised additionally 1 mol /I of NaCI. Further four dilutions were done automatically.
  • the viscosity at five different concentrations was measured at 25 ° C with.
  • the IV value [d L/g] was determined in usual manner by extrapolating the viscosities to infinite dilution.
  • the error range is about ⁇ 2 dL/g.
  • aqueous polyacrylamide compositions according to the present invention While it is possible to perform some steps of the process in fixed plants, it is preferred to perform the entire process of manufacturing aqueous polyacrylamide compositions according to the present invention in a modular manner using relocatable units.
  • Each relocatable unit bundles certain functions of the plant.
  • Examples of such relocatable units comprise units for storing and optionally cooling the monomers and other raw materials, hydrolyzing acrylonitrile, mixing monomers, polymerization and gel comminution. Details will be provided below.
  • individual units are connected with each other in a suitable manner thereby obtaining a production line.
  • “Relocatable unit” means that the unit is transportable basically as a whole and that it is not necessary to disassemble the entire unit into individual parts for transport. Transport may happen on trucks, railcars or ships.
  • such modular, relocatable units are containerized units which may be transported in the same manner as closed intermodal containers for example on trucks, railcars or ships.
  • Intermodal containers are large standardized (according to ISO 668) shipping containers, in particular designed and built for intermodal freight transport.
  • Such containers are also known as ISO containers.
  • Such ISO containers may have external dimensions of a height of ⁇ 2.59 m, a width of ⁇ 2.44 m and a length of about 6.05 m. Larger ISO containers have external dimensions of a height of ⁇ 2.59 m, a width of ⁇ 2.44 m and a length of -12.19 m.
  • the relocatable units may be fixed on trucks or on trailers.
  • trucks or trailers advantageously also function as platform for the units on the ground.
  • two or more different units may be mounted together on a truck or trailer.
  • the relocatable units are combined at the manufacturing site, thereby obtaining modular production plants for performing the process according to the present invention.
  • Such a modular construction using relocatable units provides the advantage, that the plants may be easily relocated from one location to another location if polyacrylamides are no longer needed at one location but at another location.
  • aqueous polyacrylamide solutions are injected into a subterranean, oil-bearing formations through one or more than one injection wells sunk into the formation. Such an injection may continue for months or even years. However, at some point in time no further oil production is possible. The modular plant may then be easily relocated to another location, for example to another oilfield.
  • the steps of the process according to the present invention may be carried out at one location. I n other embodiments, the steps of the process may be distributed over 2 or 3 different locations apart from each other and products and/or intermediate products are transported from one location to another location in course of the process.
  • the process is carried out at least at a manufacturing-site, hereinafter also referred to as“location B”.
  • Location B may be a site-of-use, i.e. a location at which the aqueous
  • polyacrylamide compositions are used or at least a location close to such a site-of- use.
  • location B may be on an oil field or in a mining area.
  • Specific examples comprise oil wells which into which aqueous polyacrylamide solutions are injected in course of enhanced oil operations, production wells whose productivity is enhanced by injection of fracturing fluids comprising polyacrylamides as friction reducers, or wells which are drilled and aqueous polyacrylamide solutions are used for making the drilling fluid.
  • the plant may be deployed in between a plurality of such oil and/or gas wells or at one of them and the aqueous polyacrylamide solution is distributed to all injection wells.
  • location B may be at or close to a tailings ponds in which mineral tailings are dewatered using aqueous polyacrylamide solutions.
  • location B may be at a paper production site, at sewage works or at seawater desalination plants or at sites for manufacturing agricultural formulations.
  • step [2] At location B, at least the steps of polymerization (step [2]), comminution of the gel obtained and mixing with water (steps [3] and [4]) are carried out. It is furthermore of course necessary to provide the monomer mixture to location B.
  • the aqueous monomer solution for polymerization is prepared at location B and also bio-acrylamide may be
  • compositions obtained may be directly used at location B.
  • an aqueous monomer premix may be manufactured at a different location A and transported from location A to location B for polymerization.
  • bio-acrylamide may be manufactured at such a location A.
  • location A may be a location at a central point over an oilfield or in a mining area comprising possibilities for storing and mixing monomers and optionally manufacturing bio-acrylamide.
  • an aqueous monomer premix may be provided to a number of different locations B for polymerization and further handling, for example in a tank truck. Such a process avoids the need to have available possibilities for storing and mixing the monomers at every location B.
  • the aqueous polyacrylamide compositions may be transported from location B, i.e. the location they are manufactured, to other locations C for using them.
  • the transport may be carried out using a truck.
  • location B may be on an oilfield at one specific wellsite but also other wellsites are provided with aqueous polyacrylamide compositions from the plant at location B.
  • location B may be at a central point in an oilfield area and may serve a number of different locations C with aqueous polyacrylamide compositions for use.
  • Such a process avoids the need to have available possibilities for storing and mixing the monomers and for polymerization at every site-of-use.
  • the two possibilities may be combined with each other, i.e. a monomer premix is transported from a location A to a location B, and the aqueous
  • locations A, B, and C are not specifically limited. Generally, in order to limit the costs of transporting the aqueous polyacrylamide compositions and/or monomer premix, the locations should not be that far apart from each other. Having said that, the abovementioned dimensions of mining areas or subterranean, oil-bearing formations should be kept in mind. So, even when location A is at a central point in an oilfield or mining area as outlined above, location A and location B may be apart from each other up a few hundred kilometers.
  • the distance between location A and location(s) B may range from 1 to 3000 km, in particular from 10 km to 3000 km, for example from 10 to 1500 km, and the distance between location B and locations C may be from 1 km to 500 km, for example from 5 km to 100 km.
  • Acrylamide may be synthesized by partial hydrolysis of acrylonitrile using suitable catalysts. It is known in the art to use copper catalysts or other metal containing catalysts and it is also known to use biocatalysts capable of converting acrylonitrile to acrylamide. Pure acrylamide is a solid, however, typically acrylamide -whether made by bio catalysis or copper catalysis- is provided as aqueous solution, for example as aqueous solution comprising about 50 % by wt. of acrylamide.
  • acrylamide can be distinguished from acrylamide obtained by means of copper catalysts or other metal containing catalysts because the latter still comprises at least traces of copper or other metals.
  • biocatalysts may still comprise traces of the biocatalyst.
  • an aqueous acrylamide solution which has been obtained by hydrolyzing acrylonitrile in water in presence of a biocatalyst capable of converting acrylonitrile to acrylamide.
  • a biocatalyst capable of converting acrylonitrile to acrylamide.
  • aqueous solutions of bio acrylamide for use in the process according to the present invention may be manufactured at another location, for example in a fixed chemical plant, and shipped to the manufacturing- site.
  • the manufacture of bio acrylamide is also performed (hereinafter designated as process step [0]).
  • Manufacturing bio acrylamide at location B or at location A in another embodiment saves significant transport costs.
  • Acrylonitrile is a liquid and may be transported as pure compound.
  • the molecular weight of acrylamide is ⁇ 34 % higher than that of acrylonitrile and acrylamide is typically provided as ⁇ 50 % aqueous solution. So, for a 50 % aqueous solution of acrylamide the mass to be transported is about 2.5-fold as much as compared to transporting pure acrylonitrile.
  • Transporting pure, solid acrylamide means transporting only ⁇ 34 % more mass as compared to transporting pure acrylonitrile, however, additional equipment for handling and dissolving the solid acrylamide is necessary at the site-of-use.
  • step [0] is only optional for the process according to the present invention, however, in a preferred embodiment of the invention, the process according to the invention includes step [0].
  • step [0] acrylonitrile is hydrolyzed in water in presence of a biocatalyst capable of converting acrylonitrile to acrylamide thereby obtaining an aqueous acrylamide solution.
  • Step [0] is performed at location B or at location A.
  • the storage unit comprises a storage vessel.
  • the volume of the storage vessel is not specifically limited and may range from 50 m 3 to 150 m 3 , for example it may be about 100 m 3 .
  • the storage vessel should be double walled and should be horizontal. Such a construction avoids installing a pit for the collection of any leakage thereby ensuring an easier and quicker relocation of the storage unit. Double-walled vessels may be placed on every good bearing soil.
  • the storage unit furthermore comprises means for charging and discharging the vessel, means for controlling the pressure in the vessel, for example a valve for settling low-pressure or overpressure,
  • thermocontroller and means for controlling the temperature of the acrylonitrile which preferably should not exceed 25° C. It furthermore may comprise means for measurement and control to the extent necessary.
  • relocatable storage units comprise relocatable cuboid, storage tanks, preferably double-walled tanks.
  • any considerable form, shape and size of container is suitable and applicable for the storage and/or provision of acrylonitrile in the sense of the present invention.
  • standard iso-tanks are applicable for the storage and/or provision of acrylonitrile.
  • Other examples comprise tank containers having a cuboid frame, preferably a frame according to the ISO 668 norm mentioned above and one or more storage vessels mounted into the frame. Such normed tank containers may be stacked and transported on trucks, railcars or ships in the same manner closed intermodal containers.
  • temperature control may be performed by any kind of temperature controlling unit. Temperature control may require -depending on the climatic conditions prevailing at locations A or B- cooling or heating the contents of the storage units. Regarding the monomers, temperature control typically means cooling, because it should be avoided that the monomers become too hot.
  • an internal heat exchanger may be used for cooling or heating, i.e. a heat exchanger mounted inside of the storage vessel. The coolant is provided to the heat exchanger by a suitable cooling or heating unit mounted outside of the storage vessel.
  • an external temperature control cycle for example a cooling cycle is used, which comprises a pump which pumps the monomer from the storage vessel through a heat exchanger and back into the storage vessel.
  • the temperature control cycle may be a separate, relocatable temperature control unit comprising pump and heat exchanger and which is connected with the storage vessel by pipes or flexible tubes.
  • the temperature control cycle may be integrated into relocatable storage unit. It may -for example- be located at one end of the unit besides the storage vessel.
  • Figure 1 schematically represents one embodiment of a monomer storage unit comprising an integrated temperature control cycle. It comprises a frame (1).
  • the frame may in particular be a cuboid frame preferably having standardized container dimensions which eases transport.
  • the relocatable storage unit furthermore comprises a double-walled vessel mounted into the frame comprising an outer wall (2) and an inner wall (3). I n other embodiments, there is no such frame (1) but the storage vessel is self-supporting.
  • the storage vessel is filled with acrylonitrile.
  • the storage unit furthermore comprises an external temperature control cycle comprising at least a pump and a temperature control unit. For cooling, acrylonitrile is circulated by means of a pump (4) from the storage vessel to the temperature control unit (5) and back into the storage vessel.
  • the amount of acrylonitrile to be circulated in the temperature control cycle in order to control the temperature at an acceptable level, for example below 25° C depends in particular on the outside temperature and the internal temperature envisaged. In one embodiment, 10% to 100% of the volume of acrylonitrile in the vessel may be circulated per hour.
  • Figure 2 represents schematically another embodiment of a monomer storage unit. It comprises a cuboic, preferably double-walled storage vessel (6). If necessary, the storage vessel (6) is connected with an external, relocatable temperature control unit (7).
  • Acrylonitrile may be provided to location A by road tankers, ISOtanks or rail cars and pumped into the relocatable storage vessel(s).
  • the acrylonitrile may be removed from the relocatable storage vessel through a bottom valve by means of gravity or it may be pumped, for example from the upper side using a suitable pump.
  • nitrile hydratase enzymes can be used, which are capable of catalyzing the hydrolysis of acrylonitrile to acrylamide.
  • nitrile hydratase enzymes can be produced by a variety of
  • microorganisms for instance microorganisms of the genus Bacillus, Bacteridium, Micrococcus, Brevibacterium, Corynebacterium, Pseudomonas, Acinetobacter, Xanthobacter, Streptomyces, Rhizobium, Klebsiella, Enterobacter, Escherichia Coli, Erwinia, Aeromonas, Citrobacter, Achromobacter, Agrobacterium, Pseudonocardia and Rhodococcus.
  • WO 2005/054456 discloses the synthesis of nitrile hydratase within microorganisms and therein it is described that various strains of
  • Rhodococcus rhodochrous species have been found to very effectively produce nitrile hydratase enzymes, in particular Rhodococcus rhodochrous NCIMB 41164.
  • Such microorganisms suitable as biocatalyst for the enzymatic conversion of acrylonitrile to acrylamide, which are known for a person skilled in the art, are able to be applied in a relocatable bioconversion unit according to the present invention.
  • the specific methods of culturing (or cultivation, or fermentation) and/or storing the microorganism as well as the respective sequences of polynucleotides which are encoding the enzyme, particularly the nitrile hydratase are known in the art, e.g.
  • WO 2005/054456, WO 2016/050816 are applicable in context of the present invention.
  • nitrile hydratase and amidase producing microorganisms may be used for converting a nitrile compound into the corresponding amide compound as it is described for example in WO 2016/050816.
  • N Hase nitrile hydratase producing microorganism
  • microorganism or“microorganism” or“biocatalysts” or the like
  • the terms“nitrile hydratase (N Hase) producing microorganism” or“microorganism” or“biocatalysts” or the like have the meaning to be able to produce (i.e. they encode and express) the enzyme nitrile hydratase (also referred to as, e.g., N Hase) either per se (naturally) or they have been genetically modified respectively.
  • Microorganisms which have been“genetically modified” means that these microorganisms have been manipulated such that they have acquired the capability to express the required enzyme NHase, e.g. by way of incorporation of a naturally and/or modified nitrile hydratase gene or gene cluster or the like.
  • nitrile hydratase (NHase) producing microorganism” or“microorganism” or“biocatalysts” or the like include the cells and/or the processed product thereof as such, and/or suspensions containing such microorganisms and/or processed products. It is also envisaged that the microorganisms and/or processed products thereof are further treated before they are employed in the embodiments of the present invention.“Further treated” thereby includes for example washing steps and/or steps to composition the microorganism etc. It is also envisaged that the microorganisms that are employed in the embodiments of the present invention have been pre-treated by a for example drying step.
  • the microorganism can be grown in a medium containing acetonitrile or acrylonitrile as an inducer of the nitrile hydratase.
  • the biocatalyst for converting acrylonitrile to acrylamide may be obtained from culturing the microorganism in a suitable growth medium.
  • the growth medium also called fermentation (culture) medium, fermentation broth, fermentation mixture, or the like, may comprise typical components like sugars, polysaccharides, which are for example described in WO 2005/054489 and which are suitable to be used for the culturing the microorganism of the present inventions to obtain the biocatalyst.
  • the fermentation broth preferably is removed in order to prevent putrefaction, which could result in a reduction of nitrile hydratase activity.
  • the methods of storage described in WO 2005/054489 may be applied according to the present invention ensuring sufficient biocatalyst stability during storage.
  • the storage does not influence biocatalytic activity or does not lead to a reduction in biocatalytic activity.
  • the biocatalyst may be stored in presence of the fermentations broth components. Preferred in the sense of the present invention is that the biocatalyst may be stored in form of a frozen suspension and may be thawed before use.
  • biocatalyst may be stored in dried form using freeze-drying, spray drying, heat drying, vacuum drying, fluidized bed drying and/or spray granulation, wherein spray drying and freeze drying are preferred.
  • Biocatalyst make-up The biocatalysts that are used according to the present invention in a relocatable plant can for example be cultured under any conditions suitable for the purpose in accordance with any of the known methods, for instance as described in the mentioned prior art of this specification.
  • the biocatalyst may be used as a whole cell catalyst for the generation of amide from nitrile.
  • the biocatalyst may be (partly) immobilized for instance entrapped in a gel or it may be used for example as a free cell suspension.
  • entrapment cross linkage such as glutaraldehyde- polyethyleneimine (GA-PEI) crosslinking, cross linking to a matrix and/or carrier binding etc., including variations and/or combinations of the aforementioned methods.
  • G-PEI glutaraldehyde- polyethyleneimine
  • the nitrile hydratase enzyme may be extracted and for instance may be used directly in the process for preparing the amide.
  • inactivated or partly inactivated cells such cells may be inactivated by thermal or chemical treatment.
  • the microorganisms are whole cells.
  • the whole cells may be pre-treated by a drying step. Suitable drying methods and/or drying conditions are disclosed e.g. in WO 2016/050816 and WO 2016/050861 and the know art can be applied in the context of the present invention for the use in a relocatable bioconversion unit.
  • microorganisms that are employed in the context of the present invention are in a preferred embodiment used in an aqueous suspension and in a more preferred embodiment are free whole cells in an aqueous suspension.
  • aqueous suspension thereby includes all kinds of liquids, such as buffers or culture medium that are suitable to keep microorganisms in suspension.
  • Such liquids are well- known to the skilled person and include for example storage buffers at suitable pH such as storage buffers which are used to deposit microorganisms, TRIS-based buffers, saline based buffers, water in all quality grades such as distilled water, pure water, tap water, or sea water, culture medium, growing medium, nutrient solutions, or fermentation broths, for example the fermentation broth that was used to culture the microorganisms.
  • storage buffers at suitable pH such as storage buffers which are used to deposit microorganisms, TRIS-based buffers, saline based buffers, water in all quality grades such as distilled water, pure water, tap water, or sea water, culture medium, growing medium, nutrient solutions, or fermentation broths, for example the fermentation broth that was used to culture the microorganisms.
  • the aqueous suspension is frozen and thawed before use, in particular without loss in activity.
  • the biocatalyst may be provided as powder or as aqueous suspension. If provided as powder it is frequently advisable to prepare an aqueous suspension before adding the catalyst into the bioconversion unit.
  • the biocatalyst suspension may be conducted by suspending the biocatalyst powder in water in a vessel comprising at least a mixing device, for example a stirrer, one or more inlets for water, the biocatalyst and optionally further additives and one outlet for the biocatalyst suspension.
  • the volume of the vessel may be for example from 0.1 m 3 to 1 m 3 .
  • the concentration of the biocatalyst in the aqueous biocatalyst suspension may be for example from 1 % to 30% by wt., for example from 10 to 20% by wt. relating to the total of all components of the aqueous suspension.
  • a biocatalyst suspension may be added directly to the bioconversion unit. In another embodiment a concentrated suspension may be diluted before adding it to the bioconversion unit.
  • the hydrolysis of acrylonitrile to acrylamide by means of a biocatalyst is carried out in a suitable bioconversion unit, preferably a relocatable bioconversion unit.
  • the bioconversion is performed by contacting a mixture comprising water and acrylonitrile with the biocatalyst.
  • the term“contacting” is not specifically limited and includes for example bringing into contact with, admixing, stirring, shaking, pouring into, flowing into, or incorporating into. It is thus only decisive that the mentioned ingredients come into contact with each other no matter how that contact is achieved.
  • step [0] comprises the following steps:
  • step (b) performing a bioconversion on the composition obtained in step (a).
  • the bioconversion can for example be conducted under any conditions suitable for the purpose in accordance with any of the known methods, for instance as described in the mentioned prior art of this specification like e.g. WO 2016/050817, WO 2016/050819, WO 2017/055518.
  • the conversion of acrylonitrile to the acrylamide may be carried out by any of a batch process and a continuous process, and the conversion may be carried out by selecting its reaction system from reaction systems such as suspended bed, a fixed bed, a fluidized bed and the like or by combining different reaction systems according to the form of the catalyst.
  • the method of the present invention may be carried out using a semi-batch process.
  • the term "semi-batch process" as used herein may comprise that an aqueous acrylamide solution is produced in a discontinuous manner.
  • a certain amount of acrylonitrile and the biocatalyst are placed in the bioconversion unit. Further acrylonitrile is then added during the bioconversion until a desired content of acrylamide of the composition is reached. After such desired content of acrylamide is reached, the obtained composition is for example partly or entirely recovered from the reactor, before new reactants are placed therein.
  • the acrylonitrile may be fed such that the content of acrylonitrile during step (b) is maintained substantially constant at a predetermined value.
  • the acrylonitrile content and/or the acrylamide content during step (b) may be monitored.
  • Methods of monitoring the acrylonitrile contents are not limited and include Fourier Transform Infrared Spectroscopy (FTIR).
  • FTIR Fourier Transform Infrared Spectroscopy
  • the heat-balance of the reaction may be used for monitoring the process. This means that monitoring via heat-balance method takes place by measuring the heat energy of the system during bioconversion and by calculating the loss of heat energy during the reaction in order to monitor the process.
  • the conversion of acrylonitrile to the acrylamide may preferably be carried out at atmospheric pressure, it may be carried out under pressure in order to increase solubility of acrylonitrile in the aqueous medium.
  • biocatalysts are temperature sensitive and the hydrolysis is an exothermic reaction temperature control is important.
  • the reaction temperature is not specifically restricted provided that it is not lower than the ice point of the aqueous medium. Flowever, it is desirable to carry out the conversion at a temperature of usually 0 to 50° C, preferably 10 to 40° C, more preferably 15 to 30° C.
  • Further suitable condition for the bioconversion according to the present invention are for example described in WO 2017/055518 and are preferably applicable for the method in a relocatable bioconversion unit.
  • biocatalyst may vary depending on the type of biocatalyst to be used, it is preferred that the activity of the biocatalyst, which is introduced to the reactor, preferably the relocatable bioconversion unit, is in the range of about 5 to 500 U per mg of dried cells of microorganism.
  • Methods for determining the ability of a given biocatalyst (e.g. microorganism or enzyme) for catalyzing the conversion of acrylonitrile to acrylamide are known in the art.
  • activity of a given biocatalyst to act as a nitrile hydratase in the sense of the present invention may be determined as follows: First reacting 100 m I of a cell suspension, cell lysate, dissolved enzyme powder or any other preparation containing the supposed nitrile hydratase with 875 m I of a 50 mM potassium phosphate buffer and 25 m I of acrylonitrile at 25° C on an Eppendorf tube shaker at 1,000 rpm for 10 minutes. After 10 minutes of reaction time, samples may be drawn and immediately quenched by adding the same volume of 1.4% hydrochloric acid. After mixing of the sample, cells may be removed by
  • the concentration of acrylamide shall particularly be between 0.25 and 1.25 mmol/l - if necessary, the sample has to be diluted accordingly and the conversion has to be repeated.
  • the enzyme activity may then be deduced from the concentration of acrylamide by dividing the acrylamide concentration derived from H PLC analysis by the reaction time, which has been 10 minutes and by multiplying this value with the dilution factor between HPLC sample and original sample.
  • Activities >5 U/mg dry cell weight, preferably >25 U/mg dry cell weight, more preferably >50 U/mg dry cell weight, most preferably >100 U/mg dry cell weight indicate the presence of a functionally expressed nitrile hydratase and are considered as nitrile hydratase in context with the present invention.
  • the concentration of acrylonitrile during the bioconversion should not exceed 6 % by wt. and may for example be in the range from 0.1 % by wt. to 6 % by wt., preferably from 0.2 % by wt. to 5 % by wt., more preferably from 0.3 % by wt. to 4 % by wt., even more preferably from 0.5 % by wt. to 3 % by wt., still more preferably from 0.8 % by wt. to 2 % by wt. and most preferably from 1 % by wt. to 1.5 % by wt., relating to the total of all components of the aqueous mixture.
  • WO 2016/050818 teaches a method of additional dosing of acrylonitrile, which is suitable to be used and applied in the present invention.
  • the concentration of acrylamide in the obtained solution is in the range from 10% to 80%, preferably in the range from 20% to 70%, more preferably in the range from 30% to 65%, even more preferably in the range from 40% to 60%, most preferably in the range from 45% to 55% by weight of acrylamide monomers.
  • the reaction should be carried out in such a manner that the final concentration of acrylonitrile in the final acrylamide solution obtained does not exceed 0.1 % by weight relating to the total of all components of the aqueous solution. Typical reaction times may be from 2 to 20 h, in particular 4 h to 12 h, for example 6 h to 10 h.
  • the reactor contents is allowed to further circulate for some time to complete the reaction, for example for 1 hour to 3 hours.
  • the remaining contents of acrylonitrile should preferably be less than 100 ppm ACN.
  • Suitable reactors for performing the bioconversion are known to the skilled artisan. Examples comprise vessels of any shape, for example cylindrical or spherical vessels, or tube reactors. In one embodiment, the continuous tank reactor as disclosed in WO 2016/006556 A1 may be used for bioconversion. Further suitable reactors for the bioconversion according to the present invention are for example described in US20040175809, EP2336346, EP2518154, JP2014176344,
  • Such reactors are preferably applicable for the process according to the present invention.
  • Such reactors comprise particularly a pumping circuit, a heat-exchanger and/or an agitating element.
  • the bioconversion unit is a relocatable bioconversion unit.
  • relocatable bioconversion unit is similar to the relocatable storage unit for acrylonitrile as described above. Using largely the same equipment for storing acrylonitrile or other monomers and the bioconversion step contributes to an economic process for manufacturing aqueous acrylamide solutions.
  • the bioconversion unit comprises a reaction vessel.
  • the volume of the reaction vessel is not specifically limited and may range from 10 m 3 to 150 m 3 , for example it may be about 20 m 3 to 50 m 3 .
  • the reaction vessel should be double walled and should be horizontal. Such a construction avoids installing a pit for the collection of any leakage thereby ensuring an easier and quicker relocation of the reaction unit.
  • the bioconversion unit furthermore comprises means for mixing the reaction mixture and means for controlling the temperature of the contents of the vessel.
  • the hydrolysis of acrylonitrile to acrylamide is an exothermal reaction and therefore heat generated in course of the reaction should be removed in order to maintain an optimum temperature for bioconversion.
  • the bioconversion unit furthermore usually comprises means for measurement and control, for example means for controlling the temperature or for controlling the pressure in the vessel.
  • the preferred bioconversion unit comprises an external temperature control cycle comprising a pump which pumps the aqueous reactor contents from the storage vessel through a heat exchanger and back into the storage vessel, preferably via an injection nozzle.
  • a separate, relocatable temperature control unit comprising pump and heat exchanger and which is connected with the
  • the temperature control cycle is integrated into the relocatable bioconversion unit. It may -for example- be located at one end of the unit besides the reaction vessel.
  • the reaction vessel may furthermore comprise means for mixing the aqueous reaction mixture, for example a stirrer.
  • the external temperature control cycle described above may also be used as means for mixing.
  • the stream of the aqueous reaction mixture which passes through the temperature control cycle and which is injected back into the reaction vessel causes a circulation of the aqueous reaction mixture within the reaction vessel which is sufficient to mix the aqueous reaction mixture.
  • no stirrer is used for the mobile bioconversion unit.
  • a stirrer is an additional mechanical device, which increases the technical complexity.
  • bioconversion can be ensured.
  • a transportation step is easier, since no stirrer as additional technical component has to be removed before transportation.
  • a bioconversion unit without a stirrer offers more flexibility in form, shape, mechanical stability requirements and size for the bioconversion unit. I n particular, a horizontal set-up for the relocatable
  • bioconversion unit can be realized easier without a stirrer and with mixing just via the external temperature control cycle.
  • Adding acrylonitrile to the contents of the bioconversion unit may be performed in various ways. It may be added into the reaction vessel or it may be added into the temperature control cycle, for example after the pump and before the heat exchanger or after the heat exchanger. I njecting acrylonitrile into the temperature control cycle ensures good mixing of the reaction mixture with freshly added acrylonitrile. Preferably, acrylonitrile is added between pump and heat exchanger.
  • FIG 3 schematically represents an embodiment of the relocatable bioconversion unit with an integrated temperature control cycle.
  • the bioconversion unit comprises a frame (10), a double-walled reaction vessel mounted into the frame comprising an outer wall (11) and an inner wall (12). Preferred volumes of the reaction vessel have already been mentioned. In other embodiments, the reaction vessel is self- supporting and there is no frame (10). The reaction vessel is filled with the reaction mixture.
  • the bioconversion unit furthermore comprises an external temperature control cycle comprising at least a pump (13) and a temperature control unit (14). The reaction mixture is circulated by means of a pump (13) from the reaction vessel to the temperature control unit (14) and is injected back into the storage vessel, preferably via an injection nozzle (16).
  • acrylonitrile is injected into the temperature control cycle thereby ensuring good mixing (15). It may be added before or after the temperature control unit.
  • Fig. 3 shows an embodiment in which acrylonitrile is added into the temperature control cycle between the pump and the heat exchanger.
  • the stream of reaction mixture injected back into the reaction vessel causes a circulation of the reaction mixture in the reaction vessel which ensures sufficient mixing of the contents of the reaction mixture.
  • the amount of reaction mixture cycled per hour through the temperature control cycle is chosen such that sufficient mixing to the contents of the reactor as well as sufficient temperature control is achieved.
  • the amount of reaction mixture cycled per hour through the temperature control cycle may be from 100 % to 1000 % of the total volume of the reaction mixture in the bioconversion unit, in particular from 200 % to 1000 % and for example from 500% to 800%.
  • Off-gases of the bioconversion unit may comprise acrylonitrile, acrylic acid and acrylamide. If necessary, according to the applicable rules such off-gases may be treated in a manner known in the art. For example, it may be possible to combust the off-gases.
  • all off-gases containing acrylonitrile, acrylic acid and acrylamide may be washed in a scrubber.
  • the scrubber vessel may have a volume of 1 m 3 to 100 m 3 , preferably a volume of 5 m 3 to 100 m 3 , more preferably a volume of 10 m 3 to 100 m 3 . It may be for example an ISOtank or relocatable storage vessel, preferably a double walled vessel.
  • the scrubber water may preferably be collected in a tank and it may be re-used in the next bio-conversion batch.
  • reaction vessel After bioconversion, the reaction vessel comprises an aqueous solution of acrylamide, which still comprises the biocatalyst suspended therein.
  • the biocatalyst preferably becomes removed completely, essentially completely, or partially before polymerization, however, removing the biocatalyst may not be absolutely necessary in every case. Whether it is necessary to remove the biocatalyst substantially depends on two factors, namely whether remaining biocatalyst negatively affects the polymerization and/or the properties of the polyacrylamide obtained, and/or the biocatalyst negatively affects the application of the obtained polyacrylamide solution. In one embodiment, at least 75 %, preferably at least 90 % by weight of the biomass -relating to the total of the biomass present- should be removed.
  • the method for removing the biocatalyst is not specifically limited. Separation of the biocatalyst may take place by for example filtration or centrifugation. In other embodiments, active carbon may be used for separation purpose.
  • the aqueous acrylamide solution comprising the biocatalyst is removed from the bioconversion unit, passed through a unit for removing the biocatalyst, and thereafter the aqueous acrylamide solution is filled into a suitable storage unit for acrylamide, preferably a relocatable storage unit for acrylamide as described above.
  • the aqueous acrylamide solution comprising the biocatalyst is removed from the bioconversion unit, passed through a unit for removing the biocatalyst and thereafter the aqueous acrylamide solution is filled directly into the monomer make-up unit, i.e. without intermediate storing in an acrylamide storage unit.
  • the aqueous acrylamide solution comprising the biocatalyst is removed from the bioconversion unit and is filled directly, i.e. without removing the biocatalyst, into the monomer make-up unit.
  • the biocatalyst is still present in course of monomer make-up and is removed after preparing the aqueous monomer solution (step [1]) as described below.
  • the aqueous acrylamide solution comprising the biocatalyst is removed from the bioconversion unit, passed through a unit for removing the biocatalyst and thereafter filled back into the bioconversion unit. I n order to ensure complete discharge of the bioconversion unit before re-filling it with the acrylamide solution, the unit for removing the biocatalyst should comprise a buffer vessel having a volume sufficient for absorbing the contents of the bioconversion unit.
  • biocatalyst removal are for example applicable for partwise and/or complete removal of the biocatalyst. Further, it is preferred, that the completely or partly removed biocatalyst may be reused for a subsequent bioconversion reaction.
  • acrylic acid or salts thereof may be used as comonomer besides acrylamide.
  • any kind of acrylic acid may be used for the process according to the present invention, for example acrylic acid obtained by catalytic oxidation of propene.
  • Acrylic acid may be provided in the acid form to locations A or B and it may become neutralized at the locations A and B.
  • a partially of fully neutralized aqueous solution of acrylic acid may be provided to locations A or B, for example an aqueous solution of sodium acrylate.
  • ammonium acrylate available by enzymatic hydrolysis of acrylonitrile may be used for carrying out the process according of the present invention (hereinafter also“bio acrylate”).
  • the manufacture of ammonium acrylate by enzymatic hydrolysis of acrylonitrile is also performed at locations A or B in a modular unit.
  • Suitable enzymes have been disclosed in WO 97/21827 A1 and the literature cited therein, and the publication describes also suitable conditions for carrying out the reaction.
  • the manufacture of bio-acrylate may be carried out using stirred tank reactors or loop reactors, and in particular, the relocatable
  • bioconversion unit described above may also be used.
  • Acrylic acid may be provided as pure compound, its molecular weight is ⁇ 36 % higher than that of acrylonitrile, and consequently more mass needs to become transported.
  • Step [1] Preparation of an aqueous monomer solution course of step [1] an aqueous monomer solution comprising at least water, acrylamide and optionally further water-soluble, monoethylenically unsaturated monomers is prepared. Step [1] may be performed at location A or at location B. Monomer storage
  • step [1] it is possible to run step [1] as just-in-time-process, i.e. providing the monomers when monomers are needed and directly withdrawing the monomers from the transport vessels.
  • step [1] it is possible to run step [1] as just-in-time-process, i.e. providing the monomers when monomers are needed and directly withdrawing the monomers from the transport vessels.
  • step [1] in order to ensure an uninterrupted operation is preferred to hold available at least some storage capacity for the monomers.
  • Acrylamide and other water-soluble, monoethylenically unsaturated monomers such as acrylic acid, ATBS, or DMA3Q, or mixtures thereof preferably may be stored in relocatable storage units. Details of such relocatable storage units for monomers have already been outlined above for acrylonitrile and we refer to the description above.
  • the monomers may be provided to locations A or B by road tankers, ISO tanks, or rail cars and pumped into the relocatable storage unit(s).
  • Relocatable storage units basically may have any shape and orientation. They may be for example cylindrical or rectangular and the storage units may be in horizontal or vertical orientation. The volume and the dimensions are only limited by the condition that the storage units are relocatable. The volume may be -by the way of example- up to 200 m 3 , for example storage units having a volume from 60 to 80 m 3 or from 120 to 180 m 3 .
  • a relocatable storage unit with integrated temperature control cycle as depicted in Figure 1 as shown above may be used for storing the monomers.
  • a relocatable storage unit with a separate, external temperature control cycle as depicted in Figure 2 as shown above may be used for storing the monomers.
  • the relocatable storage unit is a vertical cylinder having a conical section at its lower end and a bottom valve for removing the liquids.
  • Such a construction has the advantage that emptying can be affected simply by means of gravity. It may also comprise a cooling cycle.
  • the storage units may be connected with each other, for example by pipes, so that they can become filled and emptied together and furthermore, advantageously, only single cooling unit may be used to cool all storage units together.
  • the temperature of the monoethylenically unsaturated monomers such as acrylamide, acrylic acid, ATBS or DMA3Q should not exceed 25° C to 30° C.
  • Pure associative monomers as described above may be waxy solids and may be stored at room temperature. They may also be stored as aqueous solutions, for example as aqueous solutions comprising about 85 % by weight of the associative monomer. Because the amounts of associative monomers are significantly smaller than the amounts of other monoethylenically unsaturated monomers smaller storage units than that described above may be used.
  • Acidic monomers such as acrylic acid or ATBS are often partially or completely neutralized for polymerization using suitable bases.
  • Bases such as aqueous solutions of NaOH may also be stored in storage vessels as described above.
  • a cooling cycle is not necessary.
  • a heating such as a heating element in the vessel may be necessary because concentrated NaOH freezes at about +15° C.
  • an aqueous monomer solution is provided to a location B, wherein the aqueous monomer solution comprises water and 15 % to 50 % by weight, in particular from 15 % to 35 % by weight of water-soluble,
  • the water-soluble, monoethylenically unsaturated monomers comprise at least acrylamide, preferably bio acrylamide which preferably is manufactured in a preceding step [0].
  • the monomer concentration may be selected by the skilled artisan according to his/her needs. Details about adequately selecting the monomer concentration will be provided below.
  • the monomer concentration is from 15 % by weight to 24.9 % by weight, for example from 20 to 24.9 % by weight, relating to the total of all components of the aqueous monomer solution.
  • the aqueous monomer solution is
  • the water-soluble, monoethylenically unsaturated monomers to be used are mixed with each other. All monomers and optionally additives may be mixed with each other in a single step, but it may also be possible to mix some monomers and add further monomers in a second step. Also, water for adjusting the concentration of the monomers may be added. Water eventually used for rinsing lines in course of transferring the monomer solution into the polymerization unit, needs to be taken into consideration when adjusting the concentration. Further additives and auxiliaries may be added to the aqueous monomer solution.
  • Examples of such further additives and auxiliaries comprise bases or acids for adjusting the pH value.
  • the pH-value of the aqueous solution is adjusted to values from pH 4 to pH 7, for example pH 6 to pH 7.
  • the aqueous monomer solution comprises at least one stabilizer for the prevention of polymer degradation.
  • the stabilizers for the prevention of polymer degradation are what are called“free-radical scavengers”, i.e. compounds which can react with free radicals (for example free radicals formed by heat, light, redox processes), such that said radicals can no longer attack and hence degrade the polymer.
  • free-radical scavengers i.e. compounds which can react with free radicals (for example free radicals formed by heat, light, redox processes), such that said radicals can no longer attack and hence degrade the polymer.
  • the stabilizers may be selected from the group of non-polymerizable stabilizers and polymerizable stabilizers.
  • Polymerizable stabilizers comprise a monoethylenically unsaturated group and become incorporated into the polymer chain in course of polymerization.
  • Non-polymerizable stabilizers don’t comprise such
  • stabilizers are non-polymerizable stabilizers selected from the group of sulfur compounds, sterically hindered amines, N-oxides, nitroso compounds, aromatic hydroxyl compounds or ketones.
  • sulfur compounds include thiourea, substituted thioureas such as N,N‘-dimethylthiourea, N,N‘-diethylthiourea, N,N‘-diphenylthiourea, thiocyanates, for example ammonium thiocyanate or potassium thiocyanate, tetramethylthiuram disulfide, and mercaptans such as 2-mercaptobenzothiazole or 2- mercaptobenzimidazole or salts thereof, for example the sodium salts, sodium dimethyldithiocarbamate, 2,2‘-d ith iobis(benzothiazole), 4,4‘-thiobis(6-t-butyl-m- cresol).
  • substituted thioureas such as N,N‘-dimethylthiourea, N,N‘-diethylthiourea, N,N‘-diphenylthiourea
  • thiocyanates for example ammonium thio
  • sterically hindered amines such as l,2,2,6,6-pentamethyl-4- piperidinol and sulfur compounds, preferably mercapto compounds, especially 2- mercaptobenzothiazole or 2-mercaptobenzimidazole or the respective salts thereof, for example the sodium salts, and particular preference is given to 2- mercaptobenzothiazole or salts thereof, for example the sodium salts.
  • the amount of such non-polymerizable stabilizers -if present- may be from 0.1 % to 2.0 % by weight, relating to the total of all monomers in the aqueous monomer solution, preferably from 0.15 % to 1.0 % by weight and more preferably from 0.2 % to 0.75 % by weight.
  • the stabilizers are polymerizable stabilizers substituted by a monoethylenically unsaturated group.
  • stabilizers comprising monoethylenically unsaturated groups comprise (meth)acrylic acid esters of 1,2,2,6,- pentamethyl-4-piperidi nol or other monoethylenically unsaturated groups comprising l,2,2,6,6-pentamethyl-piperidin-4-yl groups.
  • suitable polymerizable stabilizers are disclosed in WO 2015/024865 Al, page 22, lines 9 to 19.
  • the stabilizer is a (meth)acrylic acid ester of 1,2,2,6,6- pentamethyl-4- piperidi nol.
  • the amount of polymerizable stabilizers -if present- may be from 0.01 to 2% by weight, based on the sum total of all the monomers in the aqueous monomer solution, preferably from 0.02 % to 1 % by weight, more preferably from 0.05 % to 0.5 % by weight.
  • the aqueous monomer solution comprises at least one non- polymerizable surfactant. Adding such surfactants in particular is advisable when associative monomers are used. For such kind of polyacrylamides, the surfactants lead to a distinct improvement of the product properties. Examples of suitable surfactants including preferred amounts have been disclosed in WO 2015/158517 Al, page 19, line, 23 to page 20, line 27. If present, such non-polymerizable surfactant may be used in an amount of 0.1 to 5% by weight, for example 0.5 to 3 % by weight based on the amount of all the monomers used. Also adding a defoamer may be advisable when associative monomers are used.
  • aqueous monomer solution basically any kind of equipment suitable for mixing monomers may be used for example a stirred vessel.
  • the preparation of the aqueous monomer solution is performed in a relocatable monomer make-up unit.
  • a relocatable monomer make-up unit is similar to the relocatable bioconversion unit as described above. Using largely the same equipment for storing acrylonitrile or other monomers, the bioconversion step and for monomer make-up contributes to an economic process for manufacturing aqueous acrylamide solutions.
  • the monomer make-up unit comprises a monomer make-up vessel in which the monomers, water and optionally further components are mixed.
  • the volume of the monomer make-up vessel is not specifically limited and may range from 10 m 3 to 150 m 3 , for example it may be about 20 to 90 m 3 .
  • the monomer make-up vessel should be double walled and should be horizontal. Such a construction avoids installing a pit for the collection of any leakage thereby ensuring an easier and quicker relocation of the monomer make-up unit.
  • the monomer make-up unit furthermore comprises means for controlling the temperature of the aqueous monomer solution.
  • the temperature of the aqueous monomer solution should be not more than 30° C, preferably not more than 25° C, for example from -5° C to +5° C.
  • the monomer make-up unit furthermore comprises means for measurement and control.
  • the monomer make-up unit comprises an external temperature control cycle comprising a pump which pumps the aqueous reactor contents from the storage vessel through a heat exchanger and back into the storage vessel, preferably via an injection nozzle.
  • the temperature control cycle may be a separate, relocatable temperature control unit comprising pump and heat exchanger and which is connected with the monomer make-up vessel by pipes or flexible tubes.
  • the temperature control cycle may be integrated into relocatable storage unit. It may - for example- be located at one end of the unit besides the monomer make-up vessel.
  • the monomer make-up vessel may be equipped with a stirrer for mixing the components of the aqueous monomer solution with each other.
  • the external temperature control cycle may be used as means for mixing.
  • the stream of the aqueous monomer mixture which passes through the temperature control cycle and which is injected back into the monomer make-up vessel causes a circulation of the aqueous reaction mixture within the reaction vessel which is sufficient to mix the aqueous reaction mixture.
  • FIG 4 represents a schematically one embodiment of the relocatable monomer make-up unit.
  • the monomer make-up unit comprises a frame (20), a double-walled monomer make-up vessel mounted into the frame comprising an outer wall (21) and an inner wall (22).
  • the monomer make-up vessel is self-supporting and a frame is not necessary.
  • the monomer make-up vessel is filled with the monomer mixture.
  • the monomer make-up unit furthermore comprises an external temperature control cycle comprising at least a pump (23) and a temperature control unit (24).
  • the monomer mixture is circulated by means of a pump (23) from the storage vessel to the temperature control unit (24) and is injected back into the storage vessel, preferably via an injection nozzle (25).
  • the monomers may be added directly into the storage vessel or into the temperature control cycle (26) as indicated in Figure 4.
  • the stream of monomer mixture injected back into the monomer make-up vessel causes a circulation of the monomer mixture in the storage vessel which ensures sufficient mixing of the contents of the monomer mixture.
  • a separate temperature control cycle may be used.
  • the monomers to be mixed with each other and with water are preferably mixed in the monomer make-up vessel, however in another embodiment, it is possible to add the monomers into the temperature control cycle. It is frequently advisable, to first add water to the monomer make-up vessel and then one or more further monomers and/or acids or bases and/or further additives. If acidic monomers such as acrylic acid are used, they should be neutralized before adding acrylamide. For copolymers comprising acrylic acid and acrylamide at first the necessary amount of water may be added into the vessel, followed by NaOH, thereafter acrylic acid and thereafter acrylamide.
  • additives which optionally might be present such as complexing agents, defoamers surfactants, or stabilizers as mentioned above may be dissolved in aqueous solvents, preferably water in suitable dissolution units and the solutions also added into the monomer make-up vessel.
  • aqueous monomer solution After mixing the aqueous monomer solution it is transferred from the monomer make-up vessel (or any other vessel serving as monomer make-up vessel such as the bioconversion unit) to the polymerization unit.
  • an aqueous monomer premix is prepared at another location A different from B and the aqueous monomer premix is transported to location B.
  • step [1] comprises at least three sub-steps [la], [lb], and [lc] of
  • the concentration of the monomers in the aqueous monomer premix preferably is from 40 % to 75 % by weight of relating to the total of all components of the aqueous monomer premix, more preferably 50 % to 75 % by weight and for example 60 % to 75 % by weight.
  • the concentration of the monomers in the monomer premix may be the same as that of the aqueous monomer solution, i.e. the monomer premix may be used without further dilution.
  • the concentration of the monomers in the monomer premix is higher as that of the aqueous monomer solution, i.e. the monomer premix is diluted before polymerization at location B.
  • the concentration of the monomers in the aqueous monomer premix is from more 50 % to 75 % by weight and the
  • polymerization is from 15 % to 50 % by weight.
  • the monomers in the monomer premix and any further components which may optionally be present have already been mentioned above.
  • all components in the aqueous monomer premix are in the same proportions as in the in the aqueous monomer solution, so at location B only water may optionally be added to adjust the concentration to the desired one.
  • the equipment for mixing the aqueous monomer premix may be the same as for the aqueous monomer solution and we prefer to the respective passages of the specification.
  • any kind of transport means suitable for transporting liquid chemicals may be used, for example road tankers, tank containers or transportable storage tanks. All of them preferably should be double-walled.
  • the temperature of the monomer premix in course of transport doesn’t become too high.
  • the temperature of the monomer premix should not exceed 25° C.
  • the aqueous monomer mix should not freeze. So, depending on the climatic conditions prevailing on the transport route and the composition of the aqueous monomer premix, it may be necessary to cool or heat the monomer premix during transport and therefore the transport means needs to be equipped with suitable means for temperature control. Transporting means for liquids comprising means for temperature control are known in the art.
  • step [2] the aqueous monomer solution prepared in step [1] is polymerized in the presence of suitable initiators for radical polymerization thereby obtaining an aqueous polyacrylamide gel.
  • Step [2] is carried out at location B.
  • polymer gel Due to the relatively high monomer concentration the aqueous monomer solution used solidifies in course of polymerization thereby yielding an aqueous polymer gel.
  • polymer gel has been defined for instance by L. Z. Rogovina et a I., Polymer Science, Ser. C, 2008, Vol. 50, No. 1, pp. 85-92.
  • the polymerization preferably is carried out under adiabatic conditions.
  • “Adiabatic” is understood by the person skilled in the art to mean that there is no exchange of heat with the environment. This ideal is naturally difficult to achieve in practical chemical engineering. I n the context of this invention,“adiabatic” shall
  • the polymerization of the aqueous monomer solution generates polymerization heat. Due to the adiabatic reaction conditions, the temperature of the
  • polymerization mixture increases in course of polymerization.
  • the polymerization is performed in the presence of suitable initiators for radical polymerization.
  • suitable initiators for radical polymerization are known to the skilled artisan.
  • redox initiators are used for initiating.
  • Redox initiators can initiate a free-radical polymerization even at temperatures of less than +5° C.
  • Examples of redox initiators are known to the skilled artisan and include systems based on Fe 2+ /Fe 3+ - H 2 0 2 , Fe 2+ /Fe 3+ - alkyl hydroperoxides, alkyl hydroperoxides - sulfite, for example t-butyl hydroperoxide - sodium sulfite, peroxides - thiosulfate or alkyl hydroperoxides - sulfinates, for example alkyl hydroperoxides/
  • hydroxymethane-sulfinates for example t-butyl hydroperoxide - sodium
  • water-soluble azo initiators may be used.
  • the azo initiators are preferably fully water-soluble, but it is sufficient that they are soluble in the monomer solution in the desired amount.
  • azo initiators having a 10 h t 1/2 in water of 40° C to 70° C may be used.
  • the 10-hour half-life temperature of azo initiators is a parameter known in the art. It describes the temperature at which, after 10 h in each case, half of the amount of initiator originally present has decomposed.
  • Suitable azo initiators having a 10 h t 1/2 temperature between 40 and 70° C include 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (10 h t 1/2 (water): 44° C), 2,2'-azobis(2-methylpropionamidine) dihydrochloride (10 h t 1/2 (water): 56° C), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine hydrate (10 h t 1/2 (water): 57° C), 2,2'-azobis ⁇ 2-[l-(2-hydroxyethyl)-2-imidazolin-2- yljpropane ⁇ dihydrochloride (10 h t 1/2 (water): 60° C), 2,2'-azobis(l-imino-l- pyrrolidino-2-ethylpropane) dihydrochloride (10 h t 1/2 (water): 67° C) or
  • azobis(isobutyronitrile) (10 h t 1/2 (toluene): 67° C).
  • a combination of at least one redox initiator and at least one azo initiator is used.
  • the redox initiator efficiently starts polymerization already at temperatures below +5° C. When the reaction mixture heats up, also the azo initiators decompose and also start polymerization.
  • the initiators are added to the aqueous monomer solution preferably as aqueous solutions.
  • the initiator raw material may be stored at location B in a cold storage container. Dissolving the initiators in water may be performed using suitable initiator make-up vessels.
  • the initiator make-up vessel may comprise a
  • the initiator make-up vessels furthermore may comprise means for mixing such as a stirrer. However, mixing may also be conducted by bubbling an inert gas through the aqueous mixture thereby simultaneously mixing and inerting the aqueous mixture.
  • the solutions may be filtered before use.
  • Solutions of azo initiators may be added into the monomer feed line while the aqueous monomer solution is transferred from the monomer make-up vessel to the polymerization unit.
  • solutions of azo initiators may already be added to the monomer make-up vessel, provided the monomer solution has already been cooled to temperatures below ambient temperature, preferably to less than +5° C and the 10 h t 1/2 temperature of the initiator is high enough so that the initiator doesn’t decompose prematurely.
  • Solutions of redox initiators are usually added into the monomer feed line.
  • Inertization may be preferably be performed in the monomer feed line.
  • Inert gases such as nitrogen or argon may be injected into the feed line. I n order to ensure effective mixing of the gas injected and the aqueous gases injected it is frequently desirable that the monomer feed line additionally comprises a static mixture.
  • the gas injected into the monomer feed line may be removed before entering into the first reactor device by means of a suitable degassing unit such as the degassing units described in WO 2003/066190 A1 or in CN 202492486 U.
  • the inertization may be performed in monomer make-up unit located at location B or a monomer storage unit located at location B, for example by bubbling nitrogen through the aqueous monomer solution is such units.
  • the polymerization is a continuous polymerization process comprising a pre polymerization step in a first reactor device and a second polymerization in a second reactor device.
  • the polymerization is carried out in a relocatable polymerization unit comprising a first reactor device comprising a positive displacement pump for partially polymerizing the aqueous monomer solution in the presence of initiators for radical polymerization, thereby obtaining a partially polymerized product, means for transferring the partially polymerized product to a second reactor device, and a second reactor device for continuing polymerization of the partially polymerized product. Details will follow below.
  • the relocatable polymerization unit comprises a support to which the reactor devices, means for transferring and optionally other parts of the relocatable polymerization unit are mounted.
  • the support may for example be a frame.
  • the relocatable polymerization unit is a container which comprises the reactor devices and other equipment.
  • the second reactor device is self-supporting, for example a vertical polymerization device and the first polymerization device is fixed on top of it.
  • step [2] comprises at least the following sub-steps
  • the first reactor device comprises at least one inlet for aqueous monomer solution and at least one outlet for partially polymerized product. It furthermore comprises a positive displacement pump which propels the aqueous monomer solution and partially polymerised product through the first reactor device.
  • Such positive displacement pumps may be either a reciprocating type or a rotary type.
  • Reciprocating pumps for instance involve the action of components moving back and forth within a chamber.
  • Reciprocating pumps are generally divided into two categories, the first comprising a diaphragm and the second involving a piston or plunger.
  • diaphragm pumps include either simplex and multiplex actions.
  • piston or plunger pumps include power piston or plunger pumps which may be single acting or double acting and include simplex, duplex, triplex, or multiplex actions.
  • the piston or plunger pumps may be scheme double acting which tend to be either simplex for duplex.
  • Rotary pumps include multiple rotor pumps or single rotor pumps.
  • a multiple rotor may be of the gear, lobe, circumferential piston or screw types.
  • Single rotor pumps may be of the vane, piston, progressing cavity or peristaltic types.
  • Gear pumps include pumps that comprise two or more impellers within a rotary pump casing. Typically, the impellers in a gear pump may take the form of toothed gear wheels, of helical gears or of lobed cams.
  • Multiple rotor pumps may be of the gear, lobe or circumferential piston types.
  • the first reactor device comprises a rotor within a stator and a multiplicity of cavities formed between the rotor and the stator in which the aqueous monomer solution enters and within which it is transferred as partially polymerizing aqueous monomer solution from the inlet to the outlet of the first reactor device. More preferably, the first reactor device comprises or is a progressive cavity pump.
  • the first reactor device would comprise an inlet at one end and an outlet at the other end.
  • the rotor and the stator may generally be regarded as being analogous to the rotor and the stator of a progressive cavity pump.
  • the first reactor device is a progressive cavity pump.
  • the rotor is typically of a rigid construction suitably being of an eccentric helix. Generally, it will be constructed of a metal, for instance steel.
  • the stator may generally form of a flexible material, for instance rubber or other elastic resinous material, and desirably formed as a sleeve which fits the rotor in order to create a multiplicity of cavities between the rotor and inner surface of the stator.
  • the exact number of cavities is not important but generally there will be at least 2 cavities and usually at least 4 cavities. In some cases, it may be desirable for there to be as many as 30 or more cavities but usually there would be no more than 20 cavities.
  • the rotor should fit within the stator in order to create a seal so as to prevent any significant seepage of monomer or polymerising material between the cavities.
  • the aqueous monomer solution should be introduced into a cavity at the inlet end of the first reactor device.
  • the polymerising aqueous monomer solution tends to progress through the first reactor device with essentially plug flow.
  • the rotor should suitably rotate at a speed of at least 0.25 rpm and typically at least 0.5 rpm.
  • the rotation speed may be as much as 50 rpm or more but is generally below 30 rpm and often below 20 rpm.
  • Preferably the rotation speed should be between 1 and 15 rpm.
  • the positive displacement pump may be powered by any suitable power source, for instance by a motor or other device that will drive the pump. It is possible that the power source may be located at either end of the first reactor device. However, it is preferred that the power source is located at the outlet end of the first reactor device.
  • the residence time of the polymerizing monomer or mixture of monomers from the inlet to the outlet of the first reactor device will usually be at least 20 seconds and often at least 30 seconds. Generally, the residence time would not exceed 30 minutes and typically no more than 20 minutes and often not more than 10 minutes. Desirably the residence time should be between 1 and 10 minutes, for example between 1 and 5 minutes.
  • no more than 25 % by weight of the monomers should have been polymerized in the partially polymerized product as it exits the outlet at the first reactor device, preferably no more than 15%, more preferably no more than 10 % by weight.
  • above 1 % by weight of the monomers should have been polymerized in the partially polymerized product, preferably at least 2 % by weight or even at least 3% by weight.
  • the flow characteristics of the partially polymerized product entering the second reactor device may also facilitate the flow of the polymerising product inside the second reactor device.
  • the partially polymerized product enters the second reactor device suitably through an inlet at a first end and continues to polymerise within the second reactor device and the polymer product is removed from an outlet suitably at the second end of the second reactor device.
  • the partially polymerized product continues to polymerize it moves within the second reactor device from the first end to the second end such that the layers of polymerising material should transfer within the second reactor device without any significant mixing with layers of polymerising material.
  • the temperature of the aqueous monomer solution should be less than 30° C when it enters into the first reaction device, preferably less than 20° C.
  • the temperature raises Due to the polymerization heat generated, the temperature raises.
  • the temperature raise depends in particular on the monomer concentration in the aqueous monomer solution and on the percentage of monomers polymerized.
  • the temperature of the partially polymerized product may be from 5° C to 25° C higher at the outlet of the first reactor device than the temperature of the aqueous monomer solution at the inlet of the first reactor device.
  • the viscosity of the partially polymerized product which exits the first reactor device is higher than that of the aqueous monomer solution when it enters into the first reactor device. It may be up to 50,000 mPas, preferably up to 30,000 mPas. The viscosity suitably may be at least 1,000 mPas. A particularly suitable range of viscosity has been found to be between 5,000 mPas and 25,000 mPas.
  • the viscosity can be measured by a suitable viscosity measuring instrument which can be mounted in line.
  • a suitable instrument includes the In-Line Viscometer from Cambridge Viscosity I ncorporated of Medford, Massachusetts, USA.
  • the general literature describes in line this rheometry instruments, for instance "I n Line
  • step [2-2] the partially polymerized product is transferred to a second reactor device, comprising at least an inlet and an outlet.
  • the outlet of the first reactor device and the inlet of the second reactor device are connected with each other.
  • the connection is closed in order to avoid that the partially polymerized products gets into contact with atmospheric oxygen.
  • suitable connections for transferring the partially polymerized product comprises pipes, tubing or flexible tubes, such as flexible metal tubes.
  • only the pressure of the positive displacement pump of the first reactor device may be used to transport the partially polymerized product through the connection between the two reactor devices.
  • the connection between the two reactor devices may comprise additional means for supporting the transport, for example additional pumps or screw conveyors.
  • the second reactor device preferably is pressurized by means of an inert gas, for example an inert gas having a pressure from 1.1 to 10 bar in order to ease removal of the aqueous polyacrylamide gel form the second reactor device.
  • an inert gas for example an inert gas having a pressure from 1.1 to 10 bar in order to ease removal of the aqueous polyacrylamide gel form the second reactor device.
  • the transfer of the partially polymerized product through the connection into the second reactor device should be quick in order to ensure that the polymerization does not continue substantially while being transferred.
  • step [2-3] the partially polymerized product is fed continuously into the second reactor device through an inlet and the polymerization is continued in the second reactor device thereby yielding an aqueous polyacrylamide gel which is removed from the outlet of the second reactor device.
  • the further reactor device may be mounted substantially vertically. It may be desirable for the first end to be the upper end of the second reactor device and the second end to be the lower end. In this case the partially polymerised product would enter the second reactor device through the inlet at the upper end (first end) and the polymer product to be removed from an outlet at the lower end (second end) of the second reactor device. The partially polymerized product would continue to polymerize within the second reactor device as it descends within the second reactor device.
  • the second reactor device may be an upright column type reactor with an inlet, side walls and an outlet.
  • the cross-section of the second reactor device may be circular, elliptical or any polygonal shape.
  • the walls of the second reactor device may be essentially parallel, for instance forming a cylinder and therefore being of a tubular construction.
  • the second reactor device may be conical or at least contain conical sections.
  • the second reactor device may comprise at least one tubular or at least one conical section or a combination of at least one tubular and at least one conical section.
  • the second reactor device is either a vertical fully conical reactor having an angle ( a ) between top diameter (dl) of the second reactor device and inner wall of the reactor is smaller than 90° but larger than 45° or is made up of 2 to 5 connected vertical fully conical parts, which are on top of one another, each having an angle between top diameter of a part and inner wall of smaller than 90° but larger than 45° .
  • the second reactor device is a vertical fully conical reactor having an angle ( a ) between top diameter (dl) of the reactor and inner wall of the reactor of smaller than 90° but larger than 45° .
  • the angle is smaller than 90° , but larger than 60° . More preferably, the angle is smaller than 90° , but larger than 70° . Even more preferably, the angle is smaller than 90° , but larger than 80° . Most preferably, it is smaller than 87° and larger than 83° .
  • the ratio of top diameter (dl) to bottom diameter (d2) of the reactor can be from 1.1/1 to 24/1. Preferably, it is from 2/1 to 10/1. More preferably, it is from 3/1 to 8/1. Most preferably, it is from 5/1 to 6/1.
  • the vertical fully conical parts can be the same or different.
  • the ratio of top diameter to bottom diameter of one of the vertical conical parts can be from 1.1/1 to 24/1. Preferably, it is from 1.1/1 to 10/1. More preferably, it is from 1.2/1 to 5/1. Most preferably, it is from 1.5/1 to 3/1.
  • the second reactor device can be made of any suitable material, for example steel, mild steel, stainless steel or glass fibre reinforced plastic.
  • the inner wall of the reactor may be coated with an anti-adhesive coating such as polytetrafluoro- ethylene (PTFE), perfluoroalkoxy copolymer (PFA) or fluoro ethylene propylene (FEP).
  • PTFE polytetrafluoro- ethylene
  • PFA perfluoroalkoxy copolymer
  • FEP fluoro ethylene propylene
  • the partially polymerized product may enter the second reactor device at a speed that allows a residence time of about 2 to 6 hours.
  • the residence time depends on the monomer(s) used and can be adjusted by a person skilled in the art.
  • the polymerization preferably is carried out under adiabatic conditions.
  • the temperature of the polymerizing mixture increases further.
  • the temperature may increase to 50 to 95° C in course of step [2-3], for example to 55° C to 85° C.
  • the reactor is pressurized with an inert gas, such as nitrogen or argon, which may be injected at the end of the reactor, preferably the upper end of the reactor at which also the inlet of the reactor is located.
  • the inert gas pressure in the second reactor device may be from 1.1 to 10 bar, in particular from 1.2 to 5 bar, and for example from 1.5 to 3 bar.
  • the content of unreacted monomer in the aqueous polyacrylamide gel obtained is below 0.15% by weight based on the weight of the polyacrylamides.
  • Step [3] Transferring the aqueous polyacrylamide gel to a relocatable
  • step [3] the aqueous polyacrylamide gel obtained in course if step [2] is transferred to a relocatable comminution unit.
  • the outlet of the second reactor device may be connected with the comminution unit.
  • Said connection may simply be a pipe, a tube or a flexible tube but it may also comprise means for transporting the gel such as for example pumps, screw conveyors or belt conveyors.
  • the connection comprises a pump.
  • a pump may be helpful in achieving a constant feed rate and a constant pressure for the consecutive step [4] of comminuting the polyacrylamide gel and mixing it with an aqueous liquid.
  • a pump may in particular be helpful, if it is the aim to convey the polyacrylamide gel through a comminution unit in course of step [4] causing a significant pressure drop, such as for example conveying the polyacrylamide gel through a hole perforation plate and/or conveying the gel through a relatively long pipe.
  • a pipe for transporting the gel in one embodiment of the invention, also some water may be injected into the pipe in such a manner that a water-film may be generated at the walls of the pipe.
  • a water-film facilitates the transport of the gel in the pipe by reducing friction and therefore reducing pressure loss.
  • Step [4] Comminuting the aqueous polyacrylamide gel and mixing with an aqueous liquid
  • the aqueous polyacrylamide gel is comminuted and mixed with an aqueous liquid, thereby obtaining an aqueous polyacrylamide composition having a concentration of 0.05 to 14.9 % by weight of polyacrylamides, relating to the total of all components of the aqueous polyacrylamide composition.
  • Step [4] is carried out at location B.
  • the concentration of the aqueous polyacrylamide composition may be a solution or a (soft) solid.
  • the composition is pumpable.
  • polyacrylamide composition is from 2.1 % to 14.9 % by weight, relating to the total of all components of the aqueous polyacrylamide composition, in particular from 2.1 % by weight to 10 % by weight, preferably form 3.1 % by weight to 10 % by weight. More preferably, the concentration is from 3.1 % by weight to 7 % by weight, for example from 4 % by weight to 6 % by weight.
  • a homogeneous mixture of polyacrylamides and aqueous liquid should be obtained, i.e. a homogeneous aqueous polyacrylamide composition should be obtained.
  • the invention shall not be limited to such an embodiment and shall encompass also aqueous polyacrylamide compositions which are not absolutely homogeneous.
  • Comminution and mixing with an aqueous liquid may be carried out simultaneously, they may be separate steps to be carried out consecutively or any other
  • comminution are more aqueous liquid thereafter.
  • at least some amount of aqueous liquid should be added already in course of comminution.
  • the aqueous liquid used for mixing with the aqueous polyacrylamide gel comprises water.
  • water includes any kind of water such as desalinated water, fresh water or water comprising salts, such as brines, sea water, formation water, produced water or mixtures thereof.
  • the aqueous liquid may comprise organic solvents miscible with water, however the amount of water relating to the total of all solvent should be at least 70 % by weight, preferably at least 90 % by weight, more preferably at least 95 % by weight.
  • a“winterized” polyacrylamide composition having a lowered freezing point. Such an embodiment may be helpful if the compositions are transported and/or stored in cold regions, for example in arctic regions.
  • the aqueous liquid comprises only water as solvent.
  • the aqueous liquid may optionally also comprise additives such as for example surfactants, complexing agents, defoamers, biocides, bases, acids of the like.
  • additives such as for example surfactants, complexing agents, defoamers, biocides, bases, acids of the like.
  • kind and amount of such additives may be selected according to the intended use of the aqueous polyacrylamide solution.
  • additives may also be added at a later stage, for example after complete dissolution of the aqueous
  • the particle size of the aqueous polyacrylamide gel pieces obtained in course of comminution is not specifically limited.
  • particles of aqueous polyacrylamide gel should conveniently have a size such that at least two dimensions are no more than 1 cm, preferably no more than 0.5 cm.
  • three dimensions of the aqueous polyacrylamide gel pieces should be no more than 1 cm, preferably no more than 0.5 cm.
  • There is no lower limit necessary for the aqueous polyacrylamide gel pieces since the smaller the pieces the easier it will be for the polymer to dissolve.
  • aqueous polyacrylamide gel pieces may have a size such that three dimensions are as low as 0.1 cm. Often the aqueous polyacrylamide gel pieces tend to have three dimensions each of from 0.1 cm to 0.5 cm.
  • any kind of comminution means may be used for disintegrating the aqueous polyacrylamide gel into smaller particles.
  • suitable means for comminuting aqueous polyacrylamide gels include cutting devices such as knives or perforated plates, crushers, kneaders, static mixers or water-jets.
  • Suitable comminution units may be connected directly with the polymerization unit.
  • the comminution unit may not be directly connected with the polymerization unit but distant from it and the polyacrylamide gel is transported to the comminution unit, for example by screw conveyors, belt conveyors, or pumps.
  • the comminution unit preferably also is a relocatable unit.
  • the second reactor device preferably is tubular and/or conical and is in vertical orientation with a bottom opening at its lower end.
  • a bottom opening may be connected with the comminution unit, either directly or with a pump as outlined above in between.
  • the second reactor device comprises a tubular section and a conical section at its lower end. It furthermore comprises an inlet (30) and an outlet (31) at it lower end.
  • the partially polymerized product (32) from the first reactor device enters through the inlet (30) into the second reactor device where polymerization continues.
  • polyacrylamide gel (33) in the polymerization unit enters through the bottom opening (31) into a pump (34).
  • the pump transports the aqueous polyacrylamide gel into a comminution unit (35) and the comminuted polyacrylamide gel (36) leaves the comminution unit for further processing.
  • the aqueous polyacrylamide gel is conveyed through a static cutting device, such as knives or metal grills thereby obtaining smaller gel particles.
  • a static cutting device may be located directly under the bottom opening of the second reactor device.
  • a pump as described above may transport the polyacrylamide gel to a more distant static cutting device.
  • Suitable static cutting devices comprise perforated plates or metal grills, such as disclosed, for instance, in US 4,605,689.
  • the aqueous gel is conveyed through the static cutting device together with an aqueous liquid as described above, preferably water, thereby yielding a mixture of particles of an aqueous polyacrylamide gel in an aqueous liquid.
  • the aqueous liquid is metered in before the gel enters into the static cutting device, for example into the connection between the bottom opening and the static cutting device or into the connection between the pump and the static cutting device.
  • the entire amount of the aqueous liquid to achieve the desired concentration is added at this stage but only a portion of it.
  • already 1 % of the total amount of aqueous liquid significantly improves conveying the aqueous
  • the aqueous polyacrylamide gel is conveyed through a perforated plate.
  • An extruder or a screw conveyor or pump may be used to generate the necessary pressure for passing the perforated plate.
  • a number of separate cords of aqueous acrylamide gel are formed. They may be cut by a rotating knife or may be flushed away by means of a water jet and conveyed to the dissolution unit.
  • the aqueous polyacrylamide gel is conveyed together with an aqueous liquid through a static mixer thereby yielding a mixture of particles of an aqueous polyacrylamide gel in an aqueous liquid.
  • a static mixer may be used.
  • the aqueous liquid is metered in the product line before the aqueous polyacrylamide gel enters into the static mixer, for example into the connection between the bottom opening and the static mixer, or into the connection between the pump and the static mixer.
  • the entire amount of aqueous liquid necessary for achieving the desired concentration is already added at this stage. In another embodiment, not the entire amount is added.
  • the aqueous polyacrylamide gel is cut into pieces of aqueous polyacrylamide gel by means of a water-jet cutting unit.
  • the water-jet cutting unit cuts the aqueous polyacrylamide gel by means of at least one water jet at a pressure of at least 150*10 5 Pa thereby obtaining a mixture of particles of an aqueous polyacrylamide gel in an aqueous liquid.
  • the surrounding wall section of the water jet cutting unit is a tubular section, a conical section or a combination of tubular and conical sections.
  • the aqueous polyacrylamide gel may then enter into the water jet cutting unit from one end, pass through the cutting stage to reduce the size of the aqueous
  • polyacrylamide gel and desirably the so formed aqueous polyacrylamide gel pieces should exit from the outlet.
  • Aqueous liquid from the cutting stage desirably should also exit from the outlet.
  • a mixture of aqueous polyacrylamide gel pieces and water optionally comprising dissolved polymer gel may be formed in the cutting stage.
  • the surrounding wall section of the water jet cutting unit may be in any suitable orientation. Nevertheless, it is preferred that the surrounding wall section is substantially upright, with the inlet at the upper end and the outlet at the lower end.
  • the upper end may be preferably connected directly with the bottom opening of the second reactor device by suitable means.
  • the passage of the aqueous polyacrylamide gel may be by gravity alone or may be fed into the water jet cutting unit under pressure, for instance, by pumping, mechanically feeding, by gas pressure or by the action of a vacuum.
  • the at least one water-jet has a pressure of at least 150*10 5 Pa.
  • the pressure may be considerably higher than this, for instance, up to 10,000*10 5 Pa. However, it is not normally necessary for the pressure to be as high as this and lower pressures, for instance no higher than 7,500*10 5 Pa are usually adequate.
  • the pressure of the water jet in the cutting unit has a pressure of from 150*10 5 Pa to 5,000*10 5 Pa, preferably from 200*10 5 Pa to 2,000*10 5 Pa, more preferably from 250*10 5 Pa to 1000*10 5 Pa.
  • the water jet would flow from a nozzle having a nozzle orifice of suitable diameter.
  • nozzle we mean a device which is designed to control the direction or the characteristics of a fluid flow, including to increase the velocity, as it exits.
  • the nozzle orifice diameter should be from 0.1 mm to 3.00 mm, for instance, from 0.25 mm to 2.00, or from 0.25 mm to 1.00 mm, suitably from 0.30 mm to 0.90 mm, desirably from 0.40 mm 0.80 mm. It may be desirable to employ a multiplicity of nozzles on a head in which each nozzle delivers a stream of aqueous liquid at the aforementioned pressures of at least 150 * 10 5 Pa.
  • the number of nozzles may be at least 2, for instance, from 2 to 10 nozzles.
  • the nozzles may be arranged in one plane or in different planes and angles.
  • the nozzles may be arranged in such a way, for instance over a domed surface of the head, that the multiplicity of streams radiate out in different axis.
  • Such a multiplicity of nozzles may be arranged such that the streams of aqueous liquid from an array each travelling in different directions.
  • the at least one nozzle may rotate or oscillate.
  • the at least one nozzle oscillates.
  • Such oscillation of the nozzle may produce a fan shaped water stream sweep pattern.
  • it may be of particular value to employ a multiplicity of nozzles which can oscillate.
  • the number of nozzles may be from 2 to 8, preferably from 2 to 6.
  • a multiplicity of nozzles are arranged on at least one head, each head containing from 2 to 10 nozzles. It may be desirable for the multiplicity of heads, for instance, from 2 to 10 heads, each head containing the multiplicity of nozzles, to be employed. In this case each of the heads may separately oscillate.
  • Such multiplicity of nozzles or multiplicity of heads each may be positioned circumferentially with respect to the aqueous polyacrylamide gel, such that the water streams extend inwardly.
  • the multiplicity of nozzles and/or multiplicity of heads may be positioned evenly such that the distance between all adjacent nozzles is equal. Alternatively, they may not to be evenly spaced.
  • the aqueous polyacrylamide gel would then pass within the circumferentially positioned nozzles and be cut by the multiplicity of aqueous liquid streams.
  • the at least one oscillating nozzle or head may be moved by a suitable actuator mechanism.
  • Each oscillating nozzle may have a sweep of up to 180° .
  • the sweep may be 30° to 180° , for instance from 35° to 75° .
  • the exact range of the sweep will often depend on the exact number of nozzles employed.
  • the oscillation frequency should for instance be up to 50 s 1 (cycles per second), typically from 0.5 s 1 to 50 s 1 .
  • each of the at least one nozzles or at least one head may rotate circumferentially about the aqueous polyacrylamide gel.
  • the circumferentially arranged at least one nozzle or at least one head rotates it may be desirable that each nozzle or each head may independently oscillate as given above. Alternatively, it may be desirable that when the
  • At least one nozzle or at least one head rotates they may not oscillate.
  • the rotation of the at least one nozzle or at least one head may be achieved by a suitable drive mechanism.
  • the at least one nozzle rotates and the stream of aqueous liquid generated forms a circular sweep pattern.
  • the at least one nozzle may be a multiplicity of nozzles housed on at least one head. Such at least one rotating nozzle may be rotated by the action of a suitable motorized drive mechanism.
  • the at least one rotating nozzle, or at least one head is mounted centrally and the aqueous liquid stream extends substantially perpendicular to the axis of the direction of the incoming aqueous polyacrylamide gel.
  • the aqueous liquid stream sweep pattern is disc shaped.
  • the rotating nozzle or head which is/are mounted centrally, may generate at least one stream of liquid which is not perpendicular to the direction of the incoming aqueous polyacrylamide gel, but instead is angled such that the at least one aqueous liquid stream sweep pattern is a cone shaped, for instance, an upright cone where the at least one aqueous liquid stream is angled downwards, or an inverted cone where the at least one aqueous liquid stream is angled upwards.
  • the angle is no more than 50° up or down from the position which is perpendicular to the direction of the incoming aqueous polyacrylamide gel.
  • this angle should be from 5° to 45° , more preferably from 10° to 35° , particularly from 15° to 25° .
  • the at least one rotating nozzle or rotating head is not mounted centrally but off center.
  • the rotating nozzle may be located at or close to the wall of the surrounding wall section.
  • the nozzle or head would be orientated such that it generates at least one eccentric aqueous stream sweep pattern.
  • the rotating nozzle or rotating head may rotate at a frequency of up to 3000 rpm (revolutions per minute (i.e. 50 s 1 cycles per second)).
  • the rotational frequency may be selected by the skilled artisan.
  • a higher rotational frequency for example a rotational frequency from 500 rpm to 3000 rpm
  • the water-jet cutting unit will divide the aqueous polyacrylamide gel into numerous smaller sized pieces.
  • the aqueous polyacrylamide gel pieces should conveniently have a size such that at least two dimensions are no more than 2 cm, preferably no more than 1 cm, more preferably no more than 0.5 cm.
  • three dimensions of the aqueous polyacrylamide gel pieces should be no more than 2 cm, preferably no more than 1 cm, preferably no more than 0.5 cm.
  • the aqueous polyacrylamide gel pieces have three dimensions each of from 0.1 to 0.5 cm.
  • the water-jet cutting unit may also comprise a sieve tray beneath the at least one stream of aqueous liquid. This is intended to prevent oversized aqueous
  • the sieve tray should have openings of a size corresponding to the maximum size of aqueous
  • the sieve tray may be a mesh formed by a plurality of inter-meshing wires or bars.
  • the sieve tray may be formed as a surface with a plurality of holes cut therein, for instance, analogous to a colander.
  • the sieve tray should be a static device. It should extend to cover the whole area below where the aqueous polyacrylamide gel cutting is taking place.
  • the sieve tray may be affixed to the surrounding wall section.
  • additional streams of aqueous liquid are directed at the surface of the sieve tray in order to facilitate the size reduction of the oversized aqueous polyacrylamide gel lumps captured by the tray. It may be desirable to employ one or more aqueous liquid streams of high-pressure, for instance, of at least 150*10 5 Pa in order to facilitate the cutting of the oversized aqueous polyacrylamide gel lumps such that the aqueous polyacrylamide gel is cut into small enough pieces to pass through.
  • a curtain of aqueous liquid is provided on the inside of the surrounding wall section. This curtain of aqueous liquid may help prevent aqueous
  • Such curtain of aqueous liquid may be produced by providing a secondary aqueous liquid supply.
  • the pressure of the aqueous liquid should be below 30 bar, for instance, from 3 bar to 20 bar, desirably from 5 bar to 10 bar.
  • the water may be fed to a ring main, in the form of an annulus, and mounted on the inside of the surrounding wall section.
  • the ring main or annulus should be mounted at or close to the top of the surrounding wall section to provide the maximum protection by the curtain of water.
  • the aqueous liquid flows from the ring main or annulus down the inner surface of the wall of the surrounding wall section as a curtain.
  • FIGS. 6 to 9 represent schematically several embodiments of a water-jet cutting unit for use in the present invention.
  • FIG 6 illustrates schematically a water-jet cutting unit for cutting the aqueous polyacrylamide gel.
  • the device comprises a surrounding wall section (101), in this case a tubular wall, surrounding a centrally mounted nozzle (102) which rotates and is driven by a motor (103) or propelled by the flowing aqueous liquid, which forms the stream.
  • the nozzle is supported on a fixed mounting (104).
  • a high-pressure stream of aqueous liquid (105) is ejected perpendicular to the axis of the device and rotates as the nozzle rotates.
  • the stream of aqueous liquid forms a circular disc pattern as the nozzle rotates.
  • the nozzle is fed from a aqueous liquid feed line (106) supplied by a high pressure aqueous liquid source (107).
  • a sieve tray (108) is located beneath the stream of water and prevents oversized polymer lumps from passing.
  • a secondary aqueous liquid supply (109) of low pressure is fed into a ring main (110), in the form of an annulus, located at the upper end of the tubular wall.
  • Aqueous liquid flows out of the annulus to form a water curtain (111), which prevents aqueous polyacrylamide gel from sticking to the tubular wall.
  • Aqueous polyacrylamide gel (113) enters the tubular wall from above and passes down the device where it is cut by the high-pressure water stream to form cut hydrated polymer pieces which are small enough to pass through the sieve tray and then the cut aqueous polyacrylamide gel pieces (114) exit from the bottom of the device.
  • Figure 7 illustrates a device analogous to the device of Figure 6 except the nozzle (102) provides a high-pressure stream of water which is angled downwards (105A) to form a conical pattern as the nozzle rotates.
  • the sieve tray is in the shape of an upright cone (108A). All other features are as in the case of Figure 6.
  • Figure 8 illustrates a device analogous to the device of Figure 6 except the nozzle (102) provides a high-pressure stream of water which is angled upwards (105B) to form a conical pattern as the nozzle rotates.
  • the sieve tray is in the shape of an inverted cone (108B). All other features are as in the case of Figure 6.
  • Figure 9 illustrates a device analogous to the device of Figure 6 except the nozzle (102) is positioned off center to provide an eccentric high-pressure water stream (105) sweep pattern. All other features are as in the case of Figure 6.
  • the described methods of comminuting the aqueous polyacrylamide gel may also combined with each other.
  • water-jet cutting is combined with cutting by means of a static cutting member.
  • a static cutting member is integrated with the water-jet cutting unit and consequently, the water-jet cutting comprises at least one static cutting member.
  • the at least one static cutting member may for instance be one or more knives, blades, cutting wires or any combination thereof.
  • the at least one cutting member may consist of a multiplicity of knives or blades mounted on the wall of the tubular section circumferentially with the knives or blades extending inwardly.
  • the at least one cutting member may be knives or blades mounted from a central position with the knives or blades extending out radially.
  • the at least one cutting member may be a mesh of knives, blades or cutting wires.
  • the static cutting member where employed, should extend over the whole cross-section of the surrounding wall section.
  • the aqueous polyacrylamide gel may be cut by contacting the at least one static cutting member before contacting the at least one stream of aqueous liquid.
  • FIG 10 illustrates schematically a water-jet cutting unit combined with static cutting means.
  • the device comprises a surrounding wall section (101), in this case a tubular wall, into which the aqueous polyacrylamide gel (113) enters from the top.
  • a mesh of cutting blades (112) initially cuts the hydrated polymer into strands as it descends.
  • Pligh-pressure water streams (105) are ejected from nozzles (102) that are positioned circumferentially.
  • the nozzles each oscillate laterally to each generate a fan shaped water stream sweep pattern (115) which cut the polymer strands as they descend.
  • the oscillation of the nozzles is driven by an actuator (not shown) in each case.
  • the aqueous polyacrylamide pieces (114) exit through the bottom of the device.
  • water-jet cutting may be combined with static mixing.
  • the aqueous mixture comprising pieces of polyacrylamide gel leaving the water-jet cutting unit is conveyed through at least one static mixer. Additional aqueous liquid may be added to the mixture, before it enters into the at least one static mixer.
  • water-jet cutting is combined with both, static cutting means and a static mixer.
  • the combination with static cutting means has already been described above.
  • the aqueous mixture comprising pieces of polyacrylamide gel leaving the comminution unit comprising a water-jet cutting step and a static cutting step is conveyed through at least one static mixer.
  • Additional aqueous liquid may be added to the mixture, before it enters into the at least one static mixer.
  • comminuting the aqueous polyacrylamide gel is carried out by at least one means selected from rotating water-jets, rotating knives or and a hole perforation plate.
  • at least one means selected from rotating water-jets, rotating knives or and a hole perforation plate.
  • a combination of at least one hole perforation plate and rotating water-jets or at least one hole perforation plate and rotating knives may be used.
  • the comminution unit comprises a combination of water-jet cutting and a hole perforation plate.
  • the hole perforation plate comprises holes.
  • the shape of the holes is not specifically limited. Examples comprise circular holes, ellipsoidal holes, triangular holes, quadrangular holes such as quadratic, rectangular, or rhombic holes, pentagonal holes, hexagonal holes or star-like holes but also longitudinal holes such as slots.
  • the holes may be cylindrical holes but they may also be conical.
  • the dimensions of the holes are not specifically limited. However, preferably at least one dimension of the holes should be from 0.5 to 5 mm.
  • the hole perforation plate comprises circular holes having a diameter from 0.5 to 5 mm, for example from 1 mm to 3 mm.
  • the aqueous polyacrylamide is conveyed from the polymerization unit through the hole perforation plate.
  • One or more rotating nozzles for water-jets are mounted above or below the hole perforation plate.
  • the comminution yields a mixture of polyacrylamide gel particles and aqueous liquid. It goes without saying, that at least a part of the polyacrylamide gel already dissolves in the aqueous liquid in course of comminution, so the mixture may perhaps be better characterized as polyacrylamide gel particles in an aqueous solution of polyacrylamides. The degree of homogeneity depends on the chosen comminution technology and the added amount of water in this process step.
  • comminution is followed by a step of homogenization. If not already done, the remaining amount of aqueous liquid to achieve the desired concentration of the aqueous polyacrylamide composition -if any- is added before or in course of such a homogenization step.
  • polyacrylamide solution and polyacrylamide gel pieces may be simply allowed to stand in a suitable vessel in order to homogenize without mixing.
  • the mixture obtained in course of comminution may already be filled into the transport unit used for step [5].
  • the transport time is used for homogenization.
  • the obtained mixture is further mixed using suitable means.
  • aqueous polyacrylamide composition has a viscosity which is not too high, stirring of the mixture may still be possible.
  • Other possibilities e.g. for higher viscous PAM compositions are tumbling, shaking or any mixing method known to skilled in the art for highly viscous liquids.
  • the mixture may be circulated using circulation pumps.
  • the loop may comprise one or more static mixers.
  • the step of comminution and mixing with an aqueous liquid may be followed by a dissolution step in a dissolution unit.
  • the dissolution of the aqueous polyacrylamide gel in an aqueous liquid basically may be performed in any kind of dissolution unit.
  • polyacrylamide gel is conducted in a relocatable dissolution unit.
  • suitable dissolution units comprise stirred vessels.
  • a dissolution unit may only comprise one vessel or it may comprise more than one vessel which may be operated in series or in parallel. Mixing may also be achieved by flowing the contents of the dissolution vessel out through a conduit and then recirculating back into the mixing vessel.
  • Other examples comprise a combination of static mixers with unstirred vessels or in-line dispersing such as rotor-stator units.
  • the aqueous polyacrylamide gel is dissolved in the aqueous liquid by passing the aqueous polyacrylamide gel pieces of the comminution step, preferably a mixture of aqueous polyacrylamide gel pieces in an aqueous liquid into a dissolution comprising at least a dissolution vessel and means for mixing the polyacrylamide gel with the aqueous liquid.
  • aqueous polyacrylamide gel pieces of the comminution step preferably a mixture of aqueous polyacrylamide gel pieces in an aqueous liquid into a dissolution comprising at least a dissolution vessel and means for mixing the polyacrylamide gel with the aqueous liquid.
  • polyacrylamide solution additional aqueous liquid may be added to the dissolution vessel.
  • Examples of means for mixing comprise one or more impellers or stirrers which optionally may be combined with static mixing devices. Mixing may also be achieved by flowing the contents of the dissolution vessel out through a conduit and then recirculating back into the mixing tank.
  • the dissolution unit may also comprise two or more than two dissolution vessels connected in series. The volume of the dissolution vessel is not specifically limited and may range from 10 m 3 to 150 m 3 , for example from 20 m 3 to 50 m 3 per vessel. Further embodiments of the process
  • the process comprises the additional process steps [5] and [6] which comprise transporting the aqueous polyacrylamide composition to another location for use.
  • step [5] the aqueous polyacrylamide composition is transported from location B to a different location C. Details about location C have already been disclosed above. Step [5] is an optional step.
  • aqueous polyacrylamide compositions may be transported, preferably for transport a more concentrated aqueous polyacrylamide composition is used.
  • the aqueous polyacrylamide composition to be transported in step [5] has a concentration from 1 % to 14.9 % by weight of polyacrylamides, relating to the total of all components of the aqueous
  • polyacrylamide composition preferably from 2.1 % by weight to 10 % by weight, more preferably from 3.1 % by weight to 7 % by weight, and for example from 4 % by weight to 6 % by weight.
  • a suitable transport unit is used.
  • the transport unit may have a volume from 1 m 3 to 40 m 3 , in particular 5 m 3 to 40 m 3 , preferably 10 m 3 to 30 m 3 , for example 20 m 3 to 30 m 3 or from 15 to 25 m 3 .
  • suitable transport units comprise vessels comprising at least one opening, tank containers, or tipping vessels.
  • the transport may be carried out by any transport means suitable for transporting the transport unit, for example by trucks, railcars or ships.
  • transport unit shall include separate transport units such as vessels, containers, for example ISO containers or intermediate bulk containers, which are loaded on suitable transport means for transport, for example on trailers, container cars or ships.
  • the transport means may transport one single transport unit or a plurality of transport units.
  • transport unit furthermore includes transport units in which the transport compartment is permanently fixed on the transport means, such as for example tank trucks or tanks cars.
  • the transport is carried out by trucks.
  • the transport unit may also be fixed on a truck.
  • the transport unit may be an ISO tank container. Typical dimensions of ISO containers have already been mentioned above.
  • tanks fixed on a truck may be used.
  • the tank comprises an outlet opening at the rear end of the truck and for supporting removal of the contents the tank may be tilted.
  • the tank comprises an outlet opening at the bottom side of the tank.
  • the tank may comprise a conus at the bottom side of the tank and the outlet opening in located at the lower end of the conus.
  • the tank may also be rotatable, so that the composition may become homogenized in course of transport.
  • a concrete mixer may be used for transporting the composition.
  • Filling the transport unit with the aqueous polyacrylamide composition may be carried out by pumping the composition into the transport unit.
  • the transport time i.e. the time for transporting the transport unit filled with aqueous polyacrylamide composition may be very different, depending on the distance between the locations A and B. It may range from minutes to several days, for example from 1 h to 28 days, in particular from 2 hours to 14 days, in particular 5 hours to 7 days.
  • a homogenization step as described above may be carried out in course of transport.
  • the transport unit for example a truck may comprise a rotating drum thereby effecting homogenization. Trucks comprising rotating drums are known on the art for transporting concrete.
  • the transport unit may comprise a circulation loop equipped with a pump and optionally mixing units, for example static mixers, so that the aqueous polyacrylamide concentrate can be circulated in course of transport. Step [6] Removal of the aqueous polyacrylamide concentrate
  • step [6] the aqueous polyacrylamide composition is removed from the transport unit.
  • Step [6] is carried out at location C.
  • removing the aqueous polyacrylamide composition may be carried out by any kind of technology. The details depend on the specific design of the transport unit, the kind of concentrate, in particular its viscosity, and the connected downstream processing equipment.
  • the aqueous polyacrylamide composition may be removed by means of a pump. Removal may be supported by applying pressure onto the transport unit, in particular by means of gas pressure. Furthermore, removal may also be supported -depending on the construction of the transport units- by tilting the transport unit.
  • the present invention relates to a process for producing aqueous polyacrylamide compositions by polymerizing an aqueous solution comprising at least acrylamide thereby obtaining an aqueous polyacrylamide gel and dissolving said aqueous polyacrylamide gel in water, wherein the process comprises at least the following steps:
  • a first reactor device comprising an inlet, an outlet and a positive displacement pump for partially polymerizing the aqueous monomer solution in the presence of initiators for radical polymerization, thereby obtaining a partially polymerized product
  • partially polymerized product mounted substantially vertical comprising at least one tubular or at least one conical section or combinations thereof and furthermore comprising an inlet at the upper end and an outlet at the lower end, wherein the polymerization is a continuous process comprising at least the following steps
  • aqueous polyacrylamide composition having a concentration from 0.05 to 14.9 % by weight of polyacrylamides, relating to the total of all components of the aqueous polyacrylamide composition.
  • the present invention relates to a process for producing aqueous polyacrylamide compositions by polymerizing an aqueous solution comprising at least acrylamide thereby obtaining an aqueous polyacrylamide gel and dissolving said aqueous polyacrylamide gel in water, wherein the process comprises at least the following steps:
  • aqueous monomer solution comprising at least water and 15 % to 50 % by weight -relating to the total of all components of the aqueous monomer solution- of water-soluble, monoethylenically unsaturated monomers, wherein said water-soluble, monoethylenically unsaturated monomers comprise at least acrylamide,
  • a first reactor device comprising an inlet, an outlet and a positive displacement pump for partially polymerizing the aqueous monomer solution in the presence of initiators for radical polymerization, thereby obtaining a partially polymerized product
  • a second reactor device for continuing polymerization of the partially polymerized product mounted substantially vertical comprising at least one tubular or at least one conical section or combinations thereof and furthermore comprising an inlet at the upper end and an outlet at the lower end,
  • polymerization is a continuous process comprising at least the following steps
  • aqueous polyacrylamide composition having a concentration from 1 wt. % to 14.9 % by weight of polyacrylamides, relating to the total of all components of the aqueous polyacrylamide composition,
  • the aqueous polyacrylamide composition transported in course of step [5] preferably has a concentration from 1 % to 14.9 % by weight of polyacrylamides, relating to the total of all components of the aqueous
  • polyacrylamide solution more preferably, the concentration is from 3.1 to 8 % by weight.
  • the present invention relates to a process for producing aqueous polyacrylamide compositions by polymerizing an aqueous solution comprising at least acrylamide thereby obtaining an aqueous polyacrylamide gel and dissolving said aqueous polyacrylamide gel in water, characterized in that the process comprises at least the following steps:
  • aqueous monomer solution in a polymerization unit comprising at least water and 15 % to 50 % by weight -relating to the total of all components of the aqueous monomer solution- of water-soluble, monoethylenically unsaturated monomers, wherein the aqueous monomer solution comprises at least the aqueous monomer premix,
  • a first reactor device comprising an inlet, an outlet and a positive displacement pump for partially polymerizing the aqueous monomer solution in the presence of initiators for radical polymerization, thereby obtaining a partially polymerized product
  • a second reactor device for continuing polymerization of the partially polymerized product mounted substantially vertical comprising at least one tubular or at least one conical section or combinations thereof and furthermore comprising an inlet at the upper end and an outlet at the lower end,
  • polymerization is a continuous process comprising at least the following steps
  • aqueous polyacrylamide composition having a concentration from 1 wt. % to 14.9 % by weight of polyacrylamides, relating to the total of all components of the aqueous polyacrylamide composition,
  • the aqueous polyacrylamide composition transported in course of step [5] preferably has a concentration from 1 % to 14.9 % by weight of polyacrylamides, relating to the total of all components of the aqueous
  • polyacrylamide solution more preferably, the concentration is from 3.1 to 8 % by weight.
  • Modular, relocatable plant also relates to a modular, relocatable plant for manufacturing aqueous polyacrylamide compositions by polymerizing an aqueous solution comprising at least acrylamide thereby obtaining an aqueous polyacrylamide gel, comminuting said aqueous polyacrylamide gel and mixing it with an aqueous liquid, comprising at least
  • a relocatable storage unit for an aqueous monomer solution comprising at least water and acrylamide
  • a relocatable polymerization unit comprising at least
  • a first reactor device comprising a positive displacement pump for partially polymerizing the aqueous monomer solution in the presence of initiators for radical polymerization, thereby obtaining a partially polymerized product
  • a second reactor device for continuing polymerization of the partially polymerized product mounted substantially vertical comprising at least one tubular or at least one conical section or combinations thereof and furthermore comprising an inlet at the upper end and an outlet at the lower end, and
  • a relocatable unit for comminution of the aqueous polyacrylamide gel and mixing it with an aqueous liquid thereby obtaining an aqueous polyacrylamide solution.
  • the second reactor device is vertical with an inlet at the upper side of the reactor and an outlet at the lower side of the reactor.
  • the shape of the reactor is tubular and/or conical. It may preferably comprise a tubular section and a conical section at its lower end or at least two different tubular sections.
  • the modular, relocatable plant additionally comprises
  • a relocatable storage unit for an aqueous acrylamide solution o optionally relocatable storage units for water-soluble, monoethylenically unsaturated monomers different from acrylamide, o a relocatable monomer make-up unit for preparing an aqueous monomer solution comprising at least water and acrylamide.
  • the modular, relocatable plant additionally comprises
  • a relocatable bioconversion unit for hydrolyzing acrylonitrile in water in the presence of a biocatalyst capable of converting acrylonitrile to acrylamide
  • the present invention relates to a modular relocatable plant for manufacturing aqueous polyacrylamide compositions by polymerizing an aqueous solution comprising at least acrylamide thereby obtaining an aqueous polyacrylamide gel, comminuting said aqueous polyacrylamide gel and mixing it with an aqueous liquid, comprising at least
  • a relocatable storage unit for an aqueous acrylamide solution o optionally relocatable storage units for water-soluble, monoethylenically unsaturated monomers different from acrylamide,
  • monomer premix comprising at least water and acrylamide, at locations A and/or B
  • a transport device for transporting an aqueous monomer premix from location A to location B.
  • a relocatable storage unit for an aqueous monomer solution comprising at least water and acrylamide
  • a relocatable polymerization unit comprising at least
  • a first reactor device comprising a positive displacement pump for partially polymerizing the aqueous monomer solution in the presence of initiators for radical polymerization, thereby obtaining a partially polymerized product
  • a second reactor device for continuing polymerization of the partially polymerized product mounted substantially vertical comprising at least one tubular or at least one conical section or combinations thereof and furthermore comprising an inlet at the upper end and an outlet at the lower end, and
  • a relocatable unit for comminution of the aqueous polyacrylamide gel and mixing it with an aqueous liquid thereby obtaining an aqueous polyacrylamide composition.
  • the modular, relocatable plant comprises additionally at location A
  • a relocatable bioconversion unit for hydrolyzing acrylonitrile in water in the presence of a biocatalyst capable of converting acrylonitrile to acrylamide
  • the present invention relates to a modular, relocatable plant for manufacturing aqueous polyacrylamide compositions by polymerizing an aqueous solution comprising at least acrylamide thereby obtaining an aqueous polyacrylamide gel, comminuting said aqueous polyacrylamide gel and mixing it with an aqueous liquid, comprising at least
  • a relocatable storage unit for an aqueous monomer solution comprising at least water and acrylamide
  • a relocatable polymerization unit comprising at least
  • a first reactor device comprising a positive displacement pump for partially polymerizing the aqueous monomer solution in the presence of initiators for radical polymerization, thereby obtaining a partially polymerized product
  • a second reactor device for continuing polymerization of the partially polymerized product mounted substantially vertical comprising at least one tubular or at least one conical section or combinations thereof and furthermore comprising an inlet at the upper end and an outlet at the lower end, and
  • o means for removing the aqueous polyacrylamide composition from the transport unit.
  • the present invention relates to a modular, relocatable plant for manufacturing aqueous polyacrylamide compositions by polymerizing an aqueous solution comprising at least acrylamide thereby obtaining an aqueous polyacrylamide gel, comminuting said aqueous polyacrylamide gel and mixing it with an aqueous liquid, comprising at least
  • a relocatable storage unit for an aqueous acrylamide solution o optionally relocatable storage units for water-soluble, monoethylenically unsaturated monomers different from acrylamide,
  • a transport device for transporting an aqueous monomer premix from location A to location B.
  • a relocatable storage unit for an aqueous monomer solution comprising at least water and acrylamide
  • a relocatable polymerization unit comprising at least
  • a first reactor device comprising a positive displacement pump for partially polymerizing the aqueous monomer solution in the presence of initiators for radical polymerization, thereby obtaining a partially polymerized product
  • a closed connection which connects the outlet of the first reactor device with an inlet of a second reactor device for transferring the partially polymerized product to a second reactor device
  • a second reactor device for continuing polymerization of the partially polymerized product mounted substantially vertical comprising at least one tubular or at least one conical section or combinations thereof and furthermore comprising an inlet at the upper end and an outlet at the lower end, and
  • o means for removing the aqueous polyacrylamide composition from the transport unit.
  • aqueous polyacrylamide compositions manufactured according to the present invention may be used for various purposes, for example for mining applications, oilfield applications, water treatment, waste water cleanup, paper making or agricultural applications.
  • the aqueous polyacrylamide compositions may be further diluted at the site-of-use thereby obtaining diluted aqueous polyacrylamide solutions.
  • the aqueous polyacrylamide compositions advantageously may be used as such without further dilution.
  • Compositions and/or solutions may also be formulated with further components. Further components may be selected by the skilled artisan according to the intended use.
  • Oilfield applications examples of oilfield processes in which the aqueous polyacrylamide compositions and/or solutions manufactured according to the present invention may be used include enhanced oil recovery, oil well drilling, the use as viscosifier for various purposes or the use as friction reducers, for example friction reducers for fracturing fluids.
  • the aqueous polyacrylamide compositions manufactured according to the present invention may be used for enhanced oil recovery.
  • the present invention also relates to the use of aqueous
  • polyacrylamide compositions in a process of enhanced oil recovery comprising at least the following steps:
  • the concentration of the polyacrylamide in the injection fluid is 0.02 % to 2 % by weight based on the total sum of all the components in the aqueous formulation.
  • the amount is preferably 0.05 % to 0.5% by weight, more preferably 0.1% to 0.3% by weight and, for example, 0.1 % to 0.2% by weight.
  • a homopolymer of acrylamide may be used, however preferably water-soluble copolymers comprising at least 10 %, preferably at least 20 %, and more preferably at least 30 % by weight of acrylamide and at least one additional water-soluble, monoethylenically unsaturated monomer different from acrylamide are used.
  • Suitable water-soluble comonomers have already been mentioned above and we refer to the disclosure above.
  • water-soluble comonomers may be selected from water- soluble, monoethylenically unsaturated monomers comprising at least one acid group, or salts thereof.
  • the acidic groups are preferably selected from the group of -COOH, -S0 3 H and -P0 3 H 2 or salts thereof. Preference is given to monomers comprising COOH groups and/or -S0 3 H groups or salts thereof. Suitable
  • Examples of such comonomers comprise acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid (ATBS), 2-methacrylamido-2-methylpropane-sulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutane-sulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, vinylphosphonic acid,
  • acrylic acid and/or ATBS or salts thereof may be used as comonomers.
  • the amount of acrylamide usually is from 20 % by wt. to 90 % by wt. and the amount of acrylic acid and/or ATBS or salts thereof is from 10 % by wt. to 80 % by wt., relating to the amount of all monomers in the copolymer.
  • the amount of acrylamide is from 60 % by wt. to 80 % by wt. and the amount acrylic acid and/or ATBS or salts thereof is from 20 % by wt. to 40 % by wt..
  • the copolymers to be used for enhanced oil recovery comprise at least one water-soluble, monoethylenically unsaturated monomer comprising at least one acid group, or salts thereof, preferably acrylic acid and/or ATBS or salts thereof, and at least one associative monomer.
  • associative monomers have already been disclosed above.
  • at least one associative monomer of the general formula (III), (IV), or (V) is used, preferably at least one associative monomer of the general formula (V).
  • Preferred embodiments of the associative monomers (III), (IV), and (V) have already been disclosed above and it is explicitly referred to that description.
  • the amount of acrylamide usually is from 40 % by wt. to 89.9 % by wt.
  • the amount of acrylic acid and/or ATBS or salts thereof is from 10 % by wt. to 59.9 %
  • the amount of associative monomers is from 0.1 to 5 % by wt., relating to the amount of all monomers in the copolymer.
  • the polyacrylamides for EOR comprise 45 % to 55 % by weight of acrylamide, 0.1 to 5 %, preferably 0.1 to 2 % by weight of at least one associative monomer of the general formula (V) mentioned above, including the preferred embodiments, and 40 to 54.9 % by weight of acrylic acid or salts thereof.
  • At least one production well and at least one injection well are sunk into the mineral oil deposit.
  • a deposit will be provided with a plurality of injection wells and with a plurality of production wells.
  • aqueous fluid is injected into the mineral oil deposit through the at least one injection well, and mineral oil is withdrawn from the deposit through at least one production well.
  • the“polymer flood” By virtue of the pressure generated by the aqueous fluid injected, called the“polymer flood”, the mineral oil flows in the direction of the production well and is produced through the production well.
  • the term“mineral oil” does not of course just mean a single-phase oil; instead, the term also encompasses the customary crude oil-water emulsions.
  • the aqueous injection fluid comprises an aqueous base fluid such as freshwater or water comprising salts, such as seawater or formation water.
  • the base fluid is mixed with the polyacrylamides and optionally further components.
  • further components include biocides, stabilizers, free- radical scavengers, initiators, surfactants, cosolvents, bases and complexing agents.
  • the aqueous polyacrylamide composition may be used or the aqueous polyacrylamide composition may be diluted in a first step with additional aqueous liquid and thereafter used for making the aqueous injection fluid.
  • the aqueous polyacrylamide compositions are mixed with the aqueous base fluid and optionally further components.
  • such mixing may be carried out by means of suitable mixing means, for example static mixers or mixing vessels.
  • the aqueous polyacrylamide compositions are injected into the pipeline(s) which transport(s) the aqueous injection fluid to the injection well(s) at the desired concentration.
  • Such pipelines may have a length of up to some kilometers. It has been found that the time needed for flowing through such pipeline often is sufficient for complete dissolution of the composition in the fluid. Of course, combinations are possible.
  • the pipeline may comprise mixing elements such as static mixers.
  • location B may be at an injection well or in between a plurality of such injection wells.
  • Location A is apart from location B.
  • location A is a local hub which provides a plurality of different locations B with aqueous polyacrylamide gels.
  • location A may at a central point over a subterranean, oil-bearing formation or a central point in between different subterranean, oil-bearing formations and from location A, a plurality of oil wells to be treated is provided with aqueous polyacrylamide gels for further processing.
  • the final concentration of the polyacrylamide in the injection fluid is fixed such that the aqueous formulation has the desired viscosity for the end use.
  • the viscosity of the formulation should generally be at least 5 mPas (measured at 25° C and a shear rate of 7 s 1 ), preferably at least 10 mPas.
  • the aqueous polyacrylamide compositions may be used as such for the enhanced oil recovery process.
  • Suitable compositions preferably have a concentration from 3.1 % by weight to 10 % by weight, more preferably, the concentration is from 3.1 % by weight to 7 % by weight, and for example from 4 % by weight to 6 % by weight. Friction reducers for hydraulic fracturing
  • Hydraulic fracturing involves injecting fracturing fluid through a wellbore and into a formation under sufficiently high pressure to create fractures, thereby
  • hydraulic fracturing operations it is important to ensure that the proppants are transported with the fracturing fluid into the formation and that they do not settle. Said effect can be achieved by using a thickened fluid having a high viscosity.
  • hydraulic fracturing also known as
  • “slickwater fracturing”, fluids having only a low viscosity are used. Such fluids mainly comprise water. I n order to achieve proppant transport into the formation, the pumping rates and the pressures used are significantly higher than for high- viscosity fluids. The high flow ensures proppant transport. On the other hand, the turbulent flow of the fracking fluid causes significant energy loss due to friction. In order to avoid or at least minimize such friction losses, friction reducers, for example high molecular weight polyacrylamides may be used which change turbulent flow to laminar flow. In one embodiment of the invention, the aqueous polyacrylamide compositions manufactured according to the present invention are used as friction reducers in slickwater fracturing applications.
  • the present invention also relates to the use of aqueous
  • polyacrylamide compositions as friction reducer in a process for fracturing subterranean formations comprising at least the following steps:
  • an aqueous injection fluid by mixing at least an aqueous base fluid, a proppant and an aqueous polyacrylamide composition having a concentration of 1.0 to 14.9 % by weight of polyacrylamides, relating to the total of all components of the aqueous polyacrylamide composition, wherein the concentration of the polyacrylamides in the aqueous fracturing fluid is from 20 ppm to 600 ppm, relating to the total of all components of the aqueous fracturing fluid except the proppants,
  • the aqueous base fluid may be freshwater or water comprising salts, such as seawater or formation water or produced water.
  • Suitable proppants comprise naturally-occurring sand grains, resin- coated sand, sintered bauxite, glass beads or ultra-lightweight polymer beads.
  • Fracturing fluids may be mixed using so-called blenders (often mounted on trucks), in which an aqueous base fluid, proppants, friction reducers and optionally further components are mixed.
  • blenders often mounted on trucks
  • an aqueous base fluid, proppants, the aqueous polyacrylamide composition as described above and optionally further components are mixed with each other by means of a customary blender thereby obtaining an aqueous fracturing fluid.
  • the concentration of proppants in the fracturing fluid may be constant in course of the fracturing process. In other embodiments, the concentration of proppants in the fracturing fluid may be varied in course of the fracturing process.
  • the slickwater fracturing process may start with injection of a certain amount of fracturing fluid which does not comprise any proppants and proppants are added to the fracturing fluid only at a later stage of the fracturing process.
  • the concentration of the polyacrylamides in the aqueous fracturing fluid preferably is from 20 ppm to 300 ppm, for example from 125 ppm to 250 ppm of
  • polyacrylamides relating to the total of all components of the aqueous fracturing fluid except the proppants.
  • compositions for making the aqueous fracturing fluid is selected accordingly.
  • the process according to the present invention is carried out in areas where mining, mineral processing and/or metallurgy activities takes place. Consequently, the aqueous polyacrylamide compositions as product obtained by the method of the present invention is preferably used for applications in the field of mining, mineral processing and/or metallurgy and the method for preparing the aqueous polyacrylamide composition is preferably used at the plant of the respective industry.
  • mining activities comprises extraction of valuable minerals or other geological materials from certain deposits.
  • deposits can contain ores, for example metal containing ores, sulfidic ores and/or non-sulfidic ores.
  • the ores may comprise metals, coal, gemstones, limestone or other mineral material.
  • Mining is generally required to obtain any material in particular mineral material that cannot be grown through agricultural processes or created artificially in a laboratory or factory.
  • the aqueous polyacrylamide composition according to the present invention is preferably used to facilitate the recovery of mineral material, for beneficiation of ores and for further processing of ores to obtain the desired minerals or metals.
  • aqueous polyacrylamide compositions manufactured according to the process of the present invention can be used for example at plants for alumina production, where alumina is extracted from the mineral bauxite using the Bayer caustic leach process,
  • the present invention relates to the use of an aqueous polyacrylamide composition for mining, mineral processing and/or metallurgy activities comprising the use for solid liquid separation, for tailings disposal, for polymer modified tailings deposition, for tailings management, as density and/or rheology modifier, as agglomeration aid, as binder and/or for material handling, wherein the aqueous polyacrylamide composition is prepared at the plant of the respective industry, comprising for example the following steps: hydrolyzing acrylonitrile in water in presence of a biocatalyst capable of converting acrylonitrile to acrylamide so as to obtain an acrylamide solution, polymerizing the acrylamide solution so as to obtain a polyacrylamide gel, and
  • a homopolymer of acrylamide for example can be used. Further preferred are also copolymers of acrylamide. Such copolymers of acrylamide can be anionic, cationic or non-ionic. Anionic copolymers are for example co-polymers of acrylamide with increasing proportions of acrylate groups, which give the polymers negative charges, and thus anionic active character, in aqueous solution. Anionic copolymers of acrylamide can in particular be used for waste water treatment in metallurgy like iron ore plants, steel plants, plants for electroplating, for coal washing or as flocculants.
  • Non-ionic polymers and/or copolymers of acrylamide can be used for example as nonionic flocculants suitable as settlement aids in many different mineral processing applications and are particularly effective under very low pH conditions, as encountered for example in acidic leach operations.
  • Cationic copolymers of acrylamide have in particular an increasing proportion of cationic monomers. The cationic groups, which are thus introduced into the polymer, have positive charges in aqueous solution.
  • the polymer obtained from the method of the present invention is used as flocculant in a process in which individual particles of a suspension form aggregates.
  • the polymeric materials of the present invention forms for example bridges between individual particles in the way that segments of the polymer chain adsorb on different particles and help particles to aggregate. Consequently, the polymers of the present invention act as agglomeration aid, which may be a flocculant that carries active groups with a charge and which may counterbalance the charge of the individual particles of a suspension.
  • the polymeric flocculant may also adsorb on particles and may cause destabilization either by bridging or by charge neutralization.
  • the polymer is an anionic flocculant, it may react against a positively charged suspension (positive zeta potential) in presence of salts and metallic hydroxides as suspension particles, for example.
  • the polymer of the present invention is for example a cationic flocculant, it may react against a negatively charged suspension (negative zeta potential) like in presence of for example silica or organic substances as suspension particles.
  • the polymer obtained from the method of the present invention may be an anionic flocculant that agglomerates clays which are electronegative.
  • the method of the present invention and the obtained polymer and/or copolymer of acrylamide is used for example in the Bayer process for alumina production.
  • the polyacrylamide can be used as flocculant in the first step of the Bayer-Process, where the aluminum ore (bauxite) is washed with NaOH and soluble sodium aluminate as well as red mud is obtained.
  • the flocculation of red mud is enhanced and a faster settling rate is achieved when acrylamide polymers and/or co-polymers are added.
  • polyacrylamide may be used for settling aluminum red mud slurries in alumina plants, provides high settling rates, offers better separation performance and reduces suspended solids significantly.
  • the liquor filtration operations are improved and with that the processing is made economically more efficient.
  • the polyacrylamides are used in decanters, in washers, for hydrate thickening, for green liquor filtration, as crystal growth modifiers, as thickener and/or as rheology modifier.
  • the method of the present invention and the polymers of acrylamide are used in processes for solid liquid separation as for example flocculant or dewatering aid, which facilitate thickening, clarifying, filtration and centrifugation in order to enhance settling rates, to improve clarities and to reduce underflow volumes.
  • the polyacrylamide homo- or co-polymer of the present invention increase filtration rates and yields, as well as reducing cake moisture contents.
  • the use of the method and the obtained polyacrylamide of the present invention in particular for material handling and as binder.
  • the typical rock and/or ore processing for example starts with ore extraction, followed by crushing and grinding the ore, subsequent mineral processing (processing or the
  • the handling of the mineral material can be enhanced by increasing efficiency and yield, by improving product quality and by minimizing operating costs.
  • the present invention can be used for a safer working environment at the mine site and for reduction of environmental discharges.
  • the method and the obtained polyacrylamide of the present invention can for example be used as thickener, as density and/or rheology modifier, for tailings management.
  • the obtained polyacrylamide polymer can modify the behavior of the tailings for example by rheological adjustment.
  • the obtained polyacrylamide polymers are able to rigidity tailings at the point of disposal by initiating instantaneous water release from the treated slurry. This accelerates the drying time of the tailings, results in a smaller tailings footprint and allows the released water to be returned to the process faster. This treatment is effective in improving tailings properties in industries producing alumina, nickel, gold, iron ore, mineral sands, oil sands or copper for example.
  • the obtained product from the method of the present invention is used for agglomeration of fine particulate matter and for the suppression of dust.
  • polyacrylamide polymers or copolymers are used as organic binders to agglomerate a wide variety of mineral substrates.
  • the polyacrylamide polymers or copolymers are used for iron ore pelletization as a full or partial replacement for bentonite.
  • the product from the method of the present invention can be used as binder, in particular as solid and liquid organic binders in
  • briquetting extrusion, pelletization, spheronization and/or granulation applications and gives for example excellent lubrication, molding and/or binding properties for processes such as coal-fines briquetting, carbon extrusion, graphite extrusion and/or nickel briquetting.
  • the method of the present invention and in particular the aqueous polyacrylamide composition obtained by the method is used for the beneficiation of ores which comprise for example coal, copper, alumina, gold, silver, lead, zinc, phosphate, potassium, nickel, iron, manganese, or other minerals.
  • ores comprise for example coal, copper, alumina, gold, silver, lead, zinc, phosphate, potassium, nickel, iron, manganese, or other minerals.
  • the process according to the present invention provides significant advantages as compared to known processes for the manufacture of polyacrylamide powders as well as compared to known processes for manufacturing polyacrylamide solutions on-site.
  • drying aqueous polyacrylamide gels thereby obtaining polyacrylamide powders, transporting the powders to the site of use and re dissolving the dry powders at the site of use is energy extensive and consequently the operational costs for drying are high. Furthermore, also the capital expenditure for the entire post-processing equipment including size reduction, drying, sieving, grinding is significant in relation to the total capital expenditure for the entire plant. The present process is more economic, because significant amount of energy and capital expenditures are saved.
  • the process according to the present invention has the advantage that a continuous polymerization can be combined with a continuous comminution and dissolution process.
  • the preferred embodiment of manufacturing the aqueous polyacrylamide compositions in a modular, relocatable plant close to the locations of using them and transporting them to a size-of-use allows to bundle manufacturing, i.e. it is no longer possible to erect a plant at every site-of-use.

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Abstract

L'invention concerne un procédé de production de compositions de polyacrylamide aqueuses par polymérisation d'une solution aqueuse comprenant au moins de l'acrylamide, ce qui permet d'obtenir un gel de polyacrylamide aqueux, broyage dudit gel de polyacrylamide aqueux et mélange avec un liquide aqueux, la polymérisation étant un procédé continu comprenant la polymérisation partielle de ladite solution aqueuse de monomère dans un premier système de réacteur comprenant une pompe à déplacement positif et la poursuite de la polymérisation dans un second système de réacteur. L'invention concerne également une installation modulaire relocalisable pour la mise en oeuvre du procédé décrit.
PCT/EP2019/078166 2018-10-18 2019-10-17 Procédé de production de compositions de polyacrylamide aqueuses WO2020079124A1 (fr)

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