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WO2025015262A2 - Procédé de désoxygénation à un passage pour la production de polyacrylamide - Google Patents

Procédé de désoxygénation à un passage pour la production de polyacrylamide Download PDF

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Publication number
WO2025015262A2
WO2025015262A2 PCT/US2024/037774 US2024037774W WO2025015262A2 WO 2025015262 A2 WO2025015262 A2 WO 2025015262A2 US 2024037774 W US2024037774 W US 2024037774W WO 2025015262 A2 WO2025015262 A2 WO 2025015262A2
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Prior art keywords
monomer composition
monomer
gas
degassing
liquid
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WO2025015262A3 (fr
Inventor
Claudio CARLETTI
Marshall Bond
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Kemira Oyj
Kemira Water Solutions Inc
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Kemira Oyj
Kemira Water Solutions Inc
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Publication of WO2025015262A2 publication Critical patent/WO2025015262A2/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/0036—Flash degasification

Definitions

  • the present invention relates to a method and apparatus for degassing a monomer composition.
  • the disclosure provides a method and apparatus for deoxygenation of monomer solutions during transfer from monomer holding tank to reactor. Degassing occurs in one pass by combining a jet of nitrogen with a monomer solution in a Venturi Injector.
  • Monomer degassing is a particularly important unit operation step in polymer manufacturing, specifically for acrylamide polymers, namely emulsion polyacrylamides (EPAMs) and dry polyacrylamides (DP AMs) among other polymer products.
  • acrylamide polymers namely emulsion polyacrylamides (EPAMs) and dry polyacrylamides (DP AMs) among other polymer products.
  • DO dissolved oxygen
  • monomer solutions Typically, the monomer solution is transferred to a polymerization reactor and then degassed by various methods prior to initiation of polymerization.
  • the monomer mixture is degassed in a tipping reactor after it has been cooled, examples of this method are implemented in existing polymer production plants.
  • N2 is sparged into the bulk monomer solution through a pipe inlet for 40 to 60 min or more. This allow for target DO values of ⁇ 500 ppb (more preferably ⁇ 200 ppb) to be achieved. These target DO values must be achieved prior to initiation of polymerization.
  • a second degassing option consists of sparging and degassing a monomer solution using bubbling columns. N2 is sparged into the bulk monomer solution through the bubbling columns. The introduction of gas takes place at the bottom of the column and causes a turbulent stream to enable gas exchange.
  • This second method is used in several industrial applications, but is not suitable for tipping reactors due to the large flowrates required in tipping reactors with respect to belt reactor technologies.
  • SUBSTITUTE SHEET (RULE 26) [0007]
  • the present invention addresses these limitations and needs by providing novel and efficient method and apparatus for degassing monomer solutions using a Venturi Injector.
  • This invention proposes a novel system and procedure for deoxygenation of a monomer solution during transfer from holding tank to reactor. Monomer can be transferred after cooling and degassed cold during transfer from monomer holding tank to reactor.
  • the inventive method allows for degassing to occur in one pass by injecting pressurized nitrogen into a Venturi Injector.
  • the present invention relates to a method and apparatus for degassing a monomer composition.
  • the disclosure provides a method and apparatus for deoxygenation of monomer solutions during transfer from monomer holding tank to reactor. Degassing occurs in one pass by combining a jet of nitrogen with a monomer solution in a Venturi Injector.
  • the inventive method and apparatus provide a more efficient degassing, allowing for an increased monomer degassing capacity, a reduced monomer degassing time, and decreased N2 consumption compared to traditional degassing methods.
  • the present invention provides a method of degassing a monomer composition, the method comprising:
  • steps (a)-(f) are performed successively.
  • the method further comprises
  • step (b) after step (f), determining said final DO content of said degassed monomer composition.
  • SUBSTITUTE SHEET (RULE 26) [0022] (a) said initial DO content ranges from 2-20 ppm, 4-18 ppm, 8-16 ppm, or 10-14 ppm; and/or
  • said final DO content comprises a desired DO content ranging from ⁇ 500 ppb, 10-500 ppb, 50-450 ppb, 100-400 ppb, or 200-300 ppb.
  • the method further comprises:
  • step (d) optionally after step (f), if said final DO content is greater than said desired DO content and/or if further degassing is required, recirculating said degassed monomer composition into said feed tank and subjecting said degassed monomer composition to a second degassing pass comprising repeating steps (b)-(g);
  • said temperature is sufficiently low to prevent polymerization of said liquid monomer composition and ranges from -5 to 10 °C; 0-10 °C, or 3-5 °C;
  • said N2 flow rate is controlled by a gas flow meter and one or more pressure regulators, regulator valves, and/or needle valves arranged in line between a pressurized N2 source and said Venturi Injector;
  • said gas-liquid mixture when flowing comprises a Reynolds Number (Re) ranging from 2300-8000, 3000-8000, 4000-8000, or 4000-6000, and/or comprises a turbulent flow;
  • said gas-liquid mixture comprises said cooled monomer composition and a finely divided N2 comprising dissolved N2, atomized N2, microscopic N2 bubbles, and/or macroscopic N2 bubbles, wherein said finely divided N2 is sufficiently small to allow gas-liquid mass transfer of DO, dissolved gasses, and/or volatile molecules from said cooled monomer composition to said finely divided N2, thereby allowing for removal of said DO, dissolved gasses, and/or volatile molecule from said cooled monomer composition;
  • said length of tubing provides a residence time for said gas-liquid mixture between said Venturi Injector and said degasser and optionally comprises coil tubing;
  • an aqueous monomer solution comprising water and at least one monomer comprising one or more nonionic monomers, one or more anionic monomers, one or more cationic monomers, or any combination thereof;
  • said one or more nonionic monomers are selected from the group of primary amide- containing monomers comprising acrylamide, methacrylamide, ethyl acrylamide, crotonamide, N- methyl acrylamide, N-butyl acrylamide, N-ethyl methacrylamide, and any combination thereof;
  • said one or more cationic monomers are selected from are selected from acryloyloxyethyltrimethyl ammonium chloride (“AETAC”), methacryloyloxyethyltrimethylammonium chloride (“MAETAC”), methacrylamidopropyltrimethylammonium chloride (“MAPTAC”), acrylamidopropyltrimethylammonium chloride (“APTAC”), methacryloyloxyethyldimethylammonium sulfate, diallyldimethylammonium chloride (“DADMAC”); dialkylaminoalkyl acrylates and dialkylaminoalkyl methacrylates and their quaternary or acid salts, including but not limited to, dimethylaminoethyl acrylate (“DMAEA”), dimethylaminoethyl methacrylate (“DMAEA”), dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethyl
  • SUBSTITUTE SHEET including but not limited to, diallyldiethylammonium chloride and diallyldimethylammonium chloride (“DADMAC”), and any combination thereof; and
  • said one or more anionic monomers contain functional groups selected from carboxylic acids, sulfonic acids, a phosphonic acids, their corresponding water soluble salts, their corresponding water dispersible salts, and any combination thereof, including but not limited to, acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), acrylamido tertiary butyl sulfonic acid (ATBS), acrylamido methanesulfonic acid, acrylamido ethanesulfonic acid, 2-hydroxy-3-acryIamide propane sulfonic acid, styrene sulfonic acid, and vinyl phosphonic acid, their corresponding alkali metal, alkaline earth metal, and ammonium salts, and any combination thereof;
  • functional groups selected from carboxylic acids, sulfonic acids, a phosphonic acids, their corresponding water
  • (b) comprises 1-70%, 5-50%, 25-45%, or 30-40% by weight of said at least one monomer; or
  • said liquid monomer composition comprises acrylamide, acrylic acid, acrylamido tertiary butyl sulfonic acid (ATBS), or any combination thereof; or
  • said degassed monomer composition is used to produce a dry polyacrylamide (DP AM) or an emulsion polyacrylamide (EPAM).
  • DP AM dry polyacrylamide
  • EPAM emulsion polyacrylamide
  • the method results in (i) an increased monomer degassing capacity, (ii) a reduced monomer degassing time, (iii) a decreased N2 consumption, or (iv) any combination of (i)-(iii), compared to a conventional method of degassing a monomer composition comprising sparging N2 gas through a pipe or bubbling column into a bulk monomer composition in a reactor or holding tank.
  • the present invention provides a degassed monomer composition obtainable by a method according to any of claims 1-9, wherein said degassed monomer composition comprises a desired final DO content ranging from ⁇ 500 ppb, 10-500 ppb, 50-450 ppb, 100-400 ppb, or 200-300 ppb.
  • SUBSTITUTE SHEET (RULE 26) [0066] (d) a length of tubing having an inner diameter (ID) and a degasser, wherein said length of tubing is arranged in line between said outlet on said Venturi Injector and said degasser.
  • the apparatus further comprises:
  • a dissolved oxygen (DO) meter arranged in contact with said liquid monomer composition and upstream of said Venturi Injector;
  • a second dissolved oxygen (DO) meter arranged in contact with a degassed liquid monomer composition and downstream of said degasser.
  • the apparatus further comprises
  • said means of cooling comprises a cooling coil and said means of stirring comprises a stirrer;
  • said means of controlling a motive flow rate comprises a progressive cavity pump and a monomer flowmeter
  • said means of controlling a N2 flow rate comprises a gas flowmeter and one or more N2 pressure regulators, one or more N2 regulator valves and/or one or more N2 needle valves arranged in line between said pressurized N2 source and said gas inlet on said Venturi Injector;
  • said length of tubing comprises straight tubing or pipe, coil tubing or pipe, or a combination thereof;
  • said degasser comprises a hydro separator and a gas vent;
  • the apparatus further comprises:
  • FIG 1 provides an exemplary Pipe and Instrumentation Diagram (PID) with numbering for a degassing test unit according to Example 1.
  • PID Pipe and Instrumentation Diagram
  • FIG 2 provides an exemplary rendering of a degassing test unit according to Example 1.
  • FIG 3 provides an exemplary rendering of a pilot plant layout of a degassing test unit according to Example 1.
  • FIG 4 provides an exemplary image of a pilot plant layout of a degassing test unit as built in Aberdeen, USA according to Example 1.
  • FIG 5 provides a second exemplary image of a pilot plant layout of a degassing test unit as built in Aberdeen, USA according to Example 1.
  • FIG 6 provides a third exemplary image of a pilot plant layout of a degassing test unit as built in Aberdeen, USA according to Example 1.
  • FIG 7 provides a fourth exemplary image of a pilot plant layout of a degassing test unit as built in Aberdeen, USA according to Example 1.
  • FIG 8 provides an exemplary graph of modeling results for dissolved oxygen (DO) vs. pipe length according to Example 2.
  • FIG 9 provides an exemplary graph of the statistical effect summary of main parameters on DO content according to Example 4.
  • FIG 10 provides an exemplary dissolved oxygen (DO) prediction plot showing actual DO vs predicted DO according to Example 4.
  • FIG 11 provides exemplary graphs of statistical profiles showing the effect of main parameters on DO content and degassing time according to Example 4.
  • in-line refers to any components or equipment in an industrial apparatus that are connected to other components or equipment by piping, tubing, or any conduit through which an industrial process stream (e.g. , monomer solution) may flow, for example by means of pumping.
  • an industrial process stream e.g. , monomer solution
  • upstream and downstream refer to relative orientation of components, equipment, or materials within an industrial process or apparatus through which fluid or liquid material may flow, for example by means of pumping.
  • a pumped fluid encounters an upstream location prior to encountering a downstream location.
  • one pass or “first pass” refers to a subjecting a monomer solution to a single application of degassing through an apparatus of the present invention.
  • the term “residence time” refers to the contact time between nitrogen gas and an industrial process stream (e.g., monomer solution) prior to degassing.
  • Reynolds Number refers to the gas-liquid mixture that forms when pressurized N2 gas is forced into a liquid monomer through the gas inlet of a Venturi Injector, thereby mixing with the liquid monomer motive fluid, which is pumped into the motive fluid inlet of the Venturi Injector.
  • a gas-liquid mixture is formed, which is pumped downstream of the Venturi Injector, optionally through a static mixer, and further optionally through a length of tubing, and into a degasser.
  • the gas-liquid mixture flow tends to be dominated by laminar (sheet-like) flow, while at high Reynolds numbers, turbulent flow is dominant.
  • Reynolds number for a flowing gas-liquid mixture may be calculated by any of several methods known in the art.
  • Laminar flow occurs when the calculated Reynolds number is less than 2300. Reynolds numbers exceeding 4000 indicate turbulent flow.
  • flow condition is known as critical. Critical flow is neither wholly laminar nor wholly turbulent and is a combination of the two flow conditions.
  • the term “motive flow rate” refers to the flow rate of a liquid into the motive fluid inlet a Venturi Injector.
  • Venturi injector refers to an eductor, which has been adapted to accept a pressurized N2 stream.
  • the term “eductor” generally refers to a device used to mix a gas with a liquid. When pressurized water enters the injector inlet, it is constricted toward the injection chamber and changes into a high-velocity jet stream. Typically, the increase in velocity through the vena contracta results in a decrease in absolute pressure, creating a vacuum that draws a liquid or gas (e.g., N2) additive through the suction port and mixes it thoroughly into the motive force fluid stream.
  • a liquid or gas e.g., N2
  • a pressurized N2 gas stream is injected or forced through the gas inlet of a Venturi Injector (i.e., an eductor) into the liquid monomer motive fluid stream, thereby providing for a higher N2 flow rate into the liquid stream and more turbulent flowing gas-liquid mixture than would otherwise be achievable under the vacuum formed by the Bernoulli effect.
  • a Venturi Injector i.e., an eductor
  • the Reynolds Number (Re) for the N2 gasliquid mixture when flowing (i) downstream of said Venturi Injector, (ii) between said Venturi Injector and said degasser, or (iii) within said length of tubing, is greater than 2300, greater than 4000, greater than 5000, or greater than 6000 for at least part of the distance between the Venturi Injector and degasser.
  • the Reynolds Number (Re) for the N2 gas-liquid mixture is greater than 4000, greater than 5000, or greater than 6000 for at least part or all of the distance between the Venturi Injector and degasser.
  • a Reynolds Number greater than 4000 for a flowing gas/liquid mixture indicates turbulent flow.
  • other forms of eductors may be directly used or adapted for use as a device for mixing pressurized or forced N2 gas into the liquid polymer motive fluid.
  • the other forms of eductors include a hootenanny or liquid jet pump, which is a simple type of pump that uses the Venturi effect to pump or move a fluid (air, liquid or gas) in an enclosed line.
  • process stream or “industrial process stream” generally refers to any aqueous fluids, solutions, slurries, or dispersions produced during any type of industrial process, for example, processes relating to chemical manufacturing, polymer manufacturing, pulp and paper industry, oil or gas extraction or recovery including recovery, extraction, refining, or waste treatment, waste treatment, water treatment, paints and coatings, food and beverage processing, mining industries, textiles, agriculture, or any portion thereof.
  • An exemplary embodiment of a process stream includes an aqueous monomer solution to be degassed and polymerized. The inventive method and apparatus for degassing may be applied to any process stream wherein degassing of an aqueous solution or process stream is required.
  • the terin “emulsion” refers to multiphasic fluid systems in which liquid droplets are dispersed in another immiscible liquid.
  • An emulsion is a mixture of two or more liquids that are normally immiscible (unmixable or unblendable) exhibiting liquid-liquid phase separation.
  • Emulsions comprise two phases, “dispersed/intemal phase” and “continuous/extemal phase”, which are liquids.
  • one liquid is suspended or dispersed throughout the other liquid (the continuous phase) in separate droplets.
  • Typical main components of an emulsion are the two liquid phases, typically oil and water, and an emulsifier, which stabilizes the interface between the two liquid phases.
  • Emulsifiers can be a variety of molecules, such as polymers, amphiphilic surfactants, and proteins, and they can also be colloidal particles.
  • polymer or “polymeric additives” and similar terms are used in their ordinary sense as understood by one skilled in the art, and thus may be used herein to refer to or
  • SUBSTITUTE SHEET (RULE 26) describe a large molecule (or group of such molecules) that may comprise recurring units.
  • Polymers may be formed in various ways, including by polymerizing monomers and/or by chemically modifying one or more recurring units of a precursor polymer.
  • a polymer may comprise a “homopolymer” that may comprise substantially identical recurring units that may be formed by, for example, polymerizing a particular monomer.
  • a polymer may also comprise a "copolymer” that may comprise two or more different recurring units that may be formed by, for example, copolymerizing, two or more different monomers, and/or by chemically modifying one or more recurring units of a precursor polymer.
  • a polymer or copolymer may also comprise a “terpolymer” or a “tetrapolymer” which generally refer to polymers that comprise three, four, or more different recurring monomer units.
  • the term “polymer” as used herein is intended to include both the acid form of the polymer as well as its various salts. Polymers may be amphoteric in nature, that is, containing both anionic and cationic substituents, although not necessarily in the same proportions.
  • emulsion polyacrylamide refers to an emulsion polymer in which at least one polymer is an acrylamide containing polymer.
  • the emulsion polyacrylamide (EPAM) comprises a small amount of water, for example less than about 12%, about 10%, about 5%, about 3%, about 2.5%>, about 2%, or about 1% by weight water, based on the total amount of all components of the emulsion polyacrylamide (EPAM).
  • emulsion polymer generally refers to inverse emulsions (water-in-oil) in which water droplets containing the polymer are suspended in an oil phase, also termed a hydrophobic phase.
  • the emulsion polymer comprises a small amount of water, for example less than about 12%, about 10%, about 5%, about 3%, about 2.5%, about 2%, or about 1% by weight water, based on the total amount of all components of the emulsion polymer.
  • the emulsion polymer is encapsulated in an oil bubble (droplet) called a micelle. It is held in there with surfactants. The surfactants keep the micelle surface tension greater that the surrounding water.
  • EPAMs may comprise ⁇ 33% active polymer, 10% oil and the remainder water and surfactants.
  • a DP AM is 95% active, which enables more efficient transport and storage.
  • dry polymer refers to a solid polymer in powder form, in granular form, or a combination thereof, which contains little water or is anhydrous.
  • a non-limiting example is polyacrylamide powder, or dry polyacrylamide (DP AM), is an acrylamide-containing polymer or copolymer.
  • polyacrylamide generally refer to polymers and copolymers comprising acrylamide moieties, and the terms encompass any polymers or copolymers, including terpolymers, comprising acrylamide moieties, e.g., one or more acrylamide (co)polymers of acrylamide and additional monomers capable of copolymerizing with acrylamide.
  • PAMs may comprise any of the polymers or copolymers discussed herein.
  • the term “monomer” generally refers to nonionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, betaine monomers, and amphoteric ion pair monomers.
  • nonionic monomer generally refers to a monomer that possesses a neutral charge.
  • exemplary nonionic monomers may comprise but are not limited to comprising
  • SUBSTITUTE SHEET (RULE 26) monomers selected from the group consisting of acrylamide (“AMD”), methacrylamido, vinyl, allyl, ethyl, and the like, all of which may be substituted with a side chain selected from, for example, an alkyl, arylalkyl, dialkyl, ethoxyl, and/or hydrophobic group.
  • a nonionic monomer may comprise AMD.
  • vinyl amide e.g., acrylamide, methacryl
  • Nonionic monomers include N-isopropylacrylamide, N-vinyl formamide, methacrylamide; N-alkylacrylamides, including but not limited to, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, and N- butylacrylamide; N,N-dialkylacrylamides, including, but not limited to, N,N-dimethylacrylamide and N,N-diethylacrylamide; N-alkyl methacrylamides; alkyl acrylates; hydroxyalkyl acrylates and methacrylates, including but not limited to, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3- hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl
  • anionic monomers may refer to either anionic monomers that are substantially anionic in whole or (in equilibrium) in part, at a pH in the range of about 1.0 to about 10.0.
  • the “anionic monomers” may be neutral at low pH (e.g., from a pH of about 0-1, 0-2, or 0-3) depending on the pKa values of acidic protons contained therein.
  • Some anionic monomers are obtained in anionic form as alkali metal salts, alkaline earth metal salts, and ammonium salts, e.g., acrylic acid and sodium acrylamido tertiary butyl sulfonic acid (ATBS).
  • anionic monomers which may be used herein include but are not limited to those comprising acrylic, .methacrylic, maleic monomers and the like, acrylic acid, calcium diacrylate, and/or any monomer substituted with a carboxylic acid group or salt thereof.
  • anionic monomers may be substituted with a carboxylic acid group and include, for example, acrylic acid, and methacrylic acid.
  • an anionic monomer which may be used herein may be a (meth)acrylamide monomer wherein the amide group has been hydrolyzed to a carboxyl group. Said monomer may be a derivative or salt of a monomer according to other embodiments.
  • anionic monomers comprise but are not limited to those comprising sulfonic acids or a sulfonic acid group, or both.
  • the anionic monomers which may be used herein may comprise a sulfonic function that may comprise, for example, 2-acrylamido-2- methylpropane sulfonic acid (acrylamido tertiary butyl sulfonic acid or “ATBS”).
  • anionic monomers may comprise organic acids.
  • anionic monomers may comprise acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamido methylpropane sulfonic acid, vinylphosphonic acid, styrene sulfonic acid and their salts such as sodium, ammonium and potassium.
  • anionic monomers may comprise acrylic acid, methacrylic acid; sulfonic acids, phosphonic acids, maleic acid, itaconic acid, vinyl sulfonic
  • SUBSTITUTE SHEET (RULE 26) acid, acrylamido tertiary butyl sulfonic acid (ATBS), acrylamido methanesulfonic acid, acrylamido ethanesulfonic acid, 2-hydroxy-3-acrylamide propane sulfonic acid, styrene sulfonic acid, vinyl phosphonic acid, and alkali metal salts, alkaline earth metal salts, and ammonium salts thereof.
  • Anionic monomers can be combined for example to form a terpolymer of acrylamide , acrylic acid and acrylamido tertiary butyl sulfonic acid (ATBS).
  • one or more acrylamide (co)polymers may comprise at least one monoethylenically unsaturated monomer comprising acid groups, for example monomers that comprise at least one group selected from - COOH, SO3H, or -PO3H2.
  • monomers may include , but are not limited to, acrylic acid, methacrylic acid, vinyl sulfonic acid, allyl sulfonic acid or 2-acrylamido -2-methylpropane sulfonic acid, particularly preferably acrylic acid and/or 2-acrylamido-2- methylpropane sulfonic acid, and most preferred acrylic acid or the salts thereof.
  • one or more acrylamide (co)polymers, or each of the one or more acrylamide (co)polymers may comprise acrylic acid and/or 2-acrylamido-2-methylpropanesulfonic acid or salts thereof.
  • cationic monomer generally refers to a monomer that possesses a positive charge. Examples thereof include acryloyloxy ethyl trimethylammonium chloride (Q9) monomers. Cationic monomers may also be selected from acryloyloxyethyltrimethyl ammonium chloride (“AETAC”), methacryloyloxyethyltrimethylammonium chloride (“MAETAC”), methacrylamidopropyltrimethylammonium chloride (“MAPTAC”), acrylamidopropyltrimethylammonium chloride (“APTAC”), methacryloyloxyethyldimethylammonium sulfate, diallyldimethylammonium chloride (“DADMAC”); dialkylaminoalkyl acrylates and dialkylaminoalkyl methacrylates and their quaternary or acid salts, including but not limited to, dimethylaminoethyl acrylate (“DM”)
  • MAETAC methacryloy
  • ppm refers to parts per million on the basis of milligrams of solute per liter of aqueous solution or slurry (e.g., mg/L).
  • ppb refers to parts per billion on the basis of micrograms of solute per liter of aqueous solution or slurry (e.g., jig/L).
  • This invention provides a method to remove oxygen from monomers to improve batch times for producing dry polyacrylamides (DP AM) and also for emulsion polyacrylamides (EPAM) in the polymerization process.
  • DPAM dry polyacrylamides
  • EPAM emulsion polyacrylamides
  • this novel method and design can be directly applied in e.g., tipping reactors but also other new technologies such as tube reactors. It can be applied to anionic and cationic DP AMs and more specifically to production sites around the world. In the future it can also be introduced in new facilities such as the one for tube reactors.
  • degassing can occur in one pass by injecting nitrogen into a Venturi Injector.
  • the kinetic energy of the monomer solution (motive force of the Venturi Injector) draws the gas, i.e., the N2 into the monomer solution.
  • the inventive method also employs pressurized, flow rate controlled N2 into the Venturi Injector. Mathematical modeling of the process shows that the target 200 ppb level will be feasible if there is sufficient residence time and turbulence in the piping after the injector.
  • Pilot plant degassing unit was designed and built based on previous modeling work. The modeling results suggested that oxygen specification with one pass through can theoretically be achieved by increasing residence time, assuming the two phases are well mixed, preferably under turbulent conditions. Thus, to test this hypothesis a pilot unit was design to test different tube length and diameter configurations.
  • the benefits of the inventive method and apparatus when scaled-up include: (i) ability to increase capacity, (ii) reduce degassing times from 40-60 min to practically zero and (ii) to save in N2 consumption.
  • Venturi Injectors have been used successfully for gas-liquid operations e.g., in water treatment and wastewater aeration. In absorption processes, the Venturi effect is used to pull gas into the liquid stream through a small orifice, allowing the gas to dissolve in the liquid.
  • Venturi inductors This is commonly used in gas scrubbers, where the gas is removed from the exhaust stream.
  • the Venturi effect can be used to introduce a gas into a liquid stream, allowing the gas to bubble up and escape from the liquid.
  • stripping processes where a gas is used to remove a volatile component from a liquid.
  • the Venturi effect creates a vacuum, which pulls gas into the liquid stream through a small orifice, resulting in effective mass transfer. Furthermore, the vacuum created by the Venturi effects eliminates the need for mechanically induced gas flow, making the system rather low cost in terms of capital expenditure (CAPEX) and also easy to operate.
  • the (N2) jet entering a liquid flow can be characterized using several variables, including the jet diameter, pipe diameter, velocity ratio, and pipe Reynolds number.
  • An important dimensionless parameter is the jet regime parameter, which determines the efficiency of mixing.
  • the variables that were studied with the pilot unit were pipe diameter, pipe length, monomer temperature, motive flow and N2 flow.
  • the present invention feeds pressurized and flow rate-controlled nitrogen into the Venturi Injector in order to increase degassing efficiency.
  • the set-up comprised a N2 tank, a monomer feed tank with a cooling coil and a stirrer, a progressive cavity pump, the Venturi Injector, the 6 or 12 m of tubbing to add extra residence time a de-gasser, discharge tank, pressure sensors, flowmeters, rotameters and a dissolve oxygen meter to measure the DO. before and after the monomer passed through the injector.
  • the present invention provides an apparatus according to FIG 1 for degassing a monomer composition, the apparatus comprising: a monomer tote bin (20) with Monomer tote bin bottom discharge valve (5) and Monomer tote bin valve (2), as well as a Test water tote bin (19) with a Test water tote bin bottom discharge valve (4) and Test water tote bin valve (1) feeding into a Tote discharge manifold (35).
  • the manifold (35) feeds into a Transfer pump SKID (21) with Transfer pump skid valve (3). Waste is discharged into Waste tote bin (6).
  • Transfer pump SKID (21) pumps liquid into Monomer feed tank with cooling coil and stirrer (22). Cooling coil is attached to Chill water control valve (11), Chill water supply valve (12), and Chill water return valve (13). Stirrer is connected to stirrer valve (36).
  • Monomer feed tank (22) drains through Feed tank discharge valve (15) into Progressive cavity pump (23), which is piped into Venturi Injector (25) comprising motive fluid inlet (32), Venturi Injector gas inlet (33), and Venturi Injector outlet (34).
  • Venturi Injector outlet (34) is connected to static mixer (26) and coil tubing (27), which feeds Degasser (hydro separator and gas vent) (28). After gas liquid separation, the degassed solution feeds through Hydro separator discharge valve (14), into Discharge tank (29) with DO probe (30). Discharge tank is equipped with Discharge tank exhaust valve (7).
  • Nitrogen flow to the discharge tank (29) is controlled by Discharge tank N2 feed valve (10).
  • Nitrogen flow to the Venturi Injector is controlled by Nitrogen valve to the gas flowmeter (9).
  • N2 needle valve (16) controlled the rate of flow through Gas flowmeter (31).
  • Example 1 Degassing test unit design and degassing procedure
  • the inventive apparatus for one-pass deoxygenation of a monomer solution contained a N2 tank, a monomer feed tank with a cooling coil and a stirrer, a progressive cavity pump, a Venturi Injector, a 6 m or 12 m of tubing coil to add extra residence time, a degasser, a discharge tank, a dissolved oxygen (DO) meter to measure the DO before and after the monomer passed through the Venturi Injector (eductor), pressure sensors, flowmeters, rotameters, and additional components according to the diagram in FIG 1.
  • FIGS 2-3 Exemplary images of different views of the degassing test unit pilot layout as built in Aberdeen, USA are shown in FIGS 4-7.
  • Degassed monomer solution may be (i) recirculated through the degassing system in a second (or third, fourth, etc.) pass, (ii) stored in a holding tank, preferably under a N2 atmosphere, or (iii) subjected to polymerization conditions.
  • N 2 flow rate Scale is 10 - 100 SCFH; 4.72 L/min - 47.2 L/m
  • N 2 flow rate Scale is 10 - 100 SCFH; 4.72 L/min - 47.2 L/m
  • Modeling results indicate that final DO content of a solution is predicted by modeling to be
  • ⁇ 1 strongly correlated with length of the coiled tube downstream of N2 jet injection in the Venturi Injector (25). It was rationalized from these results that residence time of the gas-liquid mixture in the tubing between Venturi Injector (25)and degasser (28) would allow for more efficient mass action of DO between the liquid phase and the gas phase and would also allow for more time N2 and O2 to react to form nitric oxide. Nitric oxide is a gas phase product of deoxygenation with N2, and is separated from the aqueous solution at the degasser, along with N2, O2, and other volatile components of the gas/liquid mixture. It was rationalized from these modeling results that longer tubing would allow for longer residence times and allow for longer contact between N2 and 02, causing higher degassing efficiency.
  • Table 1 Results for degassing of a water-glycol solution.
  • Results indicate that the inventive method for deoxygenation effectively reduced DO content of a glycol-water solution from greater than 10 ppm to 1.570-0.34 ppm, frequently less than the target of 500 ppb after one pass.
  • the most effective deoxygenation trials resulted in 34 ppb, 90 ppb, and 201 ppb. These results match or outperform the preferred target DO content of 200 ppb after one pass.
  • Example 4 Pilot trials for degassing of a monomer mixture in one pass
  • Pilot trial one pass degassing of an aqueous monomer solution (acrylamide, 38 wt. % active) was performed with the aim of evaluating the inventive degassing system.
  • the monomer mixture is representative of the production in an industrial plant. Degassing was performed according to Example 1.
  • a dissolved oxygen (DO) prediction plot showing actual DO vs predicted DO is shown in FIG 10. Results of this statistical analysis show that the selected parameters give a satisfactory description of the results.
  • Target levels are represented by horizontal dashed lines. Blue lines represent the boundary conditions for achieving target final DO levels (e.g., 500 bbp or lower) and pumping
  • Results shown in FIG 11 illustrate the impact of every operational variable on the objective variables, which are DO and time to pump. These results provide further confirmation that the most relevant variable is motive flow, followed by tube inner diameter. Although the preferred target values of 200 ppb were not achieved in the tests, the motive flow maximum level of 10.2 L/min was set due to a technical limitation of the available pump. Also, for lack of pumping capacity the higher flow rates were not achievable with the smaller tube diameters. Thus, the system can be improved to obtain preferred target DO of ⁇ 200 ppb.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Degasification And Air Bubble Elimination (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne un procédé et un appareil de dégazage d'une composition monomère. En particulier, la divulgation concerne un procédé et un appareil de désoxygénation de solutions monomères pendant le transfert d'un réservoir de maintien de monomère à un réacteur. Le dégazage se produit en un seul passage par combinaison d'un jet d'azote avec une solution monomère dans un injecteur Venturi. Les procédés et l'appareil de dégazage inventifs assurent une performance de dégazage améliorée.
PCT/US2024/037774 2023-07-13 2024-07-12 Procédé de désoxygénation à un passage pour la production de polyacrylamide Pending WO2025015262A2 (fr)

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FI20236045 2023-09-21

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US20070123624A1 (en) * 2005-11-30 2007-05-31 Otten Jay G Method of drying an absorbent polymer with a surfactant
US9334376B2 (en) * 2009-12-24 2016-05-10 Nippon Shokubai Co., Ltd Water-absorbable polyacrylic acid resin powder, and process for production thereof
US9731225B2 (en) * 2011-12-21 2017-08-15 Tetra Laval Holdings & Finance S.A. Deaerator and method for deaeration
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