WO2014043306A1 - Process for preparing water soluble polymers with no insoluble gels and low levels of residual monomers - Google Patents
Process for preparing water soluble polymers with no insoluble gels and low levels of residual monomers Download PDFInfo
- Publication number
- WO2014043306A1 WO2014043306A1 PCT/US2013/059377 US2013059377W WO2014043306A1 WO 2014043306 A1 WO2014043306 A1 WO 2014043306A1 US 2013059377 W US2013059377 W US 2013059377W WO 2014043306 A1 WO2014043306 A1 WO 2014043306A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymerization
- piston
- reagents
- inner chamber
- wet gel
- Prior art date
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 26
- 239000000499 gel Substances 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229920003169 water-soluble polymer Polymers 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000011240 wet gel Substances 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 73
- 238000006243 chemical reaction Methods 0.000 claims description 15
- -1 poly(acrylamide) Polymers 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000012966 redox initiator Substances 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000001419 dependent effect Effects 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 239000002738 chelating agent Substances 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 238000011109 contamination Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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
- C08F6/00—Post-polymerisation treatments
- C08F6/008—Treatment of solid polymer wetted by water or organic solvents, e.g. coagulum, filter cakes
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1812—Tubular reactors
- B01J19/1818—Tubular reactors in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/20—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by expressing the material, e.g. through sieves and fragmenting the extruded length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/262—Alkali metal carbonates
Definitions
- the present invention rela tes to novel methods and apparatuses for preparing water soluble dry polymers.
- Water soluble dry polymers are polymers that are typically hygroscopic and are stored in dry conditions.
- One key advantage of dry polymers is their weight, which makes them inexpensive to store and transport.
- Dry polymers are commonly prepared from sticky rubber like materials known as "wet gels".
- Wet gels are extremely viscous polymers formed from the polymerization of vinyl monomers in water.
- converting wet gels into dry polymers is a lengthy and energy intensive process. This process involves a drying step in which the wet gels are cut into small enough pieces that allow for the rapid removal of water by- evaporation without overheating. The dried polymer is then ground into a size that is best suited for a re-dissolving in water at a desired speed.
- Continuous operation of the cutting, drying, and grinding processes is the most cost effective manner of producing dry polymer.
- a steady supply of wet gel polymer is continuously fed into the drying step and a steady supply of dry polymer is continuously output.
- Current continuous dry steps make use of continuous polymerization reactions that are belt fed into the drying step. Maintaining quality control in these operations however is difficult because the short residence time of the monomers in a continuous polymerization reactor makes it difficult to maintain both a high molecular weight and 100% solubility of the resulting dry polymer. In addition too much un-reacted residual monomer often remains further contaminating the product.
- industry also makes use of less efficient batch processing and feeding of wet gels to preserve reliable dry polymer quality.
- At least one embodiment is directed towards a method of feeding wet gel polymer into a drying step of a water soluble dry polymer synthesis operation.
- the method comprises the steps of: a) receiving polymerization reagents into a flow loop the flow loop constructed and arranged to regulate the flow of the reagents such that they are sequentially passed into one of a plurality of pistons, b) polymerizing those polymerization reagents into wet gel polymers within one of the plurality of pistons, and c) feeding the wet gel polymers from the pistons into the drying step.
- Each piston is constructed and arranged to: receive polymerization reagents, contain a polymerization reaction, and feed wet polymer according to a coordinated sequence, timed to effect continuous feeding of wet gel into the drying step.
- the polymerization reagents include monomers and at least one other composition of matter.
- the piston may comprise an inner chamber, a scalable entry valve constructed and arranged to receive two or more flows of polymerization reagents and to deposit substantially all of the received polymerization reagents into the inner chamber, a scalable exit valve in fluidic communication with the inner chamber which passes fluid on to a drying step, and a plunger capable of pressing the contents of the inner chamber out through the exit valve.
- the entry valve may be constructed and arranged to pass substantially all of its contents into the inner chamber when the entry valve is sealed and may be constructed and arranged to receive two fluid streams, which are mixed immediately before they are passed into the inner chamber.
- the plunger may comprise a face which contacts fluids within the inner chamber, the face having a diameter that substantially fills a cross sectional area of the inner chamber and which is constructed and arranged to push substantially all fluid within the inner chamber out through the exit valve.
- the method may further comprise a stripper tank, and further comprise the step of mixing a solution of monomers and at least one other polymerization reagent within the stripper tank, keeping the temperature within the stripper tank too low for a polymerization reaction to occur, and feeding that mixture into the piston at a coordinated time.
- the stripper tank may have the same volume as the portion of the inner chamber in which polymerization will occur.
- the method may further comprise the step of purging oxygen from the stripper tank prior to feeding the polymerization reagents into the piston or inhibiting any polymerization from occurring until the piston of completely filled up.
- the inhibition may occur through one step selected from the list consisting of: adding an induction time increasing agent to the
- the method may include an induction time increasing agent added to the polymerization reagents which increases the induction time to at least the time (or possibly 5 minutes more than is) needed to completely fill ail the polymerization reagents into the inner chamber and seal the piston.
- the method may further comprise the step of providing a temperature jacket in contact with at least a portion of at least one piston, the temperature jacket constructed and arranged to regulate the temperature of at least a portion of that piston.
- the interior of the piston in which the polymerization reaction occurs may be substantially smooth and coated with a material that inhibits the adhesion of wet gel polymer to the piston.
- the polymerization reaction may be a simultaneous polymerization of acrylamide and a hydrolysis of poly(acrylamide) and in which the polymerization reagents further comprise acrylamide monomer and potassium carbonate.
- the coordination between the pistons may be such that just as a first piston has completely fed its wet gel polymer into the drying step a second piston has just completed its polymerization reaction and begins to feed its wet gel polymers into the drying step.
- FIG. 1 is an illustration of the inventive polymerization process.
- FIG. 2 illustrates a four piston reaction system sequence.
- FIG. 3 illustrates an alternative four piston reaction system sequence.
- Initiator means a composition of matter that initiates a free radical polymerization reaction upon thermal decomposition or reaction with a second component of a redox pair.
- Batch Process means a chemical process in which only a finite number of reagents can be fed into a reaction operation over a specific period of time and which produces a finite am ount of product.
- Continuous Process means an ongoing chemical process, which is capable of continuing over an unlimited period of time in which reagents can be continuously fed into a reaction operation to continuously produce product
- Continuous Process and Batch Process are mutually exclusive
- “Dry Polymer Synthesis” means the conversion of wet water soluble monomers into dry polymers according to a process which includes but is not limited to at least one action performed on the resulting polymer from the list of: cutting, drying, cooling, grinding, sifting, packaging, and any combination thereof,
- Water Soluble Dry Polymer means polymers that are hygroscopic and therefore are best stored in dry conditions.
- the apparatus (1) comprises one or more monomer storage vessels (2a-e) which are constructed and arranged to feed the monomer into a stripper tank (3).
- one or more of the monomers and/or one or more or of any other needed reagents (8a-b) can be fed into the stripper tank (3) or into a make down tank (4) upstream from the stripper tank (3) within which one or more of the reagents may be changed from the format they were stored in into a format more suitable for the reaction.
- the reaction components are then fed into a flow loop (5) which appropriately feeds into two or more piston reactors (6).
- the polymerization reaction occurs within the piston reactors (6a-b) and is passed on to a drying stage (7) where the resulting wet polymer is dried.
- the initiation sequence and charging method is optimized for continuous feeding of wet gel polymers into a drying stage (7).
- First a monomer solution is prepared irs a large make down tank (4) and is chilled to the desired initiation temperature.
- a stripper tank (3) is then provided which is of equal volume to the interior of the piston (6), The stripper tank (3) is filled with chilled monomer solution.
- the oxygen level in the stripper tank is then reduced to below 500 ppb by purging the tank with an inert gas (13) (such as nitrogen, helium, and or argon).
- an inert gas (13) such as nitrogen, helium, and or argon
- a number of additives are then added to the stripper tank from one or more additive storage containers (8a-b) including but not limited to: a chelating agent which complexes and deactivates metallic inhibitors, a polymerization delay inhibitor, at least one thermally activated initiator, an oxidizing component of a redox-initiator system, and any combination thereof.
- FIG. 1 illustrates that the piston reactors are next to each other, the positioning of the reactors can be according to any configuration. Similarly while the above example had the next piston reactor being the one immediately alongside the first piston reactor, the sequence between the reactors can be according to any order of the piston reactors.
- FIG. 2 illustrates a possible sequence of piston use for a four piston reaction system, in addition, additional reactants (14) may be added at other stages of the process and may have circulation loops of their own.
- valve (9) When the contents of the stripper tank (3) have completely filled the chamber (8) of the piston reactor (6), a special valve (9), which is constructed and arranged to completely push all of the contents of the valve (9) into the piston reactor chamber (8) is sealed and emptied. This prevents any polymerization of polymer within the valve (9).
- the valve is a Piston Type Regulator Valve.
- Representative Piston Type Regulator Valves include bu t are not limited to M4 valves manufactured by Keofitt a/s of Denmark, and sampl ing Valves such as SV-500 valves by those manufactured by Strahman Valves Inc. Bethlehem, PA, and those described in US Patents 4,552,336, 5,246,204, and 3,058,431.
- the Stripper tank itself is completely emptied eliminating any possibility of polymer build up in the tank or feed lines and is immediately ready to repeat the process and fill the next piston in the sequence.
- the bottom of the reactor is also specially sized to have the same diameter as the piston chamber. This way 100% of the wet gel polymer is pushed out of the piston chamber by the plunger.
- a supply of wet gel is continuously fed into a drying stage (7) for an unlimited amount of time.
- This continuous feeding is accomplished by the series of pistons (6) within each of which a polymerization reaction occurs.
- the gel polymer is pressed out of the piston by a plunger (10) through an exit valve (11) and into the drying stage (7).
- the reagents for poivmerization are fed into each piston according to a coordinated chronological sequence so that as soon as any one piston has completed feeding its contents, another piston begins feeding its contents, and the empty piston appropriately is re-charged, This allows the pistons to effect a continuous feed of wet gel into a drying stage.
- At least one of the pistons is one similar to or the same as used in an F-4Q Reactor produced by River City Enterprises.
- Each piston (6) comprises an entry valve (9), a plunger (10), and an exit valve (1 1 ).
- the exit valve (1 1) is a knife gate valve.
- the knife gate valve is at least one of those described in US Patents 2,883,148 and/or 4,798,365.
- the knife gate valve is a Diamond-Port as produced True Line.
- the insides of the pistons are ideal reactors for wet gel polymerization. Because wet gel polymers are extremely viscous, no internal components are present within the pistons. In at least one embodiment, the polymerizations are run adiabaticaliy and substantially no heat is allowed to escape from the interior of the piston.
- the wet gel polymer can be discharged through a large diameter knife gate valve that forms a liquid and gas tight seal when closed.
- the discharge rate is controlled by applying pressure to the plunger on the opposite side of a piston that slides along the smooth wall s of the reactor.
- the plunger displaces up to all of the entire volume of the piston chamber and empties it completely.
- the bottom valve design has an opening equal to the inside diameter of the piston interior. This allows complete discharge of the wet gel from the piston chamber before the next batch of monomer is added. As a result, the piston chamber can be refilled again and again without needing any cleaning. This avoids problems associated with contamination of newly formed wet gels with leftover products and residuals of earlier polymerizations.
- One problem currently present in polymerization reactions is contamination due to non-homogenous temperature of the reagents, if cold monomer is pumped into hot, partially polymerized monomer, the interaction results in poor quality polymer.
- Some examples of this poor quality is polymers having one or more of: incomplete water solubility, lower molecular weight, higher residual monomer, and any combination thereof.
- One way to address this is to assure that no polymerization begins until the piston chamber is completely filled and sealed assuring a constant uniform temperature. This invention includes two strategies to assure this occurs, the first is to place ail of the reagents but one reaction dependent reagent in the stripper and flow loop and to only add the last one immediately before entering the chamber.
- the second is to use an inhibitor to delay the onset of polymerization until after the chamber has been completely filled and sealed, in at least one embodiment the time short time interval is a time within the range of 5 and 10 minutes.
- the reaction dependent reagent that is not added until all of the other reagents have been added is a reducing component of a redox initiator.
- the reducing component of a redox initiator is pumped through a second loop that also flows past each piston at a specific flow rate, At the appropriate time, the flow containing the monomer and other reagents and the flow containing the reducing component of a redox initiator are simultaneously directed to a given piston. Both flows pass through the special valve where they are mixed on the way through the reactor wall.
- a delay inhibitor is used to delay the onset of polymerization for a pre-determined length of time after the addition of reducing components of the redox initiator system.
- the piston chamber is completely filled before polymerization begins.
- the delay inhibitor causes an induction time of 10-15 minutes while the feed mechanism feeds and seals the piston in 5-1 0 minutes.
- the piston is constructed and arranged to tolerate reaction temperatures of over 100° C and to contain gaseous by products.
- the piston further comprises a iemperaiure jacket which appropriately cools or heats the piston chamber walls,
- the walls contain a chamber filled with cool or hot fluid which causes this cooling or heating effect. This jacket can be used, both to regulate surface temperature during polymerization or to cool the piston chamber rapidly to accept new reagents rapidly after synthesizing and passing on hot wet gel polymers.
- the walls of the piston chamber are at least partially coated with a composition of matter that reduces adhesion of wet gel polymers.
- a conveyer belt (12) is constructed and arranged to slide downstream from one or more of the pistons, receive the extruded polymer, and thereby continuously pass the polymers on to the drying stage (7)
- the wet gel polymer produced in the piston chamber include but are not limited to high molecular weight flocculants, anionic, cationie, and nonionic polymers
- the reaction occurring within the piston chamber (or a standard reactor) is a simultaneous acrylamide polymerization and hydrolysis of
- poly(acrylamide) in the prior art, it is common to polymerize poly(acrylamide) and then subsequently hydrolyze the polymer. This is because common hydrolyzing agents are either too strong (like NaOH) and react with the monomers to form contaminants or they cause crystallization of acrylamide at low temperature (like Na 2 CO 3 ).
- potassium carbonate is added to the acrylamide monomer which results in the hydrolysis of poly(acrylamide) as it is formed, Acryiamide is more soluble in the presence of potassium carbonate than sodium carbonate which allows for increasing the concentration of monomers within the piston chamber or reactor which increases the hydrolysis.
- the potassium carbonate is not as reactive as NaOH, it does not cause unwanted side reactions with monomers,
- a solution which is 15 mole-% potassium carbonate yields 40 mole-% hydrolysis of poly(acrylamide). This one step reaction avoids the costs of a second synthesis step and avoids the need to use acrylic acid in the synthesis of anionic wet gels.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112015005536-2A BR112015005536B1 (en) | 2012-09-12 | 2013-09-12 | METHOD FOR FEEDING POLYMER IN WET GEL FOR A DRYING STAGE OF A DRY-SOLUBLE WATER-SOLUBLE POLYMER OPERATION |
ES13837334.5T ES2640927T3 (en) | 2012-09-12 | 2013-09-12 | Procedure for preparing water soluble polymers without insoluble gels and low levels of residual monomers |
CN201380045675.1A CN104619750B (en) | 2012-09-12 | 2013-09-12 | For the method preparing the water-soluble polymer of sol gel and low-level residual monomer invariably |
CA2885430A CA2885430C (en) | 2012-09-12 | 2013-09-12 | Process for preparing water soluble polymers with no insoluble gels and low levels of residual monomers |
JP2015532034A JP5898820B2 (en) | 2012-09-12 | 2013-09-12 | Process for preparing water-soluble polymers that are free of insoluble gels and have low levels of residual monomers |
EP13837334.5A EP2895530B8 (en) | 2012-09-12 | 2013-09-12 | Process for preparing water soluble polymers with no insoluble gels and low levels of residual monomers |
KR1020157009374A KR101717200B1 (en) | 2012-09-12 | 2013-09-12 | Process for preparing water soluble polymers with no insoluble gels and low levels of residual monomers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/611,026 | 2012-09-12 | ||
US13/611,026 US8785573B2 (en) | 2012-09-12 | 2012-09-12 | Process for preparing water soluble polymers with no insoluble gels and low levels of residual monomers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014043306A1 true WO2014043306A1 (en) | 2014-03-20 |
Family
ID=50233899
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2013/059377 WO2014043306A1 (en) | 2012-09-12 | 2013-09-12 | Process for preparing water soluble polymers with no insoluble gels and low levels of residual monomers |
Country Status (9)
Country | Link |
---|---|
US (1) | US8785573B2 (en) |
EP (1) | EP2895530B8 (en) |
JP (1) | JP5898820B2 (en) |
KR (1) | KR101717200B1 (en) |
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See also references of EP2895530A4 |
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ES2640927T3 (en) | 2017-11-07 |
EP2895530B8 (en) | 2017-09-13 |
BR112015005536A2 (en) | 2017-07-04 |
CN104619750B (en) | 2016-11-02 |
US8785573B2 (en) | 2014-07-22 |
KR101717200B1 (en) | 2017-03-16 |
EP2895530B1 (en) | 2017-06-28 |
BR112015005536B1 (en) | 2021-04-13 |
EP2895530A4 (en) | 2016-06-08 |
KR20150056600A (en) | 2015-05-26 |
JP2015528529A (en) | 2015-09-28 |
US20140073749A1 (en) | 2014-03-13 |
EP2895530A1 (en) | 2015-07-22 |
CA2885430C (en) | 2015-08-18 |
CN104619750A (en) | 2015-05-13 |
CA2885430A1 (en) | 2014-03-20 |
JP5898820B2 (en) | 2016-04-06 |
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