WO2013131094A2 - Procédé et système d'utilisation d'un réacteur à conduit à base de fibres - Google Patents

Procédé et système d'utilisation d'un réacteur à conduit à base de fibres Download PDF

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Publication number
WO2013131094A2
WO2013131094A2 PCT/US2013/028894 US2013028894W WO2013131094A2 WO 2013131094 A2 WO2013131094 A2 WO 2013131094A2 US 2013028894 W US2013028894 W US 2013028894W WO 2013131094 A2 WO2013131094 A2 WO 2013131094A2
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Prior art keywords
fibers
reaction
stream
phase
group
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PCT/US2013/028894
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English (en)
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WO2013131094A3 (fr
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John Lee Massingill
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Chemtor, Lp
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Priority claimed from US13/410,920 external-priority patent/US9168469B2/en
Application filed by Chemtor, Lp filed Critical Chemtor, Lp
Publication of WO2013131094A2 publication Critical patent/WO2013131094A2/fr
Publication of WO2013131094A3 publication Critical patent/WO2013131094A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
    • C10L2290/146—Injection, e.g. in a reactor or a fuel stream during fuel production of water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/545—Washing, scrubbing, stripping, scavenging for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

  • This invention relates generally to fiber reactors/contactors, and specifically to processes utilizing such devices to effect separation and reaction between two immiscible reaction components using phase transfer catalysts and co-solvents.
  • the present invention enables the reaction between constituents of two immiscible fluids in order to produce desirable end products. This is currently achieved by making dispersions of one phase in the other to generate small droplets with a large surface area where mass transfer and reaction can occur, as described in Liquid-Liquid and Solid-Solid Systems, in Chemical Engineer's Handbook, 21-1-21-29, 5th ed., (Robert H. Perry & Cecil H. Chilton eds., McGraw-Hill 1973). Dispersions are used to wash water soluble impurities out of organic process streams, to neutralize organic process streams by extracting acid and base compounds from organic process streams, and to effect chemical reactions between components of two streams. For chemical reactions, phase transfer catalysts are frequently used to enhance mass transfer across the interface of the droplets, as described in Phase-Transfer Catalysis:
  • Co-solvents can also be used for this purpose.
  • Phase-transfer catalysis (PTC) technology is used in the commercial manufacture of more than $10 billion per year of chemicals, including monomers, additives, surfactants, polymers, flavors and fragrances petrochemicals, agricultural chemicals, dyes, rubber, pharmaceuticals, and explosives.
  • PTC technology is also used in pollution prevention, pollution treatment and the removal or destruction of impurities in waste and product streams.
  • PTC technology is used in these applications because it provides many compelling benefits, such benefits being primarily related to reducing the cost of manufacture of organic chemicals and pollution prevention.
  • the many significant and advantageous process performance achievements which are routinely realized using PTC include increased productivity (increased yield, reduced cycle time, reduced or consolidated unit operations, and increased reactor volume efficiency), improved environmental performance (eliminated, reduced, or replaced solvent and reduced non- product output), increased quality (improved selectivity and reduced variability), enhanced safety (controlled exotherms and use of less hazardous raw materials), and reduced manufacturing costs (eliminated workup unit operations and use of alternative raw materials).
  • productivity increased yield, reduced cycle time, reduced or consolidated unit operations, and increased reactor volume efficiency
  • improved environmental performance eliminated, reduced, or replaced solvent and reduced non- product output
  • increased quality improved selectivity and reduced variability
  • enhanced safety controlled exotherms and use of less hazardous raw materials
  • manufacturing costs eliminated workup unit operations and use of alternative raw materials.
  • Processing of vegetable oils typically includes the following steps: 1) acid degumming to remove phospholipids such as lecithin; 2) neutralization to remove free fatty acids that can cause rancidity in processed oils (in some processes degumming and neutralization are combined); 3) washing to remove residual caustic and soap in the neutralized vegetable oil (a double wash is often recommended); 4) bleaching to remove color bodies; and 5) deodorization.
  • acid degumming to remove phospholipids such as lecithin
  • neutralization to remove free fatty acids that can cause rancidity in processed oils (in some processes degumming and neutralization are combined
  • washing to remove residual caustic and soap in the neutralized vegetable oil a double wash is often recommended
  • bleaching to remove color bodies
  • deodorization Moreover, many modern plant processes are continuous and use centrifuges to accelerate settling of oil and water layers in caustic neutralization and subsequent washing because of the formation of soap by reaction of free fatty acids and caustic, as in the PTC technology discussed above.
  • U.S. Pat. Nos. 3,754,377; 3,758,404; 3,839,487; 3,977,829; and 3,992,156 are directed to methods of effecting mass transfer between two immiscible fluids without forming
  • U.S. Pat. No. 3,758,404 (issued to Clonts) discloses a method for effecting mass transfer between immiscible, concurrently flowing liquid-liquid phases, including a conduit having a bundle of elongated fibers positioned therein.
  • the fiber bundle is positioned within the conduit at a perforated node that also acts as the point of introduction for the first liquid, which is deposited onto and within the fiber bundle as a film.
  • a second liquid is directed into the conduit and over the first liquid deposited on the fibers.
  • the large area of contact between the first and second liquids provides for an efficient mass transfer there between.
  • the first liquid deposited on the fibers is moved along the fibers by the viscous drag occurring between the two concurrently flowing fluids.
  • the first liquid in film form is moved along the fibers and eventually deposited in a collection vessel.
  • the downstream end of the fiber bundle extends outwardly of the conduit into the collection vessel for the purpose of making direct fluid contact with fluid collected off of the bundle in order to prevent dispersion between the two phases. In this manner, mass transfer is efficiently effected between the two immiscible liquids without dispersion of one liquid into the other.
  • U.S. Pat. No. 3,754,377 (issued to Clonts) provides for a gas-liquid mass transfer process which is similar to the liquid-liquid mass transfer process just described.
  • This patent teaches use of the fiber contactor to extract acidic components from natural gas and light hydrocarbons with aqueous caustic.
  • U.S. Pat. No. 3,992,156 (issued to Clonts) provides for mechanical improvements to fiber contactors, such as a method of supporting the fibers to prevent premature breakage and the use of multiple bundles of fibers and distribution tubes.
  • fiber contactors have proved to be remarkable inventions providing mass transfer at high efficiency levels without dispersion of one fluid into the other in the extraction of troublesome acidic impurities such as phenolics, hydrogen sulfide, C0 2 , and mercaptan compounds from petroleum refinery process streams.
  • U.S. Pat. No. 5,705,074 (issued to Brient) teaches the use of fiber contactors to remove phenolics and other water-soluble organic materials from aqueous refinery waste streams by an extraction process.
  • U.S. Pat. No. 5,997,731 (issued to Shunt) teaches the use of fiber contactors to neutralize an alkaline solution containing dissolved sodium sulfides, mercaptides and phenolates with a carbon dioxide-containing solvent and recover processable hydrocarbon values.
  • 5,306,831 (issued to Beshouri, et al.) teaches use of fiber contactors to remove water soluble polyol impurities in a sorbitan ester mixture by treating a polyol-containing sorbitan ester dissolved in a solution containing a hydrocarbon and a polar organic solvent with an aqueous metal halide salt solution.
  • a process for conducting chemical reactions in a conduit reactor comprising introducing streams containing reactive species proximate an upstream end of a plurality of fibers positioned longitudinally within the conduit reactor, wherein a first stream constitutes a phase substantially constrained to the surface of the fibers and a second stream constitutes a substantially continuous phase that is in contact with and is substantially immiscible with the first stream, and whereby the reactive species in the constrained phase and the reactive species of the continuous phase interact to perform a chemical reaction.
  • a phase transfer catalyst may be employed to facilitate mass transfer.
  • a collection vessel can be provided for receiving the constrained phase and the continuous phase, wherein the constrained phase comprises a layer in a first portion of the collection vessel and the continuous phase comprises a layer in a second portion in the collection vessel, and the layer comprising the continuous phase and the layer comprising the constrained phase are separately withdrawn from the collection vessel.
  • the reaction process may include co-solvents to increase solubility of chemical species produced by the process.
  • a process for conducting chemical extractions in a conduit reactor comprising introducing streams containing reactive and extractable species proximate an upstream end of a plurality of fibers positioned longitudinally within the conduit reactor, wherein a first stream containing reactive species constitutes a phase substantially constrained to the surface of the fibers and a second stream containing extractable species constitutes a substantially continuous phase that is in contact with and is substantially immiscible with the first stream, and whereby the reactive species in the constrained phase and the extractable species of the continuous phase interact to effect extraction of at least some of the extractable species from the continuous phase into the constrained phase.
  • the first stream comprises an organic solvent or an aqueous solution containing an organic co-solvent.
  • FIG. 1 illustrates a prior art example of a conduit reactor useful with the present invention
  • FIG. 2 depicts a conduit reactor system of the present invention
  • FIG. 3 depicts a shell and tube heat exchanger for incorporation into processes in accordance with some embodiments of the present invention.
  • FIG. 4 illustrates a chemical synthesis of diepoxy resin that may be accomplished using various embodiments of the present invention.
  • the present invention is directed to (1) a new and improved process for effecting covalent chemical reactions between components of a first fluid that is initiated by component(s) of a second, substantially immiscible fluid, in order to produce a chemical product, (2) a new and improved process for neutralizing and washing organic reaction products and vegetable oils and fats prior to further processing, and (3) a new and improved process for degumming and neutralizing vegetable oils.
  • Some embodiments of the present invention employ fiber reactors/contactors as described in U.S. Pat. Nos.
  • conduit apparatuses described herein comprising fibers may be utilized as reactors and/or contactors/extractors, but for simplicity will be generally referred to as conduit reactors.
  • phase transfer catalyst can be employed to facilitate mass transfer across the interface between the phases.
  • Co-solvents can also be used to enhance mass transfer across the interface of the phases, improving the rate of reaction in the fiber conduit reactor.
  • a phase transfer catalyst may be introduced to the conduit reactor in the constrained phase, the continuous phase, or both phases. Phase transfer catalysts are generally selected based on their ability to be active at the interface of the phases and further to not produce emulsions that can cause the phases to be too difficult to separate. In addition, it is possible to tailor catalysts for reaction and for easy removal from the product.
  • the catalysts considered for use in a fiber reactor may include chiral and non-chiral materials.
  • phase transfer catalysts include, but are not limited to, quaternary ammonium compounds (e.g., a quaternary ammonium salt), quaternary phosphonium compounds (e.g., a quaternary phosphonium salt), sulfonium
  • HTA-1 a phosphazenium salt
  • crown ethers polyglycols (e.g., a polyethylene glycol, a polyethylene glycol ether, a polyethylene glycol ester), a hexaalkyl guanidinium salt, TDA-1 , a lariat ether, a tertiary amine, amino acids, and derivatives (including chiral derivatives) and/or combinations thereof.
  • polyglycols e.g., a polyethylene glycol, a polyethylene glycol ether, a polyethylene glycol ester
  • TDA-1 a hexaalkyl guanidinium salt
  • TDA-1 a lariat ether
  • tertiary amine amino acids, and derivatives (including chiral derivatives) and/or combinations thereof.
  • phase transfer catalysts such as but not limited to HTA-1 (Cognis) and phosphazenium salts
  • HTA-1 Recognitions
  • phosphazenium salts complement the conduit reactor's ability to operate conveniently at any temperature and pressure appropriate to a particular covalent chemical reaction being conducted.
  • the rates of chemical reactions employing phosphazenium catalysts can be increased merely by increasing the reaction temperature without destroying the catalyst. This can result in a reduction of reaction time of up to approximately 95% by changing the catalyst, temperature, pressure, and solvent.
  • a phase transfer catalyst, or any type of catalyst, used in a fiber reactor may be bound to a polymer.
  • the non-dispersive nature of the fiber conduit reactor broadens the number of compounds that may act as phase transfer catalysts to include all surfactants and surfactant- like compounds because they will not be agitated to form dispersions/emulsions that are difficult to separate.
  • utilizing surfactants in a fiber conduit reactor also works extremely well.
  • surfactants may aid in the interaction of reactants at the interface between the constrained and continuous phases without being dispersed by the process, in effect enhancing mass transfer across the interface of the phases and improving the rate of reaction in the fiber conduit reactor.
  • Either or both of the continuous and/or constrained streams may include a surfactant.
  • surfactants which may be considered for use in a fiber conduit reactor include but are not limited to anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
  • an amphoteric surfactant refers to a surfactant that contains both an acid and a basic hydrophilic moiety in its surface.
  • anionic surfactants which may be used in a fiber conduit reactor include but are not limited to carboxylates, sulphonates (including but not limited to petroleum sulphonates, alkylbenzesulphonates, naphthalenesulphonates, and olefin sulphonates), sulphates (including but not limited to alkyl sulphates, sulphated natural oils and fats, sulphated esters, sulphated alkanolamides, and sulphated alkylphenols), and ethoxylated alkylphenols.
  • carboxylates including but not limited to petroleum sulphonates, alkylbenzesulphonates, naphthalenesulphonates, and olefin sulphonates
  • sulphates including but not limited to alkyl sulphates, sulphated natural oils and fats, sulphated esters, sulphated alkanolamides, and sulphated alkylphenols
  • Examples of cationic surfactants which may be used in a fiber conduit reactor include but are not limited to amines with amide linkages; polyoxyethylene alkyl and alicyclic amines; ⁇ , ⁇ , ⁇ ', ⁇ ' tetrakis substituted ethylenediamines; and 2-alkyl 1 -hydroxy ethyl 2-imidazo lines.
  • Examples of nonionic surfactants which may be used in a fiber conduit reactor include but are not limited to
  • ethoxylated aliphatic alcohol polyoxyethylene surfactants
  • carboxylic esters polyethylene glycol esters, anhydrosorbitol ester and its ethyoxylated derivatives
  • glycol esters of fatty acids carboxylic amides, monoalkanolamine condensates, and polyoxyethylene fatty acid amides.
  • amphoteric surfactants which may be used in a fiber conduit reactor include but are not limited to N-coco 3-aminopropionic acid/sodium salt, N-tallow 3-iminodipropionate disodium salt, N-carboxylmethyl N-dimethyl N-9-octadecenyl ammonium hydroxide, and N- cocoamidethyl N-hydroxyethylglycine sodium salt.
  • conduit reactor and vegetable oil processing also complement each other extremely well.
  • Major advantages of the conduit reactor for degumming, neutralizing, washing, and/or bleaching fats, vegetable oils, and biodiesel are (1) very efficient degumming, neutralization, washing and bleaching because of excellent phase-to-phase contact, (2) fast separation of the two phases, and (3) elimination of long-lived dispersions caused by the soaps that form as result of caustic and water reacting with fatty acids.
  • Use of co-solvents in the constrained phase is advantageous in light of the poor solubility of gums and stearate salts in water.
  • the fibers that may be employed in the conduit reactor include, but are not limited to, cellulose, cotton, jute, silk, treated or untreated minerals, metals, metal alloys, treated and untreated carbon, polymers, polymer blends, and combinations thereof.
  • Suitable treated or untreated minerals include, but are not limited to, glass, basalt, asbestos, ceramic, and combinations thereof.
  • Suitable metals include, but are not limited to, iron, steel, nickel, copper, brass, lead, tin, zinc, cobalt, titanium, tungsten, nichrome, silver, aluminum, magnesium, and alloys thereof.
  • Suitable polymers include, but are not limited to, hydrophilic polymers, polar polymers, hydrophilic copolymers, polar copolymers, and combinations thereof, such as polysaccharides, polypeptides, polyacrylic acid, polymethacrylic acid, polyhydroxyalkylesters of polyacids, functionalized polystyrene (including but not limited to, sulfonated polystyrene, sulfonated polystyrene co-extruded with polypropylene (e.g., Toray's IONEX fiber), and animated polystyrene), functionalized polyolefm (e.g., Johnson Matthey's Smopex®-101), poly(ethylene-g- sulphonic acid), polyphenolics, polynovolacs, nylon, polybenzimidazole, polyvinylidenedinitrile, polyvinylidene chloride, polyvinyl alcohols, polyesters, polyamides, polyethers, polyvinyl
  • the fibers can be treated for wetting with preferred phases and to protect from corrosion by the process streams.
  • carbon fibers can be oxidized to improve wettability in aqueous streams and polymers can display improved wettability in aqueous streams by incorporation of sufficient functionality into the polymer, including but not limited to, hydroxyl, amino, acid, ether, amino acid, or polyamino acid functionalities.
  • Hybrid fibers may also be employed, such as polyethersulfone co-extruded with perfiuorosulfonic acid and Si02 nanoparticles as acid ion exchange fibers.
  • Another example is chlorobenzyl vinylpyridine grafted polyolefm fibers as basic ion exchange fibers (e.g., Smopex® - DS 269).
  • the constrained phase can comprise any liquid that wets the fibers preferentially to the continuous phase, including but not limited to, such materials as water, water solutions, water and co-solvents, alcohols, phenols, amines (including but not limited to, polyamines, ethanolamines, and polyethanolamines), carboxylic acids, dimethyl sulfoxide, dimethyl formamide, sulfuric acid, ionic liquids (including basic ionic liquids, acidic ionic liquids and chiral ionic liquids, such as but not limited to, l-allyl-3-methylimidazolium chloride, l-ethyl-3- methylimidazolium tetrafluoroborate, l,2-dimethyl-3-n-propylimidazolium tetrafluoroborate, l,2-dimethyl-3-n-butylimidazolium tetrafluoroborate, and l,2-dimethyl-3-n-butylimid
  • any of such materials may offer a solvent/reactant system that slightly compatibilizes both phases at their interface such that the two phases can react efficiently and be separated efficiently.
  • An advantage of using an ionic liquid is that the products of the reaction can be extracted into an organic solvent, leaving the ionic liquid behind. Furthermore, the by-product of the reaction can be extracted with water and the ionic liquid recycled. This contrasts with the use of dipolar aprotic solvents, which are difficult to remove from products.
  • This type of nucleophilic displacement reaction is one of the most common reactions in organic synthesis and the conduit reactor is ideal for alkylation reactions.
  • FIG. 1 depicts the conduit reactor disclosed in U.S. Pat. No.
  • a conduit 10 has in it a bundle of elongated fibers 12 filling the conduit 10 for a portion of its length. These fibers 12 are secured to a tube 14 at a perforated node 16. Tube 14 extends beyond one end of conduit 10 and has operative ly associated with it a metering pump 18 which pumps a first (constrained) phase liquid through tube 14 and onto fibers 12. Operatively connected to conduit 10 upstream of node 16 is an inlet pipe 20 having operatively associated with it a metering pump 22. This pump 22 supplies a second (continuous) phase liquid through inlet pipe 20 and into conduit 10, where it is squeezed between the constrained coated fibers 12.
  • a gravity separator or settling tank 24 into which the downstream end of fibers 12 may extend.
  • Operatively associated with an upper portion of gravity separator 24 is an outlet line 26 for outlet of one of the liquids, and operatively associated with a lower portion of gravity separator 24 is an outlet line 28 for outlet of the other liquid, with the level of an interface 30 existing between the two liquids being controlled by a valve 32, operatively associated with outlet line 28 and adapted to act in response to a liquid level controller indicated generally by the numeral 34.
  • an inverted arrangement using organophilic fibers with a constrained phase that is substantially organic can also be used.
  • This arrangement can, for example, be used to extract organic materials from water with organic liquids constrained to the fibers.
  • a liquid such as a caustic aqueous solution
  • Another liquid such as epichlorohydrin containing resin chlorohydrin (organic phase)
  • Fibers 12 will be wetted by the aqueous caustic solution preferentially to the organic mixture.
  • the aqueous caustic solution will form a film (not shown) on fibers 12, wherein the film will be dragged downstream through conduit 10 by the passage of the organic mixture therethrough.
  • a phase transfer catalyst can be employed to facilitate mass transfer across the interface between the phases.
  • Useful phase transfer catalysts for the reaction include, but are not limited to, quaternary ammonium compounds (e.g., a quaternary ammonium salt), quaternary phosphonium
  • phase transfer catalyst may be introduced to the conduit reactor in the constrained phase, the continuous phase, or both phases.
  • phase transfer catalyst or any other catalyst used in the reactor, may be bound to a polymer.
  • both liquid phases will be discharged into separator 24, but the volume of the organic phase discharged will be greater because the aqueous caustic solution will move at a slower velocity than the organic phase.
  • separator 24 the aqueous caustic solution will collect in the lower portion as it is heavier (denser) than the organic phase.
  • the downstream end of fibers 12 within separator 24 may be disposed above, below, or at the interface between the liquid phases within separator 24, depending on the relative density of the constrained phase and the continuous phase.
  • the interface 30 within separator 24 can be kept at a level above the bottom of the downstream end of fibers 12, so that the heavier aqueous caustic film can be collected directly in the bottom of separator 24 without it being dispersed into the organic phase.
  • a caustic solution as the aqueous phase
  • epichlorohydrin containing resin chlorohydrin as the organic phase
  • any suitable materials comprising substantially immiscible phases may be employed to practice the present invention.
  • the conduit reactor can be used with constrained phases lower in density than the continuous phase. Because the liquid phases come out of the conduit reactor separated and the constrained phase follows the fibers, the present invention may be utilized even when the phases are very close in density.
  • FIG. 2 shows a conduit reactor system useful in practicing the present invention.
  • the secured fibers in Reactors 1 and 2 are wetted by the constrained phase (“Caustic in") before the mobile phase (“Organic in”) is started.
  • FIG. 2 shows how multiple fiber reactors can be used to increase efficiency of utilization of reactants and to increase conversion of reactants by essentially feeding the liquids counter-currently through the reactor sequence.
  • the continuous phase output of Reactor 1 (“Organic Out”) is introduced to Reactor 2 ("Organic In”) and further processed thereby.
  • the constrained phase output of Reactor 2 is introduced to Reactor 1 ("Caustic In") while the constrained phase output of Reactor 1 is discarded as waste (or alternatively introduced to another reactor upstream of Reactor 1 (not shown)).
  • the caustic and organic phases are depicted as flowing co-currently through each individual reactor, but the caustic and organic phases flow counter-currently through the reactor sequence. Of course, fresh caustic can be used with each reactor if desired.
  • FIG. 3 shows a conventional shell and tube heat exchanger. Combining this design with the conduit reactor yields a conduit reactor design (not shown) adapted to handle exothermic reactions that need to be cooled and endothermic reactions that need to be heated.
  • Tube Inlet modification of the inlet of the heat exchanger tubes
  • Tube Outlet modification of the inlet of the heat exchanger tubes
  • the exit end of the heat exchanger can be modified to operate as a separator (not shown) to collect the aqueous phase on the bottom near the end of the fibers (not shown) and allow the organic phase to exit from the top of the separator section.
  • FIG. 3 depicts a counter-current flow heat exchanger, a co-current arrangement could also be used in conjunction with the present invention.
  • baffles are shown on the shell side of the exchanger in FIG. 3, the invention is not so limited and a heat exchanger without baffles may be employed.
  • FIG. 4 describes the chemical synthesis of diepoxy resin from epichlorohydrin and Bisphenol A (BP A). As illustrated therein, epichlorohydrin and BP A are combined in the presence of a basic material to produce a mixture of resin intermediates, diepoxy resin, and excess epichlorohydrin (not shown). While the major reaction products are described in FIG. 4, additional minor by-products typically produced are not shown. A large excess of
  • Useful basic materials for the reaction include, but are not limited to, basic compounds such as amines (including but not limited to, ethanolamines, polyamines, and polyethanolamines), hydroxides, carbonates, bicarbonates, chlorides, phosphates, and combinations thereof. These basic materials may comprise cations including, but not limited to, lithium, sodium, potassium, calcium, quaternary complexes, and combinations thereof.
  • the resin intermediates, dichlorohydrin resin and monoepoxy-monochlorohydrin resin are converted to the diepoxy resin (polyglycidyl ether resin) by subsequent exposure to an aqueous base and a phase transfer catalyst in the conduit reactor described in FIG. 1. While the reaction depicted by FIG. 4 utilizes epichlorohydrin and BPA, any suitable epihalohydrin and any suitable polyhydric alcohol may be used to produce polyglycidyl ether resins according to the present invention.
  • One suitable polyhydric alcohol is phenol-novolac, (Bisphenol F)
  • the epichlorohydrin reaction described above is one example of a chemical reaction which could be achieved using the processes comprising the present invention.
  • Other suitable reactions include, but are not limited to, O-alkylation (etherification), N-alkylation, C-alkylation, chiral alkylation, S-alkylation, esterification, transesterification, displacement (e.g., with cyanide, hydroxide, fluoride, thiocyanate, cyanate, iodide, sulfide, sulfite, azide, nitrite, or nitrate), other nucleophilic aliphatic & aromatic substitutions, oxidation, hydrolysis, epoxidation and chiral epoxidation, Michael addition, aldol condensation, Cannizzaro reaction, Henry reaction, Wittig condensation, Darzens Condensation, carbene reactions, thiophosphorylation, reduction, carbonylation, transition metal co-catalysis, Mannich reaction, Petasis reaction, Inter
  • an organic halide (R--X) and an organic acid (R' ⁇ H) may be coupled by the process described herein to produce a coupled product (R--R), wherein R--X and R--H can be on the same molecule or different molecules.
  • the organic acid (R'H) may comprise a carbon acid, such as a cyclopentadiene, an acetoacetate, triphenylmethanes, xanthenes, thioxanthenes, benzoxazoles, fiuorenes, indenes, malononitriles, trinitromethanes or an acetylene, or the organic acid may comprise carboxylic acids; thiocarboxylic acids; phenols, alcohols, thiols, amines, ethanolamines, and the like.
  • a carbon acid such as a cyclopentadiene, an acetoacetate, triphenylmethanes, xanthenes, thioxanthenes, benzoxazoles, fiuorenes, indenes, malononitriles, trinitromethanes or an acetylene
  • the organic acid may comprise carboxylic acids; thiocarboxylic acids; phenols, alcohol
  • water, alcohols, carboxylic acids, inorganic acids, thiols, amines, or the like may be reacted with an epoxide to form a glycol or a substituted glycol such as, but not limited to, an alkyl ether alcohol, an alkyl thioether alcohol, an ester alcohol, and an amino alcohol, a phosphate ester or a borate ester.
  • a chemical reaction may be performed via a single pass through a fiber conduit reactor.
  • Examples of chemical reactions which may be processed in such a manner include any of the chemical reactions noted above, including those which include multiple consecutive stepwise reaction stages.
  • a chemical reaction (or chemical process) may be performed in multiple passes through one or more fiber conduit reactors.
  • different stages of a chemical reaction or process may be consecutively and respectively performed in different passes of a single fiber conduit reactor and/or through different fiber conduit reactors.
  • intermediate materials may be formed after each pass and, thus, isolated for at least a brief time during the chemical process.
  • the intermediate materials further processed through the fiber conduit reactor may be withdrawn from either layer residing in the collection vessel.
  • a multi-pass format may be used for any of chemical reactions noted above and may be particularly applicable to an Auwers reaction, an Acetoacetic Ester synthesis, a Baker- Venkataraman Rearrangement, and a Mannich reaction.
  • Schotten-Baumann reaction an acid chloride reacts with an amine to forman amide, a base in a second phase permits reaction to proceed.
  • the name "Schotten-Baumann reaction conditions" is used to indicate the use of a two-phase solvent system, consisting of water and an organic solvent.
  • the base within the water phase neutralizes the acid, generated in the reaction, while the starting materials and product remain in the organic phase, often dichloromethane or diethyl ether. Having the base in a separate phase prevents the amine reactant from being protonated, which otherwise would be unable to react as a nucleophile.
  • TosMIC contains a reactive isocyanide carbon, an active methylene group and a leaving group it undergo a stepwise cycloaddition fllowed by elimination of TosH
  • This example illustrates the use of a conduit reactor comprising a 12" x 1/4" stainless steel tube containing approximately 100,000 glass fibers.
  • Tests were run with approximately 100,000 glass fibers 17 inches in length in a 1/4- inch internal diameter (I.D.) stainless steel tube.
  • the liquid volume of this reactor was approximately 2.9 mL.
  • Two liquids were pumped through this tube, with the constrained phase on the glass fibers being a 23% by weight sodium hydroxide aqueous solution.
  • the continuous phase was a mixture of epichlorohydrin and resin chlorohydrin (made by reacting
  • This example illustrates the use of a conduit reactor comprising a 36".times.1/2" stainless steel tube with approximately 570,000 glass fibers.
  • Tests were run with approximately 570,000 glass fibers 40 inches in length in a 1/2- inch I.D.
  • the liquid volume of this reactor was approximately 35 mL.
  • Two liquids were pumped through this tube with the constrained phase on the glass fibers being a 23% by weight sodium hydroxide aqueous solution.
  • the continuous phase was a mixture of epichlorohydrin and resin chlorohydrin (made by reacting epichlorohydrin and bisphenol A in a 10:1 molar ratio at 70°C for 24 hours), with 0.1% tetrabutyl ammonium hydroxide coupling and phase transfer catalyst.
  • the caustic solution was introduced onto the upstream end of the glass fibers at about 12 to about 60 mL per hour.
  • the organic phase was introduced into the conduit and flowed past the fibers at rates varying between about 30 and about 3540 mL per hour. After passing through the fiber reactor, the separated organic phase was analyzed by gel permeation chromatography (GPC) for resin and chlorohydrin content and the results shown as percent conversion to diepoxy resin as listed in Table 2.
  • GPC gel permeation chromatography
  • This example illustrates the use of a conduit reactor comprising a 12".times.1/2" stainless steel tube with approximately 570,000 glass fibers.
  • Tests were run with approximately 570,000 glass fibers 16 inches in length in a 12" outside diameter (O.D.) x 1/2-inch l.D. stainless steel tube.
  • the liquid volume of this reactor was approximately 18 mL.
  • Two liquids were pumped through this tube with the constrained phase on the glass fibers being a 23% by weight sodium hydroxide aqueous solution containing 2% tetrabutyl ammonium hydroxide phase transfer catalyst.
  • the continuous phase was a mixture of benzyl alcohol and benzyl bromide (1 : 1 molar ratio) in equal weight of toluene.
  • the caustic solution was introduced onto the upstream end of the glass fibers at 60 mL/hr.
  • the organic phase was introduced into the conduit and flowed past the fibers at rate of 270 mL/hr.
  • the reactor was maintained at 75°C.
  • the organic phase separated cleanly from the aqueous phase and was analyzed by gas chromatography-mass spectroscopy (GC-MS).
  • GC-MS gas chromatography-mass spectroscopy
  • This example illustrates the use of a conduit reactor comprising a 96" x 1/2" stainless steel tube with approximately 360,000 twenty-two micron stainless steel fibers and a liquid volume of approximately 166 mL.
  • Two liquids were pumped through the reactor with the constrained phase on the stainless steel fibers being a solution comprising about 94.25%) methanol, about 3.75% sodium hydroxide, and about 2.1% water.
  • the continuous phase was soybean oil.
  • the methanolic caustic solution was introduced onto the upstream end of the stainless steel fibers at approximately 112.8 mL/hr.
  • the soybean oil was introduced into the conduit and flowed past the fibers at a rate of approximately 420 mL/hr.
  • the mole ratio of methanohoil was 6:1 with approximately 0.78% NaOH by weight of oil.
  • the reactor was maintained at approximately 75°C.
  • the organic phase separated cleanly from the aqueous phase and was analyzed by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • This example illustrates the use of a conduit reactor comprising a 48' x 1/2" stainless steel tube with approximately 540,000 eight micron mineral fibers and a liquid volume of approximately 72 mL.
  • Two liquids were pumped through the reactor with the constrained phase on the mineral fibers being a solution comprising about 98% methanol, about 2% H 2 SO 4 , and about 0.02%) water.
  • the continuous phase was cottonseed oil containing 8.5% free fatty acid (FFA).
  • FFA free fatty acid
  • the methanolic acid solution was introduced onto the upstream end of the mineral fibers at approximately 60 mL/hr.
  • the cottonseed oil was introduced into the conduit and flowed past the fibers at a rate of approximately 30 mL/hr.
  • Example 3 The same conduit reactor used in Example 3 above was used in this experiment. Two liquids were pumped through the reactor with the constrained phase on the glass fibers being an aqueous ethanolic sodium hydroxide solution. The ethanol: water ratio was varied from about 1 :9 to about 9: 1. The continuous phase used was soybean oil dissolved at 30-95%) by weight in hexane. The soybean oil used was retail soybean oil contaminated with about 1% FFA to about
  • the ethanol was included to prevent reactor plugging, which occurred in Example 5 caused by organic salts (sodium carboxylates) forming and precipitating during the reaction.
  • the reactor was maintained at 25°C or 70°C to increase solubility of sodium carboxylate salts.
  • Example 3 The same conduit reactor used in Example 3 was used in this experiment. Two liquids were pumped through the reactor with the constrained phase on the glass fibers being aqueous
  • ethanol containing about 1.73% sodium hydroxide The ethanohwater ratio employed in Runs 1 and 2 was 3:2, and in Run 2 95% ethanol was used.
  • the continuous phase used was neat soybean oil containing about 1% free fatty acids.
  • the reactor was maintained at about 70°C.
  • the reactor pressure varied from about 150 psig to about 500 psig with a flow of oil of about 4 mL/min. to
  • the fiber contactor provided about 90% removal of FFA in this time frame.
  • Example 3 The same conduit reactor used in Example 3 was used in this experiment. Two liquids were pumped through the reactor with the constrained phase on the glass fibers being water, and the organic phase comprising commercial biodiesel fuel (available from Archer Daniels Midland Company, Decatur, 111.). The phases separated quickly and easily at 1 minute contact time with minimal pressure, thereby demonstrating excellent washing characteristics, as shown in Table 10 below.
  • This example illustrates extraction using a conduit reactor comprising a 108" x 1/2" stainless steel tube with approximately 360,000 twenty-two micron stainless steel fibers and a liquid volume of approximately 187 mL.
  • Two liquids were pumped through the reactor with the constrained phase on the stainless steel fibers being an extraction solution comprising about 15% water, about 84%> ethanol (having a 95%> concentration level), and about 1%> superphosphoric acid.
  • the continuous phase was cottonseed oil miscella (30% oil in hexane) containing about 1400 ppm phosphorous.
  • the ethanol in the constrained phase was used to keep the free fatty acids in the cottonseed oil soluble to prevent the conduit reactor from plugging.
  • the extraction solution was introduced onto the upstream end of the stainless steel fibers at approximately 62 mL/min.
  • the cottonseed oil miscella was introduced into the conduit and flowed past the fibers at a rate of approximately 106 mL/min.
  • the reactor was maintained at approximately 75°C.
  • the organic phase separated cleanly from the aqueous phase.
  • the hexane was evaporated and the gum content of the cottonseed oil was analyzed by hot water precipitation (none visible) and contained 3 ppm phosphorous, meaning 1397 ppm phosphorous was removed from the cottonseed oil.
  • System pressure was approximately 15 psig.
  • About 0.18% cottonseed oil was extracted with the gums.
  • the water in the constrained phase was used to reject the cottonseed oil so very little oil was extracted with the gums.

Abstract

Procédé de réaction faisant appel à des fibres consistant à mettre en contact des composants réactifs contenus dans des flux non miscibles pour effectuer des réactions et des séparations chimiques. Le réacteur à conduit utilisé contient des fibres mouillables sur lesquelles un flux est essentiellement contraint et un second flux circule par-dessus pour créer en continu une nouvelle interface entre eux et mettre efficacement en contact les espèces réactives, favorisant ainsi leurs réactions ou leurs extractions. Des co-solvants et des catalyseurs de transfert de phase peuvent être utilisés pour faciliter le processus.
PCT/US2013/028894 2012-03-02 2013-03-04 Procédé et système d'utilisation d'un réacteur à conduit à base de fibres WO2013131094A2 (fr)

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US13/410,920 US9168469B2 (en) 2004-12-22 2012-03-02 Method and system for production of a chemical commodity using a fiber conduit reactor

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US9468866B2 (en) 2012-09-18 2016-10-18 Chemtor, Lp Use of a fiber conduit contactor for metal and/or metalloid extraction
CN108073143A (zh) * 2016-11-18 2018-05-25 中国科学院大连化学物理研究所 一种反应控制相转移催化剂析出过程催化剂颗粒度调控方法
CN108588415A (zh) * 2018-02-01 2018-09-28 燕山大学 一种双水相体系萃取分离水溶液中钨的方法
US11198107B2 (en) 2019-09-05 2021-12-14 Visionary Fiber Technologies, Inc. Conduit contactor and method of using the same

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US9468866B2 (en) 2012-09-18 2016-10-18 Chemtor, Lp Use of a fiber conduit contactor for metal and/or metalloid extraction
CN108073143A (zh) * 2016-11-18 2018-05-25 中国科学院大连化学物理研究所 一种反应控制相转移催化剂析出过程催化剂颗粒度调控方法
CN108073143B (zh) * 2016-11-18 2020-03-17 中国科学院大连化学物理研究所 一种反应控制相转移催化剂析出过程催化剂颗粒度调控方法
CN108588415A (zh) * 2018-02-01 2018-09-28 燕山大学 一种双水相体系萃取分离水溶液中钨的方法
US11198107B2 (en) 2019-09-05 2021-12-14 Visionary Fiber Technologies, Inc. Conduit contactor and method of using the same

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