WO2003074448A2 - Procede de fabrication de produis organiques a partir de flux de non-produits faisant appel a un catalyseur - Google Patents

Procede de fabrication de produis organiques a partir de flux de non-produits faisant appel a un catalyseur Download PDF

Info

Publication number
WO2003074448A2
WO2003074448A2 PCT/US2003/005855 US0305855W WO03074448A2 WO 2003074448 A2 WO2003074448 A2 WO 2003074448A2 US 0305855 W US0305855 W US 0305855W WO 03074448 A2 WO03074448 A2 WO 03074448A2
Authority
WO
WIPO (PCT)
Prior art keywords
stream
product
constituent
phase
organic
Prior art date
Application number
PCT/US2003/005855
Other languages
English (en)
Other versions
WO2003074448A3 (fr
Inventor
Peter J. Joyce
Original Assignee
Value Recovery, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Value Recovery, Inc. filed Critical Value Recovery, Inc.
Priority to AU2003230576A priority Critical patent/AU2003230576A1/en
Publication of WO2003074448A2 publication Critical patent/WO2003074448A2/fr
Publication of WO2003074448A3 publication Critical patent/WO2003074448A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • PROCESS FOR MAKING ORGANIC PRODUCTS FROM NON-PRODUCT STREAMS USING A CATALYST FIELD OF THE INVENTION The present invention pertains to the preparation of organic products from non- product streams or solutions using phase transfer catalysts.
  • waste or by-products are often formed or produced as an undesirable side effect. For instance, chemical reactions are often not 100% complete and raw materials can pass through unreacted and must be separated into by-product streams. Such waste or by-products must be treated to render them environmentally benign or disposed of, or both. The treatment and disposal of such waste or by-products can be expensive and detrimental to the environment, particularly when the waste or by-products are hazardous materials.
  • the non-product streams containing such waste or by-products may be in a solid, liquid or gas form. When the streams are liquids they can be in either an aqueous phase or an organic phase.
  • Phase transfer catalysts are used in a wide variety of chemical processes where one or more phase boundaries exist and one or more constituents cross a phase boundary.
  • a phase transfer catalyst is capable of taking one reactant from one phase and transferring it into another phase in which a second reactant is located and in which the first reactant, after transfer, is in a reactive form such that a reaction between the two reactants can occur. Following the reaction of the two reactants, the phase transfer catalyst is then recycled to the first phase to transfer the first reactant to the second phase in order to catalyze the reaction of another reactant molecule.
  • phase transfer catalysts are described in Starks, C, Liotta, C, Halpern, M.; “Phase Transfer Catalysis” Fundamentals, Applications and Industrial Perspectives", Chapman and Hall, 1994, incorporated herein by reference.
  • Phase transfer catalysis facilitates intimate contact of reactants that would not normally interact efficiently, usually because of phase solubility limitations. Phase transfer catalysis allows these reactions to proceed quickly, at low temperatures, and sometimes with great selectivity. Many phase transfer catalysts can be recycled with classic unit operations, such as extraction, distillation, adsorption, and membrane separations.
  • Fig. 1 An example of an extraction mechanism in a phase transfer catalysis system is shown at Fig. 1, which is the Starks extraction mechanism.
  • phase transfer catalyst which may be a quaternary ammonium salt
  • Q + Y " the phase transfer catalyst
  • the chemical species to be recovered is a water-soluble nucleophile, such as an anion denoted as X .
  • the organic substrate is identified as R-Y and typically is soluble in an organic solvent.
  • the final product is denoted as R-X.
  • the positively charged catalyst cation (Q + ) delivers the anion to the organic phase, where it undergoes an irreversible reaction with an organic substrate (R-Y). More specifically, once formed, the ion pair (Q + X ⁇ ) is a large organic species and distributes between the aqueous and organic phases.
  • the reacting anion (X " ) reacts in an essentially irreversible reaction with a neutrally charged organic substrate affecting the desired conversion and liberating the leaving group anion, Y " , which pairs with the quaternary ammonium cation to form the ion pair Q + Y " as mentioned above and shown in Fig. 1.
  • the ion pair, Q + Y " comprising the quaternary onium catalyst and the leaving group anion, then migrates back to the aqueous phase by a reversible reaction and can equilibrate with another target anion to regenerate Q + X " .
  • This mechanism also applies to other PTC catalysts such as PEG's or Crown Ethers and the like.
  • aryl alkyl ethers ArOR
  • ArOR aryl alkyl ethers
  • RX alkylating agents
  • aryl alkyl ethers have been prepared by reacting purchased or captively manufactured ArOH, in the form of their metal salts, ArO " M + , with alkylating agents, RX, such as epichlorohydrin, allyl chloride, benzyl chloride, benzyl bromide, methyl chloride, and ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide, other alkyl halides and benzene sulfonates, etc.
  • alkylating agents RX
  • ArOH can be formed or becomes a byproduct in the event of incomplete conversion or a waste in many chemical processes.
  • a non-product stream shall mean a stream which contains at least one byproduct or waste and is separate from the final product stream of a process.
  • a non-product stream could be an effluent stream, meaning it is a stream which is leaving a plant, or it could be a recycle stream or some other stream within a plant.
  • Recovery of ArOH may be performed by using elaborate extraction systems. Such recovery of ArOH suffers from several disadvantages, including the requirement to use an excess of inert solvent to provide an environment in which the anion is soluble. The expense required for extraction and recovery of ArOH increases even more when the aqueous streams containing ArOH are more dilute, for example under 10 weight percent of dissolved ArOH in water or other polar solvent.
  • ArO " M + in which M + is typically an alkali metal.
  • This conversion is typically performed by contacting concentrated aqueous solutions of metal hydroxides (e.g., NaOH, LiOH, KOH) with ArOH to yield ArO " M + in concentrated solution, in solid form, or as a slurry.
  • metal hydroxides e.g., NaOH, LiOH, KOH
  • epoxy compounds are prepared by reacting purchased ArOH with epichlorohydrin in the presence of aqueous sodium hydroxide and a catalyst.
  • Other purchased, recovered or manufactured ArOH compounds which are commercially reacted with epichlorohydrin include phenol, para-t-butylphenol, bisphenol A and resorcinol.
  • alkylating agents commercially reacted with ArOH include ethyl chloro-acetate and alkyl chlorides, such as methyl chloride, ethyl chloride, and allyl chloride.
  • the present invention provides a method for making a product by combining the constituents from two or more non-product streams from two different processes.
  • the streams are contacted in the presence of a catalyst under appropriate conditions to cause reaction of the first constituent with the second constituent to form the product. Then, the product is recovered.
  • the method for making an organic product involves providing from a first process a first non-product stream having a first constituent and providing from a second process a second non-product stream having a second constituent.
  • the first non-product stream and the second non-product stream are contacted in the presence of a phase transfer catalyst with other reagents, if necessary, such as an alkali base under conditions to cause reaction of the first constituent with the second constituent to form the product.
  • the product is then recovered.
  • Another embodiment of the present invention is directed to a method for continuously preparing an organic product from non-product streams. This embodiment involves carrying out a first process to provide a first product stream and a first non-product stream having a first constituent which provides an organic phase.
  • a second process is also carried out to provide a second product stream and a second non-product stream having a second constituent and having an aqueous phase.
  • the first non-product stream and the second non-product stream are then contacted in the presence of a phase transfer catalyst under conditions to cause reaction of the first constituent with the second constituent to form the organic product in the organic phase.
  • the aqueous phase is then separated from the organic phase, which is in turn divided into the organic product and the phase transfer catalyst.
  • the phase transfer catalyst is recycled.
  • Fig. 1 shows one mechanism of a phase transfer catalysis system
  • Fig. 2 is a schematic diagram of a system used to continuously convert chemical species in two waste streams to an organic product.
  • the present invention is directed to a method for making a product from two or more non-product streams or helping avoid environmental costs as a result of this product being made.
  • the term "product” shall mean any chemical entity that produces value greater than the constituents from which the product is made or a use different from either of the constituents from which the product is made.
  • product includes a chemical entity which has a utility as made.
  • Product also includes entities which can serve some utility only when combined with other constituents or which serve as intermediates in the production of an end product.
  • the term product includes entities which provide increased value as fuel.
  • a non-product stream shall mean a stream which contains at least one byproduct or waste (referred to herein as a "constituent") and is separate from the final product stream of a process.
  • a non-product stream could be an effluent stream, meaning it is a stream which is leaving a plant, or it could be a recycle stream or some other stream within a plant.
  • the steps for making a product are: providing from a first process a first non-product stream having a first constituent; providing from a second process a second non-product stream having a second constituent; contacting said first non- product stream with said second non-product stream in the presence of a catalyst under conditions to cause reaction of said first constituent with said second constituent to form the product; and recovering the product.
  • process refers to a single step in a chemical plant, a combination of steps, or the entire combination of steps in the plant.
  • the method of the invention contemplates contacting two non-product streams within a plant or contacting two non- product streams from two different plants.
  • the conditions of the contacting step refer to the pressure, temperature, and other reaction parameters of the reaction occurring between the two (or more) constituents.
  • the selected value of these parameters depend on a number of factors, including the constituents involved, the product being formed, the desired rate of production of the product, the tolerances of the equipment used, and the nature of the catalyst used and the strategy for recovering the final product.
  • any catalyst suitable for causing or enhancing the reaction between the constituents may be used.
  • One catalyst which may be used is Aliquat 128 for the reaction of Benzyl Chloride and Sodium Cyanide to form Benzyl Cyanide. It has been found to be particularly desirable to use a phase transfer catalyst such that the method of the present invention can product a product even though the two non-product streams are in different phases.
  • a phase transfer catalyst may be used when the first stream containing a constituent to be reacted is an organic stream providing an organic phase and the second stream containing the second constituent to be reacted is an aqueous stream providing an aqueous phase.
  • the constituents could also be in the gas or solid phases.
  • the recovery of the product can be done in any known manner, and the method of recovery depends on the product being recovered, among other factors.
  • recovery methods include distillation, centrifugation, crystallization, absorption, extraction, and adsorption, among others.
  • Guidance for how one might carry the method of the present invention can be found in co-pending application assigned to the common assignee of this application, entitled “PROCESS FOR MAKING ORGANIC PRODUCTS FROM AQUEOUS SOLUTIONS USING PHASE TRANSFER CATALYSIS” by Joyce, Halpern, and Bielsi, and filed on February 15, 2002.
  • phase transfer catalyst in solvent-free or low solvent conditions
  • the present invention may or may not be employed in such conditions.
  • one of the non-product streams contains a considerable amount of solvent, it is not necessary to first eliminate or reduce the amount of solvent in that stream for the present invention to work.
  • a solvent need not be added if one stream is aqueous and the other stream is organic and has little or no solvent.
  • Fig. 1 one chemical mechanism for phase transfer catalysis is shown in Fig. 1.
  • one constituent from a first non-product stream is an electrophile, which provides an organic phase
  • it is contacted with a phase transfer catalyst and a second constituent which is a nucleophile in an aqueous stream as the second non-product stream.
  • an organic solvent may or may not be added and, if added, it may be added before or during the contacting step.
  • a pH adjusting agent is also added in an amount sufficient to raise the pH to a level sufficient to ionize the chemical species, namely by removing a protonfrom the species and generating a negatively charged species.
  • the pH adjusting agent is optional in that it is added when the chemical species exists as a neutral compound but need not be added when the chemical species already exists as a target anion or as a neutral compound that can act as a nucleophile.
  • the contacting step can be carried out in any suitable reactor, either batch or continuous, the latter of which is described below in connection with Fig. 2.
  • the constituent which is initially present in the aqueous phase and is used to make the organic product can be any of a wide range of possible species.
  • Such chemical species are generally described as nucleophiles, which are defined as an anion or molecule having a high electron density which is accessible for reaction with another molecule bearing a low electron density which is accessible for reaction.
  • nucleophiles are anions and are referred to herein as "target anions.”
  • suitable compounds which contain target anions or are capable of being ionized to produce the target anion and which may be present in dilute aqueous solutions include phenol and substituted phenols (such as phenol, cresols, xylenols, t-butyl phenol, hydroquinone, catechol, resorcinol, bisphenol A, bisphenol S, bisphenol F, other bisphenols, hydrogenated bisphenols, brominated bisphenols, bromoxynil, chlorophenol, polychlorophenols, phenolic steroids, their salts and the like), cyanide salts, carboxylic acids and their salts, e.g.
  • carboxylates sodium acetate, potassium benzoate, propionic acid, acrylic acid, benzoic acid, salicylic acid and the like, heterocycles bearing an N-H group (such as pyrrole, imidazole, carbazole, indole, purines, pyrimidines and the like), mercaptans and their salts (such as methyl mercaptan, thiophenol and the like), and other anionic nucleophiles (such as cyanate, thiocyanate, azide, and the like).
  • the present invention appears to have particular applicability to a chemical species which is phenol or a substituted phenol or phenol derivative selected from the group consisting of phenol, bisphenol A, bisphenol F, cresol, and their salts.
  • the invention may be used when the target anion is cyanide also known as CN ' or carboxylate, RCOO ' where R is an alkyl or aryl group.
  • nucleophiles which are not anions may be used in the present invention.
  • Such compounds include, for example, primary, secondary, and tertiary amines such as mono alkyl, dialkyl, and trialkyl amines.
  • the relevant product of reactions using these nucleophiles are amines, ammonium salts, amides, amidinium salts, sulfonamides and the like.
  • a pH adjusting agent is needed only if the nucleophilic constituent exists in the form of a neutral compound, and has to be transformed into a target anion.
  • the pH sufficient to cause the chemical species to ionize varies over a wide range depending on a number of factors, such as the specific chemical species used and the particular pH adjusting agent used.
  • a hydrogen ion has been removed from the chemical species and has generated a negatively charged organic or inorganic species X " , namely the target anion.
  • a suitable pH includes ranges at which the target anion is present and is at least partially soluble in the aqueous solution, which is generally above pH of 3, preferably pH 9 to 13.5 for phenol and substituted phenols. It should be recognized that the pH as used herein refers to the pH in aqueous phase.
  • the pH adjusting agent could be added first to the aqueous solution or could be added after the aqueous phase has been mixed with either or both of a phase transfer catalyst and an organic phase consisting of an electrophile.
  • Any number of suitable pH adjusting agents could be used, but some typical ones are sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, lithium hydroxide, ammonium hydroxide, magnesium carbonate, calcium carbonate, tetralkyl ammonium hydroxides, sodium and potassium carbonates, hydrogen carbonates, phosphates, similar salts, and mixtures thereof.
  • this invention applies to all concentrations of the nucleophillic constituent from 0.001 weight percent all the way up to the solubility limit of that constituent.
  • the organic substrate of the present invention may be an alkylating agent or acylating agent, which may be an alkyl halide, an acyl halide, a sulfonyl halide, an anhydride or other electrophilic agent capable of liberating a leaving group when reacted with a nucleophile.
  • Suitable alkylating agents include compounds in which leaving groups are bonded to a primary or secondary or tertiary aliphatic carbon.
  • Suitable leaving groups include chloride, bromide, iodide, benzenesulfonate, toluenesulfonate, methanesulfonate and the like.
  • Suitable alkylating agents include epichlorohydrin, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, methyl chloride, dimethyl carbonate, methyl p-toluenesulfonate, dimethyl sulfate, ethyl chloride, ethyl bromide, diethyl sulfate, n- and iso- propyl chloride, n- and iso-propyl bromide, and all other alkylating agents of the formula CnHwXyOz where C is a carbon atom, H is a hydrogen atom, O is an oxygen atom, X is one of the group Chloro, Bromo, Iodo or ArS03 where Ar is an
  • a suitable acylating agent is benzoyl chloride, benzenesulfonyl chloride or p- toluene sulfonyl chloride.
  • Preferred alkyl halides include alkyl chlorides such as benzyl chloride, alkyl bromides and epichlorohydrin.
  • preferred acyl halides include benzoyl chloride and stearoyl chloride.
  • the phase transfer catalyst for transferring the target nucleophile from the aqueous phase to the organic phase to permit a reaction in the organic phase between the target anion and the electrophile to form the organic product can be any suitable phase transfer catalyst.
  • suitable phase transfer catalysts include quaternary ammonium salts, quaternary phosphonium salts, polyethylene glycols, ethers of polyethylene glycols, crown ethers, cryptands, tertiary amines, polymer bound phase transfer catalysts, phase transfer catalysts adsorbed on supports such as silica and clay and the like.
  • Suitable phase transfer catalysts also include tricaprylylmethylammonium chloride, tetrabutylammonium bromide, tetrabutyl ammonium hydrogen sulfate, methyltributylammonium chloride, benzyl triethyl ammonium chloride, trie thy lamine, tributylamine, trioctylamine, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, 18-crown-6, dibenzo-18-crown-6, polyethylene glycol with a molecular weight in the range of 300 to 3000, the dimethyl and dibutyl ethers of said polyethylene glycols, tris(3,6-dioxaheptyl)amine (also known as TDA-1) and the like.
  • TDA-1 tris(3,6-dioxaheptyl)amine
  • the phase transfer catalyst is selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt, a crown ether, and polyethylene glycol. More preferably, the phase transfer catalyst is a quaternary ammonium salt selected from the group consisting of methyltricaprylylammonium chloride and tetrabutylammonium bromide. Most preferably, the phase transfer catalyst is tricaprylylmethylammonium chloride, which is commercially available under the trademark Aliquat 336 or Aliquat 128 from Cognis Corporation, formerly Henkel Corporation and produced in Kankakee, Illinois.
  • a co-catalyst serves to enhance the reaction rate in the organic phase (i.e., the top reaction shown in Fig. 1).
  • Typical co-catalysts may include sodium iodide, potassium iodide, and other alkaline earth metal iodide species. They are preferably mixed in with the aqueous phase, either before mixing with the organic phase or afterwards.
  • the operating conditions of the contacting step should be selected to optimize the reaction in the organic phase, as shown in Fig. 1. As that reaction proceeds more quickly, then the entire scheme is caused to move more efficiently as dictated by Le Chatelier's Law.
  • the ion pair previously existing in the aqueous phase is driven to the organic phase.
  • the preferred conditions depend on a number of factors, including the specific chemical species used, the organic substrate used, and the phase transfer catalyst used.
  • the time, temperature and agitation should be selected to cause the reaction in the organic phase to proceed efficiently. Suitable temperatures in some scenarios include temperatures at which the reaction proceeds, typically -20°C to 200°C, preferably 10-80°C, and most preferably 50-70°C. As is well-known, the choice of temperature is dictated by the kinetics of the reaction.
  • Reactions which occur more slowly are preferably run at higher temperatures.
  • some reactions such as the formation of benzoyl cyanide from benzoyl chloride and cyanide, occur so quickly that it is desirable to run such reactions at low temperature, for example in an ice bath.
  • Suitable molar ratios of alkylating agent to nucleophile are 0.9: 1 to 1000: 1, preferably 0.9: 1 to 10: 1, more preferably 0.9: 1 to 5: 1.
  • the two or more non-product streams may both be in the form of liquids or in some other forms.
  • the first stream may be in gas form and the second stream may be in liquid form.
  • the first stream in gas form may comprise an electrophile and the second stream in liquid form may comprise an aqueous stream.
  • the organic phase may be in liquid form while the aqueous phase may be in gas form.
  • One such example is the reaction of methyl chloride in a gas phase with sodium phenoxide (ionized phenol) in the aqueous phase to form methoxy benzene also commonly known as anisole.
  • the two streams may be contacted with one another in any known manner.
  • the gas may be bubbled into a bath of the liquid stream or it may be added to a reduced cross-sectional flow path of the liquid using a venturi effect.
  • the two streams may be caused to flow countercurrent to one another.
  • the gas condenses shortly after contacting the liquid.
  • an organic product is prepared from non-product streams.
  • a first process 40 forms a product in product line 42 and a non-product stream having a first constituent which provides an organic phase in non-product line 44 from feed in feed line 46.
  • a second process 50 forms a product in product line 52 and a non-product stream having a second constituent which provides an aqueous phase in non-product line 54 from feed in feed line 56.
  • a phase transfer catalyst from its feed tank 10 is mixed with the two non product streams in a reactor 16, where the three are contacted with one another.
  • the streams may be contacted with one another in any known way, including in a way which causes the streams to flow countercurrent to one another.
  • a pH adjusting agent may also have its own feed tank and may be directed to reactor 16 or in any of the lines leading to the reactor. In the event that additional solvent need be added, it may be added to the first constituent along non-product line 44.
  • phase separator 20 which may be a liquid-liquid centrifugal separator, for example.
  • phase separator 20 may be a liquid-liquid centrifugal separator, for example.
  • Aqueous raffinate stream 22 is typically discarded or further treated, as needed, to remove residual water-soluble organic components that were part of the original feed or were unreacted.
  • Organic phase stream 24 is directed to a distillation column 26, where the organic phase is divided into at least the product in product stream 28 and the catalyst in catalyst stream 30.
  • Another organic byproduct stream 32 (which includes catalyst degradation products) is shown in Fig. 2, although this stream might not be present if there is a high level of purity or if there is some impurity but it is acceptable to mix this impurity in with the catalyst in catalyst stream 30.
  • Catalyst stream 30 is recycled by being directed to catalyst feed tank 10.
  • a membrane filter may be used as an alternative to using a distillation column. In this event, the permeate stream is the product and the retentate stream includes the catalyst and any catalyst degradation products with a molecular weight higher than the cut-off weight for the membrane.
  • non- product streams it may be desirable to condition either or both non- product streams prior to the contacting step occurring in reactor 18. Such conditioning might include, for example, removing certain contaminants from the non-product streams, heating the non- product streams, or diluting the non-product streams.
  • conditioning might include, for example, removing certain contaminants from the non-product streams, heating the non- product streams, or diluting the non-product streams.
  • it may be desirable to add a certain amount of either constituent. For example, if the first constituent is provided in an amount less than the amount stoichiometrically required for reaction with the second constituent then, prior to or during the contacting step, an additional amount of the first constituent may be added to provide the amount required for high conversion of the second reactant.
  • the present invention is suitable for the preparation of an aryl alkyl ether from phenol or a substituted phenol, ArOH, which is dissolved in a first non-product stream and an alkyl halide from a second non-product stream.
  • the pH of the byproduct or waste stream is 7 or higher.
  • An advantage of the present invention is that ArOH does not need to be purchased, recovered, or manufactured. Cost savings are further achieved in the present invention by avoiding the waste treatment cost associated with treating the byproduct or waste stream containing ArOH. Often, waste streams containing ArOH, such as phenol, or chlorinated phenol, are classified as hazardous waste. Thus, the cost savings associated with minimizing treatment of hazardous waste in the present invention may be significant.
  • Another advantage of the present invention is that pollution prevention is achieved by reducing the quantity of waste ArOH and converting it into a value added product, ArOR. Another advantage of the present invention is that because no solvent is added emissions and other environmental issues associated with a solvent are eliminated or significantly reduced. Of course, there may be situations where a solvent is already a component of one of the streams and it is not economically advantageous to remove the solvent.
  • benzyl cyanide from benzyl chloride and sodium cyanide
  • benzyl cyanide from benzyl bromide and potassium cyanide
  • benzyl cyanide from benzyl bromide and lithium cyanide
  • benzyl acetate from benzyl chloride and sodium acetate
  • benzyl benzoate from benzyl chloride and sodium or potassium or lithium benzoate
  • Others include the following listed on Table 1 provided below, with a preferred phase transfer catalyst being the quaternary ammonium salt sold under the trademark Aliquat 128, formerly known as Aliquat 336.
  • solvents include benzene, toluene, methyl isobutyl ketone, dichloro methane, dichloroethane, dichlorobenzene, xylene, kerosene, alkanes, low water solubility alcohols, esters and ethers and the like which are largely immiscible with water but in which the electrophile can be used with minimal decomposition is side reactions, may also be used.
  • the above are typical examples and do not represent a comprehensive list.
  • One particular application of the invention could be to the effluent end of a fermentation plant, in which the invention could be used to recover products from dilute aqueous streams and convert them at low concentrations into salable products.
  • lactic acid is made from many fermentation processes, and this could be used to form ethyl lactate by combining the aqueous effluent stream containing lactic acid with ethyl chloride, which might be present in a non-product stream from the production of polyvinyl chloride or vinyl chloride monomer.
  • Example 1 allyl phenyl ether was prepared from a dilute aqueous solution containing phenol in water and allyl bromide in the presence of a phase transfer catalyst.
  • benzyl phenyl ether was prepared from a dilute aqueous solution containing phenol in water and benzyl chloride in the presence of a phase transfer catalyst.
  • benzyl chloride 0.65 g (0.5 mmoles) Aliquat 336, 0.67 g (5.0 mmoles) durene, sodium iodide 0.48 g (3.2 mmoles), 2.82 g (30 mmoles) phenol and a solution of 1.61g (40 mmoles) NaOH in 300.0 g water.
  • the reaction was mechanically stirred at 50°C and samples were taken after 10, 30 and 60 min. The theoretical yield of 59% based on limiting reactant phenol was obtained after 120 min. Analysis was done with an internal standard of Durene (tetramethylbenzene) on a Gas Chromatograph.
  • the reaction mixture was stirred mechanically at 69°C (measured inside the flask) at the rate of about 620 rpm (measured periodically). Aliquots of the organic (lower) phase were taken after 0, 10, 30, 60, 120 and 180 minutes from the time of mixing the phases. The organic reaction mixture after 180 minutes consisted of 29.1 % of unreacted butyl bromide by GC. The theoretical yield of butyl acrylate based on limiting reactant sodium acrylate was 59.0%. Analysis was done with an internal standard of Durene (tetramethylbenzene) on a Gas Chromatograph.
  • benzyl cyanide in the organic phase and was obtained at a 99.0% theoretical yield based on limiting reactant sodium cyanide after 135 minutes. Analysis was done with an external standard of Durene (tetramethylbenzene) on a Gas Chromatograph.
  • benzoyl cyanide was prepared by dissolving 0.49 g (10 mmol) sodium cyanide and Aliquat 336 43 mg (0.1 mmol) and sodium hydroxide 135 mg (3.2 mmol) in 50.17 g water. Sodium hydroxide was added to keep the pH of the mixture above 8.0 and thus alkaline to prevent evolution of hydrogen cyanide gas. The mixture was stirred magnetically and cooled to 7°C by an external ice bath. Benzoyl Chloride, 1.85 g (13 mmol), was added to the reaction mixture. After 10 minutes the reaction was complete and the theoretical yield of benzoyl cyanide based on limiting reactant sodium cyanide was 93.3%. Analysis was done with an external standard of Durene (tetramethylbenzene) on a Gas Chromatograph.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Toxicology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation d'un produit à partir de flux de non-produits, notamment de flux et de liquides de déchets ou de produits dérivés. Ce procédé fait appel à un catalyseur de transfert de phase pour améliorer la réaction entre deux ou entre plusieurs constituants, chaque constituant provenant d'un flux de non-produits séparé. Puisque les flux de non-produits présentent des phases différentes, un catalyseur de transfert de phase peut être utilisé pour faire passer une espèce chimique de la phase aqueuse à la phase organique dans laquelle il réagit. Dans un mode de réalisation, la solution aqueuse est en contact avec un électrophile et un catalyseur de transfert de phase et éventuellement, un agent d'ajustement de pH, dans le cas où l'espèce chimique de la solution aqueuse a besoin d'être ionisée. L'invention concerne un procédé permettant une préparation continue d'un produit consistant à effectuer deux procédés consistant à obtenir deux flux de non-produits, puis à mettre en contact les deux flux de non-produits en présence d'un catalyseur de transfert de phase, puis à séparer la phase aqueuse de la phase organique, et à diviser ensuite la phase organique en un produit et en un catalyseur de transfert de phase, lesquels sont ensuite recyclés ou rejetés. Le catalyseur peut enfin rester dans la phase aqueuse ou être rejeté de cette phase.
PCT/US2003/005855 2002-03-01 2003-02-27 Procede de fabrication de produis organiques a partir de flux de non-produits faisant appel a un catalyseur WO2003074448A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003230576A AU2003230576A1 (en) 2002-03-01 2003-02-27 Process for making organic products from non-product streams using a catalyst

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US36100102P 2002-03-01 2002-03-01
US60/361,001 2002-03-01

Publications (2)

Publication Number Publication Date
WO2003074448A2 true WO2003074448A2 (fr) 2003-09-12
WO2003074448A3 WO2003074448A3 (fr) 2003-11-27

Family

ID=27789057

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/005855 WO2003074448A2 (fr) 2002-03-01 2003-02-27 Procede de fabrication de produis organiques a partir de flux de non-produits faisant appel a un catalyseur

Country Status (2)

Country Link
AU (1) AU2003230576A1 (fr)
WO (1) WO2003074448A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007122638A2 (fr) * 2006-04-26 2007-11-01 Ratnamani Bio-Chemicals & Pharmaceuticals Pvt. Ltd. Procede ameliore de preparation d'intermediaires de lamotrigine
US8283486B2 (en) 2007-11-09 2012-10-09 Shin-Etsu Chemical Co., Ltd. Norbornane skeleton structure-containing organosilicon compound and method of producing same
CN109651193A (zh) * 2019-01-22 2019-04-19 江苏佳麦化工有限公司 一种苯甲酰氰的合成方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5235077A (en) * 1991-03-25 1993-08-10 E. I. Du Pont De Nemours And Company Process for preparing phenyl esters of substituted acids
US5242996A (en) * 1990-05-24 1993-09-07 Nippon Paint Co., Ltd. Modified epoxy resins having acetylenically unsaturated functions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242996A (en) * 1990-05-24 1993-09-07 Nippon Paint Co., Ltd. Modified epoxy resins having acetylenically unsaturated functions
US5235077A (en) * 1991-03-25 1993-08-10 E. I. Du Pont De Nemours And Company Process for preparing phenyl esters of substituted acids

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE HCAPLUS [Online] ASATRYAN E.M.: 'Dehydrochlorination of chlororganic compounds in chlororprene production wastes under conditions of phase-transfer catalysis', XP002974802 Retrieved from STN Database accession no. 1984:611758 & ARMYANSKII KHIMICHENSKII ZHURNAL vol. 37, no. 7, 1984, pages 435 - 440 *
DATABASE HCAPLUS [Online] KRISHNANKUMAR V.K.: 'Novel Method of recovering phenolic substances from aqueous alkaline waste streams', XP002974803 Retrieved from STN Database accession no. 1984:108607 & INDUSTRIAL & ENGINEERING CHEMISTRY PROCESS DESIGN AND DEVELOPMENT vol. 23, no. 2, 1984, pages 410 - 413 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007122638A2 (fr) * 2006-04-26 2007-11-01 Ratnamani Bio-Chemicals & Pharmaceuticals Pvt. Ltd. Procede ameliore de preparation d'intermediaires de lamotrigine
WO2007122638A3 (fr) * 2006-04-26 2008-03-13 Ratnamani Bio Chemicals & Phar Procede ameliore de preparation d'intermediaires de lamotrigine
US8283486B2 (en) 2007-11-09 2012-10-09 Shin-Etsu Chemical Co., Ltd. Norbornane skeleton structure-containing organosilicon compound and method of producing same
EP2058316B1 (fr) * 2007-11-09 2014-04-09 Shin-Etsu Chemical Co., Ltd. Composé organosilicié contenant une structure de squelette de norbornane et son procédé de fabrication
CN109651193A (zh) * 2019-01-22 2019-04-19 江苏佳麦化工有限公司 一种苯甲酰氰的合成方法

Also Published As

Publication number Publication date
AU2003230576A1 (en) 2003-09-16
WO2003074448A3 (fr) 2003-11-27
AU2003230576A8 (en) 2003-09-16

Similar Documents

Publication Publication Date Title
US6846946B2 (en) Process for making organic products and improving the quality of non-product streams using phase transfer catalysis
JP5026727B2 (ja) 高純度シアン酸エステルの製造方法
EP1658279A1 (fr) Procede de preparation de carbonate de propylene
JP5928149B2 (ja) イミド酸化合物の製造方法
CN101337938B (zh) 醋酸盐离子液体的合成方法
WO2003074448A2 (fr) Procede de fabrication de produis organiques a partir de flux de non-produits faisant appel a un catalyseur
CN104710597A (zh) 制备液体环氧树脂的方法
WO2021109530A1 (fr) Procédé de préparation d'alcool par hydrolyse d'un produit organométallique
US9249164B2 (en) Process for preparing an acryloyloxysilane
CA2791274A1 (fr) Compose epoxy de grande purete et son procede de production
US5675029A (en) Cyclic process for activation, use and recovery of phase-transfer catalysts
ZA200406394B (en) Process for making organic products from non-product streams using phase transfer catalysis.
CN106470966A (zh) 萃取脱水方法
IL177747A (en) Processes for producing 3-methyl-2-butenyl acetate
EP0965577B1 (fr) Procédé de séparation du carbonate de dialkyle et du carbamate d'alkyle
CN103242204A (zh) 纯化苯肼-β-羧酸酯化合物的方法
JP2005512806A (ja) 反応混合物を分離し、４級塩および塩基をリサイクルする方法
AU7169191A (en) Nitrate ester preparation
US20180057429A1 (en) System and method for preparing aromatic derivative
JPS62164639A (ja) フエノ−ル類とカテコ−ル類の分離法
CA3223464A1 (fr) Procede de production d'acetates d'alkyle tres purs
CN1119312C (zh) 邻羟基扁桃酸钠的工业化连续制备方法
CN117603232A (zh) 一种（z）-3-己烯-1-溴化镁格式试剂的制备方法
CN1354739A (zh) 生产碳酸二烷酯的方法
CN1474807A (zh) 制造烷磺酰氯的方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase in:

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP