EP0837842A4 - Procedes et dispositifs d'obtention de produits d'oxydation intermediaires par regulation des conversions et des temperatures dans un liquide atomise - Google Patents

Procedes et dispositifs d'obtention de produits d'oxydation intermediaires par regulation des conversions et des temperatures dans un liquide atomise

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Publication number
EP0837842A4
EP0837842A4 EP96915863A EP96915863A EP0837842A4 EP 0837842 A4 EP0837842 A4 EP 0837842A4 EP 96915863 A EP96915863 A EP 96915863A EP 96915863 A EP96915863 A EP 96915863A EP 0837842 A4 EP0837842 A4 EP 0837842A4
Authority
EP
European Patent Office
Prior art keywords
liquid
temperature
conversion
droplets
coalescing
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP96915863A
Other languages
German (de)
English (en)
Other versions
EP0837842A1 (fr
Inventor
Mark William Dassel
Eustathios Vassiliou
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RPC Inc
Original Assignee
Twenty First Century Research Corp
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
Priority claimed from US08/477,195 external-priority patent/US5801282A/en
Priority claimed from US08/477,234 external-priority patent/US5502245A/en
Priority claimed from US08/478,257 external-priority patent/US5580531A/en
Priority claimed from US08/475,340 external-priority patent/US5558842A/en
Priority claimed from US08/587,967 external-priority patent/US5883292A/en
Priority claimed from US08/620,974 external-priority patent/US5654475A/en
Application filed by Twenty First Century Research Corp filed Critical Twenty First Century Research Corp
Publication of EP0837842A1 publication Critical patent/EP0837842A1/fr
Publication of EP0837842A4 publication Critical patent/EP0837842A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • 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
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B01J10/002—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out in foam, aerosol or bubbles
    • 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
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • 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
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    • B01J19/24—Stationary reactors without moving elements inside
    • 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
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/247—Suited for forming thin films
    • 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
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/14—Adipic acid
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    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00058—Temperature measurement
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    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00083—Coils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • 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
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    • 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
    • B01J2219/00103—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor in a heat exchanger separate from the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J2219/00105—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2219/0011—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling involving reactant liquids
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    • 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
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B01J2219/00123—Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
    • B01J2219/00126—Cryogenic coolants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B01J2219/00128—Controlling the temperature by direct heating or cooling by evaporation of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B01J2219/0013—Controlling the temperature by direct heating or cooling by condensation of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00252—Formation of deposits other than coke
    • 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
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to methods and apparatuses for making reaction products, and especially intermediate oxidation products, wherein a first reactant incorporated in an atomized liquid reacts with a gas containing a second reactant, and especially an oxidant, under controlled conditions.
  • Reactions where a first reactant, dissolved in a liquid, reacts with a second reactant contained in a gas under increased surface area conditions are known to the art. Such reactions are carried out in devices as scrubbers, burners, reaction vessels, and the like, for example.
  • Atomization of liquids into a gaseous atmosphere is one of the above mentioned techniques described in the art.
  • the atomization techniques for conducting reactions disclosed in the art so far, are rather crude and lack innovative features for controlling such reactions with respect to desired reaction product if the reaction product is an intermediate, yield in reaction product, conversion and conversion rate, temperature profiles in the reaction zone, average droplet size or diameter, evaporation rates, and the like.
  • the reaction product is substantially the final product expected under the crude overall conditions of the reaction.
  • the final product of reaction is carbon dioxide, with desired minimization of carbon monoxide and nitrogen oxides as much as possible.
  • a scrubber for removing acidic compounds from a gas may use an atomized liquid containing alkali or alkaline earth compounds which react with the acidic compounds in the gas to form the corresponding salts.
  • ammonia and phosphoric acid react under atomization conditions to form ammonium orthophosphate, which is a final reaction product.
  • intermediate reaction or oxidation products such as adipic acid, phthalic acid, isophthalic acid and terephthalic acid, for example, may be advantageously obtained under atomization conditions.
  • reactant gas in these cases is typically air, but may also be oxygen.
  • Sufficient reactant gas, with or without non-reactive diluents e.g., nitrogen
  • reactant gas is sparged - at relatively high rate - so that the liquid reaction medium is aerated to maximum capacity (typically 15-25 % aeration).
  • reactant gas reactant containing gas feed
  • Costly reactant gas feed compressors are required to compress makeup reactant gas for sparging. These are expensive to install and operate (high electric or steam consumption), and have many utility problems resulting in excessive plant downtime.
  • oxygen-only gas feed to the reactor may be undesirable because high sparging requirements result in low oxygen conversion in the reactor; low conversion results in high oxygen concentration within the reactor; and high oxygen concentration within the reactor may result in excessive over-oxidation of liquid reactants and liquid solvents with attendant high chemical yield loss (i.e., burning these to carbon monoxide and carbon dioxide). If the oxygen in the reactor is diluted with recycle nitrogen or gaseous-recycle inerts, then both high recompression investment and costs, and recompression utility problems are introduced.
  • the current technology also suffers from a relatively low ratio of gas-liquid surface area to liquid reaction mass.
  • the presently available art does not maximize this ratio.
  • the present invention maximizes said ratio in order to:
  • Using a non-volatile catalyst in a gas-phase reaction system must necessarily often be subject to severe plugging problems as most organic acids resulting from oxidation reactions are non-volatile solids - unless dissolved in a liquid reaction medium.
  • the present invention relates to methods and devices of making intermediate oxidation products, wherein a first reactant incorporated in an atomized liquid reacts with a gas containing an oxidant under controlled conditions. More particularly, this invention pertains a method of preparing an intermediate oxidation product from a first liquid containing a first reactant and a gas containing an oxidant;
  • the intermediate oxidation product may be then separated from the second liquid.
  • Pre-coalescing temperature is the temperature of the droplets just before they coalesce into the second liquid.
  • Transient temperature difference is the difference of temperature of the droplets between the pre-coalescing temperature and the atomization temperature.
  • Atomization temperature is the temperature of the first liquid in the atomizer, just before the first liquid has been atomized.
  • Atomization distance is the distance between the atomizer and the mass of second liquid.
  • transient temperature sub-difference is a difference in droplet temperature between a point positioned towards the atomization location and a point positioned toward the second liquid location, within the path that the droplets follow.
  • Transient temperature sub-differences are useful because they give information regarding the temperature profile within the reaction chamber and additional data relative to the progress of the reaction. Their use is within the scope of this invention.
  • a transient temperature sub-difference between a point close to the atomizer and a point close to the second liquid may be used in lieu of the transient temperature difference, as defined above.
  • Pre-coalescing transient conversion is the conversion taking place from the point that the first liquid is atomized to form first droplets to the point just before the first droplets coalesce to a mass of liquid, as described hereinwith. This occurs in just one cycle of droplet formation and droplet coalescence
  • conversion without any modification refers to conversion of a reactant to a reaction product.
  • conversion is defined as the percentage ratio of moles of reaction product formed during the reaction to the total moles of reactant in the feedstock, multiplied by the reciprocal of the number of moles of reaction product produced theoretically when one mole of reactant is completely converted to said reaction product.
  • Pre-coalescing temperature of the droplets, transient temperature difference of the droplets, transient temperature sub-difference of the droplets, and pre- coalescing transient conversion are called determinants since they are determining parameters regarding control of the oxidation.
  • the oxidation is driven by different variables, as described in detail hereinbelow, in a manner that one or more of the following are caused to occur: the pre-coalescing temperature attains a value within a predetermined pre-coalescing temperature range, the transient temperature difference attains a value within a predetermined transient temperature difference range, any transient temperature sub-difference attains a value within a predetermined transient temperature sub-difference range, and the conversion attains a value within a predetermined pre-coalescing transient conversion range.
  • corrections have to be made for different factors which may influence the transient temperature difference one way or another, by well known to the art techniques, involving measurements and calculations. Since changes in the transient temperature difference may be more important than its absolute value, high accuracy in the measurements and calculations is not required in most occasions. Similar corrections and techniques may be employed for the rest of the determinants.
  • the determinant which happens to be outside its respective predetermined range and further away from its respective most preferred set value takes preferably precedence or it is said to prevail.
  • the computerized controller temporarily assigns lower priority to data from the other determinants, and handles first the data received regarding the prevailing determinant.
  • the prevailing determinant has been closer to its respective most preferred set value than another determinant, the other determinant takes precedence or prevails.
  • the determinant further away from its respective most preferred set value takes precedence or prevails until all determinants attain their most preferred set value.
  • each respective predetermined range is divided in 100 arbitrary units, arbitrarily assumed to be equivalent in both cases, and all values are prorated within these equivalent arbitrary units (both inside each range and outside each range).
  • overriding program rules may be used to override the above sequences, especially in occasions involving safety matters. For example, if the pre-coalescing temperature or the transient temperature difference or any transient temperature sub-difference start rising at a rate faster than a preset value, the corresponding determinant should take over, regardless of precedence as described above, and cause commensurate change in one or more variables at a high enough rate to offset said rise on time, before any catastrophic outcome.
  • monitoring carbon monoxide and carbon dioxide in the off-gases is a prudent precaution, since unexpected or higher than normal amounts of carbon monoxide and/or carbon dioxide signify poorly controlled or uncontrolled oxidation.
  • Similar overriding rules, applied by the controller described below, help prevent poor yields, poor conversions, and even explosions.
  • Control of the parameter or determinant may be performed by a step selected from a group consisting of changing the predetermined level of catalyst in the droplets, changing the atomization temperature of the droplets, changing the reaction pressure in the reaction chamber, changing the atomization distance, changing the average droplet diameter, changing the first flow rate (the rate at which the droplets are produced), changing the second flow rate (the rate at which the gas flows), changing the volatilization rate at which volatile ingredients in the first liquid volatilize, changing the first content (content of first reactant in the first liquid), changing the second content (content of oxidant in the gas), and a combination thereof.
  • the pre-coalescing transient conversion may be monitored by a chromatographic method.
  • a major portion of the oxidation product is an organic compound
  • the first reactant comprises an organic compound
  • the oxidant is oxygen, and even more preferably,
  • the first reactant comprises a compound selected from a group consisting of cyclohexane, cyclohexanone, cyclohexylhydroperoxide, cyclohexanol, o- xylene, m-xylene, p-xylene, a mixture of at least two of cyclohexane, cyclohexanone, cyclohexanol, and cyclohexylhydroperoxide, and a mixture of at least two of o-xylene, p-xylene, and m-xylene.
  • the oxidant comprises oxygen
  • a major portion of the intermediate oxidation product comprises a compound selected from a group consisting of adipic acid, cyclohexanol, cyclohexanone, cyclohexylhydroperoxide, phthalic acid, isophthalic acid, terephthalic, a mixture of at least two of adipic acid, cyclohexanone, cyclohexanol, and cyclohexylhydroperoxide, and a mixture of at least two of phthalic acid, isophthalic acid, and terephthalic acid.
  • the method may involve a step of separating the intermediate oxidation product from the second liquid by filtration.
  • Spraying is the preferred way of atomizing the first liquid from a point over the surface of the second liquid at the atomization distance, by preferably an airless technique.
  • the method may preferably further comprise a step of internally condensing condensibles substantially under reaction pressure. Also, the method of non ⁇ destructive oxidation may be conducted in a reaction zone surrounded by a thick film or curtain of liquid.
  • the preferable predetermined pre-coalescing transient conversion range is 0.05% to 80%
  • the predetermined pre-coalescing temperature range is 50 to 250° C
  • the transient temperature difference is in the range of 0.1 to 100° C.
  • the invention also pertains a device for preparing a reaction product from a first liquid containing a first reactant and a gas containing a second reactant comprising a reaction chamber having an upper end, a lower end, a wall, and a reaction zone, in which zone the first liquid is brought in contact with the gas for reacting at a reaction pressure, wherein the improvement comprises:
  • a monitor selected from a group consisting of a first temperature monitor for measuring the atomization temperature, a second temperature monitor for measuring pre-coalescing temperature and/or transient temperature difference and/or any transient temperature sub-difference, a conversion detector for monitoring pre-coalescing transient conversion of the first reactant to reaction product in the droplets before the droplets coalesce onto the mass of the second liquid, and a combination thereof;
  • a controller connected to at least one of the first temperature monitor, the second temperature monitor, and the conversion detector in order to obtain respective information, the controller being adapted to point a parameter or determinant selected from a group consisting of pre-coalescing temperature of the droplets, transient temperature difference of the droplets, transient temperature sub-difference of the droplets, pre-coalescing transient conversion, and a combination thereof, toward respective predetermined ranges.
  • the device may also comprise a separator communicating with the reaction chamber for separating the reaction product from the second liquid, and/or a recirculation branch for recirculating at least part of the second liquid into the first liquid.
  • the conversion detector preferably comprises a chromatography apparatus.
  • the atomizer is preferably disposed toward the upper end, and directed toward the lower end at the atomization distance. It is preferably airless.
  • FIGURE 1 illustrates schematically a preferred embodiment of the present invention, wherein control of pre-coalescing transient conversion is achieved by changing the atomization distance through a movement of the atomizer.
  • FIGURE 1A illustrates schematically a preferred embodiment of the present invention, wherein control of pre-coalescing temperature and/or pre-coalescing transient conversion is achieved by changing the atomization distance through a movement of the atomizer.
  • FIGURE 2 illustrates schematically another preferred embodiment of the present invention, wherein control of pre-coalescing transient conversion is achieved by changing the atomization temperature.
  • FIGURE 2A illustrates schematically another preferred embodiment of the present invention, wherein control of pre-coalescing temperature and/or transient temperature difference is achieved by changing the atomization temperature.
  • FIGURE 3 illustrates schematically still another preferred embodiment of the present invention, wherein control of pre-coalescing transient conversion is achieved ether by changing the pressure in the reaction chamber, or by changing the second flow rate, or by changing the second content.
  • FIGURE 3A illustrates schematically still another preferred embodiment of the present invention, wherein control of pre-coalescing temperature and/or of transient temperature difference is achieved ether by changing the pressure in the reaction chamber, or by changing the second flow rate, or by changing the second content.
  • FIGURE 4 illustrates schematically still another preferred embodiment of the present invention, wherein control of transient pre-coalescing conversion is achieved by changing the first content.
  • FIGURE 4A illustrates schematically still another preferred embodiment of the present invention, wherein control of pre-coalescing temperature is achieved by changing the first content.
  • FIGURE 5 illustrates schematically still another preferred embodiment of the present invention, wherein control of pre-coalescing transient conversion is achieved by changing the droplet size or diameter.
  • FIGURE 5A illustrates schematically still another preferred embodiment of the present invention, wherein control of pre-coalescing temperature is achieved by changing the droplet size or diameter.
  • FIGURE 6 illustrates schematically still another preferred embodiment of the present invention, wherein control of pre-coalescing transient conversion is achieved by changing the first flow rate.
  • FIGURE 6A illustrates schematically still another preferred embodiment of the present invention, wherein control of pre-coalescing temperature and/or transient temperature difference is achieved by changing the first flow rate.
  • FIGURE 7 illustrates schematically still another preferred embodiment of the present invention, wherein control of pre-coalescing transient conversion is achieved by changing the volatilization rate.
  • FIGURE 7A illustrates schematically still another preferred embodiment of the present invention, wherein control of pre-coalescing temperature and/or transient temperature difference is achieved by changing the volatilization rate.
  • FIGURE 8 illustrates schematically still another preferred embodiment of the present invention, wherein control of pre-coalescing transient conversion or of pre-coalescing temperature is achieved by changing the atomization distance through moving the level of the surface of the second liquid.
  • FIGURE 9 illustrates schematically the sample collector utilized in the embodiments of Figure 8.
  • FIGURE 10 illustrates schematically a filter arrangement comprised in the separator according to another preferred embodiment of the present invention.
  • FIGURE 11 illustrates schematically still another preferred embodiment of the present invention, wherein an eductor is utilized to recirculate non-condensible off- gases, a condenser is used to condense condensibles, and part of the condensibles return to the reaction chamber, where a thick film or curtain is formed for preventing solids buildup on the walls.
  • FIGURE 12 illustrates schematically still another preferred embodiment of the present invention, wherein a pump is utilized to recirculate non-condensible off- gases, a condenser is used to condense condensibles, and part of the condensibles return to the reaction chamber, where a thick film or curtain is formed for preventing solids buildup on the walls.
  • FIGURE 13 illustrates schematically still another preferred embodiment of the present invention, wherein both condensibles and non-condensibles leave the reactor through the lower end.
  • FIGURE 14 illustrates schematically still another preferred embodiment of the present invention, wherein a cooling mantle surrounds the reaction chamber.
  • FIGURE 15 illustrates schematically still another preferred embodiment of the present invention, wherein a cooling coil performs condensation inside the reaction chamber.
  • FIGURE 16 illustrates schematically still another preferred embodiment of the present invention, wherein condensation inside the reactor is performed by spraying a cooling liquid along with atomization of the first liquid.
  • FIGURE 17 illustrates schematically still another preferred embodiment of the present invention, wherein condensation inside the reactor is performed by spraying a cooling liquid towards the walls of the reaction chamber.
  • FIGURE 18 illustrates schematically a reaction chamber having thermocouples for measuring transient temperature sub-difference.
  • FIGURE 19 illustrates schematically a preferred embodiment of the present invention, wherein oxidation rate of the reaction in a reaction chamber is controlled by adjusting the temperature and or conversion of first reactant to intermediate oxidation product at different locations of the system.
  • the present invention relates to methods of making intermediate oxidation products, wherein a first reactant incorporated in an atomized liquid reacts with a gas containing an oxidant, under controlled conditions.
  • the atomization conditions are subject to intricate critical controls and requirements as described and claimed hereinbelow.
  • the present invention enables economic oxidation reactions at improved yield with reduced compression costs and investment, using proven catalyst systems, with reduced off-gas waste-stream discharge to the atmosphere, with reduced off-gas cleanup investment and costs, without solids plugging or buildup problems, with high utility, high conversion rates, and with reduced oxygen concentrations in the reaction chamber.
  • the ability to operate at lower oxygen concentration, made possible by this invention, with acceptable conversion rates in the reactor improves yield by reducing over-oxidations, and may eliminate safety (explosion) problems associated with operation in the explosive oxygen/fuel envelope by operating in the non-explosive oxygen/fuel envelope.
  • the oxidation is conducted within the droplets, which are in a liquid phase, the process still maintains the advantage of being able to employ efficient liquid-soluble catalyst systems, with the added advantage of attaining reaction conditions almost as efficient as those encountered in a homogeneous gaseous phase. Reactions in a gaseous phase would require costly and uncertain gas-phase catalysts or solid-phase catalyst systems.
  • this invention enables a low off-gas waste-stream rate, if so desired, which reduces the off-gas waste-stream rate to the environment, and reduces off- gas cleanup investment and costs.
  • the low off-gas waste-stream rate may be made possible with a near-stoichiometric gaseous oxygen feed combined with high conversion rates and/or chemical yields, for example.
  • reaction chamber non-condensible off-gas is commonly purged to the atmosphere without partial recycle back to the reaction chamber. This results in increased oxygen consumption and related cost, but is done to avoid high, non-economic recompression costs and investment.
  • recompression costs and investment are high due to a high non-condensible load, and high recycle pressure requirement.
  • condensation is employed at a stage before the pressure drop (internal condensation), as shown in the embodiment of Figure 11 (before valve 864) for example, the increased oxygen consumption and related cost, and the high, non-economic recompression costs and investment associated with the conventional technology are avoided.
  • this embodiment it is possible to recycle oxygen-containing off-gas back to the reaction chamber with relatively low or no recompression requirement and cost. The recycle may be even eliminated without incurring significant adverse economic impact.
  • condensation is employed at such a stage, the recompression requirement is minimal - compared to the conventional technology - due to the low non-condensible off-gas rate, especially when near-stoichiometric oxygen feed is used.
  • the low non-condensible off-gas rate is due to the combination of near- stoichiometric oxygen feed, with one or more of high oxygen conversion rate, high chemical yield, and internal condensation, enabled and provided for by the instant invention.
  • Internal condensation is condensation which takes place within the system, before the pressure is relieved.
  • External condensation is condensation which takes place outside the system, after the pressure has been relieved.
  • Inside or internal inside condensation is condensation which takes place inside the reaction chamber.
  • Outside condensation or internal outside condensation is condensation which takes place inside the system before the pressure is relieved, but outside the reaction chamber.
  • the instant invention when near-stoichiometric oxygen feed is desired, it is achievable by the high conversion of the oxygen feed to the reaction chamber per pass, hence needing little recycle requirement.
  • the high chemical yield results in low non-condensible by-product formation, thereby significantly reducing off-gas purge load generated in the reaction chamber.
  • Reduced off-gas purge load in turn reduces oxygen purge from the reaction chamber.
  • Reduced oxygen purge from the reaction chamber minimizes oxygen recycle requirement.
  • the implementation of internal condensation further reduces recompression requirement, as internal condensation outside the reactor reduces condensible vapor recycle requirement, and the implementation of internal condensation inside the reactor reduces oxygen recycle requirement further still.
  • internal condensation especially inside the reactor, significantly reduces oxygen physical yield-loss.
  • solids buildup in the reaction chamber is prevented by washing the walls of the reaction chamber with preferably cooler, preferably catalyst- free liquid solvent, or with preferably catalyst-free liquid reactant, or with a mixture thereof. All surfaces of the reaction chamber, or a certain portion of those surfaces prone to solids buildup, may be washed in this manner.
  • the wash liquid may be sprayed onto the surfaces so washed, or may be generated in situ as a result of internal inside condensation. Solids buildup is prevented because the solids in contact with these surfaces are continuously washed out of the reaction chamber.
  • reaction in the wash-liquid is greatly minimized by the lower temperature or absence of catalyst, the short hold-up-time or a combination thereof. All solids produced in the reaction chamber are removed from the reaction chamber with the wash liquid.
  • the ways to control average droplet diameters in atomization is well-known to the art, and it includes, but is not limited to, nozzle design, variable nozzle characteristics, pressure of atomized material, pressure of gas if gas is used for the atomization process, and the like.
  • pre-coalescing temperature and/or transient temperature difference, and/or pre-coalescing transient conversion can be controlled, for example, by regulating the oxygen concentration in the reaction chamber. This is to be done by using oxygen as the limiting reagent. In this instance, the rate of oxygen feed to the reaction chamber would be increased or decreased as required to control pre-coalescing temperature and/or transient temperature difference and/or pre-coalescing transient conversion.
  • Pre-coalescing temperature and/or transient temperature difference and/or pre-coalescing transient conversion are increased - holding all other variables constant - by increasing oxygen feed rate, and thereby increasing oxygen concentration in the reaction chamber.
  • Pre-coalescing temperature and/or transient temperature difference and/or pre-coalescing transient conversion are decreased - holding all other variables constant - by decreasing oxygen feed rate, and thereby decreasing oxygen concentration in the reaction chamber.
  • pre-coalescing temperature and/or transient temperature difference and/or pre-coalescing transient conversion are increased - holding all other variables constant - by increasing the concentration of catalyst in the liquid feed to the reaction chamber.
  • Pre-coalescing temperature and/or transient temperature difference and/or pre-coalescing transient conversion are decreased - holding all other variables constant - by decreasing the concentration of catalyst in the liquid feed to the reaction chamber.
  • pre-coalescing temperature and/or transient temperature difference and/or pre-coalescing transient conversion are increased - holding all other variables constant - by increasing the hold-up time of the liquid feed in the reaction chamber.
  • Pre-coalescing temperature and/or transient temperature difference and/or pre-coalescing transient conversion are decreased -holding all other variables constant - by decreasing the hold-up time of the liquid feed in the reaction chamber.
  • Hold-up time of the liquid feed in the reaction chamber is controlled by varying the height of the gas-phase through the droplets fall. Hold-up time is increased by increasing the height, and decreased by decreasing the height.
  • the height may be controlled in several ways. For example, it may be controlled by:
  • the height of the liquid pool can be determined and controlled by a variety of ways well known to the art.
  • pre-coalescing temperature and/or transient temperature difference and/or pre-coalescing transient conversion are increased - holding all other variables constant - by decreasing the size of the liquid droplets in the reaction chamber.
  • Pre-coalescing temperature and/or transient temperature difference and/or pre-coalescing transient conversion are decreased - holding all other variables constant - by increasing the size of the liquid droplets in the reaction chamber.
  • Droplet size inversely affects pre-coalescing temperature and/or transient temperature difference and/or pre-coalescing transient conversion by controlling oxygen mass transfer into the liquid reaction media.
  • the ratio of surface area to volume for a spherical droplet is inversely proportional to the diameter of a droplet, and since oxygen transport from the gas-phase is directly proportional to the surface area of a droplet, then the ratio of oxygen mass transport to the liquid volume contained in a droplet varies inversely with the diameter of the droplet. Therefore, the relative oxygen mass transfer for larger droplets is smaller than that for smaller droplets, and pre-coalescing temperature and/or transient temperature difference and/or pre-coalescing transient conversion are correspondingly reduced when all other variables are held constant.
  • pre- coalescing transient conversion is increased - holding all other variables constant - by increasing the pre-coalescing temperature and/or the transient temperature difference of the liquid droplets. Conversion is decreased - holding all other variables constant - by decreasing the pre-coalescing temperature and/or the transient temperature difference of the liquid droplets in the reaction chamber.
  • the heat of reaction may be removed from the liquid reaction mass as vaporized liquid reactant and vaporized liquid solvent. These vaporized materials may be condensed either outside or inside the reaction chamber as it will be discussed hereinbelow. Removal of heat inside the reaction chamber may be conducted for example by using condensation sprays, or condensation surfaces, or a combination thereof.
  • a controller points the pre-coalescing temperature of the droplets, transient temperature difference of the droplets, transient temperature sub-difference of the droplets, pre-coalescing transient conversion in the droplets, or a combination thereof, toward predetermined ranges.
  • the controller is adapted to change one or more variables, such as the preferable variables listed as examples hereinwith, so that said change will favor a respective change in the pre-coalescing temperature, or transient temperature difference, or pre-coalescing transient conversion, or a combination thereof toward the predetermined range.
  • the pre-coalescing temperature and transient temperature difference depend on the particular oxidation.
  • the preferable range of pre-coalescing temperature is 50 - 150° C, more preferably 80 - 130° C, and even more preferably 90 - 120° C.
  • the preferable transient temperature difference is in the range of 0.1 to 100° C , more preferably 5 - 100° C, more preferably 10 - 50° C, and even more preferably 15 - 35° C.
  • the preferred pre-coalescing temperature is in the range of 50 to 250° C.
  • Appropriate ranges of pre-coalescing temperature, transient temperature difference , and predetermined pre-coalescing transient conversion may be determined without undue experimentation for other oxidations or miscellaneous conditions of the same oxidation.
  • the preferable predetermined pre-coalescing transient conversion range is
  • the controller is preferably adapted or programmed to select and change one or more additional variables in order to receive the desired result.
  • the temperatures may be monitored by any temperature-measuring devices, such as for example thermocouples, IR thermometers, and the like.
  • overriding program rules may be used to override the normal program of the controller, especially in occasions involving safety matters.
  • the temperature in the reaction chamber may preferably be monitored, and if it is found to start rising at a rate faster than a preset value, the controller should cause commensurate changes in one or more variables at a high enough rate to offset said rise timely, before any catastrophic outcome.
  • monitoring carbon monoxide and carbon dioxide in the off-gases is a prudent precaution, since unexpected or higher than normal amounts of carbon monoxide and/or carbon dioxide signify poorly controlled or uncontrolled oxidation. Similar overriding rules applied by the controller help prevent poor yields, conversions, and even explosions.
  • the droplets have an average droplet diameter and they are produced at a desired first flow rate, the gas flows at a second flow rate, the droplets may contain volatile ingredients volatilizing at a volatilization rate, the first liquid contains a first reactant at a first content, the gas contains oxidant at a second content.
  • the ratio of the oxidant to the inert or other gas determines the content of oxidant in the gas.
  • pre-coalescing transient conversion is the conversion of first reactant to intermediate oxidation product as droplets of first liquid travel from the atomizer to the sample collector. It should be understood that information regarding the amounts of first reactant and oxidation product, if present, are monitored in the first liquid and they are provided to the computerized controller through the conversion monitor along with information regarding the percent moles of intermediate oxidation product in the sample collector. This whole information is collectively called pre-coalescing transient conversion information.
  • the analyses and/or computations from different lines are conducted by well known to the art techniques, and they have been omitted from the Figures for purposes of clarity. More specifically the pre-coalescing transient conversion is defined as the ratio [(O 2 - O 1 )x100]/[R 1 xn], where:
  • O 1 is the percent moles of intermediate oxidation product in the first liquid
  • O 2 is the percent moles of intermediate oxidation product as provided to the conversion monitor by the sample collector
  • R 1 is the percent moles of first reactant in the first liquid; and n is the number of moles of intermediate oxidation product produced when one mole of first reactant is completely converted to said intermediate oxidation product.
  • pre- coalescing temperature, transient temperature difference, and pre-coalescing transient conversion are of essence for controlling oxidation reactions, and not just the overall temperature or conversion over the whole process, as employed so far in the art.
  • Control of pre-coalescing temperature, or transient temperature difference, or both with or without control of pre-coalescing transient conversion not only helps in improving the yield, but in addition it helps in avoiding reactions leading to complete oxidation, combustion, or even explosion.
  • a device 10 for preparing an intermediate oxidation product from a first liquid containing a first reactant and a gas containing a second reactant comprises a reaction chamber 12, which chamber has an upper end 14, a lower end 16 and a reaction zone 18.
  • the reaction chamber 12 also has a wall having an inside surface 21.
  • the chamber 12 is preferably of cylindrical shape turning to conical at the vicinity of the lower end 16, and finally leading to a liquid outlet 22 connected to an outlet line 24.
  • the outlet line 24 leads to a separator 15 where the intermediate oxidation products are separated from reactants following line, and unreacted reactants, usually containing various amounts of intermediate oxidation products, solvents, catalysts, and other adjuncts, return to a recirculation tank 19 through line 11.
  • the separator may be as simple a device as a filter, or as complicated as a battery of tanks, washers, extractors, distillation columns, etc., suitable to each particular case.
  • a by-pass line 50 connected to the system through a by-pass valve 52 is used to by-pass the separator 15, if so desired.
  • a gas outlet 23 leading to an outlet gas line 25 there is provided a liquid dispensing ring 44 on the wall 20 of the reaction chamber 12.
  • the liquid dispensing ring 44 is connected to line 11", which provides liquid, preferably recovered.
  • the ring 44 is adapted to distribute said liquid substantially uniformly on the inside surface 21 of the wall 20 in the form of a thick film or curtain 45.
  • the reaction chamber 12 is preferably adapted to withstand such temperatures and pressures, which are appropriate for the reaction conditions in the reaction chamber 12, and be suitable for the reactants and reaction products.
  • Such materials and construction characteristics are well known to the art. For example, depending on the particular reaction, carbon steel, stainless steel, or Hastalloy may be required.
  • the inside surface 21 may be protected by coatings or linings of vitreous or other materials.
  • an atomizer 26 preferably comprising a plurality of nozzles 27.
  • the atomizer 26 is preferably of the airless type (does not need an atomizing gas for its operation). Airless atomizers are well known to the art.
  • the atomizer 26 may be steady at a certain position of the reaction chamber 12, or it may be movable, preferably in an up/down mode.
  • a driving mechanism 28, supporting the atomizer 26 is preferably connected to the reaction chamber 12 in the vicinity of the upper end 14.
  • the driving mechanism 28 may be a hydraulic or pneumatic cylinder, or it may be of mechanical nature, such as one of the screw type, for example. It is mainly important that the driving mechanism 28 is adapted to move the atomizer 26 in a preferably up/down mode in a controllable manner, and without introducing leaks to the reaction chamber 12.
  • a gas inlet 34 preferably located in the vicinity of the lower end 16 of the reaction chamber 12, is connected to a gas inlet feed line 36, which provides the gas containing the second reactant.
  • a sample collector 30 which is adapted to collect droplets of liquid and transfer them preferably as a miniature stream of liquid to a conversion detector (the word detector according to the present invention includes the meaning of monitor) 32 through sample line 33.
  • the conversion detector 32 may also monitor the amount of first reactant and the amount of the intermediate oxidation product in the recirculation tank 19 through a sample line 17. This information along with information on the nature and quantity of what is added in line 41 , for example, can accurately determine the amounts of intermediate oxidation product and first reactant going to the atomizer 26.
  • a heat exchanger 38 is adapted to provide recirculated reactant mixture from the recirculation tank 19 to a replenishment receptacle 40, through inlet line 39.
  • the replenishment receptacle 40 is also provided with fresh reactants, catalysts, solvents, and other adjuncts necessary for the reaction in each particular case through inlet line 41.
  • the replenishment receptacle 40 may be a container comprising temperature control (not shown) and a high pressure pump (not shown), which provides mixture made in the receptacle 40 to the nozzles 27 of the atomizer 26 through line 42 at a desired atomization temperature.
  • Line 42 has a flexible, preferably coiled portion 43, so that it can follow any movements of the atomizer 26.
  • the device 10 also comprises a controller 35, preferably computerized, which is fed information regarding pre-coalescing transient conversion of reactants to intermediate oxidation product from conversion detector 32 through input line 31 , and it controls heat exchanger 38 through output line 27, the drive mechanism 28 through output line 29, and the replenishment receptacle 40 through output line 37.
  • controller 35 preferably computerized, which is fed information regarding pre-coalescing transient conversion of reactants to intermediate oxidation product from conversion detector 32 through input line 31 , and it controls heat exchanger 38 through output line 27, the drive mechanism 28 through output line 29, and the replenishment receptacle 40 through output line 37.
  • the monitor or detector 32 may be any instrument which is adaptable to detect the intermediate oxidation product or products. It may, for example, comprise a chromatography apparatus, a UV spectrograph, an IR spectrograph, a visible light spectrograph, a mass spectrometer, a NMR instrument, a conductivity monitor, an ionization detector, a flame detector, any other suitable instrument, or a combination thereof.
  • the monitor or detector 32 comprises a HPLC (High
  • the HPLC instrument has more than one columns, so that if the separation time in a column is longer than desired, consecutive samples are introduced in different columns and a multiplicity of separations are conducted in parallel so that the interval between monitoring consecutive samples falls within desired limits. If it is desired to also analyze also non-polar organic moieties, it would be preferable to also include a gas chromatographic monitor or detector coupled with an appropriate monitor, such as an ionization monitor, for example.
  • the method and the devices of the instant invention are particularly suitable for oxidation reactions of organic compounds, wherein the major portion of the oxidation product is an oxidation intermediate different than CO, CO 2 , or a mixture thereof.
  • One of the reasons why this is so, is that, due to the intricate criticalities of the present invention, the reaction rates, reaction homogeneity, yield, and other important properties are considerably improved, while in the absence of said criticalities complete oxidation to CO/CO 2 would take place.
  • the same conditions of atomization without said criticalities are presently used in combustion engines of automobiles and other devices, to substantially completely oxidize
  • organic compounds such as gasoline to a mixture of CO/CO 2 .
  • the major portion of the oxidation product may be substantially cyclohexanol, cyclohexanone, cyclohexylhydroperoxide, caprolactone, adipic acid, the like, and mixtures thereof.
  • Organic acids are preferable oxidation products.
  • a first liquid containing the first reactant, cyclohexane enters the reaction chamber 12 through line 42 in a manner that it is atomized by the atomizer 26 and nozzles 27, in a manner to form a plurality of droplets 48.
  • the first liquid enters the atomizer at a desired atomization temperature, which in the case of cyclohexane is preferably in the range of 50-150° C, more preferably in the range of 80 - 130° C, and even more preferably in the range of 90 - 120°.
  • Atomization temperature of the first liquid is the temperature of the liquid just before it is atomized.
  • the temperature of the just formed droplets may be the same or different than the atomization temperature.
  • the first liquid also preferably contains a solvent, such as acetic acid, for example, a catalyst, such as a cobalt compound, soluble in the first liquid, for example, and an initiator, such as cyclohexanone, methylethylketone, acetaldehyde, the like, and mixtures thereof, for example.
  • a solvent such as acetic acid
  • a catalyst such as a cobalt compound
  • an initiator such as cyclohexanone, methylethylketone, acetaldehyde, the like, and mixtures thereof, for example.
  • the pressure in the case of oxidation of cyclohexane to adipic acid should preferably be high enough to maintain the cyclohexane, solvents, initiators, etc., substantially in the liquid state. Although pressures even in excess of 1 ,000 psia are possible, pressures in the range of 100 to 400 psia are preferable, and pressures in the range
  • the atomizer 26 is initially preferably placed, by the drive mechanism 28, at a low position close to the lower end 16 of the reaction chamber 12 (although in Figure 1 the atomizer 26 happens to have a position in the vicinity of the upper end 14 of the reaction chamber 14), at a distance from a mass of a second liquid 54, which has a second surface 56, and which is collected and disposed of at the lower end 16 of the reaction chamber 12 through liquid outlet 22.
  • the second liquid is a combination of coalesced droplets 48 and liquid from the thick film or curtain 45.
  • the distance between the nozzle of the atomizer which is closest to the surface 56 of the mass 54, and the surface 56 of the mass of the second liquid 54 is defined as the atomization distance.
  • the atomization distance is defined as the distance between the nozzle of the atomizer which is closest to the point where the liquid outlet 22 meets the reaction chamber, and that point.
  • the atomization distance at the beginning of the operation is preferably about one third to one fourth of the maximum atomization distance.
  • the maximum atomization distance is the atomization distance when the atomizer is as far away from the surface 56 of the second liquid mass 54 as the design of the device 10 and the atomizer 26 allows.
  • the atomizer has the maximum atomization distance in Figure 1.
  • a gas containing the oxidant preferably oxygen in the case of cyclohexane
  • the gas in addition to the oxidant, may also contain rather inert gases, such as nitrogen and/or carbon dioxide for example.
  • the droplets fall in a downwardly direction from the atomizer 26, they start reacting with the oxidant, which is oxygen for example.
  • the second liquid 54 is removed, preferably continuously, through the liquid outlet 22, and it is pumped (pump not shown) through liquid outlet line 24 to a separator 15, where the intermediate oxidation product, adipic acid for example, is separated from the liquids by techniques well known to the art. In some occasions, other by-products of the oxidation may also be removed in the separator, if so desired. Reactants, solvents, catalysts, and the like, return through line 11 to the recirculation tank 19.
  • Part of the second liquid, after the above product and/or by-product removal treatment, may be directed to the liquid dispensing ring 44, through line 11', if so desired, where it is dispensed in the form of the thick film or liquid curtain 45, and covers the inside surface 21 of the wall 20 of the reaction chamber 12.
  • the temperature of this film, when it is dispensed from the dispensing ring 44 is arranged to be lower than the atomization temperature.
  • cyclohexane to adipic acid for example, it is preferably in the range of 20° to 80° C, and more preferably in the range of 20° to 40° C.
  • any solid products which are insoluble in the droplets are washed down by the liquid curtain 45, and they form the second liquid 54 along with the coalesced droplets 48, as already mentioned. Thus, no sticking of solids takes place on the inside surface 21 of the wall 20.
  • unrecycled liquids which might be just solvents, or just reactants with or without catalysts or other adjuncts, or other liquids, or any combination thereof, may replace or supplement the recycled liquid coming from line 11'.
  • the second liquid transported in line 24 may by-pass the separator 15 through by-pass valve 52 and by-pass line 50 either partially or totally. This option may be utilized, especially at the beginning of the operation, if the pre-coalescing transient conversion is under a desired pre- coalescing transient conversion level.
  • Measures are taken for the level or surface 56 of second liquid 54 not to move over the point at which the sample collector 30 is positioned, to prevent flooding of the sample collector 30 with second liquid 54, which will produce false sampling.
  • Monitoring a liquid level is very well known to the art and may be conducted with any suitable type of "liquid level monitor", available in the market.
  • the liquid level monitor is then arranged to control the supply of liquids entering the reaction chamber 12 as curtain 45 though line 11', as droplets through the atomizer 26, or exiting the reaction chamber 12 as second liquid 54 through outlet liquid line 24, or any combination thereof, so as to keep the level or surface 56 of the second liquid mass 54 within desired limits under the sample collector 30.
  • Such an arrangement is very simple, and it is not shown in Figure 1 for clarity purposes.
  • the monitor 32 comprises a chromatography apparatus, which more preferably is a High Performance (or Pressure) Liquid Chromatography apparatus (HPLC).
  • HPLC High Performance Liquid Chromatography apparatus
  • This apparatus may preferably have an adequate number of columns, so that it is capable of making a respective number of overlapping determinations of the intermediate oxidation product present in the droplets just before they coalesce into the mass of the second liquid 54, so that the pre- coalescing transient conversion of the first reactant to intermediate reaction product is checked as frequently as desired in each particular case. If the column, for example, separates the intermediate oxidation product in 8 minutes, and the desired interval between determinations is 2 minutes in a particular case, four columns are needed.
  • Sampling of the liquid in the recirculation tank 19 or at a point just before it is atomized may be desirable, and it may be carried out in the same detector 32, through line 17 or other lines (not shown) respectively, or by means of another detector (not shown).
  • controller 35 controls the heat exchanger 38 through its output line 46, which along with the temperature of the liquids provided through line 41 , determines the temperature in the replenishment receptacle 40, which temperature is substantially the same as the atomization temperature for all practical purposes.
  • Controller 35 through its output line 37, controls the feed rate of first liquid through line 42.
  • controller 35 through its output line 29, controls the drive mechanism 28.
  • the drive mechanism 28 is ordered by the controller 35 to lower the level of atomizer in a manner that the atomization distance, as defined above, decreases.
  • the change of atomization distance is preferably conducted in increments, preferably in the range of 10 to 50% of the atomization distance at the particular time, and more preferably in the range of 10 to 30%.
  • other ranges may be more appropriate, depending on the particular conditions, materials, previous determination, and the like.
  • the following increment may be 30%, for example.
  • the next increment may be 5%, for example, until the conversion falls within the desirable range, and preferably in the most desirable range. It should be pointed out again, however, that the desirable ranges may change, depending on materials, conditions, etc.
  • the distance between the sample collector 30 and the level or surface 56 of the second liquid mass 54 is preferably in the range of 5 - 10% of the maximum atomization distance
  • the pre-coalescing transient conversion After the pre-coalescing transient conversion is found to be within the most desired, it continues to be monitored with a goal in most cases to stay somewhere in the vicinity of the middle value of said most desired range. Continuous monitoring and control are highly desirable, since the conditions in the reaction chamber may vary, causing changes in the pre-coalescing transient conversion values.
  • the preferable predetermined pre-coalescing transient conversion range is 0.05% to 80%
  • the pre-coalescing transient conversion can be also calculated or measured from samples of the second liquid, after taking into account any factors which change the concentration of the reaction product in the droplets.
  • a thermocouple 60a adapted to monitor the pre-coalescing temperature of the droplets.
  • the controller 35 in this case is fed information regarding the pre-coalescing temperature through input line 60a' and the pre-coalescing transient conversion of reactants to intermediate oxidation product from conversion detector 32 through input line 31.
  • the controller 35 controls heat 10 exchanger 38 through output line 46, the drive mechanism 28 through output line 29, and the replenishment receptacle 40 through output line 37, and feed rate in line 42.
  • thermocouple 60a which in turn feeds the pre-coalescing temperature information to the controller 35 through input line 60a'.
  • part of the droplets also fall into the sample collector 30, just above the surface 56 of the second liquid mass 56, from where, they are directed to the conversion detector or monitor 32, to be analyzed regarding pre-coalescing transient conversion.
  • the information obtained in 20 the conversion detector or monitor 32 is fed to computerized controller 35 through its input line 31, where it is processed by well known to the art techniques along with information received through line 60a' regarding the pre-coalescing temperature of the droplets.
  • the controller 35 makes decisions based on the pre-coalescing temperature first. If the pre-coalescing temperature is above the pre- coalescing temperature range, the drive mechanism 28 is ordered by the controller 35 to lower the level of atomizer in a manner that the atomization distance, as
  • the change of atomization distance is preferably conducted in increments, preferably in the range of 10 to 50% of the atomization distance at the particular time, and more preferably in the range of 10 to 30%.
  • increments may be more appropriate, depending on the particular conditions, materials, previous determination, and the like. For example, if a 10% decrease in atomization distance is found not to have an appreciable result, the following increment may be 30%, for example.
  • the next increment may be 5%, for example, until the pre- coalescing temperature falls within the desirable range, preferably in the most desirable range, and even more preferably if it attains a value in the vicinity of its most preferred set value.
  • thermocouple 60a The distance between the thermocouple 60a and the level or surface 56 of the second liquid mass 54 is preferably in the range of 5 - 10% of the maximum atomization distance.
  • the preferred pre-coalescing temperature range is 50 - 150° C, more preferably 80 - 130° C, and even more preferably 90 - 120° C.
  • the pre-coalescing temperature is found to be within the most desired range (90 - 120° C, for example, in the case of cyclohexane to adipic acid under certain conditions), it continues to be monitored with a goal in most cases to stay somewhere in the vicinity of the middle value of said most desired range (about 105° C, for example, which is the most desired value). Continuous monitoring and control are, of course, highly desirable, since the conditions in the reaction chamber may vary, causing changes in the pre-coalescing temperature.
  • the above operation is conducted for as long as the pre-coalescing transient conversion is closer to its most preferable set value than the pre-coalescing temperature.
  • the pre-coalescing transient conversion is found to be further away to its respective most preferred value than the pre-coalescing temperature, or if it is driven to fall outside its respective predetermined range, then the pre-coalescing transient conversion takes precedence, and an operation as described in the previous embodiment is conducted.
  • the reaction chamber 112 is provided with an atomizer 126 in the vicinity of its upper end 114, and a sample collector 130 positioned in the vicinity of its lower end 116.
  • thermocouple 160 there is also provided a supplementary heat exchanger 158 and a temperature measuring device, such as a thermocouple 160, for example.
  • the liquid dispensing ring 144 is shown at the beginning of the conical portion of the reactor, but it may take any position on the wall of the reactor, or it may be omitted all together. The same holds true for all embodiments of the present invention.
  • the sample collector 130 is connected to the conversion monitor or detector 132 through line 133 for providing samples of droplets 148 trapped in the collector just (and coalesced, of course in the collector) before they coalesce onto the second liquid mass 154.
  • the thermocouple 160 and the conversion monitor or detector 132 are connected, preferably electrically, to the controller 135 through input lines 160' and 131 , respectively.
  • controller 135 is connected, preferably electrically, to the supplemental heat exchanger 158 through output line 158' in order to control said supplemental heat exchanger 158.
  • controller 135 is connected, preferably electrically, to the supplemental heat exchanger 158 through output line 158' in order to control said supplemental heat exchanger 158.
  • the first liquid containing the first reactant, cyclohexane for example enters the reaction chamber 112 through line 142 in a manner that it is atomized by the atomizer 126, in a manner to form a plurality of droplets 148.
  • a gas containing the oxidant preferably oxygen in the case of cyclohexane
  • the gas in addition to the oxidant, may also contain rather inert gases, such as nitrogen and/or carbon dioxide for example. Off gases mixed with vapors of reactants, solvents, mist, and the like exit the reaction chamber through outlet gas line 125 and are treated as it will exemplified at a later section.
  • the droplets start reacting with the oxidant, which is oxygen for example.
  • the oxidant which is oxygen for example.
  • a part of the droplets 148 fall into the sample collector 130, from where, they are directed to the conversion detector or monitor 132, to be analyzed regarding pre-coalescing transient conversion.
  • the information obtained in the conversion detector or monitor 132 is fed to computerized controller 135 through its input line 131 , where it is processed by well known to the art techniques. Also, the atomization temperature from thermocouple 160 is fed to the computerized controller 135. The controller 135 controls the heat exchanger 158 through its output line 158'.
  • the heat exchanger is ordered by the controller 135 to lower the atomization temperature, monitored by thermocouple 160. Similarly, if the pre-coalescing transient conversion is under the "pre-coalescing transient conversion range", according to this invention, the heat exchanger is ordered by the controller 35 to increase the atomization temperature.
  • the upper and lower limits of the atomization temperature depend on the reactants, conditions of the reaction, and the like.
  • the upper limit should preferably be maintained not higher than 170° C, and more preferably not higher than 150° C, while the lower limit should preferably maintained not lower than 50° C, and more preferably not lower than 70° C.
  • the change of atomization temperature is preferably conducted in increments, preferably in the range of 5 to 10% of the atomization temperature at the particular time.
  • thermocouple 160a is disposed at the lower end 116 of the reaction chamber 112 for monitoring the pre-coalescing temperature.
  • a shield 190 positioned under the thermocouple 160a, is to protect the thermocouple 160a from temperature changes due to drafts of ascending gases.
  • thermocouple 160 is disposed within the atomizer 126 for measuring the atomization temperature. Both thermocouples 160 and 160a are connected to the controller 135 through input lines 160' and 160a', respectively. In turn, the controller 135 is connected, preferably electrically, to the supplemental heat exchanger 158 through output line 158' in order to control said supplemental heat exchanger 158. For purposes of clarity, basically only the elements of the device 110, which illustrate this embodiment and its operation, are shown.
  • the first liquid containing the first reactant, cyclohexane for example enters the reaction chamber 112 through line 142 in a manner that it is atomized by the atomizer 126 to form a plurality of droplets 148.
  • thermocouple 160a A part of the droplets 148 fall onto the thermocouple 160a, which in turn the pre-coalescing temperature information to the computerized controller 135 through its input line 160a', where it is processed by well known to the art techniques. Also, the atomization temperature from thermocouple 160 is fed to the computerized controller 135 through input line 160'. The controller 135 controls the heat exchanger 158 through its output line 158'.
  • the heat exchanger is ordered by the controller 135 to lower the atomization temperature, monitored by thermocouple 160. Similarly, if the pre-coalescing temperature is under the pre-coalescing temperature range, according to this invention, the heat exchanger is ordered by the controller 35 to increase the atomization temperature.
  • the upper and lower limits of the atomization temperature depend on the reactants, conditions of the reaction, and the like.
  • the upper limit should preferably be maintained not higher than 170° C, and more preferably not higher than 150° C, while the lower limit should preferably maintained not lower than 50° C, and more preferably not lower than 70° C.
  • the change of atomization temperature is preferably conducted in increments, preferably in the range of 5 to 10% of the atomization temperature at the particular time.
  • the pre-coalescing temperature After the pre-coalescing temperature, is found to be within the most desired range (90 - 120° C, for example, in the case of cyclohexane to adipic acid for example under certain conditions), it continues to be monitored with a goal in most cases to stay somewhere in the vicinity of the middle or most preferred set value of said most desired range (about 115° C, for example). As in the previous embodiment, continuous monitoring and control are highly preferable, since the conditions in the reaction chamber may vary, causing changes in the transient conversion values.
  • the transient temperature difference takes precedence. If it is at a higher value than its most desired set value, the heat exchanger is ordered by the controller 135 to lower the atomization temperature, monitored by thermocouple 160. Similarly, if the transient temperature difference is at a lower value than its desired set value, according to this invention, the heat exchanger is ordered by the controller 35 to increase the atomization temperature.
  • the upper and lower limits of the atomization temperature depend on the reactants, conditions of the reaction, and the like.
  • the upper limit should preferably be maintained not higher than 170° C, and more preferably not higher than 150° C, while the lower limit should preferably maintained not lower than 50° C, and more preferably not lower than 70° C.
  • the change of atomization temperature is preferably conducted in increments, preferably in the range of 5 to 10% of the atomization temperature at the particular time.
  • the transient temperature difference After the transient temperature difference is found to be within the most desired range, it continues to be monitored with a goal in most cases to stay somewhere in the vicinity of the middle or most preferred set value of said most desired range. As in the previous embodiment, continuous monitoring and control are highly preferable, since the conditions in the reaction chamber may vary, causing changes in the transient temperature difference values.
  • the reaction chamber 212 is provided with an atomizer 226 in the vicinity of its upper end 214, and a sample collector 230 positioned in the vicinity of its lower end 216.
  • a pressurizing pump 263 communicating with the reaction chamber 212 through line 236, a flow meter 266 in the line 236, a gas mixing valve 268 connected on one side to an oxidant feed line 247 and an other gas line 249, and a pressure measuring device, such as a pressure gauge 262, for example for monitoring the pressure inside the reaction chamber 212.
  • the liquid dispensing ring 244 is shown at about the middle of the wall of the reaction chamber 212, but it may take any position on the wall, or it may be omitted all together.
  • the sample collector 230 is connected to the conversion monitor or detector 232 through line 233 for providing samples of droplets 248 trapped in the collector, just (and coalesced, of course, in the collector) before they coalesce onto the second liquid mass 254.
  • the pressure gauge 262, the flow meter 266, and the conversion monitor or detector 232 are connected, preferably electrically, to the controller 235 through input lines 262', 266', and 231 , respectively.
  • the controller 235 is connected, preferably electrically, to the pressurizing pump 263 through output line 263', to the gas mixing valve 268 through output line 268', and to valve 264 through output line 264'.
  • the controller 235 is adapted to control the pressurized pump 263, the gas mixing valve 268, and the valve 264.
  • the pressurized pump 263, the gas mixing valve 268, and the valve 264 For purposes of clarity, basically only the elements of the device 210, which illustrate this embodiment and its operation, are shown.
  • the valve 264 is initially closed or turned to the off position.
  • the gas mixing valve 268 is regulated to deliver a desired ratio of oxidant to inert gas (which ratio determines the content of oxidant in the total gas, defined earlier as the second content) to the pressurizing pump 263, obtained from lines 247 and 249, respectively.
  • the pressurizing pump is then turned on until the desired pressure is attained in the reaction chamber 212.
  • the valve 264 is opened to such a degree that the desired pressure is maintained in the reaction chamber.
  • second flow rate being the flow rate of the gas, as defined above
  • the pump is turned to a lower speed and the valve 264 is turned to a less open position in a manner to maintain the desired pressure at a lower second flow rate. This is continued until both the pressure and second flow rate attain desired values.
  • the second flow rate as measured from the flowmeter 266, is too low, the pump is turned to a higher speed and/or the valve 264 is turned to a more open position in a manner to maintain the desired pressure at a higher second flow rate. This is continued until both the pressure and the second flow rate attain desired values.
  • the first liquid After both pressure and the second flow rate have attained their initial desired values, the first liquid, after having been heated to the atomization temperature as described before, which liquid contains the first reactant, cyclohexane for example, enters the reaction chamber " 212 through line 242 in a manner that it is atomized by the atomizer 226, and forms a plurality of droplets 248.
  • the mixed gas containing the oxidant preferably oxygen in the case of cyclohexane
  • the desired ratio of the gases depends on the reaction and conditions, and it may have any value suitable for the circumstances.
  • the preferable oxidant is oxygen and the other gas is an inert gas, such as nitrogen or carbon dioxide, for example.
  • Off gases mixed with vapors of reactants, solvents, mist, and the like exit the reaction chamber 212 through outlet gas line 225, and are treated as it will be exemplified at a later section.
  • the second liquid 254 is removed, preferably continuously, through the liquid outlet line 224 as in the previous embodiments.
  • Part of the second liquid, after removal of the oxidation product and/or by ⁇ products, in the separator 15 shown in Figure 1 , may be directed to the liquid dispensing ring 244, through line 211', if so desired, where it is dispensed in the form the thick film or liquid curtain 245, as in the previous embodiments.
  • a part of the droplets 248 fall into the sample collector 230, from where, they are directed to the conversion detector or monitor 232, to be analyzed regarding pre- coalescing transient conversion.
  • the information obtained in the pre-coalescing transient conversion detector or monitor 232 is fed to computerized controller 235 through its input line 231 , where it is processed by well known to the art techniques. Also, the pressure within the reaction chamber from gauge 262, and the flow rate of gases (second flow rate) through line 236 measured by the flow meter 266 are fed to the computerized controller 235 through input lines 262' and 266', respectively. As aforementioned, the controller 235 controls the pressurizing pump 263 through its output line 263', valve 264 through its output line 264', and gas mixing valve 268 through its output line 268'.
  • Controlling the pressurizing pump means that the controller is adapted to change the pressure and flow output of the pressurizing pump based on data received from input lines 231, 266', and 262' , said data being processed according to a desired program.
  • Controlling the valve 264 means that it is adapted to open/close said valve 264 to a desired degree based on data received from input lines 231, 266', and 262' , said data being processed according to a desired program.
  • Controlling the gas mixing valve 268 means that it is adapted to regulate said valve 268 in a manner to feed the pressurizing pump 263 with a mixture of oxidant provided by line 247 and other (such as inert for example) gas provided by line 249, so that the mixture has a desired weight ratio, based on data received from input lines 231 , 266', and 262', said data being processed according to a desired program.
  • Programming computerized controllers is well known to the art.
  • two elements which can determine the pressure inside the reaction chamber 212, as well as the second flow rate in this embodiment, are the pressurizing pump 263 and the valve 264.
  • Other elements in line 225 such as condensers (not shown), gas recirculation assemblies (not shown), and the like for example, may also influence the pressure, mostly temporarily, but they have been omitted from Figure 3 for purposes of clarity. They will be discussed at a later section.
  • the flow or delivery rate of gas by the pressurizing pump 263 and the degree of opening of the valve 264 have to be coordinated in order to achieve a desired pressure inside the reaction chamber.
  • the data received in the computerized controller 235 may be used after being processed in a number of ways, or combinations thereof, to control the pre- coalescing transient conversion and maintain it within the pre-coalescing transient conversion range.
  • One way is to vary the flow rate of the gas (second flow rate) entering the reaction chamber 212 through line 236. If the pre-coalescing transient conversion, as measured in the pre-coalescing transient conversion monitor or detector 232 has a higher value than the desired pre-coalescing transient conversion range, the computerized controller 235 orders the pressurizing pump to decrease the second flow rate as measured by the flowmeter 266. At the same time, the valve 264 is ordered by controller 235 to attain a somewhat more closed or restricted position so that the pressure inside the reaction chamber 212, as measured by the pressure gauge 262, tends to remain within the desired range. This is continued until the second flow rate has attained a newly desired value, and pressure is within the desired range.
  • the computerized controller 235 orders the pressurizing pump to increase the second flow rate as measured by the flowmeter 266.
  • the valve 264 is ordered by controller 235 to attain a somewhat more open position, so that the pressure inside the reaction chamber 212, as measured by the pressure gauge 262, tends to remain within the desired range. This is continued until the second flow rate has attained a newly desired value and the pressure is within the desired range.
  • the second flow rate changes (increase or decrease) from one value to a newly desired value should preferably be in increments, preferably in the range of 5-20% and more preferably in the range of 5- 10%. Also, changes should preferably be ordered by the computerized controller in time intervals long enough to contain at least one new pre-coalescing transient conversion measurement in the conversion monitor or detector 232.
  • the same process is repeated until the pre-coalescing transient conversion finally falls within the desired pre-coalescing transient conversion range.
  • Another way is to vary the ratio of the oxidant to the inert or other gas entering the reaction chamber 212 through line 236. If the pre-coalescing transient conversion, as measured in the conversion monitor or detector 232 has a higher value than the desired pre-coalescing transient conversion range, the computerized controller 235 orders the gas mixing valve 268 to decrease said ratio. If the pre- coalescing transient conversion, as measured in the conversion monitor or detector 232 has a lower value than the desired pre-coalescing transient conversion range, the computerized controller 235 orders the gas mixing valve 268 to increase said ratio.
  • the ratio changes (increase or decrease) from one value to a newly desired value should preferably be in increments, preferably in the range of 5-20% and more preferably in the range of 5-10%. Also, changes should preferably be ordered by the computerized controller in time intervals long enough to contain at least one new pre-coalescing transient conversion measurement in the conversion monitor or detector 232.
  • the computerized controller 235 orders the pressurizing pump to slow down.
  • the valve 264 is ordered by controller 235 to attain a somewhat more open position so that the second flow rate, as measured by the flow meter 266, tends to remain within the desired range. This is continued until the pressure has attained a newly desired value, and the second flow rate is within the desired range.
  • the computerized controller 235 orders the pressurizing pump to speed up. At the same time, the valve 264 is ordered by controller 235 to attain a somewhat more closed position so that the second flow rate, as measured by the flow meter 266, tends to remain within the desired range. This is continued until the pressure has attained a newly desired value, and the second flow rate is within the desired range.
  • the pressure changes (increase or decrease) from one value to a newly desired value should preferably be in increments, preferably in the range of 2-20% and more preferably in the range of 5-10%. Also, changes should preferably be ordered by the computerized controller in time intervals long enough to contain at least one new pre-coalescing transient conversion measurement in the conversion monitor or detector 232.
  • the same process is repeated until the pre-coalescing transient conversion finally falls within the desired pre-coalescing transient conversion range.
  • the reaction chamber 212 is provided with an atomizer 226, having a thermocouple 260, in the vicinity of its upper end 214, and a thermocouple 260a in the vicinity of the lower end 216 of the reaction chamber 212.
  • the thermocouple 260a is connected to the controller 235 through input line 260a' for providing the temperature of droplets 248 before they coalesce onto the second liquid mass 254.
  • the pressure gauge 262, the flow meter 266, the thermocouple 260, and the thermocouple 260a are connected, preferably electrically, to the controller 235 through input lines 262', 266', 260', and 260a', respectively.
  • the controller 235 is connected, preferably electrically, to the pressurizing pump 263 through output line 263', to the gas mixing valve 268 through output line 268', and to valve 264 through output line 264'.
  • the controller 235 is adapted to control the pressurized pump 263, the gas mixing valve 268, and the valve 264.
  • this embodiment is very similar to the operation of the previous embodiment, with the difference that the determinant in this case is the transient temperature difference or the pre-coalescing temperature, or a combination thereof.
  • thermocouple 260a measures their temperature in the form of an electrical signal, which is fed to computerized controller 235 through its input line 260a', where it is processed by well known to the art techniques.
  • the atomization temperature in the atomizer 226 is measured by thermocouple 260, in the form of another electrical signal, which is fed to computerized controller 235 through its input line 260', where it is processed along with the rest of the information that the controller 235 receives.
  • the data received in the computerized controller 235 may be used after being processed in a number of ways, or combinations thereof, to control the pre- coalescing temperature and/or the transient temperature difference, and maintain them within their respective predetermined ranges.
  • One way is to vary the flow rate of the gas (second flow rate) entering the reaction chamber 212 through line 236. If the prevailing determinant, has a higher value than the desired respective predetermined range, the computerized controller 235 orders the pressurizing pump to decrease the second flow rate as measured by the flowmeter 266. At the same time, the valve 264 is ordered by controller 235 to attain a somewhat more closed or restricted position so that the pressure inside the reaction chamber 212, as measured by the pressure gauge 262, tends to remain within the desired range. This is continued until the second flow rate has attained a newly desired value, and pressure is within the desired range.
  • the computerized controller 235 orders the pressurizing pump to increase the second flow rate as measured by the flowmeter 266.
  • the valve 264 is ordered by controller 235 to attain a somewhat more open position, so that the pressure inside the reaction chamber 212, as measured by the pressure gauge 262, tends to remain within the desired range. This is continued until the second flow rate has attained a newly desired value and the pressure is within the desired range.
  • the second flow rate changes (increase or decrease) from one value to a newly desired value should preferably be in increments, preferably in the range of 5-20% and more preferably in the range of 5-10%. Also, changes should preferably be ordered by the computerized controller in time intervals long enough to allow for adequate equilibrium for prevention of over-shooting.
  • Another way is to vary the ratio of the oxidant to the inert or other gas entering the reaction chamber 212 through line 236. If the prevailing determinant has a higher value than the desired respective predetermined range, the computerized controller 235 orders the gas mixing valve 268 to decrease said ratio. If the prevailing determinant has a lower value than the desired respective predetermined range, the computerized controller 235 orders the gas mixing valve 268 to increase said ratio.
  • the ratio changes (increase or decrease) from one value to a newly desired value should preferably be in increments, preferably in the range of 5-20% and more preferably in the range of 5-10%. Also, changes should preferably be ordered by the computerized controller in time intervals long enough to allow for adequate equilibrium for prevention of over-shooting.
  • the computerized controller 235 orders the pressurizing pump to slow down.
  • the valve 264 is ordered by controller 235 to attain a somewhat more open position so that the second flow rate, as measured by the flow meter 266, tends to remain within the desired range. This is continued until the pressure has attained a newly desired value, and the second flow rate is within the desired range.
  • the computerized controller 235 orders the pressurizing pump to speed up.
  • valve 264 is ordered by controller 235 to attain a somewhat more closed position so that the second flow rate, as measured by the flow meter 266, tends to remain within the desired range. This is continued until the pressure has attained a newly desired value, and the second flow rate is within the desired range.
  • the pressure changes (increase or decrease) from one value to a newly desired value should preferably be in increments, preferably in the range of 2-20% and more preferably in the range of 5-10% of the pressure at that time.
  • changes should preferably be ordered by the computerized controller in time intervals long enough to obtain adequate equilibrium for prevention of over-shooting.
  • the reaction chamber 312 is provided with an atomizer 326 in the vicinity of its upper end 314, and a sample collector 330 positioned in the vicinity of its lower end 316.
  • a reactant mixing valve 369 which is adapted to mix first reactant from line 370 and other liquids from line 371 in order to produce the first liquid in line 342 having a first content of first reactant.
  • the sample collector 330 is connected to the conversion monitor or detector 332 through sample line 333 for providing samples of droplets 348 trapped in the collector just (and coalesced, of course in the collector) before they coalesce onto the second liquid mass 354.
  • the conversion monitor or detector 332 is connected, preferably electrically, to the controller 335 through input line 331 for transferring pre-coalescing transient conversion information.
  • the controller 335 is connected, preferably electrically, to the reactant mixing valve 369 through output line 369' in order to control said reactant mixing valve 369.
  • the reactant mixing valve 369 For purposes of clarity, basically only the elements of the device 310, which illustrate this embodiment and its operation, are shown.
  • first reactant from line 370 and other liquids from line 371 are mixed in proportions regulated by the reactant mixing valve 369, in order to produce the first liquid in line 342 so that said first liquid has a first content of first reactant.
  • the liquids from line 371 may contain solvents, catalysts, promoters, initiators, recycled ingredients, first reactant, and the like. If the liquids from line 371 contain first reactant, the content of these liquids in first reactant has to be taken into account in the determination of the first content of first reactant in line 342, so that the reactant mixing valve 369 allows accordingly less first reactant from line 370.
  • the first liquid containing the first reactant, cyclohexane for example, in a first content enters the reaction chamber 312 through line 342 in a manner that it is atomized by the atomizer 326, and forms a plurality of droplets 348.
  • the second liquid 354 is removed, preferably continuously, through the liquid outlet line 324 as in the previous embodiments.
  • a part of the droplets 348 fall into the sample collector 330, from where, they are directed to the conversion detector or monitor 332, to be analyzed regarding pre- coalescing transient conversion.
  • the information obtained in the conversion detector or monitor 332 is fed to computerized controller 335 through its input line 331 , where it is processed by well known to the art techniques.
  • the controller 335 controls the reactant mixing valve through its output line 369'.
  • the reactant mixing valve 369 is ordered by the controller 335 to increase the first content by increasing the ratio of the first reactant from line 370 to liquids from line 371.
  • the reactant mixing valve 369 is ordered by the controller 335 to decrease the first content by decreasing the ratio of the first reactant from line 370 to liquids from line 371.
  • the change of first content is preferably conducted in increments, preferably in the range of 5 to 10% of the first content at the particular time.
  • the reaction chamber 312 is provided a thermocouple 360a, positioned in the vicinity of the lower end 316, and shielded by shield 390.
  • the thermocouple 360a is electrically connected to the controller 335 through input line 360a' for providing pre-coalescing temperature data.
  • first reactant from line 370 and other liquids from line 371 are mixed in proportions regulated by the reactant mixing valve 369, in order to produce the first liquid in line 342 so that said first liquid has a first content of first reactant.
  • thermocouple 360a A part of the droplets 348, produced and treated as described in the above embodiment, fall onto the thermocouple 360a, and their temperature is measured by said thermocouple and provided to the controller 335 though input line 360a', where it is processed by well known to the art techniques.
  • the controller 335 controls the reactant mixing valve through its output line 369'.
  • the reactant mixing valve 369 is ordered by the controller 335 to lower the first content by decreasing the ratio of the first reactant from line 370 to liquids from line 371.
  • the reactant mixing valve 369 is ordered by the controller 335 to increase the first content by increasing the ratio of the first reactant from line 370 to liquids from line 371.
  • pre-coalescing temperature After the pre-coalescing temperature is found to be within the most desired range, said pre-coalescing temperature continues to be monitored with a goal in most cases to stay somewhere in the vicinity of the middle value of said most desired range.
  • reaction chamber 412 is provided with an atomizer 426 in the vicinity of its upper end 414, and a sample collector 430 positioned in the vicinity of its lower end 416.
  • the atomizer 426 may be operable by gas or preferably without the need of gas
  • the atomizer 426 of this embodiment is adapted to control at will the droplet size or diameter through a regulator 472.
  • atomizers are well known in the art.
  • droplet diameter may change by changing the pressure of the liquid to be atomized, changing the orifice size, changing the frequency and/or intensity in the case of ultrasonic or other pulsation operated atomizers, changing the pressure of the gas in the case of gas operated atomizers, changing the rotation or the speed in the case of centrifugal atomizers, etc.
  • the regulator 472 represents any mechanism well known to the art, which is adapted to controllably change any variable parameter of the atomizer which controls average diameter of the droplets.
  • the sample collector 430 is connected to the conversion monitor or detector
  • the conversion monitor or detector 432 is connected, preferably electrically, to the controller 435 through input line 431 for transferring pre- coalescing transient conversion information.
  • the controller 435 is connected, preferably electrically, to the regulator 472 through output line 472' in order to control said regulator 472.
  • the first liquid containing the first reactant, cyclohexane for example enters the reaction chamber 412 through line 442 in a manner that it is atomized by the atomizer 426, and forms a plurality of droplets 448.
  • a part of the droplets 448 fall into the sample collector 430, from where, they are directed to the conversion detector or monitor 432, to be analyzed regarding pre- coalescing transient conversion.
  • the information obtained in the conversion detector or monitor 432 is fed to computerized controller 435 through its input line 431 , where it is processed by well known to the art techniques.
  • the controller 435 controls the regulator 472 through its output line 472'.
  • the regulator 472 is ordered by the controller 435 to increase the average diameter of the droplets. Similarly, if the pre- coalescing transient conversion is under the "pre-coalescing transient conversion range", according to this invention, the regulator 472 is ordered by the controller 435 to decrease the average diameter of the droplets.
  • the change in droplet diameter is preferably conducted in increments, preferably in the range of 10 to 20 % of the average droplet diameter at the particular time.
  • pre-coalescing transient conversion After the pre-coalescing transient conversion is found to be within the most desired range, said pre-coalescing transient conversion continues to be monitored with a goal in most cases to stay somewhere in the vicinity of the middle value of said most desired range (about 40%, for example). As in previous embodiments, continuous monitoring and control are highly preferable, since the conditions in the reaction chamber may vary, causing changes in the pre-coalescing transient conversion values.
  • the device 410 may also optionally comprise an optical monitor 474, preferably of the fiber optic type, connected to an image analyzer 476 though line 474', which image analyzer is in turn connected to the computerized controller 435 through input line 476'.
  • the image analyzer 476 determines the average droplet diameter from the image received from the optical monitor 474, and sends this information to the controller 435, which then incorporates said information to the rest of the processed data, so that it can be better control the average droplet diameter, by comparing for example the change ordered to regulator 472 with the droplet size change as a result of it.
  • thermocouple 460a is connected, preferably electrically, to the controller 435 through input line 460a' for transferring pre-coalescing temperature information.
  • the controller 435 is connected, preferably electrically, to the regulator 472 through output line 472' in order to control said regulator 472.
  • the regulator 472 is connected, preferably electrically, to the regulator 472 through output line 472' in order to control said regulator 472.
  • the first liquid containing the first reactant, cyclohexane for example enters the reaction chamber 412 through line 442 in a manner that it is atomized by the atomizer 426, and forms a plurality of droplets 448.
  • thermocouple 460a A part of the droplets 448 fall onto the thermocouple 460a, and their temperature is measured and provided to computerized controller 435 through its input line 460a', where it is processed by well known to the art techniques.
  • the controller 435 controls the regulator 472 through its output line 472'.
  • the regulator 472 is ordered by the controller 435 to increase the average diameter of the droplets. Similarly, if the pre-coalescing temperature is under the predetermined pre-coalescing temperature, according to this invention, the regulator 472 is ordered by the controller 435 to decrease the average diameter of the droplets.
  • the change in droplet diameter is preferably conducted in increments, preferably in the range of 10 to 20 % of the average droplet diameter at the particular time.
  • the pre-coalescing temperature After the pre-coalescing temperature is found to be within the most desired range (90 - 120° C, for example, in the case of cyclohexane to adipic acid, for example, under certain conditions), said pre-coalescing temperature continues to be monitored with a goal in most cases to stay somewhere in the vicinity of the middle value of said most desired range (about 120° C, for example).
  • continuous monitoring and control are highly preferable, since the conditions in the reaction chamber may vary, causing changes in the pre-coalescing temperature values. Valves regulating ratios of liquids, and controlled by computerized controllers according to a desirable program are well known in the art.
  • the reaction chamber 512 is provided with an atomizer 526 in the vicinity of its upper end 514, and a sample collector 530 positioned in the vicinity of its lower end 516.
  • a first liquid pump 577 which is adapted to regulate a first flow of the first liquid in line 542, and a flow meter 578 adapted to measure the rate of the first flow of the first liquid in line 542.
  • the flow meter 578 is connected, preferably eclectically, to the computerized controller 535 through input line 578'.
  • the sample collector 530 is connected to the conversion monitor or detector 532 through sample line 533 for providing samples of droplets 548 trapped in the collector just (and coalesced, of course in the collector) before they coalesce onto the second liquid mass 554.
  • the conversion monitor or detector 532 is connected, preferably electrically, to the controller 535 through input line 531 for transferring pre-coalescing transient conversion information.
  • the controller 535 is connected, preferably electrically, to the first liquid pump 577 through output line 577' in order to control said first liquid pump 577.
  • the controller 535 is connected, preferably electrically, to the first liquid pump 577 through output line 577' in order to control said first liquid pump 577.
  • the first liquid pump 577 pumps first liquid in line 542 at a desired first flow rate.
  • the first liquid containing the first reactant, cyclohexane for example, in a first content enters the reaction chamber 512 through line 542 in a manner that it is atomized by the atomizer 526 at a first flow rate, and forms a plurality of droplets 548.
  • the information obtained in the conversion detector or monitor 532 is fed to computerized controller 535 through its input line 531 , where it is processed by well known to the art techniques.
  • the flow rate measurement from the flow meter 578 is fed to the controller 535 and processed in coordination with the information from line 531.
  • the controller 535 in turn controls the first liquid pump 577 through its output line 577', in a manner to increase or decrease the flow rate of first liquid in a programmed manner.
  • the first liquid pump 577 is ordered by the controller 535 to increase the first flow rate, by increasing, for example, the pumping action. Similarly, if the pre-coalescing transient conversion is under the pre- coalescing transient conversion range, as earlier defined, the first liquid pump 577 is ordered by the controller 535 to decrease the first flow rate, by decreasing, for example, the pumping action.
  • the change in first flow rate is preferably conducted in increments, preferably in the range of 5 to 10% of the first flow rate at the particular time.
  • pre-coalescing transient conversion After the pre-coalescing transient conversion is found to be within the most desired range, said pre-coalescing transient conversion continues to be monitored with a goal in most cases to stay somewhere in the vicinity of the middle value of said most desired range.
  • the reaction chamber 512 is provided with an atomizer 526 in the vicinity of its upper end 514, a thermocouple 560 positioned within the atomizer for monitoring the atomization temperature, and a thermocouple 560a, positioned in the vicinity of the lower end 516 of the reaction chamber 512.
  • the thermocouples 560 and 560a are connected, preferably electrically, to the controller 535 through its input lines 560' and 560a', respectively, for providing atomization temperature and pre- coalescing temperature data to said controller 535.
  • the controller 535 is connected, preferably electrically, to the first liquid pump 577 through output line
  • the first liquid pump 577 pumps first liquid in line 542 at a desired first flow rate.
  • the first liquid containing the first reactant, cyclohexane for example, in a first content enters the reaction chamber
  • thermocouple 560a A part of the droplets 548 fall onto thermocouple 560a, where their temperature is measured and fed to computerized controller 535 through its input line 560a', where it is processed by well known to the art techniques. Also, the atomization temperature, measured by thermocouple 560 is fed to the controller 535 through its input line 560', where it is also processed. The flow rate measurement from the flow meter 578 is fed to the controller 535 through input line 578' and processed in coordination with the information from input lines 560a' and 560'. The controller 535 in turn controls the first liquid pump 577 through its output line 577', in a manner to increase or decrease the flow rate of first liquid in a programmed manner.
  • the first liquid pump 577 is ordered by the controller 535 to increase the first flow rate, by increasing, for example, the pumping action.
  • the first liquid pump 577 is ordered by the controller 535 to decrease the first flow rate, by decreasing, for example, the pumping action.
  • the change in first flow rate is preferably conducted in increments, preferably in the range of 5 to 10% of the first flow rate at the particular time.
  • the reaction chamber 612 is provided with an atomizer 626 in the vicinity of its upper end 614, and a sample collector 630 positioned in the vicinity of its lower end 616.
  • a volatiles mixing valve 679 which is adapted to mix volatiles from line 680 and other liquids from line 681 in order to produce the first liquid in line 642.
  • the sample collector 630 is connected to the conversion monitor or detector 632 through sample line 633 for providing samples of droplets 648 trapped in the collector just (and coalesced, of course in the collector) before they coalesce onto the second liquid mass 654.
  • the conversion monitor or detector 632 is connected, preferably electrically, to the controller 635 through input line 631 for transferring pre-coalescing transient conversion information.
  • the controller 635 is connected, preferably electrically, to the volatiles mixing valve 679 through output line 679' in order to control said volatiles mixing valve 679.
  • the volatiles mixing valve 679 For purposes of clarity, basically only the elements of the device 610, which illustrate this embodiment and its operation, are shown.
  • volatiles from line 680 and other liquids from line 681 are mixed in proportions regulated by the volatiles mixing valve 679, in order to produce the first liquid in line 642 so that said first liquid has a desired content of volatiles.
  • the volatiles are substances, of usually lower boiling point than that of the first reactant, which under the conditions of the reaction have a tendency to volatilize as the first liquid is atomized in the reaction chamber and lower conversion rates.
  • the volatiles have preferably low or no reactivity under the reaction conditions. In the case of oxidation of cyclohexane to adipic acid, acetic acid and/or acetone, for example, would represent volatiles.
  • the liquids from line 681 contain first reactant, along with solvents, catalysts, promoters, initiators, recycled ingredients, and the like.
  • a part of the droplets 648 fall into the sample collector 630, from where, they are directed to the conversion detector or monitor 632, to be analyzed regarding pre- coalescing transient conversion.
  • the information obtained in the conversion detector or monitor 632 is fed to computerized controller 635 through its input line 631 , where it is processed by well known to the art techniques.
  • the controller 635 controls the volatiles mixing valve 679 through its output line 679'.
  • the volatiles mixing valve 679 is ordered by the controller 635 to increase the introduction of volatiles from obtained from line 680. Similarly, if the pre-coalescing transient conversion is under the "pre- coalescing transient conversion range", according to this invention, the volatiles mixing valve 679 is ordered by the controller 635 to decrease or eliminate the introduction of volatiles from line 680.
  • the increase or decrease of volatiles is preferably conducted in increments, preferably in the range of 2 to 5% based on the total weight of the first liquid at that particular time.
  • pre-coalescing transient conversion After the pre-coalescing transient conversion is found to be within the most desired range, said pre-coalescing transient conversion continues to be monitored with a goal in most cases to stay somewhere in the vicinity of the middle value of said most desired range.
  • catalyst may be added through line 680 at a desired base level. Addition of higher amounts of catalyst will favor increase of pre-coalescing transient conversion, while addition of lower amounts of catalyst will favor decrease of pre- coalescing transient conversion.
  • the increase or decrease of catalyst level is preferably conducted in increments, preferably in the range of 5 to 10% based on the total weight of the catalyst contained in the first liquid at that particular time.
  • the reaction chamber 612 is provided with an atomizer 626 in the vicinity of its upper end 614, a thermocouple 660 within the atomizer 626, and a thermocouple 660a positioned in the vicinity of its lower end 616.
  • the thermocouple 660a is connected, preferably electrically, to the controller 635 through input line 660a' for providing pre-coalescing temperature information to said controller 635.
  • volatiles from line 680 and other liquids from line 681 are mixed in proportions regulated by the volatiles mixing valve 679, in order to produce the first liquid in line 642 so that said first liquid has a desired content of volatiles.
  • the liquids from line 681 contain first reactant, along with solvents, catalysts, promoters, initiators, recycled ingredients, and the like.
  • the first liquid containing the first reactant, cyclohexane for example enters the reaction chamber 612 through line 642 in a manner that it is atomized by the atomizer 626, and forms a plurality of droplets 648.
  • thermocouples 660a and 660 The atomization and pre-coalescing temperature information obtained by thermocouples 660a and 660 is fed to computerized controller 635 through its input lines 660a' and 660, respectively, where it is processed by well known to the art techniques according to a desired program.
  • the controller 635 controls the volatiles mixing valve 679 through its output line 679'.
  • a part of the droplets 648 fall into the sample collector 630, from where, they are directed to the conversion detector or monitor 632, to be analyzed regarding prevailing determinant.
  • the volatiles mixing valve 679 is ordered by the controller 635 to increase the introduction of volatiles from obtained from line 680. Similarly, if the prevailing determinant is under the prevailing determinant predetermined range, according to this invention, the volatiles mixing valve 679 is ordered by the controller 635 to decrease or eliminate the introduction of volatiles from line 680.
  • the prevailing at the time determinant continues to be monitored with a goal in most cases for both determinants to stay somewhere in the vicinity of the middle value of their most desired range, as already explained.
  • catalyst may be added through line 680 at a desired base level. Addition of higher amounts of catalyst will favor increase of pre-coalescing temperature, transient temperature difference and pre-coalescing transient conversion, while addition of lower amounts of catalyst will favor decrease of pre- coalescing temperature, transient temperature difference, and pre-coalescing transient conversion.
  • the reaction chamber 712 is provided with an atomizer 726 in the vicinity of its upper end 714, and a sample collector 730 adapted to be floating as a boat on liquid 754 at the lower end 716 of the reaction chamber 712.
  • the sample collector 730 also supports a thermocouple 760a for measuring pre-coalescing temperature.
  • the atomizer 726 is provided with first liquid from line 742, which contains a flow meter 778.
  • a retaining tank 753 connected to the vicinity of the lower end 716 of the reaction chamber 712 through two pumps 751a and 751b.
  • the retaining tank 753 is also connected to pump 751 c, which is adapted to transfer liquid to a separator (shown as 15 in Figure 1).
  • a level controller 755 which controls pump 751c, based on the level of liquid in retaining tank 753, by well known to the art techniques.
  • the level controller activates pump 751c through output line 751c' when the liquid exceeds level A, and deactivates said pump 751c when the liquid goes lower than level B.
  • the sample collector 730 is connected to the conversion monitor or detector
  • sample collector 730 has a boat like configuration provided with a closed float portion 730a, and a sample portion 730b, as better shown in Figure 9.
  • the flexible coiled portion 733' of line 733, and the flexible coiled portion 760a" of the line 760a' allow the boat ⁇ like sample collector 730 to move freely along with the surface 756 of the second liquid mass 754.
  • thermocouple 760a supported by the floating sample collector 730, is connected to the controller 735 through input line 760a', which has the coiled portion 760a".
  • the thermocouple transfers, preferably eclectically, pre-coalescing temperature data to the controller 735.
  • the conversion monitor or detector 732 is also connected, preferably electrically, to the controller 735 through input line 731 for transferring pre- coalescing transient conversion information.
  • the flow meter 778 is connected, preferably electrically, to the controller 735 through input line 778' for transferring flow rate information regarding the first liquid entering the reaction chamber 712 through the atomizer 726.
  • the controller 735 is connected, preferably electrically, to pumps 751a and 751b through output lines 751a 1 and 751b, respectively, for controlling said pumps 751a and 751b.
  • the first liquid containing the first reactant, cyclohexane for example enters the reaction chamber 712 through line 742 in a manner that it is atomized by the atomizer 726, and forms a plurality of droplets 748.
  • a part of the droplets 748 fall into the sample collector 730, from where, they are directed through line 733 and its flexible portion 733' to the conversion detector or monitor 732, to be analyzed regarding pre-coalescing transient conversion.
  • Part of the droplets also fall onto the thermocouple 760a, which measures the pre- coalescing temperature, and then transfers this information to the controller 735 though line 760a' and through its coiled portion 760a".
  • the information obtained in the conversion detector or monitor 732 is also fed to the computerized controller 735 through its input line 731 , where it is processed by well known to the art techniques.
  • the controller 735 controls pumps 751a and 751b, as aforementioned.
  • pump 751a is ordered by the controller 735 to stop its pumping action, and pump 751b is activated. This causes the surface 756 of the second liquid mass 754 to rise, resulting in smaller atomization distance, as defined earlier. In turn, smaller atomization distance causes the prevailing determinant to decrease.
  • pump 751a is ordered by the controller 735 to start or continue its pumping action, and pump 751b is deactivated. This causes the surface 756 of the second liquid mass 754 to drop, resulting in higher atomization distance. In turn, higher atomization distance causes the prevailing determinant to increase.
  • the level 756 of the second liquid mass 754 may be determined by the controller 735 either indirectly by correlating the amounts of incoming first liquid (through the atomizer, as measured by the flow meter 778 and obtained by the controller 735 through line 778', and through pump 751 b) and outcoming second liquid 754 through pump 751a, or directly by use of a level measuring device (not shown for purposes of clarity) in the reaction chamber.
  • Level measuring devices are well known in the art.
  • the level of liquids in the retaining tank 753 is controlled by level controller 755. When the level goes under level B, pump 751c is deactivated by the controller 755. If the liquid level exceeds level A, pump 751c is activated again by controller 755.
  • the retaining tank 753 should contain enough liquid at its lowest level B to take care of any given variations of liquid level 756 in the reaction chamber 712.
  • the increase or decrease of atomization distance is preferably conducted in increments, preferably in the range of 2 to 5% of the atomization distance at the time the measurement is made.
  • the separator 15 can be any assembly of equipment, simple or complicated, which is capable of separating the intermediate oxidation product from the second liquid.
  • Such equipment is well known to the art, as described for example in a plethora of patents regarding separation of adipic acid from the mother liquor (second liquid in this case).
  • the separator 15 may comprise, according to this invention, two filters 15a and 15b connected in parallel, as better shown in Figure 10.
  • the separator 15 may also comprise valves 15w, 15x, 15y, and 15z, as well as an optional heat removal device 15i, which may take the form of a crystallizer.
  • valves 15x and 15y are initially open, while valves 15w and 15z are closed. While valves 15w and 15z are closed, any solid oxidation product previously accumulated in filter 15a, such as adipic acid for example, is separated from said filter 15a, either manually or automatically (back- flush, scraping, and the like well known to the art, for example / not shown).
  • valves 15w and 15z are opened and valves 15x and 15y are closed, so that filtering of solid oxidation product takes place now in filter 15a, while filter 15b is being emptied. This cycle is repeated in the process.
  • alternate devices may be used, such as for example, rotary drum filters and the like.
  • the apparatus or device 810 of the present invention also comprises a condenser 857 connected to the gas outlet 823 through line 825, and to condensate tank 859, which serves as a reservoir of condensate collected from condenser 857.
  • the condensate tank 859, through valve 865 is connected to line 865', which in turn is connected to the liquid dispensing ring 844, or it is connected to line 865", which in turn leads to line 811 for recycling the condensed liquids to the recycling tank 819.
  • the valve 865 is adapted to direct the condensed liquids totally to line 865', or totally to line 865", or partially to line 865' and partially to line 865", or be closed and not permit any transfer of condensed liquids.
  • the device 810 also comprises a heat exchanger 838 connected to the recycling tank 819; an eductor or aspirator 861 , connected to the heat exchanger 838; a pump 877 connected to the eductor 861 at the intake and to the atomizer 826 at the other end.
  • the eductor 861 is adapted to produce vacuum to line 867' through regulating valve 867 (when the regulating valve 867 is in an open position) and through check valve 867a, which allows flow from line 867' toward the pump but not vice versa.
  • Line 867' is connected to line 857' between the condenser 857 and the valve 864.
  • An additional pump may be placed between the eductor 861 and the heat exchanger 838, which in coordination with pump 877 may control the vacuum produced by the eductor 861 toward line 867'. It may be also utilized to prevent starvation of pump 877 from first liquid.
  • the heat exchanger 838 may be part of the condenser 857 (not shown as such in Figure 11), so that heat received from condensibles is used as heat source for the heat exchanger 838.
  • Lines 841a, 841b, and 841c are used to supply the recirculation tank with appropriate amounts of raw materials, catalysts, solvents, initiators, promoters and the like.
  • first liquid from the recycling tank is heated to the desired temperature in heat exchanger 838.
  • the heated first liquid is pumped through pump 877 to the atomizer 826, where it is broken into droplets 848, which finally coalesce onto the second liquid 854 as already discussed in previous embodiments.
  • gas containing an oxidant preferably oxygen
  • Any off-gases produced during the reaction which are usually non-condensible unless subjected to extremely low temperatures, along with condensibles leave the reaction chamber 812 through gas outlet 823. Following line 825, they enter the condenser 857, where the condensibles condense to condensate, which condensate is accumulated into the condensate tank 859.
  • the condensate is directed, at least partially, through valve 865 to line 865', from where it is fed to the liquid dispensing ring 844 and forms said curtain 845, useful to prevent sticking of any reaction or other solid products to the walls of the reactor 812.
  • This condensate has the advantage over the recycled liquid coming through line 11' of Figure 1 , for example, that in most cases it is substantially catalyst free. This is because in the practice of this invention, non volatile catalysts, such as metal salts for example, are utilized in most occasions.
  • the 865 is caused to direct the condensate to line 865", which feeds it to line 811 , so that the condensate is finally transferred to the recirculation tank 819.
  • the valve 865 is adapted to direct the condensed liquids totally to line 865', or totally to line 865", or partially to line 865' and partially to line 865", or be closed and not permit any transfer of condensed liquids.
  • valve 864 is preferably controllable to open and close to any degree demanded by the operation. If it is desired to remove all non-condensible gases from the system, valve 864 is opened to a desired degree for the pressure inside the system to be maintained to desired levels, and valve 867 is completely closed. If it is desired to only partially remove non-condensibles, both valves 864 and 867 are opened to the desired degree, so that vacuum formed by the eductor or aspirator 861 , recirculates the part of non-condensibles caused by the vacuum to enter the reaction chamber 812.
  • the apparatus or device 910 of the present invention also comprises a condenser 957 connected to the gas outlet 923 through line 925, and to condensate tank 959, which serves as a reservoir of condensate collected from condenser 957.
  • the condensate tank 959 is connected to the liquid dispensing ring 944.
  • the condenser 957 is also connected to a valve 964 through line 957', which valve is adapted to release non- condensibles, if in an open position.
  • the device 910 also comprises a heat exchanger 938 connected to the recycling tank 919 and to the atomizer 926 at the other end. It also comprises a gas pump 961 connected to line 957' through line 967' adapted to transfer non- condensibles from line 957' to the gas inlet feed line 936. A replenish gas line 936' is also connected to line 936 for providing fresh gas containing oxidant, preferably oxygen.
  • the heat exchanger 938 may be part of the condenser 957 (not shown as such in Figure 11), so that heat received from condensibles is used as heat source for the heat exchanger 938.
  • Lines 941a, 941b, and 941c are used to supply the recirculation tank with appropriate amounts of raw materials, catalysts, solvents, initiators, promoters and the like.
  • first liquid from the recycling tank is heated to the desired temperature in heat exchanger 938, and enters the atomizer 926, where it is broken into droplets 948, which finally coalesce onto the second liquid 954 as already discussed in previous embodiments.
  • gas containing oxidant preferably oxygen
  • Any off-gases produced during the reaction which are usually non-condensible unless subjected to extremely low temperatures, along with condensibles leave the reaction chamber 912 through gas outlet 923. Following line 925, they enter the condenser 957, where the condensibles condense to a condensate, which condensate is accumulated into the condensate tank 959.
  • the condensate is directed, at least partially as discussed in other embodiments, to the liquid dispensing ring 944 and forms curtain 945, useful to prevent sticking of any reaction or other solid products to the walls of the reactor
  • the condensate may be directed elsewhere through line 959'.
  • valve 964 is preferably controllable to open and close to any degree demanded by the operation. If it is desired to remove all non-condensible gases from the system, valve 964 is opened to a desired degree for the pressure inside the system to be maintained to desired levels, and pump 961 is deactivated. If it is desired to have only partial removal of non-condensibles, valve 964 is opened to the desired degree, and pump 961 is also activated to the desired degree so that this combination causes recirculation of part of non-condensibles to the reaction chamber 912.
  • Complete recirculation of non-condensibles without substantially any non-condensibles leaving the system may be preferably conducted by not allowing new flow of inert gas diluents to take place after a certain point, so that the pressure inside the reaction chamber 912 does not finally exceed predetermined limits.
  • the second liquid 954 is directed to the separator 915, through line 924, where the intermediate oxidation product is separated and the remaining liquids are either sent to another separator (not shown) for further separation of constituents, or they are directed to the recycling tank 919 for recycling, or a combination thereof.
  • the reaction chamber 1012 has a gas outlet 1023, which coincides with the liquid outlet 1022, preferably in the vicinity of the lower end 1016 of the reaction chamber 1012.
  • Both the gas distributor 1073 fed by gas inlet line 1036, and the atomizer 1026 fed by line 1042, are preferably disposed at the upper end 1014 of the reaction chamber 1012.
  • the gas distributor 1073 and the atomizer 1026 may be combined into one unit, and the gas may be used to help or totally be responsible for the atomization process.
  • the liquid/gas output 1022/1023 has preferably a conical shape of reduced diameter as compared to the diameter of the reaction chamber 1012, as illustrated in Figure 13.
  • the liquid dispensing ring 1044 is preferably positioned either at the bottom of the reaction chamber as shown in Figure 13, or at the top 1023' of the liquid/gas output 1022/1023.
  • the liquid dispensing ring 1044 is adapted to deliver the liquids in a swirling manner.
  • a cooler (not shown) may be placed in line 1011' in order to cool the liquids to a desired temperature adequate to condense condensibles exiting from the reaction chamber 1012 through the liquid/gas output 1022/1023.
  • a liquid/gas separator 1075 for receiving the condensed condensibles and the non-condensibles from the reaction chamber 1012 through line 1025 and separating the second liquid 1054 from the non-condensibles.
  • the liquid/gas separator 1075 is in turn connected to separator 1015, which is adapted to separate the intermediate oxidation product from the reactants and other materials introduced into the system in the process.
  • first liquid is introduced to the atomizer 1026 through line 1042, where it is broken into droplets 1048, which finally coalesces in the vicinity of the lower end 1016, preferably on the curtain or thick film 1045 and within the liquid/gas output 1022/1023.
  • gas containing an oxidant preferably oxygen
  • the liquids coming in the reaction chamber through line 1011' may be derived from within the system or from outside the system. Any off-gases produced during the reaction, which are usually non-condensible unless subjected to low temperatures, along with condensibles leave the reaction chamber 1012 through the liquid/gas output 1022/1023. Following line 1025, they enter the liquid/gas separator 1075, where the second liquid 1054 is separated from the non- condensibles, which are removed through line 1057' and valve 1064, which valve may operate as already discussed in previous embodiments.
  • the second liquid 1054 is directed to the separator 1015, where it is treated as already discussed in previous embodiments.
  • condensation of condensibles may be inside the pressurized device, such as for example device 810 and 910 of Figures 11 and 12, respectively, in the respective condensers 857 and 957, before the respective valves 864 and 964, which are used to purge the non condensibles, such as miscellaneous off-gases, which may include one or more of oxygen, nitrogen, carbon monoxide, carbon dioxide, and the like, for example.
  • This particular type of condensation albeit outside the reaction chamber, is by definition internal condensation, according to this invention, and it takes place at a pressure which is substantially the same as the reaction pressure.
  • internal condensation inside the reactor may also take place, and in most occasions it is preferable to the outside internal condensation.
  • Internal condensation (before substantial pressure drop) is highly preferable to external condensation ( after substantial or total pressure drop).
  • Internal inside condensation is especially suitable in the case of employing close to stoichiometric amounts of oxidant for the oxidation process.
  • FIG. 14 One embodiment of the instant invention utilizing internal inside condensation is better shown in Figure 14, wherein only a limited number of elements is shown, for purposes of clarity. There is provided a cooling mantle 1183 surrounding the reaction chamber 1112 in all or part of its height. Otherwise, the reaction chamber 1112 comprises the same elements as in the previous embodiments.
  • the temperature of the cooler is such as to cool down the wall 1120 adequately for vapors of condensibles inside the reaction chamber to condense and form a thick film or curtain 1145. Since the catalyst (metal salt for example, such as cobalt acetate, for example) in most cases is not volatile, it does not transfer to this curtain. Further, the temperature of the thick film is lower than that of the temperature of the droplets. Thus, no substantial reaction takes place within the curtain, and in addition to other advantages, the thick film or curtain
  • FIG. 15 Another embodiment of the instant invention utilizing internal inside condensation is better shown in Figure 15, wherein only a limited number of elements is shown, for purposes of clarity.
  • a cooling coil 1283 inside the reaction chamber 1212, having an entry coolant line 1282 and a coolant exit line 1282'.
  • the coil may be extending through the whole height of the reactor or just through part of it.
  • the coil 1283 may be positioned vertical as shown in Figure 15, or horizontal, or it may have any other suitable for the circumstances direction. Otherwise, the reaction chamber 1212 comprises the same elements as in the previous embodiments.
  • the operation of this embodiment is similar to the operation of the previous embodiments with the exception that a cooler enters the coil 1283 through line 1282 and exits through line 1282'.
  • the temperature of the cooler is such as to cool down the coil 1283 adequately for vapors of condensibles inside the reaction chamber to condense on said coil 1283. Since the catalyst (metal salt for example, such as cobalt acetate, for example) in most cases is not volatile, it does not transfer to the condensate on the coil. Further, the temperature of the condensate on the coil 1283 is lower than that of the temperature of the droplets.
  • reaction chamber 1312 comprises the same elements as in the previous embodiments.
  • the operation of this embodiment is similar to the operation of the previous embodiments with the exception that a cooling liquid enters the cooling liquid sprayer 1385 through line 1384. It is then atomized by sprayer 1385.
  • the cooling liquid comprises preferably either the same solvent contained in the first liquid or first reactant contained in the first liquid.
  • the cooling liquid preferably comprises acetic acid (solvent), or cyclohexane (first reactant), or a mixture thereof.
  • no catalyst is contained in the cooling liquid.
  • the temperature at which the cooling liquid is atomized is such that condensibles condense on the droplets of the atomized cooling liquid, thus providing internal inside condensation.
  • the droplets of the first liquid do not mix with the cooling liquid droplets, for all practical purposes, while both are being suspended in the gas, so that oxidation proceeds unhindered within the droplets of the first liquid.
  • both types of droplets coalesce together at the lower end 1316 of the reaction chamber 1312 to form the second liquid 1353, which is removed through line 1324 for further treatment, as described in previous embodiments.
  • the flow rate of the cooling liquid and the flow rate of the first liquid have to be taken into account by well known to the art techniques in the controller (for example shown as 35 in Figure 1).
  • FIG. 17 A different embodiment of the instant invention utilizing internal inside condensation is better shown in Figure 17, wherein only a limited number of elements is shown, for purposes of clarity.
  • a cooling liquid sprayer 1485 preferably at the upper end 1414 of the reaction chamber 1412 having an entry cooling liquid line 1484.
  • the sprayer 1485 has preferably a plurality of spray nozzles 1486 around its perimeter. The spray nozzles 1486 are directed toward the wall 1420 of the reaction chamber 1412. Otherwise, the reaction chamber 1412 comprises the same elements as in the previous embodiments.
  • cooling liquid enters the cooling liquid sprayer 1485 through line 1484. It is then atomized by sprayer 1485 through nozzles 1486, and falls on the walls 1420 of the reaction chamber 1412, where it forms a thick film or curtain 1445.
  • the cooling liquid comprises preferably either the same solvent contained in the first liquid or first reactant contained in the first liquid.
  • the cooling liquid preferably comprises acetic acid (solvent), or cyclohexane (first reactant), or a mixture thereof.
  • no catalyst is contained in the cooling liquid.
  • the temperature at which the cooling liquid is atomized is such that condensibles condense on the droplets of the atomized cooling liquid, and also on the curtain 1445, thus providing internal inside condensation. Since the catalyst (metal salt for example, such as cobalt acetate, for example) in most cases is not volatile, it does not transfer to the curtain 1445. Further, the temperature of the thick film is lower than that of the temperature of the first liquid droplets. Thus, no substantial reaction takes place within the curtain 1445, and in addition to other advantages, the thick film or curtain 1445 prevents solid buildup on the walls of the condenser. Liquids and droplets ar finally mixed together at the lower end 1416 of the reaction chamber 1412, as the second liquid 1454, which is removed through line 1424 for further treatment, as described in previous embodiments.
  • thermocouples 1560b and/or sample collectors 1530' arranged within the reaction zone 1534, which are connected to a preferably computerized controller (not shown).
  • the thermocouples 1560b and/or sample collectors 1530' may be positioned in any appropriate places of the reaction zone 1534 in order to monitor the temperature and/or conversion of the falling droplets at different distances between the upper end 1532 and the lower end 1542 of the reaction chamber 1522.
  • the thermocouples 1560b take the temperature of the droplets and feed this information to the controller (not shown), as described in previous embodiments.
  • the sample collectors provide coalesced liquid from the falling droplets to a conversion monitor (not shown), which in turn provides conversion information to the controller (not shown), as described in previous embodiments.
  • the controller based on this information, gives appropriate orders to the other components of the device to prevent the temperature from deviating outside predetermined limits, if so desired, not only for purposes of controlling the reaction but also to prevent catastrophic results in case that the reaction heat released is excessive. This presents an additional safeguard.
  • thermocouples 1560b in the reaction zone1534 for determining the rate of temperature rise, or temperature profile in the droplet path
  • the temperature difference between two of these thermocouples is called transient temperature sub- difference. The higher the temperature changes from thermocouple to thermocouple (transient temperature sub-difference) the more drastic the changes ordered by the controller.
  • a device 1610 for preparing an intermediate oxidation product from a first liquid containing a first reactant and a gas containing a second reactant comprises a reaction chamber 1612, which chamber has an upper end 1614, and a lower end 1616.
  • the chamber 1612 is preferably of cylindrical shape turning to conical at the vicinity of the lower end 1616, and finally leading to a liquid outlet 1622 connected to an outlet line 1624.
  • the outlet line 1624 leads to a pump 1618, which is connected to a first valve 1619 though line 1624a.
  • the first valve 1619 is adapted to connect line 1624a to either line 1624b or line 1624c or partially to line 1624b and partially to line 1624c.
  • Line 1624b leads back to the reaction chamber 1612 (through line 1642) at an atomizer 1626, preferably located at the upper end 1614 of the reaction chamber 1612.
  • the atomizer 1626 has preferably a plurality of nozzles 1627, which more preferably are of the airless type, well known in the art.
  • the atomizer 1626 may be steady at a certain position of the reaction chamber 1612, or it may be movable, preferably in an up/down mode, as previously described, for example.
  • Line 1624c leads to a second valve 1619a, which is adapted to connect line
  • Line 1624c leads to a separator 1615 where the intermediate oxidation products are separated from reactants, unreacted reactants, usually containing various amounts of intermediate oxidation products, solvents, catalysts, and other adjuncts, return to a recirculation tank (not shown) through line 1611.
  • the separator may be as simple a device as a filter, or as complicated as a battery of tanks, washers, extractors, distillation columns, etc., suitable to each particular case, as also described previously.
  • Line 1624f leads to a device 1612a, which may be another reaction chamber or a battery of reaction chambers, or other devices including but not limited to of tanks, washers, extractors, distillation columns, etc.
  • the device 1612a is connected to separator 1615 through line 1611a, especially in the case that device 1612a is a simple reaction chamber or a battery of reaction chambers.
  • a gas inlet 1634 preferably located in the vicinity of the lower end 1616 of the reaction chamber 1612, is connected to a gas inlet feed line 1636, which provides the gas containing the second reactant, which is preferably an oxidant, such as oxygen for example.
  • thermocouple 60 is preferably disposed within the atomizer in order to measure the atomization temperature, which is the temperature of the first liquid just before being atomized.
  • One or more thermocouples 60a are disposed within the reaction chamber 1612, while thermocouple 60b is disposed within the second liquid 1654 at the lower part of the reaction chamber 1612, in order to measure the temperature of the second liquid 1654.
  • a sample collector 1630 which is adapted to collect droplets of liquid and transfer them preferably as a miniature stream of liquid to a conversion detector (the word detector according to the present invention includes the meaning of monitor) 1632 through sample line 1633, as also previously described.
  • the conversion detector 1632 may also monitor the amount of first reactant and the amount of the intermediate oxidation product as the first liquid enters the atomizer through appropriate sample line(s), not shown for purposes of clarity. This information along with information on the nature and quantity of what is added in line 1641 , for example, can accurately determine the amounts of intermediate oxidation product and first reactant going to the atomizer 1626.
  • the conversion in the second liquid 1654 may also be detected and monitored through sample line 1633', which connects line 1624a with the conversion detector 1632.
  • the device 1610 also comprises a controller 1635, preferably computerized, which is fed information regarding temperature through input lines 60', 60a' and 60b'.
  • the controller 1635 is also fed information regarding conversion of reactants to intermediate oxidation product from detector 1632 through input line 1631.
  • the controller 1635 controls, through one ore more output lines 1636, any of a plurality of means for adjusting conversions and/or temperatures in order to control the oxidation rate, as described in detail earlier
  • means and their operation include but are not limited to heat exchangers (for example heat exchanger 1645 in line 1642), and other means for changing the atomization temperature, the reaction pressure, the atomization distance, the average droplet diameter, the first flow rate (rate of production of droplets from the first liquid), the second flow rate (flow rate of the gas), the volatilization rate (volatilization of volatile ingredients contained in the droplets), the first content (the content of first reactant in the first liquid), the second content (content of second reactant, preferably oxidant in the gas), the catalyst content (in the first liquid), and a combination thereof.
  • heat exchangers for example heat exchanger 1645 in line 1642
  • the monitor or detector 1632 may be any instrument which is adaptable to detect the intermediate oxidation product or products. It may, for example, comprise a chromatography apparatus (such as GC and/or HPLC, for example), a UV spectrograph, an IR spectrograph, a visible light spectrograph, a mass spectrometer, a NMR instrument, a conductivity monitor, an ionization detector, a flame detector, any other suitable instrument, or a combination thereof.
  • a chromatography apparatus such as GC and/or HPLC, for example
  • the monitor or detector 1632 comprises a HPLC (High Pressure/Performance Liquid Chromatography instrument) in combination with a UV monitor. It is also preferable that the HPLC instrument has more than one columns, so that if the separation time in a column is longer than desired, consecutive samples are introduced in different columns and a multiplicity of separations are conducted in parallel so that the interval between monitoring consecutive samples falls within desired limits. If it is desired to also analyze also non-polar organic moieties, it would be preferable to also include a gas chromatographic monitor or detector coupled with an appropriate monitor, such as an ionization monitor, for example.
  • HPLC High Pressure/Performance Liquid Chromatography instrument
  • HPLC HPLC
  • GC polar and non ⁇ polar ingredients
  • the methods and the devices of the instant invention are particularly suitable for oxidation reactions of organic compounds, wherein the major portion of the oxidation product is an oxidation intermediate different than CO, CO 2 , or a mixture thereof.
  • One of the reasons why this is so, is that, due to the intricate criticalities of the present invention, the reaction rates, reaction homogeneity, yield, and other important properties are considerably improved, while in the absence of said criticalities complete oxidation to CO/CO 2 would take place.
  • the same conditions of atomization without said criticalities are presently used in combustion engines of automobiles and other devices, to substantially completely oxidize (combust or burn in other words) organic compounds such as gasoline to a mixture of CO/CO 2 .
  • the major portion of the oxidation product may be substantially cyclohexanol, cyclohexanone, cyclohexylhydroperoxide, caprolactone, adipic acid, the like, and mixtures thereof.
  • Organic acids are preferable intermediate oxidation products.
  • thermocouples and two sampling lines regarding conversion are shown, a smaller or larger number of these elements may be used. Minimally, however, one thermocouple or one sample line has to be utilized.
  • the device 1610 does not necessarily have to have all the elements shown, such as for example device(s) 1612a.
  • a first liquid containing the first reactant, cyclohexane enters the reaction chamber 1612 through line 1642 and it is atomized by the atomizer 1626 and nozzles 1627, in a manner to form a plurality of droplets 1648.
  • the first liquid enters the atomizer at a desired atomization temperature, which in the case of cyclohexane is preferably in the range of 50-150° C, more preferably in the range of 80 - 130° C, and even more preferably in the range of 90 - 120°. Other temperatures may of course be used depending on the particular circumstances.
  • Atomization temperature of the first liquid is the temperature of the liquid just before it is atomized.
  • the temperature of the just formed droplets may be the same or different than the atomization temperature.
  • the first liquid also preferably contains a solvent, such as acetic acid, for example, a catalyst, such as a cobalt compound, soluble in the first liquid, for example, and an initiator, such as cyclohexanone, methylethylketone, acetaldehyde, the like, and mixtures thereof, for example.
  • the pressure in the case of oxidation of cyclohexane to adipic acid should preferably be high enough to maintain the cyclohexane, solvents, initiators, etc., substantially in the liquid state. Although pressures even in excess of 1 ,000 psia are possible, pressures in the range of 100 to 400 psia are preferable, and pressures in the range of 150 to 300 psia more preferable.
  • a gas containing the oxidant preferably oxygen in the case of cyclohexane
  • the gas in addition to the oxidant, may also contain rather inert gases, such as nitrogen and/or carbon dioxide for example. Off gases, mixed with vapors of reactants, solvents, mist, and the like exit the reaction chamber through outlet gas line 1625.
  • the second liquid 1654 is removed, preferably continuously, through the liquid outlet 1622, and it is pumped through liquid outlet line 1624 by means of pump 1618.
  • valve 1619 opens to a desired degree so that some of the second liquid, having the desired conversion level, passes to either the separator 1615 through lines 1624c and 1624d or to device 1612a through lines 1624c and 1624f for further treatment.
  • the valve 1619a may direct the whole liquid portion from line 1624c to either the separator 1615 or the device 1612a, or partially to separator 1615 and partially to device 1612a, depending on the particular circumstances.
  • Replenishment liquid containing first reactant, etc. enters the system through replenishment line 1641.
  • the composition and amount of the replenishment liquid entering the system is such as to replenish, preferably quantitatively, the amounts of ingredients removed through line 1624c.
  • the whole amount of the second liquid is recirculated to the atomizer 1626 through lines 1624b and 1642, until a desired conversion has been reached, at which point the second liquid is removed from the reaction chamber 1612 through properly activated valve 1619 (and, if so desired, valve 1619a) and line 1624c to enter separator 1615 or device 1612a, or partially separator 1615 and partially device 12a for further treatment.
  • New first liquid enters the system through replenishment line 1641, and the cycle is repeated.
  • the intermediate oxidation product adipic acid for example
  • the separator 1615 the intermediate oxidation product, adipic acid for example
  • the separator 1615 the intermediate oxidation product, adipic acid for example
  • the separator 1615 the intermediate oxidation product, adipic acid for example
  • Reactants, solvents, catalysts, and the like return to a recirculation tank (not shown) through line 1611. If at least part of the second liquid 1654 is at least partially directed to device 1612a, it may also be redirected to separator 1615, after any treatment in the device 1612a, through line 1611a.
  • thermocouple 60a which in turn feeds the temperature information to the controller 1635 through input line 60a'.
  • the atomization temperature and the temperature of the second liquid are also fed to the controller 1635 through input lines 1660' and 1660b', respectively.
  • part of the droplets also fall into the sample collector 1630, from where, they are directed to the conversion detector or monitor 1632, to be analyzed regarding conversion. If solids are present in the droplets, care should be taken to prevent clogging of liquid transporting lines by use of appropriate dilution, and the like.
  • a small stream of second liquid is directed to the conversion detector 1632 through line 1633' for analysis regarding conversion.
  • the monitor 1632 comprises a chromatography apparatus, which more preferably is a High Performance (or Pressure) Liquid Chromatography apparatus (HPLC), and even more preferably combined with a GC (gas chromatography) apparatus.
  • HPLC High Performance Liquid Chromatography apparatus
  • GC gas chromatography
  • This system may preferably have an adequate number of columns, so that it is capable of making a respective number of overlapping determinations of the intermediate oxidation product present in the or of the second liquid 1654, so that the respective conversion of the first reactant to intermediate reaction product is checked as frequently as desired in each particular case. If the column, for example, separates the intermediate oxidation product in 8 minutes, and the desired interval between determinations is 2 minutes in a particular case, four columns are needed.
  • Sampling of the liquid in other locations may also be desirable, and it may be carried out in the same detector 1632 or in a different detector (not shown).
  • the information obtained in the conversion detector or monitor 1632 is fed to computerized controller 1635 through its input line 1631 , where it is processed by well known to the art techniques along with information received through lines 1660', 1660a', and 1660b' regarding the respective temperatures.
  • the controller 1635 controls heat exchanger 1645 (not shown) or any of a plurality of means, mentioned earlier, which may be utilized to adjust any determinant, as described in detail in our co-pending applications.
  • heat exchanger 1645 which exemplifies one means for adjusting the determinants to control the oxidation rate, will be discussed here, with the understanding that the same principles apply regarding any other means.
  • thermocouple 1660 measuring the temperature inside the reactor, takes precedence, followed by the atomization temperature of thermocouple 1660, and then followed by the temperature of the second liquid 1654, as measured by thermocouple 1660b.
  • the conversion of first reactant to intermediate oxidation product in the sample collector 1630 takes then precedence, followed by the conversion of first reactant to oxidation product as provided in the path of lines
  • thermocouples 1660a and sample collectors 1630 it is preferable, and sometimes critical, especially in the case of fast reactions or very long reaction chambers, to adjust more than one determinant for controlling the oxidation rate, there are other occasions, especially in the case of relatively slow reactions, which permit the use of only single determinant.
  • thermocouples 1660a and sample collectors 1630 it is preferable to use a plurality of thermocouples 1660a and sample collectors 1630, so that the temperature and conversion are monitored in the whole length of the reaction chamber.
  • the controller 1635 is preferably adapted, by well known to the art techniques, to make decisions regarding what action to take in order to adjust a determinant, not only by the absolute values of the measurements, but also by the differences of the absolute values and the rate that any change in determinant takes place. For example, if the temperature difference between thermocouples 60 and 60a rises at a faster rate than desired, the controller will have to order more drastic measures than if the temperature in thermocouple 1660a albeit high, does not rise at a high rate, especially as compared to the temperature of thermocouple 1660. The same applies between thermocouples 1660a, if more thermocouples 1660a are present, and between conversions and conversion changes from samples provided by different sample collectors 1630, if more sample collectors 1630 are available.
  • the controller 1635 makes decisions based on the temperature provided by thermocouple 60a first. If that temperature is above the desired temperature range, heat exchanger 1645 is ordered by the controller 1635 to lower the temperature of the first liquid passing from line 1642 to the atomizer 1626. This change is preferably conducted in increments, preferably in the range of 10 to 50%, and more preferably in the range of 10 to 30% of the temperature at which the liquid enters the heat exchanger, as measured by a thermocouple (not shown for purposes of clarity) and provided to controller 1635. However, other ranges may be more appropriate, depending on the particular conditions, materials, previous determination, and the like.
  • the following increment may be 30%, for example.
  • the next increment may be 5%, for example, until the temperature falls within the desirable range, preferably in the most desirable range, and even more preferably if it attains a value in the vicinity of its most preferred set value.
  • the preferred temperature range is 50 - 150° C, more preferably 80 - 130° C, and even more preferably 90 - 120° C.
  • other temperatures considerably higher or considerably lower than the ones given above may be more suitable, even in the case of cyclohexane to adipic acid.
  • the desired range may be constant or it may vary with time, conversion, and other desired parameters.
  • the other determinants may be directed toward their desirable ranges, one after the other in the order described above, for as long as they do not interfere with the first determinant. If the first determinant is absent, the second determinant takes precedence, and the same technique is followed, until the second determinant falls within its predetermined range, as described above for the first determinant.
  • thermocouple 1660 should be lower than the range for thermocouple 1660a.
  • the temperature changes shown by thermocouple 1660b are necessarily slower than the ones shown by thermocouple 1660a, due to the mass of the second liquid 1654.
  • the determinant is the temperature of thermocouple 1660b, it is important that the volume of the second liquid 1654 at the lower end 1616 of the reaction chamber 1612 is as small as possible to respond as fast as possible in temperature changes of the droplets in the reaction chamber 1612.
  • one temperature determinant and one conversion determinant are utilized at the same time for controlling the oxidation rate.
  • Fast oxidations and/or long reaction chambers may require more than one sample collector 1630, while slow oxidations and/or short reaction chambers may rely only in conversion measured in the second liquid 1654 through line 1633'.
  • the controller 1635 gives orders to the heat exchanger 1645 from conversion data in a similar manner as it does from temperature data. Conversions per time interval of measurement (in a single pass or any desired number of recirculations) may preferably be maintained between 0.05% and 80%, although other values may be appropriate, depending on the particular case. This is also true in the case of adipic acid formation, where in some occasions the values of conversion may be extremely small and in other occasions extremely large. The range of 0.05% to 80%, however, still remains a preferable range.
  • catalysts used for the oxidation are transition metals having more than one valence states. Their major catalytic action is exhibited when they are at a higher valance state than their lowest valance state at which they exist as ions.
  • One good example is cobalt in the case of oxidation of cyclohexane to adipic acid. An initiation period before the oxidation starts has often been attributed by researches to the addition of cobalt ions at a valance state of II.
  • the cobalt catalyst is added at valance state II because cobaltous acetate, for example, is more readily available and it is less expensive than cobaltic acetate.
  • this period of oxidation becomes considerably smaller because of the high surface area provided.
  • cobaltous ion can be pre-oxidized to cobaltic ion.
  • oxidations according to this invention are non ⁇ destructive oxidations, wherein the oxidation product is different than carbon monoxide, carbon dioxide, and a mixture thereof.
  • the oxidation product is different than carbon monoxide, carbon dioxide, and a mixture thereof.
  • small amounts of these compounds may be formed along with the oxidation product, which may be one product or a mixture of products.
  • C 5 - C 8 aliphatic dibasic acids from the corresponding ketones, alcohols, and hydroperoxides of saturated cycloaliphatic hydrocarbons, such as for example preparation of adipic acid from cyclohexanone, cyclohexanol, and cyclohexylhydroperoxide;
  • numerals differing by 100 represent elements which are either substantially the same or perform the same function. Therefore, in the case that one element has been defined once in a certain embodiment, its re-definition in other embodiments illustrated in these figures by the same numerals or numerals differing by 100 is not necessary, and it has been often omitted in the above description for purposes of brevity. In Figure 19, this rule has not been followed for all numerals.
  • inlet line and output line have been used to signify lines adapted to transfer materials for the operation of the process, such as volatiles, intermediate oxidation products, off-gases, and the like, for example.
  • input line and output line have been used to signify lines adapted to transmit signals, which are mostly electrical, but they could also be hydraulic, pneumatic, optical, acoustic, and the like, for example.
  • a diagonal arrow through an element denotes that the element is controlled though a line, preferably electrical, connected to the arrow.
  • Internal condensation according to this invention is condensation of condensibles, which takes place within the pressurized system and before pressure drop to about atmospheric pressure. Internal inside condensation is condensation in the reaction chamber
  • Condensibles are substances having a boiling point higher than 15° C, while non condensibles are substances that have a boiling point of 15° C and lower. It should be understood that when referring to condensibles, it is meant “mostly condensibles” and when referring to non-condensibles it is meant “mostly non- condensibles”, since small amounts of one kind will be mixed with the other kind at substantially all times.

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Abstract

L'invention porte sur des procédés et dispositifs d'obtention de produits d'oxydation intermédiaires par atomisation d'un premier liquide contenant un réactif dans un gaz contenant un oxydant de manière à former un produit d'oxydation intermédiaire autre que le CO ou le CO2. La régulation de l'oxydation s'obtient par le contrôle et l'ajustement de la température et de la conversion pendant une ou plusieurs étapes de la réaction, et par le contrôle et l'ajustement de la conversion transitoire (la conversion intervenant dans l'intervalle de temps entre la formation des gouttelettes et leur coalescence en une masse liquide) du premier réactif en produit d'oxydation juste avant la coalescence des gouttelettes en une masse d'un deuxième liquide ou en contrôlant la température de précoalescence (température des gouttelettes juste avant leur coalescence en une masse liquide), ou la différence de température de transition (différence entre la température de précoalescence et celle des gouttelettes juste avant leur atomisation), ou la sous-différence de température de transition (différence de température entre deux positions à l'intérieur de la zone de réaction), ou leurs combinaisons. Cette invention a notamment pour avantage de réduire l'importance des déchets et d'influer très favorablement sur l'environnement.
EP96915863A 1995-06-07 1996-05-17 Procedes et dispositifs d'obtention de produits d'oxydation intermediaires par regulation des conversions et des temperatures dans un liquide atomise Withdrawn EP0837842A4 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
US475340 1983-03-14
US08/477,195 US5801282A (en) 1995-06-07 1995-06-07 Methods of making intermediate oxidation products by controlling pre-coalescing temperature and transient temperature difference in an atomized liquid
US08/477,234 US5502245A (en) 1995-06-07 1995-06-07 Methods of making intermediate oxidation products by controlling transient conversion in an atomized liquid
US08/478,257 US5580531A (en) 1995-06-07 1995-06-07 Devices for making reaction products by controlling transient conversion in an atomized liquid
US08/475,340 US5558842A (en) 1995-06-07 1995-06-07 Devices for making reaction products by controlling pre-coalescing temperature and transient temperature difference in an atomized liquid
US478257 1995-06-07
US477195 1995-06-07
US587967 1996-01-17
US08/587,967 US5883292A (en) 1996-01-17 1996-01-17 Reaction control by regulating internal condensation inside a reactor
US620974 1996-03-25
US08/620,974 US5654475A (en) 1996-03-25 1996-03-25 Methods of making intermediate oxidation products by controlling oxidation rates in an atomized liquid
PCT/US1996/007056 WO1996040610A1 (fr) 1995-06-07 1996-05-17 Procedes et dispositifs d'obtention de produits d'oxydation intermediaires par regulation des conversions et des temperatures dans un liquide atomise

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EP0837842A4 true EP0837842A4 (fr) 1999-03-31

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BR9609096A (pt) 1999-08-10
WO1996040610A1 (fr) 1996-12-19
EP0837842A1 (fr) 1998-04-29
JP2002515017A (ja) 2002-05-21
KR19990022376A (ko) 1999-03-25

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