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  • 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
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  • 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
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  • 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
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  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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  • B01J19/247—Suited for forming thin films
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  • 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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  • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
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  • B01J2219/00051—Controlling the temperature
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  • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
  • B01J2219/00069—Flow rate 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
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2219/00051—Controlling the temperature
  • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
  • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
  • B01J2219/00094—Jackets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00051—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
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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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  • 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
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  • B01J2219/00121—Controlling the temperature by direct heating or cooling
  • B01J2219/00128—Controlling the temperature by direct heating or cooling by evaporation of reactants
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  • B01J2219/0013—Controlling the temperature by direct heating or cooling by condensation of reactants
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  • 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
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  • B01J2219/00162—Controlling or regulating processes controlling the pressure
• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00186—Controlling or regulating processes controlling the composition of the reactive mixture
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • 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

• 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.
• 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.
• 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.
• 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 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 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.
• 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.
• 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.
• 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.
• organic compounds such as gasoline to a mixture of CO/CO 2 .
• 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.
• 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 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.
• 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.
• 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 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.
• 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 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 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.
• 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.
• 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 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 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.
• 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.
• 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 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 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.
• 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.
• 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'.
• 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
• 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 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 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.
• 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.
• HPLC HPLC
• GC polar and non ⁇ polar ingredients
• 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.
• 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.
• 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 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.
• 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'.
• 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.
• 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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• 1996
  • 1996-05-17 WO PCT/US1996/007056 patent/WO1996040610A1/en not_active Application Discontinuation
  • 1996-05-17 EP EP96915863A patent/EP0837842A4/de not_active Withdrawn
  • 1996-05-17 KR KR1019970708856A patent/KR19990022376A/ko not_active Application Discontinuation
  • 1996-05-17 BR BR9609096A patent/BR9609096A/pt not_active Application Discontinuation
  • 1996-05-17 JP JP50058497A patent/JP2002515017A/ja active Pending

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