WO2016144664A2 - Fabrication d'acrylonitrile améliorée - Google Patents

Fabrication d'acrylonitrile améliorée Download PDF

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Publication number
WO2016144664A2
WO2016144664A2 PCT/US2016/020560 US2016020560W WO2016144664A2 WO 2016144664 A2 WO2016144664 A2 WO 2016144664A2 US 2016020560 W US2016020560 W US 2016020560W WO 2016144664 A2 WO2016144664 A2 WO 2016144664A2
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Prior art keywords
effluent
stream
reactor
absorber
acrylonitrile
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PCT/US2016/020560
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English (en)
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WO2016144664A3 (fr
Inventor
Timothy Robert Mcdonel
Jay Robert COUCH
David Rudolph Wagner
Paul Trigg Wachtendorf
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Ineos Europe Ag
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Publication of WO2016144664A2 publication Critical patent/WO2016144664A2/fr
Publication of WO2016144664A3 publication Critical patent/WO2016144664A3/fr

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00Preparation of carboxylic acid nitriles
    • C07C253/24Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00Preparation of carboxylic acid nitriles
    • C07C253/24Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00Preparation of carboxylic acid nitriles
    • C07C253/32Separation; Purification; Stabilisation; Use of additives
    • C07C253/34Separation; Purification

Definitions

  • the invention relates to an improved process in the manufacture of acrylonitrile and methacrylonitrile.
  • the invention is directed to an improved process using an effluent compressor.
  • methacrylonitrile are known; see for example, U.S. Patent No. 6,107,509.
  • Typical recovery and purification of acrylonitrile/methacrylonitrile produced by the direct reaction of a hydrocarbon selected from the group consisting of propane, propylene or isobutylene, ammonia and oxygen in the presence of a catalyst has been accomplished by transporting the reactor effluent containing acrylonitrile/methacrylonitrile to a first column (quench) where the reactor effluent is cooled with a first aqueous stream, transporting the cooled effluent containing acrylonitrile/methacrylonitrile into a second column (absorber) where the cooled effluent is contacted with a second aqueous stream to absorb the acrylonitrile/methacrylonitrile into the second aqueous stream, transporting the second aqueous stream containing the acrylonitrile/methacrylonitrile from the second column to a first distillation column (recovery column) for separation of the crude acrylonitrile/methacrylonitrile from the second column
  • 3,885,928; 3,352,764; 3,198,750 and 3,044,966 are illustrative of typical recovery and purification processes for acrylonitrile and methacrylonitrile.
  • the reactor pressure is constrained by the absorber off- gas pressure and the minimum necessary pressure drop between the reactor and the absorber. In a conventional process, this predetermined pressure in the reactor is about 8 psig and typically results in a conversion rate of about 80% of hydrocarbon feed to reactor product effluent comprising acrylonitrile.
  • the reactor product effluent is then conveyed to a quench vessel. In the quench vessel, the reactor product effluent is quenched to produce quenched effluent comprising acrylonitrile product.
  • the quenched effluent is conveyed to an absorber via a pipe.
  • the quenched effluent is combined with refrigerated water to produce rich water comprising acrylonitrile, and off-gas from the absorber is burned in an absorber off-gas incinerator (AOGI) or absorber off-gas oxidizer (AOGO).
  • AOGI absorber off-gas incinerator
  • AOGO absorber off-gas oxidizer
  • the rich water comprising acrylonitrile that is generated in the absorber is then conveyed from the absorber to a recovery column for further processing.
  • the absorber is run at atmospheric pressure and refrigerated or cooled water is added to the absorber to mix with the quenched acrylonitrile product and generate the rich water comprising acrylonitrile.
  • An aspect of the disclosure is to provide a safe, effective and cost effective
  • a process includes reacting, at a first pressure and in the presence of a catalyst, ammonia, oxygen, and a hydrocarbon selected from the group consisting of propane, propylene, isobutane and isobutylene, and combinations thereof, to provide a reactor effluent stream that includes acrylonitrile.
  • the process further includes quenching the reactor effluent stream with a first aqueous stream to provide a quenched stream that includes acrylonitrile and compressing the quenched stream to provide an effluent compressor stream that includes acrylonitrile.
  • the process includes conveying, at a second pressure, the effluent compressor stream to an absorber and in the absorber, absorbing acrylonitrile in a second aqueous stream to provide a rich water that includes acrylonitrile, wherein the second pressure is greater than the first pressure.
  • a process includes reacting, at a first pressure and in the presence of a catalyst, ammonia, oxygen, and a hydrocarbon selected from the group consisting of propane, propylene, isobutane and isobutylene, and combinations thereof, to provide a pressurized reactor off-gas.
  • the process further includes conveying the pressurized off-gas to an absorber and expanding a non-absorbed effluent from the absorber.
  • An apparatus includes a reactor configured to react, at a first pressure and in the presence of a catalyst, ammonia, oxygen, and a hydrocarbon selected from the group consisting of propane, propylene and isobutylene, and combinations thereof, to provide a reactor effluent stream comprising acrylonitrile; a quench vessel configured to quench the reactor effluent stream with a first aqueous stream to provide a quenched stream comprising acrylonitrile; an effluent compressor configured to compress the quenched stream to provide an effluent compressor stream comprising acrylonitrile at a second pressure; and an absorber configured to receive the effluent compressor stream and allow for absorbing of the acrylonitrile in a second aqueous stream to provide a rich water comprising acrylonitrile.
  • a reactor configured to react, at a first pressure and in the presence of a catalyst, ammonia, oxygen, and a hydrocarbon selected from the group consisting of propane, propylene and isobutylene
  • An ammoxidation process includes reacting ammonia, oxygen, and a hydrocarbon selected from the group consisting of propane, propylene, isobutane and isobutylene, and combinations thereof in the presence of a catalyst, at a pressure (absolute) of about 140 kPa or less and a velocity of about 0.5 to about 1.2 meters/second to provide a reactor effluent stream.
  • a process for absorbing a reactor effluent stream that includes acrylonitrile includes quenching the reactor effluent stream with a first aqueous stream to provide a quenched stream that includes acrylonitrile; compressing the quenched stream to provide an effluent compressor stream that includes acrylonitrile;
  • a process for absorbing a reactor effluent stream that includes acrylonitrile includes quenching the reactor effluent stream with a first aqueous stream to provide a quenched stream that includes acrylonitrile; compressing the quenched stream to provide an effluent compressor stream that includes acrylonitrile; conveying the effluent compressor stream to an absorber; and in the absorber, absorbing acrylonitrile in a second aqueous stream having a temperature of about 4 °C to about 45 °C to provide a rich water that includes acrylonitrile.
  • an ammoxidation system includes a turbine effective for
  • an ammoxidation process includes reacting ammonia, oxygen, and a hydrocarbon selected from the group consisting of propane, propylene, isobutane and isobutylene, and combinations thereof in the presence of a catalyst, at a pressure of about 100 kPa (absolute) or less and a velocity of about 0.5 to about 1.2 meters/second to provide a reactor effluent stream.
  • an ammoxidation apparatus includes a reactor configured to react, at a first pressure of about 100 kPa (absolute) or less and in the presence of a catalyst, ammonia, oxygen, and a hydrocarbon selected from the group consisting of propane, propylene and isobutylene, and combinations thereof, to provide a reactor effluent stream comprising acrylonitrile.
  • an ammoxidation system includes a turbine for driving a single drive operatively coupled to at least one air compressor and at least one effluent compressor, the air compressor configured to provide air to an ammoxidation reactor, the effluent compressor configured to provide an effluent compressor stream to an absorber, and the ammoxidation reactor and absorber configured to allow for independent pressure control.
  • FIG. 1 is a schematic flow diagram of an embodiment in accordance with aspects of the disclosure as applied to the manufacture of acrylonitrile.
  • FIG. 2 is a schematic flow diagram of another embodiment in accordance with aspects of the disclosure as applied to the manufacture of acrylonitrile.
  • FIG. 3 is a schematic flow diagram illustrating an aspect that includes more than one reactor, quench column and effluent compressor.
  • FIG. 4 is a schematic flow diagram illustrating a single line drive.
  • FIG. 1 is a schematic flow diagram of an embodiment in accordance with aspects of the disclosure as applied to the manufacture of acrylonitrile.
  • an apparatus 100 comprises reactor 10, quench vessel 20, effluent compressor 30, and absorber 40.
  • Ammonia in stream 1 and hydrocarbon (HC) feed in stream 2 may be fed as combined stream 3 to reactor 10.
  • HC feed stream 2 may comprise a hydrocarbon selected from the group consisting of propane, propylene and isobutylene, and combinations thereof.
  • a catalyst (not shown in FIG. 1) may be present in reactor 10.
  • Oxygen containing gas may be fed to reactor 10.
  • air may be compressed by an air compressor (not shown in FIG. 1) and fed to reactor 10.
  • cyclone 22 may be the first cyclone of a multistage cyclone system that may be configured to convey a stream comprising acrylonitrile to a plenum (not shown in FIG. 1). The stream comprising acrylonitrile may exit the plenum and out of a top portion of reactor 10 as reactor effluent stream 4.
  • cyclone 22 may be configured to separate catalyst that may be entrained in the stream comprising acrylonitrile that enters inlet 17, and return the separated catalyst back to the catalyst bed in reactor 10 through a catalyst return dip leg (not shown in FIG. 1).
  • Reactor effluent stream 4 comprising acrylonitrile produced in reactor 10 may be conveyed through line 11 to quench vessel 20.
  • the first pressure is about 140 kPa or less, in another aspect about 135 kPa or less, in another aspect about 130 kPa or less, in another aspect about 125 kPa or less, in another aspect, about 101 kPa to about 140 kPa, in another aspect, about 110 kPa to about 1400 kPa, in another aspect, about 125 kPa to about 145 kPa, in another aspect, about 120 kPa to about 140 kPa, in another aspect, about 130 kPa to about 140 kPa, in another aspect, about 125 kPa to about 140 kPa, in another aspect, about 125 kPa to about 135 kPa, in another aspect, about 120 kPa to about 137 kPa, and in another aspect, about 115 kPa to about 125 kPa.
  • reactor effluent stream 4 may be cooled by contact with quench aqueous stream 5 entering quench vessel 20 via line 12.
  • Quench aqueous stream 5 may comprise an acid in addition to water.
  • the cooled reactor effluent comprising acrylonitrile (including co-products such as acetonitrile, hydrogen cyanide and impurities) may then be conveyed as quenched stream 6 to effluent compressor 30 via line 13.
  • Quenched stream 6 may be compressed by effluent compressor 30, and exit
  • Compressor effluent compressor 30 as compressor effluent stream 7.
  • Compressor effluent stream 7 may have a second or compressed pressure P2.
  • Compressor effluent stream 7 may be conveyed to a lower portion of absorber 40 via line 14.
  • acrylonitrile may be absorbed in a second or absorber aqueous stream 8 that enters an upper portion of absorber 40 via line 15.
  • the aqueous stream or rich water stream 18 that include acrylonitrile and other co-products may then be transported from absorber 40 via line 19 a recovery column (not shown in FIG. 1) for further product purification.
  • Non-absorbed effluent 9 exits from the top of absorber column 40 through pipe 16.
  • Non-absorbed effluent 9 may comprise off-gases, which can be burned in absorber off-gas incinerator (AOGI) or absorber off-gas oxidizer (AOGO).
  • AOGI absorber off-gas incinerator
  • AOGO absorber off-gas oxidizer
  • effluent compressor 30 functions by pulling quenched stream 6 through line 13.
  • Effluent compressor 30 may compress quenched stream 6 so that it exits effluent compressor 30 as compressed effluent compressor stream 7 that has a higher pressure (second pressure) than the reactor pressure (first pressure).
  • the pressure in line 14 of compressed effluent compressor stream 7 is about 2 to about 11.5 times greater than the operation pressure of reactor 10, in another aspect, about 2 to about 12.5 times, in another aspect, about 2.5 to about 10, in another aspect, about 2.5 to about 8, in another aspect, about 2.5 to about 5, in another aspect, about 2.5 to about 4, in another aspect, about 2.5 to about 3.2, in another aspect, about 2 to about 3.5, in another aspect, about 2 to about 3, in another aspect, about 3 to about 11.25, in another aspect, about 5 to about 11.25, and in another aspect, about 7 to about 11.25 (all based on an absolute comparison).
  • the second pressure is about 300 to about 500 kPa, in another aspect, about 340 kPa to about 415 kPa, in another aspect, about 350 kPa to about 400 kPa, in another aspect, about 250 kPa to about 500 kPa, in another aspect, about 200 kPa to about 400 kPa, in another aspect, about 250 kPa to about 350 kPa, in another aspect, about 300 kPa to about 450 kPa, and in another aspect, about 360 kPa to about 380 kPa.
  • the second pressure is such that the absorber may be operated with a flow rate of aqueous stream 8 of about 15 to about 20 kg /kg of acrylonitrile final product produced when aqueous stream 8 is uncooled or unrefrigerated and/or is 4 to about 45 °C and wherein the absorber rich water stream contains about 5 weight percent or more organics, in another aspect, about 6 weight percent or more organics, and in another aspect, about 7 weight percent or more organics.
  • the flow rate of aqueous stream 8 may be about 15 to about 19 kg /kg of acrylonitrile, in another aspect, about 15 to about 18 kg /kg of acrylonitrile, and in another aspect, about 16 to about 18 kg /kg of acrylonitrile.
  • the uncooled or unrefrigerated aqueous stream is about 20 to about 45 °C, in another aspect, about 25 to about 40°C, in another aspect, about 25 to about 35 °C, and in another aspect, about 25 to about 30°C.
  • a cooling system (not shown in FIG. 1) may be located at or downstream of compressor 30, wherein the cooling system is configured to cool compressed effluent compressor stream 7 to a predetermined temperature, e.g., about 105 °F. (about 40.5 °C) prior to entering absorber 40.
  • absorber 40 may include forty to sixty (40-60) trays. In an aspect, absorber 40 may include fifty (50) trays. Compressed effluent compressor stream 7 may enter absorber 40 below the bottom tray of the absorber. In an aspect, absorber 40 may be operated with variable flow rates of refrigerated water in second aqueous stream 8, including zero amount of refrigerated water.
  • absorber 40 may be operated at pressure that is higher than the
  • rich water refers to water having about 5 weight percent or more organics, in another aspect, about 6 weight percent or more organics, and in another aspect, about 7 weight percent or more organics.
  • the water used to absorb acrylonitrile in the absorber may be process or municipal water (e.g., having a temperature of about 4-45 °C).
  • process or municipal water is more than about 95 weight percent water, in another aspect, about 97 weight percent or more water, in another aspect, about 99 weight percent or more water, and in another aspect, about 99.9 weight percent or more water.
  • the temperature of second aqueous stream 8 may be in the range of about 4 to about 45 °C, in another aspect, about 10 to about 43 °C, and in another aspect, about 27 to about 32 °C.
  • aqueous stream 8 may be devoid of cooled or refrigerated water. In an aspect, aqueous stream 8 may have a higher temperature than the temperature required in an aqueous stream in a conventional process. In an aspect, aqueous stream 8 may comprise refrigerated water, and when aqueous stream 8 comprises refrigerated water, the flow rate of aqueous water stream 8 may be less than the flow rate required in an aqueous stream in a conventional process. In this aspect, the first aqueous stream has a temperature of about 20 °C to about 50 °C, in another aspect, about 25 °C to about 45 °C, and in another aspect, about 30 °C to about 40 °C.
  • the first aqueous stream may be provided to the absorber at a rate of about 25 kg to about 35 kg first aqueous stream per kg of acrylonitrile produced, and in another aspect, about 27 kg to about 33 kg first aqueous stream per kg of acrylonitrile produced.
  • reactor 10 may be operated under a pressure that is lower than the pressure required in a conventional process.
  • reactor 10 typically needs to be run at a pressure of about 8 psig to achieve a conversion rate of, for example, 80% or more of hydrocarbon feed to effluent product comprising acrylonitrile.
  • the process includes operating reactor 10 at pressure that is about 35 to about 50% (absolute basis) lower than in a conventional process.
  • the process comprises operating reactor 10 at a pressure of about 4-5 psig.
  • the fluidized bed reactor is at the heart of an acrylonitrile plant. Failure to
  • a reactor may have an internal diameter of about 5 to about 15 meters, in one aspect, about 7 to about 12 meters, in another aspect, about 8 to about 11 meters, and in another aspect, about 9 to about 11 meters.
  • Reactor diameter is also one of the parameters that leads to most scale-up caution since there are limited mitigation options available, absent reactor change-out, to correct a scale-up of diameter that has gone too far.
  • a reactor internal diameter of greater than about 9 m up to about 11 m can be combined with suitable operating conditions and reactor internals to achieve acceptable fluidization conditions for the production of acrylonitrile and methacrylonitrile whilst operating at reactor pressures of about 140 kPa or less, in another aspect about 135 kPa or less, in another aspect about 130 kPa or less, in another aspect about 125 kPa or less, in another aspect, about 101 kPa to about 140 kPa, in another aspect, about 110 kPa to about 140 kPa, in another aspect, about 125 kPa to about 145 kPa, in another aspect, about 120 kPa to about 140 kPa, in another aspect, about 130
  • the air grid design provides about a 30 to 40% (minimum) of catalyst bed pressure drop at reactor turndown.
  • the fluidization velocity (based on effluent volumetric flow and reactor cross- sectional area ("CSA") excluding cooling coils and dip legs area) can be operated at up to 1.2 m/s, preferably between 0.55 and 1, for reactors having a 9 to 11 m internal diameter.
  • Attrition loss may be determined using known methods, such as for example, Hartge et al., The 13 th International Conference on Fluidization - New Paradigm in Fluidization Engineering, Art. 33 (2010), methods based on ASTM D4058 and ASTM D5757, and U.S. Patent No.
  • total catalyst loss from the reactor may be about 0.35 to about 0.45 kg/metric ton of acrylonitrile produced.
  • a ratio of reactor diameter to a reactor cylindrical height (tangent to tangent) of about 0.45 to about 0.6 has been found to be effective when operating with a fluidization velocity (based on effluent volumetric flow and reactor cross-sectional area excluding cooling coils and dip leg area) between about 0.4 m and 1.05 m/s preferably between about 0.55 and 0.85 m/s.
  • the design of the cyclone is critical to the operating pressure of the reactor, the catalyst losses (including caused by attrition) and the required height of the reactor (tangent to tangent). It has been found that the above satisfactory reactor operating window can be achieved with ratio of first stage cyclone inlet velocities to reactor effluent velocities of about 20 to about 30 and/or ratio of a height of a first stage cyclone is about 4% to about 7% of a reactor height (tangent to tangent). As shown in Fig. 3, the cyclone height is determined from a distance from a top 101 of the cyclone to a distal section 107 of the cyclone.
  • reactor 10 may be configured to have a greater throughput capacity for a predetermined catalyst than a conventional reactor having the same predetermined catalyst and predetermined reactor height.
  • a method is provided for increasing reactor throughput capacity for a predetermined catalyst and predetermined reactor height. The method includes increasing reactor diameter while maintaining a predetermined top pressure. The method may comprise maintaining a predetermined reactor design velocity.
  • a process includes operating or reacting in a reactor a hydrocarbon, wherein the reactor has a predetermined reactor internal diameter of more than about 40% to about 60% a cylindrical height of the reactor (tangent to tangent), and in another aspect, about 45% to about 55%.
  • reactor height tangent to tangent
  • reactor height may be about 10 to about 25 meters, in another aspect, about 10 to about 20 meters, in another aspect, about 12 to about 18 meters, and in another aspect, about 14 to about 16 meters.
  • the process includes operating or reacting in a reactor a hydrocarbon, wherein the reactor has a fluidized bed height that is about 40% to about 60% of the reactor cylindrical height (tangent to tangent), in another aspect, about 42% to about 50%, in another aspect, about 45% to about 55%, and in another aspect, about 44% to about 47%.
  • a conventional process that includes operating a reactor having a fluidized bed height that is about 25% of the reactor height (tangent to tangent) and thus, a greater disengagement height.
  • the process includes operating or reacting in a reactor a hydrocarbon, wherein the reactor has a fluidized bed height that is about 70% to about 110% of the reactor diameter, in another aspect, about 70% to about 100%, in another aspect, about 75% to about 90%, in another aspect, about 80% to about 90%, in another aspect, about 85% to about 95%, and in another aspect, about 85% to about 90%.
  • a fluidized bed height that is about 70% to about 110% of the reactor diameter, in another aspect, about 70% to about 100%, in another aspect, about 75% to about 90%, in another aspect, about 80% to about 90%, in another aspect, about 85% to about 95%, and in another aspect, about 85% to about 90%.
  • the process includes operating or reacting in a reactor a hydrocarbon, wherein the reactor has a top pressure in the range of about 0.25 to about 0.45 kg/cm 2 , in another aspect, about 0.3 to about 0.5 kg/cm 2 , in another aspect, about 0.2 to about 0.4 kg/cm 2 , and in another aspect, about 0.2 to about 0.5 kg/cm 2 .
  • a reactor top pressure in this range provides the benefit of improved catalyst performance over a reactor top pressure that is higher than this range.
  • the method includes operating the reactor in the range of about 0.4 to about 0.45 kg/cm 2 .
  • the method includes operating or reacting in a reactor a hydrocarbon, wherein the effluent volumetric flow has a linear velocity of about 0.5 to about 1.2 m/sec (based on effluent volumetric flow and reactor cross-sectional area ("CSA") excluding cooling coils and dip legs area, i.e., -90% of open CSA), It has been found that it is possible to design and operate the reactor system using this velocity whilst also achieving good fluidization/catalyst performance and reasonable catalyst entrainment/catalyst losses from cyclones, such that velocities may be maintained in about this range to the extent possible as reactor capacity is increased.
  • CSA effluent volumetric flow and reactor cross-sectional area
  • the reactor may be operated with a velocity of up to about 0.75 m/sec to about 0.95 m/sec (based on 90% CSA and effluent gas), and maintain a top pressure of about 0.25 to about 0.5 kg/cm 2 , and in another aspect, about 0.2 to about 0.45 kg/cm 2 .
  • a ratio of cyclone inlet velocity in meters/second to a reactor effluent velocity in meters/second is 20 or greater, in another aspect, about 20 to about 30, in another aspect, about 22 to about 25, in another aspect, about 23 to about 26, and in another aspect, about 27 to about 29.
  • the process may produce up to about 100% or more acrylonitrile product than a method wherein reactor is operated wherein the reactor diameter is about 40% of the reactor height, the fluidized bed height is about 25% of the reactor height, and the fluidized bed height is about 65% of the reactor diameter.
  • the apparatus and method provides a reactor capacity that is about 12.5 metric tons/hr or 100 ktpa per reactor based on 8000 operating hours per year. Where the reactor diameter is 10.5 m the single reactor capacity can be between 15 and 20 metric tons/hr.
  • the reactor needs to be equipped with at least 3 nozzles for measuring fluidized bed differential pressures as listed below:
  • the 1st of these nozzles is located near the bottom of the fluidized bed (above the air distributor).
  • the nozzles may be about 0.1 to about 0.7 meters above the air distributor, and in another aspect, about 0.2 to about 0.4 meters.
  • the 2nd nozzle is typically located about 2 meters above the 1st nozzle (still within the fluidized bed). The exact distance must be known for the calculations.
  • the 3rd nozzle is located at the top of the reactor (above the fluidized bed).
  • the bed height may be calculated as follows:
  • Bed Height (distance between the 1st and 2nd nozzles) x (1st - 3rd differential pressure) / (1st - 2nd differential pressure)
  • the units for the two pressure measurements need to be the same for each but can be any typical unit of pressure (for example lbs/in 2 , inches of water column, or millimeters of water column).
  • the units for the distance between the taps can be any typical unit of distance (for example feet or meters).
  • the bed height will be in the same units chosen.
  • Differential pressures are preferably measured with two differential pressure transmitters - one for the 1st - 2nd nozzle differential pressure measurement and one for the 1st - 3rd nozzle differential pressure measurement.
  • the nozzles are typically purged with flowing air to keep them clear.
  • air velocity for nozzle purge is about 2 to about 8 m/sec.
  • apparatus 100 may comprise a water spray system 23 (as shown in FIG. 1 and FIG. 2) that is configured to spray water stream 24 to at least one surface of effluent compressor 30 to reduce fouling on that surface.
  • a variable speed turbine may be used with the effluent compressor 30.
  • the cooled effluent gas when reactor 10 is operated with a top pressure of about 5 psig, the cooled effluent gas must be compressed before further processing can take place.
  • gas leaves a compressor suction separator and flows to a first section of effluent compressor 30.
  • Demineralized water may be spray-injected into the compressor suction line and also into diffuser passages. This water injection may be configured to maintain a water film on rotating and stationary surfaces so that deposits will not accumulate.
  • the water injection may be configured to minimize the gas (and therefore minimize the rate of polymer formation) throughout the effluent compressor.
  • the gas temperature may be lowered by vaporization of some of the water spray. The net benefit may be an acceptable service factor for the effluent compressor.
  • Gas from the first section of the effluent compressor may be passed through an effluent compressor intercooler.
  • the cooled gas may flow to a compressor interstage separator, in which condensate is removed.
  • Gas from the separator may be conveyed to a second section of the effluent compressor, wherein water sprays may be used in the same manner as in the first section of effluent compressor 30.
  • the effluent gas may be cooled in an effluent compressor aftercooler or exchanger. A mixture of gas and condensate may leave the aftercooler or exchanger and enter absorber 40 below the bottom tray of absorber 40.
  • Process condensate may be removed from the inter-stage separator and returned by pressure-difference to the suction separator, where it mixes with condensate from a secondary effluent cooler upstream of the effluent compressor.
  • the combined process condensate may be recycled to the process-side inlets of the secondary effluent cooler and the compressor inter-stage cooler.
  • Net condensate may be sent to the inlet of an aftercooler.
  • the condensate may be sprayed over the tube sheets of these exchangers to provide a wash liquid to aid in keeping the insides of the exchanger tubes clean.
  • effluent compressor 30 may have casing and wheels configured to allow the injection of demineralized make-up water into the suction and wheel passages, in a predetermined amount to maintain a water film throughout the compressor.
  • This wash water may be provided and controlled by a controller. Provision may be made for addition of inhibitor to the wash water.
  • effluent compressor 30 may be sized to handle reactor effluent gas after quenching and cooling to about 105 °F (40.5 °C).
  • the gas rate and composition may be derived from predetermined yields and rates.
  • a portion of the absorber off gas may be used as stripping gas for the quench bottoms stripper. This stripping gas may be returned to absorber 40 via effluent compressor 30, and the effluent compressor 30 may be sized for this incremental flow.
  • the effluent compressor frame size may be configured to allow for about 5% overcapacity. In another aspect, additional overcapacity up to about 35%, in another aspect, about 25%, in another aspect, about 15%, and in another aspect, about 10% total may be provided if within the same frame size.
  • the maximum discharge temperature may be 200 degrees F (93.3 °C), as maintained by water sprays.
  • the process condensate phase may be conveyed to the absorber sump or utilized in other processes, while gas flows upwards through the absorber trays (which may be valve-type trays) against a descending stream of absorption water or second aqueous stream 8.
  • Lean water for absorption may be withdrawn from the recovery column, cooled, and sent to the top tray of the absorber. In an aspect, no refrigeration is supplied to the lean water, and none is provided for any other portion of the absorber.
  • the gas leaving the top of the absorber is practically free of acrylonitrile and other organics, but may contain carbon monoxide and unconverted hydrocarbons such as propane. Environmental requirements may make it necessary to destroy these compounds before discharging of the off-gas to the atmosphere.
  • Destruction of these compounds may be accomplished with an incinerator or oxidizer system, such as AOGO 21.
  • the absorber bottoms or rich water contains the recovered acrylonitrile and other organics, and this rich water stream may be sent to the acrylonitrile recovery column.
  • apparatus 300 comprises the same features of apparatus 100, and further includes expander 302.
  • Expander 302 may be configured to expand or reduce the pressure of non-absorbed effluent 9 from absorber 40 to a lower pressure.
  • expander 302 may be configured to reduce the pressure of non-absorbed effluent 9 by a factor of about 17.5 to 22.5.
  • expander 302 may be configured to reduce the pressure of non-absorbed effluent 9, which may be the same as the pressure in the absorber.
  • expander 302 may be configured to reduce the pressure of about 35-45 psig of non-absorbed effluent 9 to provide expanded non-absorbed effluent 25 having a lower pressure of about 2 psig or less.
  • the expanding results in a reduction in pressure of the non-absorbed effluent from the absorber from a pressure (absolute) of about 300 kPa to about 500 kPa to a pressure (absolute) of about 115 kPa or less.
  • Expanded non-absorbed effluent 25 may be conveyed from expander 302 to AOGO 21 via line 26.
  • Apparatus 300 may include pre-heater 303.
  • Pre-heater 303 may be configured to pre-heat non-absorbed effluent 9 from a temperature of about 25 °C to about 40 °C to a temperature of about 350 °C or more, and in another aspect about 37.7 °C to a temperature of about 371.1 °C.
  • pre-heating non-absorbed effluent 9 before it enters expander 302 condensing in expander 302 may be avoided or reduced.
  • its temperature is lowered is lowered from a temperature of about 300 °C to about 400 °C to a temperature of about 200 °C to about 260 °C.
  • fuel gas required to burn expanded non-absorbed effluent 25 in absorber off-gas incinerator (AOGI) or absorber off-gas oxidizer (AOGO) 21 may be less than the fuel gas required to burn non-absorbed effluent 9, which has not been expanded. It has been found that by increasing the expander pressure drop in expander 302, less fuel gas may be required to burn expanded non-absorbed effluent 25 in AOGO 21. For example, it has been found that by increasing the pressure drop in expander 302, temperature T3 may be about 500 °F. (about 260 °C) instead of about 400 °F (about 204.4 °C). When the expanded non-absorbed effluent 25 has a temperature T3 of about 500 °F.
  • apparatus 500 may include a first train 501 and a second train 502. Each train may be similar to or the same as apparatus 100 or 300 previously described. As shown in FIG. 3, each train may include its own reactor 10, quench vessel 20, effluent compressor 30 and absorber 40, and the trains may be operated in parallel. In an aspect, each train may include its own AOGO 21. In an aspect, each absorber of each train may be configured to receive its own second or absorber aqueous stream 8 that is supplied in a line 15 that is separate from the other train. Each line 15 of each train may receive an absorber aqueous stream 8, wherein stream 8 was used in operation or generated in operation of acrylonitrile recovery column 503. Rich water streams 18 from each absorber of each train may be conveyed to the acrylonitrile recovery column 503. These rich water streams may be combined before further processing.
  • an ammoxidation system includes a turbine effective for driving a single drive line that includes an air compressor and at least one effluent compressor.
  • the turbine may be selected from the group consisting of a steam turbine, a gas turbine, an electric turbine, and a variable speed electric turbine.
  • high pressure steam is provided to a steam turbine 412.
  • steam provided to the steam turbine 412 has a pressure of about 600 psig or more, and in another aspect, about 600 to about 700 psig.
  • the steam turbine 412 is effective for driving a single drive line 417 that includes one or more air compressors 402, one or more effluent compressors 30, and at least one expander 302.
  • the air compressor 402 is configured to provide air to the reactor 10
  • the effluent compressor 30 is configured to provide an effluent stream to the absorber 40.
  • the reactor 10 and absorber 40 may each include valves (not shown).
  • the valves are configured to allow independent control of reactor 10 and absorber 40.
  • the valve on the reactor 10 may be vented to atmosphere to prevent formation of a vacuum in the reactor 10.
  • the method and apparatus of the present disclosure provides more flexibility in operation than conventional methods and apparatuses.
  • the method and apparatus of the present disclosure provides more flexibility in turndown or using lower rates when less production of acrylonitrile is needed than in conventional methods and apparatuses.
  • An effluent compressor typically is less expensive than chiller equipment that is required to provide refrigerated water to an absorber in a conventional process. For this reason, the apparatus and method present disclosure may have a lower capital expenditure than for conventional apparatus and method. [72] In an aspect, it has been found that the above method may achieve a higher reactor product conversion than in a conventional process that does not include compressing a quenched stream and absorbing at a third pressure that is greater than the first pressure.
  • rich water comprising acrylonitrile may be generated in the absorber with either less refrigerated water and/or water that is warmer than the refrigerated water used as the absorbing aqueous stream in conventional processes.
  • an ammoxidation process includes reacting ammonia, oxygen, and a hydrocarbon selected from the group consisting of propane, propylene, isobutane and isobutylene, and combinations thereof in the presence of a catalyst, at a pressure of about 100 kPa (absolute) or less and a velocity of about 0.5 to about 1.2 meters/second to provide a reactor effluent stream.
  • the reacting may be conduted at a pressure of about 5 kPa (absolute) to about 100 kPa (absolute), in another aspect, about 10 kPa (absolute) to about 90 kPa (absolute), in another aspect, about 20 kPa (absolute) to about 80 kPa (absolute), in another aspect, about 30 kPa (absolute) to about 70 kPa (absolute), and in another aspect, about 40 kPa (absolute) to about 60 kPa (absolute).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé qui consiste à faire réagir, à une première pression et en présence d'un catalyseur, l'ammoniac, l'oxygène et un hydrocarbure choisi parmi le groupe constitué de propane, de propylène et d'isobutylène, et des combinaisons de ces derniers, pour fournir un flux effluent de réacteur qui comprend de l'acrylonitrile. Le procédé consiste à tremper le flux effluent de réacteur avec un premier flux aqueux pour fournir un flux trempé qui comprend l'acrylonitrile. Le procédé consiste à comprimer le flux trempé pour fournir un flux de compresseur effluent comprenant l'acrylonitrile, et acheminer, à une seconde pression, le flux de compresseur effluent vers un absorbeur. Le procédé consiste à absorber, dans l'absorbeur, l'acrylonitrile dans un second flux aqueux pour obtenir une eau riche comprenant l'acrylonitrile, l'absorption étant réalisée à une pression supérieure à la première pression.
PCT/US2016/020560 2015-03-06 2016-03-03 Fabrication d'acrylonitrile améliorée WO2016144664A2 (fr)

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