WO2023105430A1 - Procédé intégré pour la conversion de glycérol en acrylonitrile - Google Patents

Procédé intégré pour la conversion de glycérol en acrylonitrile Download PDF

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Publication number
WO2023105430A1
WO2023105430A1 PCT/IB2022/061869 IB2022061869W WO2023105430A1 WO 2023105430 A1 WO2023105430 A1 WO 2023105430A1 IB 2022061869 W IB2022061869 W IB 2022061869W WO 2023105430 A1 WO2023105430 A1 WO 2023105430A1
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WO
WIPO (PCT)
Prior art keywords
glycerol
stream
acrylonitrile
dehydration
section
Prior art date
Application number
PCT/IB2022/061869
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English (en)
Inventor
Aiguo Liu
Liesl SCHINDLER
Corey TYREE
Original Assignee
Trillium Renewable Chemicals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from NL2030511A external-priority patent/NL2030511B1/en
Application filed by Trillium Renewable Chemicals, Inc. filed Critical Trillium Renewable Chemicals, Inc.
Publication of WO2023105430A1 publication Critical patent/WO2023105430A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule

Definitions

  • the present invention relates to a process for the preparation of acrylonitrile from glycerol.
  • Acrylonitrile is used as a monomer in the production of the homopolymer polyacrylonitrile, as well as for producing copolymers such as styrene-acrylonitrile (SAN) acrylonitrile butadiene styrene (ABS), acrylonitrile styrene acrylate (ASA), and other synthetic rubbers such as acrylonitrile butadiene (NBR). It is further used as an intermediate in the production of nylon and acrylamide.
  • Acrylonitrile also finds increasing use as a precursor in production of carbon fibre, which is a suitable material for high technology use especially in the aerospace and automotive industries. It is estimated that more than 6.5 million metric tons of ACN per year are produced worldwide.
  • By-products include the solvent acetonitrile (CH 3 CN), hydrogen cyanide (HCN), and acrolein (CH?-CH- CHO).
  • the reaction typically takes place in a fluidized reactor at temperature in the range of 400 to 500 °C, with an operation pressure usually below 3 bar.
  • the feed typically contains a minimally stoichiometric excess of ammonia and oxygen over propylene.
  • ACN and by-products are recovered by water absorption in an absorption column.
  • the water is chilled to about 5 °C and a higher water/ACN ratio is applied.
  • the SOHIO process further involves the use of multiple distillation columns to separate and purify the main product ACN and other by-products.
  • Glycerol (1,2,3-propanetriol; glycerine) is a significant (about 10 wt%) by-product of the production of biodiesel, wherein e.g. vegetable oils, animals fats, or used cooking oils are subjected to a transesterification process to produce biodiesel, crude glycerol and water. Due to the large-scale production of biodiesel, efforts are being made to convert glycerol into more value-added chemicals.
  • the preparation of acrylonitrile from glycerol generally involves a dehydration and an ammoxidation step, as described in for example US20100048850A1.
  • the dehydration step involves the dehydration of glycerol in the presence of a tungsten-containing dehydration catalyst to produce acrolein and water according to
  • the ammoxidation step involves the catalytic conversion of acrolein in the presence of ammonia and oxygen to acrylonitrile according to
  • the gaseous ammoxidation product stream comprises smaller amounts of acetonitrile and other by-products.
  • This effluent stream is typically subjected to quenching through a steam generator, acid neutralization column to remove residual ammonia and subsequently passed over an absorption column to which cooled water is supplied as an absorbent.
  • a concentrated stream of acrylonitrile, water and other by-products is obtained, from which the acrylonitrile product may be isolated by successive distillation steps.
  • step (iii) optionally providing the acrolein stream obtained in step (ii) to a purification column to produce a concentrated acrolein stream and a residual stream comprising unconverted glycerol (iv) converting the acrolein streams obtained in step (ii) and optionally step (iii) in the presence of ammonia, oxygen and an ammoxidation catalyst to an acrylonitrile stream
  • the glycerol stream mainly comprising glycerol and water recovered from the stripping column is at least partially recycled to the absorption column, where it is utilised to absorb acrylonitrile and optional by-products (such as acetonitrile) from the acrolein ammoxidation effluent.
  • acrylonitrile and optional by-products such as acetonitrile
  • the acrylonitrile-depleted glycerol stream recovered from the acrylonitrile separation step as an absorbent in the ammoxidation effluent absorption step
  • significant improvements in water use and waste discharge can be obtained.
  • the use of a, preferably recycled, glycerol stream in the absorption process allows for operation at ambient temperatures without the need of cooling the absorbent, thus further reducing operating and/or capital expenses of the process.
  • the process according to the present disclosure is particularly advantageous when crude glycerol is used as a feed for the acrylonitrile manufacturing process, and wherein a crude glycerol purification unit is used to purify the crude glycerol prior to providing it as a feed stream for the dehydration to acrolein.
  • the process according to the present disclosure is particularly advantageous for processes for producing acrylonitrile from glycerol comprising one or more glycerol dehydration and acrolein ammoxidation steps.
  • the use of according to the present disclosure can be generally integrated in acrylonitrile processes existing in the art, wherein an ammoxidation reaction effluent stream is subjected to absorption by a glycerol absorbent in an absorption column, and wherein at least a part of the glycerol absorbent is provided by a glycerol recycle stream, a purified crude glycerol feed or a combination thereof produced elsewhere in the process.
  • Figure 1 is a schematic diagram showing a process according to an embodiment of the invention.
  • Figure 2 is a schematic diagram showing a process according to an embodiment of the invention.
  • the present disclosure provides a process and a system for producing acrylonitrile from glycerol.
  • a liquid feed stream comprising glycerol is provided to a dehydration reactor comprising a catalyst bed comprising a suitable dehydration catalyst.
  • concentration of the feed stream is typically in the range of 5 - 80 wt% by proper dilution with water.
  • the inlet temperature of the feed is set to be in the range of 250 - 300 °C using a preheater.
  • the feed flow rate is generally set in the range of 0.5 to 15 per hr WHSV (weight hour space velocity) and the inlet pressure is normally set in the range of 1.1 - 2 bar (absolute).
  • glycerol is dehydrated in the presence of the dehydration catalyst to produce acrolein and water according to
  • the catalyst bed is typically separated into at least two stages with a heat exchanger installed in between, as this design allows to supply heat to sustain the temperature inside catalyst bed at least 250 °C.
  • the dehydration catalyst may be any catalyst that is capable of converting glycerol to acrolein under the conditions as described herein. Suitable examples of such catalysts are disclosed in, for example, W02006087083A2 and WO2013017942 typically comprise a porous carrier containing at least one metal oxide selected from tantalum oxide (Ta 2 O 5 ), niobium oxide (Nb 2 O5), alumina (AI 2 Oa), titanium oxide (TiCh) , zirconia (ZrCh), tin oxide (SnCh), silica (SiCh) or silico-aluminate (SiCh - AI2O3), impregnated with acidic functions such as borate (BO3), sulphate (SO4), tungstate (WO3), phosphate (PO4), silicate (SiCh) or molybdate (MoOs).
  • Ta 2 O 5 tantalum oxide
  • Nb 2 O5 niobium oxide
  • AI 2 Oa
  • the dehydration catalyst comprises about 20% WO3 on a commercially available ZrCh or SiCh porous support in pellet form, having a diameter of about 1.0 to 3.0mm, and with majority of pores in the meso pore size range (2-50nm).
  • At least two dehydration reactors comprising a dehydration catalyst are set in parallel in order to achieve continuous operation by keeping one on-line and the other off-line for catalyst regeneration.
  • at least one dehydration reactor is online during the dehydration reaction and at least one dehydration reactor is offline during the dehydration step, and the dehydration catalyst in at least one of the offline dehydration reactors is regenerated.
  • Catalyst regeneration typically involves nitrogen flushing, followed by dosing air into the nitrogen stream at the reaction temperature until pure air level is reached, whilst maintaining the temperature inside the reactor below 350 °C.
  • the acrolein product stream from the dehydration step may optionally be purified by first passing the reaction product stream from the dehydration reactor through a quenching chamber with an outside cooling loop and injection inhibitor such as 4-hydroxy-2,2,6,6-tetramethylpiperidin-l-oxyl ("TEMPOL”), followed by feeding the cooled product stream into a distillation column where a purified is obtained from the top and a residual stream comprising unconverted glycerol may be withdrawn from the bottom.
  • injection inhibitor such as 4-hydroxy-2,2,6,6-tetramethylpiperidin-l-oxyl
  • acrolein stream obtained in the dehydration step, and optionally step purified as for example described above, is subsequently converted in the presence of ammonia, oxygen and an ammoxidation catalyst to acrylonitrile according to
  • the optionally purified acrolein is mixed with ammonia, air, and or other inert diluents as needed and heated to 250 - 350 °C before feeding into an ammoxidation reactor.
  • Molar ratios to acrolein in the feed are set in the range of 1.1 - 10 for oxygen, 1.1 to 1.5 for ammonia, and the acrolein concentration is typically set in the range of 1 to 5% v/v, with inert diluent gas making up the remaining balance.
  • the temperature inside the ammoxidation reactor is typically controlled below 450 °C by either external cooling or inter-stage cooling.
  • External cooling can be achieved by applying, for example a multi-tubular reactor, while inter-stage cooling typically applies a multi-stage fixed bed reactor with heat exchangers built in between two stages or a fluidized bed reactor with built-in cooling loops.
  • Suitable ammoxidation catalysts are known in the art and typically comprise one or more mixed oxides chosen for example from molybdenum, bismuth, iron, antimony, tin, vanadium, tungsten, antimony, zirconium, titanium, chromium, nickel, aluminium, phosphorus or gallium.
  • the ammoxidation step produces a gaseous effluent stream comprising acrylonitrile and possible by-products such as acetonitrile.
  • the ammoxidation effluent stream is subjected to purification steps known in the art, typically comprising quenching through a steam generator and absorption in an acid neutralization column to remove residual ammonia.
  • the ammoxidation product stream is provided as a feed to the bottom stage of an absorption column, to which a liquid absorbent stream comprising glycerol is continuously supplied at the top stage.
  • the ammoxidation product stream is intimately contacted with liquid absorbent to produce a liquid stream comprising mainly glycerol and acrylonitrile, as well as possible by-products.
  • the liquid absorbent stream may consist essentially of glycerol, or may be a mixture comprising glycerol and water.
  • the liquid absorbent comprises at least 5 wt% glycerol, preferably at least 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt% or 90 wt% glycerol.
  • the liquid absorbent comprises at most 100 wt% glycerol, preferably at most 95 wt%, 90 wt%, 85 wt%, 80 wt%, 70 wt%, 60 wt%, 50 wt%, 40 wt%, or 30 wt% glycerol.
  • the glycerol content in the liquid absorbent may be varied in order to control the desired concentrations of acetonitrile in addition to acrylonitrile.
  • a concentration of glycerol in the range of 30 - 60 % wt may be preferred range in to recover both acrylonitrile and acetonitrile in desired amounts.
  • a glycerol-containing absorbent allows for using the absorbent for the ammoxidation reaction products at ambient temperatures rather at than at temperatures of about 5 °C which is customary for process using water as the sole absorbent in the art.
  • the liquid absorbent comprising glycerol is provided at a temperature in the range of 10-40 °C, preferably in the range of 20- 30 °C, more preferably in the range of 22-28 °C, most preferably about 25 °C.
  • a liquid stream comprising mainly glycerol, acrylonitrile and possible by-products such as acetonitrile is withdrawn from the absorption column.
  • the acrylonitrile and possible by-products can be recovered from the glycerol stream by a suitable separation process to produce an acrylonitrile product stream and an acrylonitrile-depleted glycerol stream.
  • the liquid product stream from the glycerol absorption step is fed to a distillation column in order to separate the products from the glycerol absorption solvent.
  • a stripping column is used to separate the glycerol absorbent from the acrylonitrile and possible by-products.
  • the separated acrylonitrile, possibly further comprising acetonitrile, stream is sent to product purification unit for further separation and purification by means known in the art.
  • At least a portion of the acrylonitrile-depleted glycerol stream is recycled as a glycerol absorbent feed stream to the absorption column.
  • at least 50 %, preferably at least 80 %, more preferably at least 90 %, most preferably at least 95 % by volume of the acrylonitrile-depleted glycerol stream is recycled as a glycerol absorbent feed stream to the absorption column.
  • the liquid absorbent used for absorbing nitrile products from the ammoxidation reaction effluent is at least partially provided by glycerol recovered from the subsequent nitrile-glycerol separation (e.g., distillation or steam-stripping) step.
  • the use of glycerol or a glycerol/water mixture as an absorbent for the gaseous ammoxidation reaction products requires smaller volumes of absorbent while obtaining the same degree of acrylonitrile recovery.
  • the acrylonitrile-depleted glycerol stream recovered from the acrylonitrile separation step at least partially as the glycerol absorbent in the ammoxidation effluent absorption step, significant improvements in overall solvent use and waste discharge can be obtained.
  • the glycerol feed stream provided to the dehydration reactor is at least partially provided as a purified glycerol stream from a crude glycerol purification unit.
  • a purified glycerol stream is withdrawn from a crude glycerol purification unit upstream of a first dehydration reactor and provided to the dehydration reactor for conversion to acrolein.
  • the crude glycerol purification unit generally comprises in an inlet for receiving a crude glycerol feed and one or more outlets for discharging a purified glycerol stream and a water stream, and may comprise any combination of elements necessary to process a crude glycerol feed to the desired level of purity and suitability for any subsequent steps, including dehydration to acrolein. Generally, this comprises means for removing any potential high boiling species, such as residual fatty acids and their esters, that may coke and deactivate the dehydration catalyst. Furthermore, the crude glycerol purification unit is typically equipped with means for recovering any water that may be present in the crude feed.
  • the column typically comprises a wiped film evaporator located upstream of a distillation column, wherein the wiped film evaporator may be used as a preheater, as well as for removal from any heavies and salt from the crude glycerol feed.
  • the column preferably is of a multiple side-draw design allowing to separate various components present in the crude glycerol feed.
  • the column reboiler preferably comprises a down flow tubular evaporator that is suitable for handling fluids of high viscosity.
  • the entire crude glycerol purification unit is typically operated under vacuum (e.g., about 15 mbar).
  • the crude glycerol feed provided to the crude glycerol purification unit may at least partially be formed by a crude glycerol stream resulting from industries such as biodiesel plants.
  • a minor portion, for example between 5-20 % by volume, of recycled glycerol from the glycerol absorption and separation cycle (the major portion typically being recycled to the absorption column as described above) is provided as a feed to the crude glycerol purification unit reboiler.
  • this minor recycle stream acts as a bleeding stream to remove any heavy components that are potentially generated during the glycerol absorption and subsequent separation cycle.
  • a purified glycerol stream is withdrawn from the crude glycerol purification unit, which is typically combined with recovered water withdrawn from the same unit and used as a feed for the glycerol dehydration reactor.
  • the glycerol liquid absorbent may comprise a combination of glycerol recovered and recycled from the acrylonitrile separation step and purified glycerol from the crude glycerol purification unit.
  • the amount of unreacted glycerol to be recycled to the crude glycerol purification unit depends on the extent of glycerol conversion in the dehydration reaction; it may be up to 100% considering that the crude glycerol purification unit is designed to separate and remove any un-wanted components, and only provide water and glycerol for supplying to the dehydration reaction. Thus, by this design, a full raw material conversion and zero/near-zero waste discharge can be achieved.
  • the present invention wherein glycerol or a glycerol-water mixture instead of pure water is used for the recovery of ammoxidation products, including acrylonitrile and possible by-products such as acetonitrile, from a gaseous reaction product stream, advantageously utilizes considerably smaller volumes of absorbent and allows the absorption to be carried out at ambient temperatures. Moreover, the use of glycerol as the main absorbent permits the use of multiple (recycled) glycerol streams obtained elsewhere in the process.
  • process for the recovery of acrylonitrile from an ammoxidation reaction effluent stream comprising providing the ammoxidation reaction effluent stream to an absorption column; absorbing acrylonitrile from the ammoxidation reaction effluent stream using a liquid absorbent comprising glycerol to produce a stream comprising glycerol and acrylonitrile; and separating acrylonitrile from the stream comprising glycerol and acrylonitrile.
  • the liquid absorbent comprises at least 5 wt% glycerol, preferably at least 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt% or 90 wt% glycerol.
  • the liquid absorbent comprises at most 100 wt% glycerol, preferably at most 95 wt%, 90 wt%, 85 wt%, 80 wt%, 70 wt%, 60 wt%, 50 wt%, 40 wt%, or 30 wt% glycerol.
  • the process combines the advantages of using glycerol rather than water for absorbing acrylonitrile and optional other products and the utilization of various glycerol recycle streams produced elsewhere in the process, including recycle streams that have first been subjected to purification in a front end crude glycerol purification unit.
  • the process design can potentially reduce raw material consumption and be more efficient in energy integration between acrylonitrile production and direct use of crude glycerol as feed stock.
  • a dehydration section comprising an inlet for receiving a glycerol feed stream and an outlet for discharging an acrolein stream, the dehydration section comprising a dehydration reactor, wherein the dehydration reactor is configured to convert the glycerol stream to an acrolein stream;
  • a purification section comprising an inlet fluidly connected to the outlet of the dehydration section, an outlet for discharging a concentrated acrolein stream, and an outlet for discharging a residual stream comprising unconverted glycerol, the purification section comprising a purification column configured to produce a concentrated acrolein stream and a residual stream comprising unconverted glycerol;
  • An ammoxidation section comprising an inlet fluidly connected to the outlet of the purification section, and an outlet for discharging an acrylonitrile stream, wherein the ammoxidation section comprises an ammoxidation reactor configured to receive an acrolein feed stream and to convert the acrolein feed stream to an acrylonitrile stream;
  • An absorption section comprising an inlet fluidly connected to the outlet of the ammoxidation section, an inlet for receiving a glycerol absorbent stream, and an outlet for discharging a glycerol absorbent stream comprising an acrylonitrile product, wherein the absorption section comprises an absorption column configured to produce a glycerol absorbent stream comprising an acrylonitrile product;
  • a separation section comprising an inlet fluidly connected to the outlet of the absorption section, an outlet for discharging a acrylonitrile-depleted glycerol stream, and an outlet for discharging an acrylonitrile product stream, wherein the separation section comprises one or more apparatuses configured to separate the acrylonitrile product and optional other products from the glycerol absorbent stream; and
  • the system further comprises a crude glycerol purification unit as described herein above, located upstream of the dehydration section, wherein an outlet of the crude glycerol purification unit is fluidly connected to the inlet for receiving a glycerol feed stream of the dehydration section.
  • an outlet of the crude glycerol purification unit is fluidly connected to the inlet for receiving a glycerol absorbent stream of the absorption section.
  • system further comprises means for recycling at least portion of the residual stream comprising unconverted glycerol from the outlet of the purification section to the inlet of the crude glycerol purification unit.
  • system further comprises means for recycling at least portion of a glycerol bleed stream from an outlet of the separation section to an inlet of the crude glycerol purification unit.
  • FIG. 1 a schematic diagram illustrating a system 100 for producing acrylonitrile from glycerol according to an embodiment of the present disclosure is shown.
  • a liquid feed stream 107 comprising glycerol is provided to a dehydration reactor 101.
  • a dehydration reaction product stream is withdrawn from the dehydration reactor 101 and, following quenching and distillation steps (not shown) provided as a purified acrolein feed stream 108 to ammoxidation reactor 102.
  • ammoxidation reactor 102 acrolein is converted in the presence of a suitable ammoxidation catalyst, ammonia, oxygen or air and inert diluent gases as needed, to acrylonitrile.
  • a gaseous effluent stream comprising acrylonitrile and possible by-products such as acetonitrile is withdrawn from the ammoxidation reactor 102. Residual ammonia present in the effluent may be removed by acid neutralization (not shown).
  • the ammoxidation product stream is then provided as a feed 109 to the bottom stage of absorption column 103, to which a liquid absorbent stream 110 comprising glycerol is continuously supplied at the top stage.
  • a liquid stream 111 comprising glycerol, acrylonitrile and optional by-products is withdrawn from absorption column 103 and provided as a feed to stripping column 104, wherein the absorbent solution is separated from the acrylonitrile and optional by-products to provide an acrylonitrile stream 112 and an acrylonitrile-depleted glycerol stream 113. At least a portion of the acrylonitrile-depleted glycerol stream 113 is recycled to the absorption column
  • 104 may be sent to one or more purification units for further separation and purification by means known in the practice.
  • FIG. 2 a schematic diagram 200 illustrating a system for producing acrylonitrile from glycerol according to another embodiment of the present disclosure is shown.
  • a crude glycerol purification unit 205 is provided upstream of a dehydration reactor 201, to which a crude glycerol feed stream 214, preferably from a renewable source, may be provided.
  • crude glycerol is purified in glycerol purification unit 205 to produce a purified glycerol stream 215.
  • At least a portion of purified glycerol stream 215 is employed as a feed stream 207 for dehydration reactor 201.
  • a dehydration reaction product stream 218 is withdrawn from the dehydration reactor 201, quenched and provided to a purification section 206, wherein the dehydration product stream is purified by distillation.
  • a purified acrolein feed stream 208 is obtained from the top of distillation column and provided to ammoxidation reactor 202. The bottom of the column may be discharged as waste stream or optionally recycled back as a glycerol recycle stream 219 to the crude glycerol purification unit 205 unit if any unconverted glycerol or intermediate reaction products need to be recovered.
  • ammoxidation reactor 202 acrolein is subjected to ammoxidation as described above to produce an ammoxidation product stream which is provided as a feed 209 to the bottom stage of absorption column 203, to which a liquid absorbent stream 210 comprising glycerol is continuously supplied at the top stage.
  • the glycerol absorbent stream 210 may at least partially be provided as a purified glycerol effluent stream 216 from crude glycerol purification unit 205.
  • glycerol absorbent stream 210 may at least partially be provided as a recycled glycerol stream 213 from a stripping column 204 located downstream of the absorption column 203.
  • a liquid stream 211 comprising glycerol, acrylonitrile and possible by-products is withdrawn from absorption column 203 and provided as a feed to stripping column 204, wherein the absorbent solution is separated from the acrylonitrile and optional by-products to provide an acrylonitrile stream 212 and an acrylonitrile-depleted glycerol stream 213.
  • At least a portion of the acrylonitrile-depleted glycerol stream is recycled as glycerol absorbent stream 213 to the absorption column 203.
  • Another, typically smaller, portion may be recirculated as a purging stream 217 to crude glycerol purification unit 205 where any heavy components are removed to avoid their accumulation in the absorbent solution.
  • the acrylonitrile stream 212 obtained from stripping column 204 may be sent to one or more purification units for further separation and purification by means known in the practice.
  • the absorption column has 10 theoretical stages, and the absorption solvent is fed at the top (stage 1) of column.
  • the ammoxidation product stream is fed at bottom (stage 10).
  • the solvent enters the column at ambient temperature (25 °C) at a flow rate required to achieve 99.5% recovery of acrylonitrile from the product stream.
  • Different absorption solvents i.e. pure water, 50 wt% glycerol in water, 80 wt% glycerol in water, and 90 wt% glycerol in water, were simulated using the ASPEN® Rad- Frac model. The results are shown in in Table 2 below.
  • the mass ratio is defined as the ratio between the mass flow rate of absorption solvent that is required to achieve the targeted 99.5% recovery of ACN and the mass flowrate of ACN in the feed stream.
  • the numbers corresponding to each component represent the proportion of recovery (recovery rate) for the component by the corresponding absorption solvent.
  • the simulations were run under identical conditions, except for the exit temperature of the liquid solvent which was allowed to vary due to differences in heat capacity of each solvent.

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

Abstract

La présente invention concerne des procédés de production d'acrylonitrile à partir de glycérol, comprenant une étape de déshydratation pour produire de l'acroléine et une étape d'ammoxydation pour produire de l'acrylonitrile. Le procédé comprend le recyclage d'un ou de plusieurs flux de glycérol. La présente invention concerne en outre un procédé de récupération d'acrylonitrile à partir d'un flux d'effluent de réaction d'ammoxydation, comprenant l'absorption du flux d'effluent gazeux dans un absorbant de glycérol. L'invention concerne également un système pour la mise en œuvre du procédé.
PCT/IB2022/061869 2021-12-08 2022-12-07 Procédé intégré pour la conversion de glycérol en acrylonitrile WO2023105430A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US202163287100P 2021-12-08 2021-12-08
US63/287,100 2021-12-08
NL2030511 2022-01-12
NL2030511A NL2030511B1 (en) 2022-01-12 2022-01-12 Integrated process for the conversion of glycerol to acrylonitrile

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3257446A (en) * 1962-07-06 1966-06-21 Distillers Co Yeast Ltd Purification of acrylonitrile
WO2006087083A2 (fr) 2005-02-15 2006-08-24 Arkema France Processus de deshydratation de glycerol en acroleine
US20100048850A1 (en) 2007-02-16 2010-02-25 Arkema France Method for the synthesis of acrylonitrile from glycerol
WO2013017942A2 (fr) 2011-07-29 2013-02-07 Arkema France Procédé perfectionné de mise en œuvre de réactions de déshydratation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3257446A (en) * 1962-07-06 1966-06-21 Distillers Co Yeast Ltd Purification of acrylonitrile
WO2006087083A2 (fr) 2005-02-15 2006-08-24 Arkema France Processus de deshydratation de glycerol en acroleine
US20100048850A1 (en) 2007-02-16 2010-02-25 Arkema France Method for the synthesis of acrylonitrile from glycerol
WO2013017942A2 (fr) 2011-07-29 2013-02-07 Arkema France Procédé perfectionné de mise en œuvre de réactions de déshydratation

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