process to produce acetic acid, and method to improve liquid-liquid separation of condensate

专利摘要:
process to produce acetic acid, and, method to improve liquid-liquid separation of a condensate this production method to produce acetic acid suppresses the hydrogen iodide concentration and improves the liquid separation of the top product of a distillation tower . a mixture including hydrogen iodide, water, acetic acid, and methyl acetate is distilled in a first distillation tower (3); the top product, and a side cut current or bottom product stream including acetic acid are separated from this mixture; the top product is cooled in a condenser (c3) and condensed; the condensed liquid is separated into an upper and a lower phase by a decanter (4); and acetic acid is produced. in this method, a mixture having a water concentration of at least an effective amount and not greater than 5% by weight (for example, 0.5-4.5% by weight) and a concentration of methyl acetate of 0.5 -9% by weight (for example, 0.5-8% by weight) is fed to the distillation tower and distilled. as a result, a region having a high concentration of water is formed within the distillation tower at a higher position than the feed position for the mixture, hydrogen iodide and ethyl acetate are reacted in this area of high water concentration , and methyl iodide and acetic acid are generated.
公开号:BR112014022682B1
申请号:R112014022682
申请日:2013-03-12
公开日:2020-04-14
发明作者:Nakajima Hidehiko；Miura Hiroyuki；Shimizu Masahiko；Ueno Takashi
申请人:Daicel Corp；
IPC主号:

专利说明:

PROCESS TO PRODUCE ACETIC ACID, AND, METHOD TO IMPROVE A LIQUID-LIQUID SEPARATION OF A CONDENSATE
TECHNICAL FIELD [0001] The present invention relates to a process for producing high quality acetic acid while inhibiting corrosion of an apparatus (for example, a distillation column).
PREVIOUS TECHNIQUE [0002] With reference to a process for producing acetic acid, an industrially used production process includes allowing methanol to continuously react with carbon monoxide in the presence of a catalyst containing a group 8 metal in the Periodic Table (as a catalyst for rhodium or an iridium catalyst), an ionic iodine (eg lithium iodide), and methyl iodide and in the presence of water to give acetic acid. In this process, usually, a reaction mixture obtained by methanol carbonylation is subjected to flash distillation, the volatile component resulting from flash distillation is distilled in a first distillation column to form a top product from a column top and a heavy component from the bottom of the column, and a stream of acetic acid is removed as a side stream (side shear stream) from the first distillation column. In addition, the top product of the first distillation column is cooled and condensed to form an aqueous phase and an organic phase, which are separated from each other. The aqueous phase mainly contains water and acetaldehyde, and the organic phase mainly contains methyl iodide. In addition, the acetic acid stream is subjected to a second distillation column to remove water and other impurities to obtain or separate a further purified acetic acid stream as a side stream (side cut stream) or bottom stream. The second distillation column is mainly used for dehydration in
Petition 870190088814, of 09/09/2019, p. 17/77 / 56 many cases. Due to the fact that a top product from the top of the second distillation column has a low water content, the top product is rarely separated into two phases (an aqueous phase and an organic phase) even after cooling and condensation. In such a process, the accumulation of hydrogen iodide in the first and second distillation columns deteriorates the quality of the acetic acid produced due to contamination with hydrogen iodide and causes corrosion of an apparatus (such as the first and second distillation columns).
[0003] For the purpose of removing hydrogen iodide, it has been reported that hydrogen iodide is converted to methyl iodide, which has a lower boiling point, by a reaction of hydrogen iodide with methanol, and iodide The resulting methyl chloride is separated as a lower boiling current.
[0004] Japanese Patent Application Publication Open to Public Inspection No. 6-40999 (JP-6-40999A, Patent Document 1) describes that introducing a small amount of methane below a feed point, in which a feed composition is fed to a distillation zone, converts hydrogen iodide to methyl iodide which is removed as a light fraction stream from the tip of a distillation column.
[0005] Japanese Patent Application Publication Open to Public Inspection No. 52-23016 (JP-52-23016A, Patent Document 2) describes a process for removing and collecting iodine-containing components and drying acetic acid, which comprises: introducing a acetic acid stream containing water, methyl iodide and hydrogen iodide in a first intermediate distillation zone; removing methyl iodide and others as a fraction of top product from the first distillation zone; remove hydrogen iodide and others from the bottom of the first distillation zone; remove a side stream (acetic acid stream) from the middle section of the first distillation zone
Petition 870190088814, of 09/09/2019, p. 18/77 / 56 to introduce the current in the upper section of a second distillation zone; introduce methanol into the lower section of the second distillation zone; removing a top product stream containing methyl iodide and others from the second distillation zone; and removing a stream of produced acetic acid substantially free of hydrogen iodide and methyl iodide from the bottom or from a location near the bottom of the second distillation zone.
[0006] Japanese Patent No. 4489487 (JP-4489487B, Patent Document 3) describes a process for separating hydrogen iodide, which includes distilling a mixture containing hydrogen iodide, water, and a component that has a boiling point greater than that of water (for example, acetic acid) to separate hydrogen iodide, in which an alcohol (for example, methanol) is fed to a distillation column so that a zone that has a water concentration of 5% by weight in the Distillation column can be formed between the alcohol feed positions.
[0007] In the production of acetic acid, it is also known to remove hydrogen iodide by using the relationship between a concentration of water and a concentration of hydrogen iodide in a distillation column. For example, British Patent No. 1350726 (Patent Document 4) describes that due to a peak concentration of hydrogen halides occurring in a middle portion of a distillation column, if a side stream is removed from the middle portion of the column of distillation then the hydrogen halides will be removed from it, in a case in which a liquid carboxylic acid composition has a water concentration ranging from 3% to 8% by weight. In addition, this document describes that a reaction product of methanol and carbon monoxide is subjected to flash distillation and then a fraction separated by flash distillation is introduced into the distillation column to concentrate hydrogen iodide in a side stream of the middle portion of the distillation column, thus removing the iodide from
Petition 870190088814, of 09/09/2019, p. 19/77 / 56 hydrogen.
[0008] Japanese Patent Application Publication Open to Public Inspection No. 2006-160645 (JP-2006-160645A, Patent Document 5) describes a process for producing acetic acid, which includes: distilling a mixture containing hydrogen iodide, water, methanol, methyl iodide, acetic acid and methyl acetate in a water content of no more than 5% by weight in a distillation column, remove a fraction containing hydrogen iodide from the top of the column, and remove acetic acid as a side cut current by side cut or a column bottom chain to reduce the hydrogen iodide concentration to no more than 50 ppm. According to this process, distillation at a water concentration of no more than 5% by weight in the distillation system allows the inhibition of the hydrogen iodide concentration in the distillation system.
[0009] This document describes that the mixture can be distilled by introducing at least one component selected from the group consisting of methanol, methyl acetate and an alkali metal hydroxide in an appropriate position of the distillation column (for example, at the bottom, or between the bottom section and the middle section) to maintain or preserve the water content not greater than 5% by weight in the distillation column and that such a process can remove hydrogen iodide. In addition, Patent Document 5 describes in Examples and Comparative Examples that a liquid mixture containing 34% by weight of methyl iodide, 9.8% by weight of methyl acetate, 1.2% by weight of water, 55% by weight of acetic acid, and 190 ppm by weight of hydrogen iodide was distilled, and the resulting distillate from the top of the column was separated into an upper layer and a lower layer.
[00010] Although these processes may inhibit the concentration of hydrogen iodide in the distillation column, the efficiency of removing hydrogen iodide is still insufficient to produce a high quality acetic acid. Furthermore, even if the top product of the
Petition 870190088814, of 09/09/2019, p. 20/77 / 56 distillation is condensed, the top product will sometimes not be efficiently separated into an aqueous phase (upper phase or light phase) and an organic phase (lower phase or heavy phase). In particular, when the liquid mixture is distilled and the top product (top product) at the top of the column is cooled and condensed according to Patent Document 5, the condensate has an inefficient separability in upper and lower phases. In addition, even if the condensate is separated into the lower phase and the upper phase, it will be impossible to stably perform or operate these processes due to an unstable phase separation surface (liquid interface) between these phases. In this way, sometimes the continuous operation of the production equipment faces an obstruction or problem.
[00011] Japanese Patent Application Publication Open to Public Inspection No. 2009-501129 (JP-2009-501129A, Patent Document 6) describes a process for producing acetic acid, which includes: separating a reaction mixture obtained by carbonylation methanol in a catalyst stream and acetic acid stream in a catalyst separation column; in a first distillation column, separate the acetic acid stream into a first top product containing methyl iodide, methyl acetate and a portion of water, and a first highest boiling stream containing portions of water and propionic acid , and removing a first side chain containing acetic acid by side cutting; feeding the first side stream to a second distillation column; and removing and collecting a second side stream containing acetic acid by side cutting. This document describes a process for reducing a concentration of a hydrogen halide contained in an acetic acid product, which includes converting hydrogen iodide in the distillation column to methyl iodide and separating hydrogen iodide in the form of methyl iodide from the top of the distillation column to inhibit condensation of the hydrogen halide. The method for converting hydrogen iodide includes a method for feeding
Petition 870190088814, of 09/09/2019, p. 21/77 / 56 the first distillation column with water or water and a first component (A) (where the first component (A) is at least one member selected from the group consisting of methanol and methyl acetate) and a method for feeding the first distillation column with the first component (A) from a lower position relative to a first side chain port for lateral cutting of a first side chain. In addition, the document states that due to the fact that the water supply to the first distillation column develops (shape) a zone having a high concentration of water in the distillation column and causes condensation of hydrogen halide in the zone, the supply of water together with the first component (A) allows efficient conversion of hydrogen halide into a low boiling component.
[00012] Patent Document 6 describes, in Examples, that methanol (4.9 mol / h), methyl acetate (7.4 mol / h) and water (21.1 mol / h) were fed from the 27 ° dish at the top of the distillation column (having 30 dishes) (Examples 3 and 4), and methanol was fed from the 43 ° dish at the top of the distillation column (having 50 dishes) (Comparative Example 2). [00013] According to the process, unfortunately, a feed liquid has a high concentration of methyl acetate, and in addition, the concentration of methyl acetate in a stream or top product (vapor phase component) from the top of the column distillation is further increased due to the additional condensation of methyl acetate in the distillation column and the by-product methyl acetate formed by the methanol feed. Thus, if the top fraction of the distillation column is cooled, the resulting condensate cannot be separated into an aqueous phase (an upper phase predominantly containing water and acetaldehyde) and an organic phase (a lower phase predominantly containing methyl iodide) . In addition, even if the condensate is separated into the phases, these phases are mixed to form a mixed phase due to a small difference in
Petition 870190088814, of 09/09/2019, p. 22/77 / 56 specific gravity between the light phase and the heavy phase, so that the distillation column cannot be operated steadily. In particular, in an industrial process, the limit (the interface) between the aqueous phase and the organic phase varies depending on the rapid expansion of carbon monoxide in the reaction system, the flow and pressure fluctuations in the flash distillation stage and others . Therefore, the aqueous phase and the organic phase cannot be clearly separated, so that the process apparatus cannot be operated continuously. In addition, feeding methanol or methyl acetate into the column from a lower position than that of a mixing dish increases the diameter of the distillation column insignificantly, resulting in low economic efficiency.
RELATED TECHNICAL DOCUMENTS
PATENT DOCUMENT [00014] Patent Document 1: JP-6-40999A (Paragraph No. [0043]) [00015] Patent Document 2: JP-52-23016A (Claims, page 5, the inner right column, page 7 , the bottom left column to the bottom right column) [00016] Patent Document 3: JP-4489487B (Claims) [00017] Patent Document 4: British Patent Specification No. 1350726 (page 2, lines 66 to 76) [00018] Patent Document 5: JP-2006-160645A (Claims, Paragraph [0036]) [00019] Patent Document 6: JP-2009-501129A (Claims, Paragraphs [0043] [0085], Examples 3 and 4, Comparative Example 2)
SUMMARY OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION [00020] Therefore an objective of the present invention is to provide a process for producing acetic acid, the process that improves the liquid-liquid separation of a low boiling current (top current) from a
Petition 870190088814, of 09/09/2019, p. 23/77 / 56 distillation column while inhibiting the condensation of hydrogen iodide, and a method to improve liquid-liquid separation from the low boiling current (top current).
[00021] Another objective of the present invention is to provide a process for producing high-quality acetic acid by effectively inhibiting contamination with an impurity (e.g., hydrogen iodide), and a method for improving the quality of acetic acid.
[00022] Yet another objective of the present invention is to provide a process for producing acetic acid, useful for efficiently separating a low boiling current (top product) into an aqueous phase and an organic phase by cooling and condensing the current of a distillation column, and operating a production apparatus stable and continuously.
MEANS TO SOLVE THE PROBLEMS [00023] The inventors of the present invention carried out intensive studies to achieve the above objectives and finally found that a mixture under feeding of a decreasing agent (a hydrogen iodide decreasing agent) to a distillation column achieves the following (1) and (2), in which the decreasing agent contains an effective amount of water in a concentration not greater than 5% by weight and an effective amount of methyl acetate in a concentration not greater than 9% by weight: (1 ) a zone that has a high concentration of water is formed in the distillation column above a loading site (part or feeding site) of a volatile component to the distillation column, and methyl acetate is allowed to effectively react with hydrogen iodide in the high concentration zone to produce methyl iodide (a lower boiling point component) and acetic acid, where methyl iodide has a high miscibility with an organic phase, unlike acetic acid has a high miscibility with an aqueous phase and is predominantly different at the boiling point of methyl iodide (predominantly different at the boiling point of
Petition 870190088814, of 09/09/2019, p. 24/77 / 56 water formed by the reaction of methanol with hydrogen iodide); and (2) since a low boiling current (top product) contains methyl acetate in a predetermined proportion, the low boiling point current (top product) of the distillation column is cooled and condensed to neatly and efficiently separate the resulting condensate in an organic phase containing methyl iodide and an aqueous phase containing acetic acid, and thus the liquid-liquid separation of the low-boiling current (top product) of the distillation column can be significantly improved. The present invention was carried out on the basis of the above findings.
[00024] That is, a process for producing acetic acid according to the present invention comprises: distilling a mixture containing hydrogen iodide, water, methyl iodide, acetic acid, and methyl acetate to form a top product containing a component lowest boiling point; and condensing the top product to form separate liquid phases. In the process, acetic acid is produced by distilling a mixture containing an effective amount of water in a concentration not greater than 5% by weight and an effective amount of methyl acetate in a concentration not greater than 9% by weight (methyl acetate at a concentration of 0.5 to 9% by weight) to separate the mixture into a top stream (fraction) containing methyl iodide and a side cut or bottom stream containing acetic acid.
[00025] The mixture can have a concentration of methyl acetate of 0.07 to 1.2 mol / L and a water concentration of 0.28 to 2.8 mol / L, and can be distilled continuously. The water content of the mixture can be about 0.5 to 4.5% by weight (for example, about 1 to 4.3% by weight). The content of methylated acetate in the mixture can be about 0.5 to 8% by weight (for example, about 0.5 to 7.5% by weight or about 0.8 to 7.5% by weight) . The mixture may additionally contain dimethyl ether. The concentration of dimethyl ether can be
Petition 870190088814, of 09/09/2019, p. 25/77 / 56 about 0.15 to 3% by weight.
[00026] The mixture can be fed to a distillation column from an intermediate or lower portion in height of the distillation column. In addition, a zone having a high water concentration can be formed within the distillation column in a position higher than a feed position in which the mixture is fed to the distillation column; in the zone of high water concentration, hydrogen iodide may be allowed to react with methyl acetate to produce methyl iodide and acetic acid; and distillation can provide the top product containing the resulting methyl iodide.
[00027] The present invention includes the process for producing acetic acid, in which methanol is allowed to continuously react with carbon monoxide by the use of a catalyst containing a group 8 metal in the Periodic Table (such as a rhodium catalyst or an iridium catalyst) ), an ionic iodide (for example, lithium iodide), and methyl iodide in the presence of water; the reaction product is separated into a low-volatile phase component and a volatile phase component by flash distillation; the volatile phase component as the mixture is distilled to form the top product containing methyl iodide and a side shear or bottom chain (or a side shear and bottom chain) containing acetic acid; and the top product is condensed to form an aqueous phase and an organic phase. In the process to produce acetic acid, the volatile phase component is distilled while being adjusted to a water concentration of an effective amount and not greater than 5% by weight and a concentration of methyl acetate from 0.5 to 9% by weight in an atmosphere of distillation of the volatile phase component in terms of a liquid or condensed form.
[00028] At least one member of the group consisting of methyl acetate, methanol and dimethyl ether, and if necessary water, can be added (or fed) to the mixture (volatile phase component) or an atmosphere of
Petition 870190088814, of 09/09/2019, p. 26/77 / 56 distillation of the mixture (volatile phase component) to adjust the concentrations of water and methyl acetate, and the resulting volatile phase component can be distilled. In addition, a distillation atmosphere of a volatile phase component can be formed in the distillation column at a height equal to or higher than that of a volatile phase component feed site.
[00029] Furthermore, the mixture can have a hydrogen iodide concentration of about 100 to 10,000 ppm. Such a mixture can be distilled to form (or separate) a side shear stream containing acetic acid. The concentration of hydrogen iodide in a side shear stream can be about 1 to 350 ppm.
[00030] Furthermore, in order to efficiently separate the top product in an aqueous phase and an organic phase by condensing the top product, the separated bottom phase (organic phase or heavy phase) may have a concentration of methyl acetate of about 1 to 15% by weight, and the upper phase (aqueous phase or light phase) may have a lower concentration of methyl acetate of about 0.4 to 8% by weight than that of the lower fraction.
[00031] The present invention also includes a method for separating liquid-liquid from a condensate, comprising: distilling a mixture containing hydrogen iodide, water, methyl iodide, acetic acid, and methyl acetate to form a top product containing a lower boiling point component, and condense the top product. In this method, the mixture containing an effective amount of water in a concentration of no more than 5% by weight and methyl acetate in a concentration of 0.5 to 9% by weight is distilled to reduce a concentration of hydrogen iodide in the product top and side cutting chain, and the condensation of the top product improves liquid-liquid separation from condensate. In the method, the concentration of hydrogen iodide in the top product and in a side cutting current can be reduced by adjusting the
Petition 870190088814, of 09/09/2019, p. 27/77 / 56 methyl acetate concentration in the mixture to 0.5 to 8% by weight (or by increasing a concentration of methyl acetate in the mixture in the range of 0.4 to 8% by weight). In addition, liquid-liquid separation of condensate can be improved by adjusting (or controlling) the concentrations of methyl iodide and methyl acetate in the lower phase (organic phase or heavy phase) to 76 to 98% by weight and 1 to 15 % by weight, respectively (with the proviso that the total of components in the lower phase (organic phase or heavy phase) is 100% by weight), and adjustment (or control) of the concentrations of water and methyl acetate in the upper phase ( aqueous phase or light phase) are adjusted to 50 to 90% by weight and 0.4 to 8% by weight, respectively (with the proviso that the total of components in the upper phase (aqueous phase or light phase) is 100% in Weight). [00032] The present invention also includes an apparatus for producing acetic acid by distilling a mixture containing hydrogen iodide, water, methyl iodide, acetic acid, and methyl acetate. The apparatus comprises a controller for adjusting (or configuring or controlling) a water concentration in the mixture to less than an effective amount of no more than 5% by weight and a concentration of methyl acetate in it to 0.5 to 9% in weight by feeding water and / or methyl acetate, and furthermore it comprises a distillation column to distill the mixture having adjusted water concentration and adjusted methyl acetate concentration to form (or obtain) a top product containing methyl iodide and a side cut or bottom chain containing acetic acid, a cooling unit (a condenser) to cool the top product of the distillation column, and a liquid-liquid separation unit (a decanter) to separate the resulting condensate from the product top cooled in two phases.
[00033] As used herein, the term "mixture" sometimes has the same meaning as a volatile phase component obtained by flash distillation. In addition, an amount of a component in a mixture
Petition 870190088814, of 09/09/2019, p. 28/77 / 56 means not an amount of the component in a vapor phase but an amount of the component in the form of condensate or liquid.
EFFECTS OF THE INVENTION [00034] According to the present invention, since a mixture containing a specific concentration of water and a specific concentration of methyl acetate is distilled to form separate phases, the concentration of hydrogen iodide (or corrosion of an apparatus ) can be inhibited and the liquid-liquid separation of a low boiling current (top product) from a distillation column can be improved. In addition, due to the conversion of hydrogen iodide to methyl iodide and the separation of the top product into an aqueous phase and an organic phase, the present invention effectively prevents contamination with an impurity (such as hydrogen iodide) to produce acetic acid from high quality. In addition, the cooling and condensation of the low-boiling current (top product) of the distillation column allows efficient separation of the current in the aqueous phase and the organic phase, so that a production apparatus can be stable and continuously operated. Accordingly, the present invention is useful as a process for industrially producing acetic acid.
BRIEF DESCRIPTION OF THE DRAWINGS [00035] Fig. 1 is a diagram to explain a process for producing acetic acid according to an embodiment of the present invention.
[00036] Fig. 2 is a diagram to explain a process for producing acetic acid according to another embodiment of the present invention.
DESCRIPTION OF THE MODALITIES [00037] Hereinafter, the present invention will be explained in detail with reference to the drawings if necessary. Fig. 1 is a diagram (a flow chart, a schematic drawing of the process, or a layout drawing of the unit
Petition 870190088814, of 09/09/2019, p. 29/77 / 56 of production) to explain a production process (or production apparatus) of acetic acid according to an embodiment of the present invention.
[00038] The process (or production apparatus) shown in Fig. 1 comprises a reactor (reaction system) 1 to allow methanol to continuously react with carbon monoxide (carrying out the methanol carbonylation reaction) in the presence of a catalyst or a catalyst and water system; a flash or evaporator device (flash evaporator) 2 to separate the reaction mixture (liquid reaction medium) into a volatile phase component and a low volatile phase component; a first distillation column (separating column) 3 to distill the volatile phase component to form (or obtain) a first top phase from a column top, a bottom chain from the bottom of the column, and a cutting chain lateral (crude acetic acid stream); a decanter 4 for cooling and condensing the first top product in a C3 condenser and for separating the first top product into an aqueous phase (upper or light phase) and an organic phase (lower or heavy phase); the second distillation column (dehydration column or purification column) 5 to distill a side cut stream (crude acetic acid stream) from the first distillation column 3 to form a second top product from a top of the second distillation column , a bottom stream from the bottom of the column, and a side cut stream (purified acetic acid stream) on one side of the column; and an impurity removal system [a third distillation column 6, a water extraction column (water extractor) 7, and a fourth distillation column 8] to remove an impurity from a condensate (an aqueous phase and an organic phase ) in a C4 capacitor.
[00039] Methanol (a liquid reagent) and carbon monoxide (a gaseous reagent) are continuously fed to reactor 1 at predetermined flow rates in the presence of a catalyst system (catalyst system)
Petition 870190088814, of 09/09/2019, p. 30/77 / 56 of carbonylation) containing a metal catalyst (such as a rhodium catalyst or iridium catalyst) and a cocatalyst [lithium iodide as an ionic iodide (or iodide salt) and methyl iodide] and an amount water, and the methanol carbonylation reaction is continuously conducted. The reaction system usually contains acetic acid, which is a reaction product and also functions as a reaction solvent, and methyl acetate, which is a by-product of a reaction of acetic acid with methanol. Within reactor 1, a liquid phase reaction system containing the metal catalyst component (such as a rhodium catalyst), ionic iodide (such as lithium iodide), methanol, acetic acid, and others is in equilibrium with a system of vapor phase containing unreacted carbon monoxide and gaseous by-products derived from the reaction (hydrogen, methane, carbon dioxide), a vaporized low-boiling component (eg methyl iodide, acetic acid as a product, methyl acetate, acetaldehyde, and hydrogen iodide), and others.
[00040] In order to keep the internal pressure of reactor 1 constant (eg reaction pressure, partial pressure of carbon monoxide, and partial pressure of hydrogen), a stream of vapor is removed from the top through a line of discharge 12 and cooled in a C1 condenser. A condensed liquid component (containing acetic acid, methyl acetate, methyl iodide, acetaldehyde, water, etc.) in the condenser is recycled (or refluxed) to reactor 1 through a recycle line (or reflux line) 13, and a non-condensed gaseous component (containing carbon monoxide, hydrogen, and others) in the condenser is discharged as an exhaust gas. In particular, the reaction system is an exothermic reaction system concomitant with heat generation, and part of the amount of heat generated in reactor 1 is removed by cooling the steam component of reactor 1 in condenser C1 and recycling the condensed component to the reactor. 1.
[00041] Components contained in the reaction mixture (reaction liquid
Petition 870190088814, of 09/09/2019, p. 31/77 / 56 crude) can include acetic acid, a volatile component having a lower boiling point than that of acetic acid [for example, a low boiling component (for example, methyl iodide as a cocatalyst, methyl acetate as a reaction product of acetic acid with methanol, methanol, water, and dimethyl ether) or a low boiling impurity (hydrogen iodide, acetaldehyde, crotonaldehyde)], and a low volatile component having a boiling point greater than that of acid acetic [eg a metal catalyst component (a rhodium catalyst, and lithium iodide as a cocatalyst) or a high boiling impurity (eg a by-product, eg propionic acid, an aldehyde condensation product such as 2-ethylcrotonaldehyde, and a C6-12 alkyl iodide such as hexyl iodide or decyl iodide)].
[00042] Consequently, the reaction mixture (a portion of the reaction mixture) is continuously fed from reactor 1 to the flash apparatus or evaporator (flash evaporator, flash distillation column) 2 through a feed line 11 for a distillation flash, and separated into a volatile phase component from the top or top (section) of the flash evaporator column 2 (a lower boiling fraction predominantly containing acetic acid as a product, methanol, methyl acetate, iodide of methyl, water, propionic acid, acetaldehyde, and hydrogen iodide as a by-product) and a low volatile phase component (a higher boiling fraction predominantly containing a metal catalyst component (high boiling component) as a catalyst for rhodium and lithium iodide).
[00043] The low volatile phase component (bottom fraction or liquid catalyst mixture) can be recycled to reactor 1 through a recycling line 21. In this embodiment, the low volatile phase component (bottom fraction or liquid mixture) catalyst) is continuously removed through a recycle line 21 from the bottom of the evaporator 2 and its
Petition 870190088814, of 09/09/2019, p. 32/77 / 56 heat is removed and it is cooled in a heat exchanger (a C6 condenser), and the cooled low-volatile phase component (liquid catalyst mixture) is recycled to reactor 1. Thus, the temperature of the reactor 1 is easily controlled. The low volatile phase component (liquid catalyst mixture) usually contains the metal catalyst component, and in addition, remaining components without evaporation (for example, acetic acid, methyl iodide, water, and methyl acetate).
[00044] A portion of the volatile phase component (or volatile phase) of the evaporator 2 is introduced into a condenser (heat exchanger) C2 through a supply line 23, and cooled and separated into a condensed component containing acetic acid (a liquid component containing acetic acid, methanol, methyl acetate, methyl iodide, water, propionic acid, acetaldehyde, hydrogen iodide, and others) and an uncondensed component (a gaseous component such as carbon monoxide or hydrogen). A portion of the condensed component (liquid component) is retained in an intermediate storage tank 9 and recycled to the reactor 1 through a recycling line 25, the other (remaining) portion of the condensed component (liquid component) is fed to the decanter 4 through a line 26, and the non-condensing component (gaseous component) is discharged as an exhaust gas. In this way, since a portion of the volatile phase component of the flash evaporator 2 is cooled and its heat is efficiently removed in the condenser (heat exchanger) C2 and then recycled to the reactor 1, the temperature of the reactor 1 is easily controlled. Consequently, since the subsequent distillation column (s) or the subsequent condenser (s) can be reduced in size (or miniaturized) even for a large production unit, acetic acid can be produced with a high purity in a resource saving and energy saving device. In particular, according to the process shown in Fig. 1, the low volatile phase component
Petition 870190088814, of 09/09/2019, p. 33/77 / 56 (bottom fraction or liquid catalyst mixture) and a portion of the volatile phase component (or volatile phase) are cooled and recycled to reactor 1. That way even when the reactor is not necessarily equipped with a unit removable heat (or heat remover) or cooling (for example, an external circulation unit such as a jacket), heat removal can be performed.
[00045] The volatile phase component (or volatile phase) is fed to a lower-intermediate part, in a height direction, of the first distillation column (separating column) 3 (for example, a column of plates) through a line 22. That is, a portion of the volatile phase component (or volatile phase) fed through the line 22 is distilled into the first distillation column (separator column) 3 and separated into a first top product (a first lowest boiling point component containing methyl iodide, methyl acetate, acetaldehyde, water, and others) removed from the top of the column or the upper part (or site) of the column, a bottom stream [a stream predominantly containing a component higher boiling point, for example, a high boiling impurity such as water, acetic acid, a entrained catalyst (such as lithium iodide), propionic acid, a C6-12 alkyl iodide (such as i hexyl odide), or an aldehyde condensation product] removed from the bottom of the column, and a side shear stream [a first liquid stream (crude acetic acid stream) predominantly containing acetic acid] on the side (a site higher than the site line (or section) of the power line 22). In this embodiment, a side cut current (crude acetic acid stream) is fed to the second distillation column 5 via a feed line 36, and the bottom stream from the bottom of the column is fed to reactor 1 via a feed line. recycle 31. A portion of or all of the bottom stream from the bottom of the column can be recycled to the evaporator 2 via a line (not
Petition 870190088814, of 09/09/2019, p. 34/77 / 56 shown).
[00046] The first top product is introduced into capacitor C3 through an introduction line 32 and cooled and condensed. The resulting condensed component (a condensate containing methyl iodide, methyl acetate, acetic acid, acetaldehyde, and others) is fed to the decanter 4 via an introduction line 33, and the resulting non-condensed component (a gaseous component predominantly containing monoxide carbon, hydrogen, and others) is discharged as an exhaust gas.
[00047] For the purpose of inhibiting the corrosion of the distillation column 3 and improving the liquid-liquid separation of the condensate in the decanter 4, the volatile component fed to the distillation column 3 through the supply line 22 contains no more than 5% by weight (for example, 1 to 3% by weight) of water and 0.5 to 9% by weight (for example, 3 to 5% by weight) of methyl acetate, in terms of condensate or liquid. In this embodiment, a water supply line 34a and a methyl acetate supply line 35a are connected to the supply line 22 to adjust (or control) the water concentration and methyl acetate concentration in the distillation column 3 ( concentrations in the volatile component).
[00048] More specifically, due to the low concentration of water in the volatile component, a zone having a high concentration of water appears above the feeding site of the volatile component in the first distillation column 3. In this zone, although hydrogen iodide is highly soluble in water is concentrated, the methyl acetate feed predominantly proceeds with a methyl acetate reaction with hydrogen iodide to shift the following equilibrium reaction (1) to the right. In this way useful methyl iodide and acetic acid can be obtained. In addition, feeding water and / or methyl acetate can shift the following equilibrium reaction (2) to the right to form methanol and acetic acid. The following reaction (3) of the resulting methanol with hydrogen iodide
Petition 870190088814, of 09/09/2019, p. 35/77 / 56 can produce useful methyl iodide and water. That is, finally, under the production of hydrogen iodide as a by-product (reaction of displacement of the equilibrium reaction (3) to the left) is inhibited, methyl iodide is produced (which has a high affinity for an organic phase and has a low boiling point), acetic acid (which has a high affinity for water and has a high boiling point) and water. In this way, methyl iodide, acetic acid and water can be effectively separated by distillation. In addition, as described below, in the decanter 4 these components can be efficiently separated into an organic phase predominantly containing methyl iodide and an aqueous phase predominantly containing water and acetic acid.
CH3COOCH3 + HI <> CH3I + CH3COOH (1)
CH3COOCH3 + H2O <> CH3OH + CH3COOH (2)
CH3OH + HI <> CH3I + H2O (3) [00049] In addition, usually, since a reflux site of the condensate (liquid reflux mixture) in the first distillation column 3 is located in an upper part (site) of the first column of distillation 3 and a distribution of the water concentration (distribution of the water concentration containing a water concentration of about 5%) is formed within the first distillation column 3, the feed site of the condensate (reflux liquid mixture) fed from the decanter 4 to the first distillation column 3 through the reflux line 42 is located or positioned above a zone having a high concentration of water and a high concentration of hydrogen iodide. Specifically, the zone having high concentrations of water and hydrogen iodide is formed between the feeding site of the volatile component and the feeding site of the reflux liquid mixture. In addition, when the water concentration is less than 5% by weight at the head of the distillation column 3, a zone having a high concentration of hydrogen iodide is not formed in column 3. Thus, water or methyl iodide in the condensate (liquid reflux mixture) can
Petition 870190088814, of 09/09/2019, p. 36/77 / 56 effectively disrupt the production of hydrogen iodide as a by-product in the zone having high concentrations of water and hydrogen iodide. [00050] Ademias, even if the low boiling current (top product) of the distillation column 3 is contaminated with unreacted hydrogen iodide, having a low boiling point, the unreacted hydrogen iodide can be condensed into an aqueous phase in the decanter 4 by condensation of the low boiling current (top product) in the condenser C3, so that the crude acetic acid stream as a side shear stream can be protected from contamination with hydrogen iodide.
[00051] The feed quantities (supplies) of water and / or methyl acetate via the water supply line 34a and the methyl acetate supply line 35a can be calculated based on an analysis of the condensate that was condensed in the capacitor C2 or the volatile phase component (or volatile phase) in line 22 or 23, in particular, the concentration of water and methyl acetate, and the flow rate of the volatile phase component (or volatile phase). The calculated amount of feed (flow) of water and that of methyl acetate are fed to line 34a and line 35a, respectively, and in this way the concentrations of water and methyl acetate in the column can be adjusted to predetermined concentrations.
[00052] A portion of the condensate that has been condensed in the condenser C3 is recycled to the reactor 1 through a recycling line 41, and another portion of the condensate is recycled to the first distillation column 3 through the reflux line 42 to reflux. More specifically, in the decanter 4, the condensate from the first cooled top product condensed in condenser C3 is separated into an aqueous phase (upper phase or light phase) and an organic phase (lower phase or heavy phase); where the aqueous phase contains water, acetic acid, methyl acetate, hydrogen iodide, acetaldehyde, and others, and the organic phase contains methyl iodide, acetate
Petition 870190088814, of 09/09/2019, p. 37/77 / 56 methyl, and others. The aqueous phase (upper phase) is fed to the first distillation column 3 through reflux line 42 to reflux. The organic phase (lower phase) is recycled to reactor 1 through the recycling line 41.
[00053] The concentration of methyl acetate is very involved in or greatly influences the liquid-liquid separation of the condensate. In other words, since methyl acetate is miscible with both the aqueous phase and the organic phase, a high concentration of methyl acetate sometimes produces uniform (homogeneous) condensate without liquid-liquid separation. The formation of uniform or homogeneous condensate fails to reuse useful methyl iodide as a catalyst system, and requires an additional purification medium in order to separate and collect acetic acid. In contrast, according to the present invention, as described above, since the volatile phase component (distillation system) containing a predetermined concentration of water and that of methyl acetate is distilled in the first distillation column 3 and the product of the top is condensed, the aqueous phase and the organic phase can be clearly separated. In this way the present invention advantageously allows the collection or reuse of a useful component and the separation and removal of an impurity component.
[00054] A side cut stream (crude acetic acid stream) from the first distillation column 3 is fed to the second distillation column (dehydration column or purification column) 5 through the supply line36 and distilled to separate into or obtain a second top product (a second lower boiling component containing a low boiling component such as water) removed from the top of the column via a line 52, the bottom stream [the high boiling component (a boiling impurity high) containing water, a carboxylic acid having a high boiling point (such as propionic acid), a C6-12 alkyl iodide (such as hexyl iodide), an aldehyde condensation product, and others] removed from the bottom of the column through of a 51 line, and
Petition 870190088814, of 09/09/2019, p. 38/77 / 56 a side cut chain [a second liquid chain containing acetic acid (purified acetic acid chain with a high purity)] removed from the side (between the bottom of the column and the feed site of the feed line 36) through a line 55.
[00055] The second top product (fraction of the lowest time period) is sent to capacitor C4 via a discharge line 52 and cooled and condensed. A portion of the condensate (the condensate predominantly containing water) is fed to the second distillation column 5 through the reflux line 53 to reflux, and another portion thereof is recycled to reactor 1 through a recycle line 54. The gaseous component does not condensate (gas) is discharged as an expelled gas.
[00056] In addition, in the process shown in Fig. 1, an impurity (for example, hydrogen iodide and acetaldehyde) is separated and removed. Specifically, the condensate (a portion of the aqueous phase and organic phase) condensed in the decanter 4 is fed to the third distillation column 6 via a line 43 and / or a line 44 and separated into a third top product (a boiling current low containing hydrogen iodide, acetaldehyde, methyl iodide, water, and others) from the top of the column and a bottom stream (a high boiling stream containing water, acetic acid, and others) from the bottom of the column. The third top product is fed to a capacitor C5 through a discharge line 62 and cooled and condensed. The resulting condensate predominantly containing acetaldehyde is returned to the third distillation column 6 via reflux line 63 to reflux. The resulting non-condensed component (gaseous component) is discharged as an expelled gas. In addition, the bottom fraction is recycled to the reactor through recycling lines 61, 90.
[00057] In addition, the condensate in condenser C5 is fed to an extractor 7 through a line 64. In the extractor, a water-soluble component (for example, acetaldehyde) is extracted with water fed through the
Petition 870190088814, of 09/09/2019, p. 39/77 / 56 water supply line 82, and thus the condensate is separated into a phase extracted in water (an aqueous phase or an upper phase predominantly containing acetaldehyde) and an organic phase (a lower or refined phase predominantly containing iodide of methyl). The extracted phase (aqueous phase) is fed to a fourth distillation column 8 through a line 74 and separated in a low boiling stream (a fraction predominantly containing acetaldehyde and others) from the top of the column and the bottom stream (a fraction predominantly containing water) from the bottom of the column. In addition, a portion of the organic (refined) phase in the extractor 7 is fed to the distillation column 6 via lines 71, 72, and another portion is recycled to reactor 1 via recycling lines 73, 90. bottom of a fourth distillation column 8 is added to (or combined with) water from the water supply line 82 via a line 81, and used for extraction of water in the extractor 7. The high boiling current (a fraction predominantly containing acetaldehyde) from the top of the column of the fourth distillation column 8 is discharged as an expelled gas.
[00058] According to the process (or production apparatus), the water concentration and the methyl acetate concentration in the distillation system of the first distillation column 3 are adjusted to no more than 5% by weight (for example, 1 to 3% by weight) and 0.5 to 9% by weight (for example, 3 to 5% by weight), respectively, by feeding water and / or methyl acetate through the water supply line 34a and the 35a methyl acetate feed line. In this way, the zone having a high concentration of hydrogen iodide can be formed in a predetermined zone in the first distillation column 3; and hydrogen iodide is allowed to contact an upward stream of methyl acetate (and methanol) having a low boiling point in the volatile phase component, so that the reaction can convert hydrogen iodide into methyl iodide to produce acetic acid and water as by-products. Furthermore, in
Petition 870190088814, of 09/09/2019, p. 40/77 / 56 decanter 4, since the methyl acetate content can be reduced, the aqueous phase (predominantly containing acetic acid, methyl acetate and hydrogen iodide) and an organic phase (predominantly containing methyl iodide and acetate methyl) can be separated with a high liquid-liquid separation efficiency. In this way, a side cut current (crude acetic acid stream) of the first distillation column 3 can be protected against contamination with hydrogen iodide, a load on the second distillation column 5 can be decreased and the corrosion of the first and second distillation columns 3, 5 can be inhibited. [00059] Fig. 2 is a flow chart to explain a process (or apparatus) for producing acetic acid according to another embodiment of the present invention. For explanation, the reference number equal to that in Fig. 1 represents the element substantially equal to that in Fig. 1.
[00060] In this embodiment, acetic acid is produced basically by the same process as that shown in Fig. 1 except that (i) a condensate obtained by condensing a volatile phase component of a flash evaporator 2 is not fed to a decanter 4, (ii) separation processes (a third distillation column, a water extractor, a fourth distillation column) to additionally separate or remove an impurity from the condensate in the decanter 4 are not shown, (iii) a gas expelled from each condenser C1 C4 is treated by a scrubber system, and (iv) in a second distillation column 5, hydrogen iodide is additionally removed by the addition of an alkaline component.
[00061] More specifically, a vapor phase is removed from a reactor 1 through a discharge line 12 and cooled in a capacitor C1; the resulting liquid condensed component is returned to reactor 1 via reflux line 13 to reflux, and the resulting non-condensed component (gaseous component) is sent to a scrubber system 92 via a discharge line 14. In addition, a mixture reaction in reactor 1 is
Petition 870190088814, of 09/09/2019, p. 41/77 / 56 fed to a flash evaporator 2 through a feed line 11 and subjected to flash distillation; a portion of the resulting volatile phase component is fed to a first distillation column 3 through a supply line 22, and the other portion of the volatile phase component passes through a supply line 23 and is cooled and condensed in a condenser C2 to produce a condensate and a non-condensing component. The condensate is recycled to the reactor 1 through a recycling line 25, and the non-condensed component (gaseous component) is fed to the scrubber system 92 through a discharge line 27. In this mode, the position (feed port) of a feed line 22 connected to the first distillation column 3 is located between the bottom position and the intermediate position of the first distillation column 3.
[00062] Furthermore, in the first distillation column 3, the volatile phase component of the flash evaporator 2 is distilled to give a first top phase removed from the top of the column, a bottom stream removed from the bottom of the column, and a stream side cut (crude acetic acid stream) removed from the side. A side cutting chain is removed from a location above the position (feed port) of the feed line 22 connected to the first distillation column 3. The first top product is introduced into a capacitor C3 through an introduction line 32 and it is cooled and condensed to give a condensed component and a non-condensed component; the condensed component (a condensate containing methyl iodide, methyl acetate, acetic acid, acetaldehyde, and others) is fed to a decanter 4 through an introduction line 33, and the non-condensed component (a gaseous component predominantly containing carbon, hydrogen, and others) is fed to the scrubber system 92 via a discharge line 38. A portion of the bottom stream is returned to a flash evaporator 2 via a line 37, and the other
Petition 870190088814, of 09/09/2019, p. 42/77 / 56 portion of the bottom stream is recycled to reactor 1 via a recycle line 31. All bottom stream can be returned to flash evaporator 2 via line 37. Condensate in the decanter 4 (in this mode , an aqueous phase) is returned to the first distillation column 3 through reflux line 42 to reflux. A condensate in the decanter 4 (in this embodiment, an organic phase) is recycled to reactor 1 through a recycling line 41.
[00063] Furthermore, a side cutting current of the first distillation column 3 is fed to a second distillation column (dehydration column or purification column) 5 through a feed line 36 and is separated by distillation in the second column of distillation 5, in a second top product removed from the top of the column via a line 52, a bottom stream removed from the bottom of the column via a line 51, and a side shear stream (high purity acetic acid stream ) removed from the side via a line 55. The second top product (fraction of the lowest time period) passes through a discharge line 52 and is cooled and condensed in a condenser C4 to give a condensate and a non-condensing component . A portion of the condensate (a condensate predominantly containing water) is returned to the second distillation column 5 through reflux line 53 to reflux, and the other portion of the condensate is recycled to reactor 1 through a recycling line 91. In addition In addition, the non-condensing component (gaseous component) is fed to the scrubber system 92 via a discharge line 56.
[00064] In the scrubber system 92, a useful component (eg, methyl iodide, acetic acid) is collected and recycled to reactor 1, and carbon monoxide is purified by PSA (pressure swing adsorption, pressure swing adsorption) or other methods and recycled to reactor 1.
[00065] It is connected to the power line 22 to power the
Petition 870190088814, of 09/09/2019, p. 43/77 / 56 volatile phase component to the first distillation column 3, a supply line 34b for feeding water and / or methyl acetate. A zone of high water concentration is formed by supplying water and / or methyl acetate via supply line 34b and maintaining the water concentration and methyl acetate concentration of the feed liquid to be fed to the first column of water. distillation 3 in predetermined ranges (for example, 1 to 3% by weight of water and 3 to 5% by weight of methyl acetate). In the zone, hydrogen iodide is concentrated and allowed to react with methyl acetate to convert to methyl iodide. In this way, the first distillation column 3 can be protected against corrosion. Since hydrogen iodide is concentrated to about a water concentration of 5% by weight, hydrogen iodide cannot be concentrated if a zone having such a water concentration is not formed in the distillation column (for example, in the case of which the water concentration at the top of the distillation column is less than 5% by weight due to insufficient water supply). However, hydrogen iodide still existing in the distillation column depending on the equilibrium reaction can be converted to methyl iodide by methyl acetate. In this way, even if a zone having a water concentration of about 5% by weight is not formed, corrosion can be inhibited. In addition, the reaction of hydrogen iodide with methyl acetate produces methyl iodide, acetic acid and water to improve liquid-liquid separation in an aqueous phase (light phase) and an organic phase (heavy phase) in the decanter 4.
[00066] As shown in Fig. 2, a supply line 35b, to feed at least one member of the group consisting of methyl acetate, methanol and dimethyl ether, and if necessary water, can be connected to the first distillation column 3 in instead of the supply line 22, and at least one member of the group consisting of methyl acetate, methanol and dimethyl ether, and if necessary water can be supplied to the column using the
Petition 870190088814, of 09/09/2019, p. 44/77 / 56 supply line 35b to maintain the concentrations of water and methyl acetate in the first distillation column 3 at predetermined concentrations (concentrations corresponding to the predetermined concentrations of water and methyl acetate in a mixture to be fed to the first column of distillation 3). In this embodiment, 35b connected to the first distillation column 3 is located at substantially the same height as that at or above the feeding site of the volatile phase component.
[00067] In addition, an addition line 57a and / or 57b for adding an alkaline component is connected to a feed line 36, connected to the second distillation column 5, and / or the second distillation column 5. The addition of the component alkali (an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, or lithium hydroxide) through the addition line (s) converts hydrogen iodide to an alkali metal iodide, resulting in the removal of iodide from hydrogen.
[00068] According to such a process (or production apparatus), since not only can hydrogen iodide be converted to methyl iodide and removed in the first distillation column 3, but also hydrogen iodide can be removed by the alkaline component in the second distillation column 5, high purity acetic acid can be produced.
[00069] Hereinafter, steps and apparatus for producing acetic acid by carbonylation of methanol will be explained in detail.
[Methanol carbonylation reaction] [00070] In the reaction step (carbonylation step), methanol is allowed to continuously react with carbon monoxide using a catalyst system (a catalyst containing a group 8 metal in the Periodic Table, a cocatalyst , and an accelerator) in the presence of water, thus being continuously carbonylated.
[00071] The catalyst containing a group 8 metal from the Periodic Table may include, for example, a rhodium catalyst and a catalyst
Petition 870190088814, of 09/09/2019, p. 45/77 / 56 of iridium (in particular, a rhodium catalyst). The catalyst can be used in the form of a halide (for example, an iodide), a carboxylate (for example, an acetate), a salt of an inorganic acid, or a complex (in particular, a form soluble in a reaction liquid, for example, a complex). As the rhodium catalyst, a rhodium iodide complex (for example, RhI3, [RhI2 (CO) 4], and [Rh (CO) 2I2]), a rhodium-carbonyl complex, and others can be mentioned. These metal catalysts can be used individually or in combination. The concentration of the metal catalyst is, for example, about 10 to 5,000 ppm (based on weight, the same applies below) and particularly about 200 to 3,000 ppm (for example, about 500 to 1,500 ppm) in entire liquid phase of the reactor.
[00072] Like the cocatalyst or accelerator, an ionic iodide or a metal iodide is used which is useful for stabilizing the rhodium catalyst and for inhibiting secondary reactions at a low water content. It is sufficient that the ionic iodide (or metal iodide) can produce an iodide ion in the liquid reaction medium. The ionic iodide (or metal iodide) can include, for example, an alkali metal iodide (for example, lithium iodide, sodium iodide, and potassium iodide). Alkali metal iodide (eg, lithium iodide) also functions as a stabilizer for the carbonylation catalyst (eg, a rhodium catalyst). These cocatalysts can be used alone or in combination. Among these cocatalysts, lithium iodide is preferred. In the liquid phase system (liquid reaction medium) in the reactor, the concentration of the cocatalyst (for example, a metal iodide) is, for example, about 1 to 25% by weight, preferably about 2 to 22% by weight , and more preferably about 3 to 20% by weight in the total liquid phase.
[00073] As the accelerator, methyl iodide is used. In the liquid phase system (liquid reaction medium) in the reactor, the iodide concentration
Petition 870190088814, of 09/09/2019, p. 46/77 / 56 of methyl is, for example, about 1 to 20% by weight, preferably about 5 to 20% by weight, and more preferably about 6 to 16% by weight (for example, about 8 to 14% by weight) in the total liquid phase.
[00074] The reaction mixture usually contains methyl acetate, which is produced by a reaction of acetic acid with methanol. The proportion of methyl acetate can be about 0.1 to 30% by weight, preferably about 0.3 to 20% by weight, and more preferably about 0.5 to 10% by weight (e.g., about 0.5 to 6% by weight) in the entire reaction mixture.
[00075] The reaction can be carried out in the absence of a solvent or it can usually be carried out in the presence of a solvent. As the reaction solvent, acetic acid, which is a product, is commonly used.
[00076] The water content of the reaction system can be a low concentration. The water content of the reaction system can be, for example, not more than 15% by weight (for example, about 0.1 to 12% by weight), preferably not more than 10% by weight (for example, about 0 , 1 to 8% by weight), more preferably about 0.1 to 5% by weight (for example, about 0.5 to 3% by weight), and usually about 1 to 15% by weight (for example , about 2 to 10% by weight) in the total liquid phase in the reaction system.
[00077] The partial pressure of carbon monoxide in the reactor can be for example about 203 to 3,040 kilopascals and preferably about 405 to 1,520 kilopascals. In the carbonylation reaction, hydrogen is formed (or generated) by a displacement reaction between carbon monoxide and water. In order to increase the activity of the catalyst, hydrogen can be fed to reactor 1, if necessary. The partial pressure of hydrogen in the reaction system can be for example about 0.5 to 250 kPa, preferably about 1 to 200 kPa, and more preferably about 5 to 150 kPa (for example, about 10 to 100 kPa) in terms of absolute pressure.
Petition 870190088814, of 09/09/2019, p. 47/77 / 56 [00078] The reaction temperature can be, for example, about 150 to 250 ° C, preferably about 160 to 230 ° C, and more preferably about 180 to 220 ° C. In addition, the reaction pressure (total pressure in the reactor) can be, for example, about 1,520 to 4,053 kilopascals.
[00079] The space-time yield of acetic acid in the reaction system can be, for example, about 5 mol / Lh to 50 mol / Lh, preferably about 8 mol / Lh to 40 mol / Lh, and more preferably about 10 mol / Lh to 30 mol / Lh
[00080] The catalyst mixture (liquid catalyst mixture) containing the catalyst system and water can be continuously fed to reactor 1. In addition, for the purpose of adjusting the reactor pressure, a vapor component (exhaust gas) can be removed from the reactor. As described above, the exhaust gas can be fed to the scrubber system, if necessary, and then a useful component (for example, methyl iodide, acetic acid) can be collected and separated by adsorption treatment and recycled to reactor 1, and / or a useful gaseous component (eg carbon monoxide) can be separated and recycled to reactor 1. In addition, in order to remove part of the reaction heat, the vapor component (exhaust gas) of the reactor can be treated by condensation by cooling with a condenser, a heat exchanger or other means. The vapor component can be separated into a condensed component (a condensate containing acetic acid, methyl acetate, methyl iodide, acetaldehyde, water, and others) and an uncondensed component (a gaseous component containing carbon monoxide, hydrogen, and others ), and the condensed component can be recycled to the reactor to control the reaction temperature of the reaction system, which is an exothermic reaction system. In addition, reactor 1 can be equipped with a removable heat unit (or heat remover) or a cooling unit (for example, a jacket) to control the reaction temperature. The reactor is not necessarily equipped with a
Petition 870190088814, of 09/09/2019, p. 48/77 / 56 removable heat or cooling device. The non-condensing component can be recycled to reactor 1, if necessary.
[Flash Evaporation] [00081] In the Flash Evaporation step (flash device), the reaction mixture continuously fed from the reactor to the flash device (evaporator or flash distillation column) is separated into a volatile phase component (component of lowest boiling point, vapor component) and a low volatile phase component (highest boiling point component, liquid component); where the volatile phase component contains acetic acid and methyl iodide, and the low volatile phase component contains a higher boiling point catalyst component (a metal catalyst component, for example, a metal catalyst and a metal iodide metal). The volatile phase component (lowest boiling point component, vapor component) corresponds to the mixture mentioned above.
[00082] Flash distillation can usually be performed using a flash distillation column. The Flash Evaporation step can be made up of a single step or it can be made up of a plurality of steps in combination. In the Flash Evaporation step, the reaction mixture can be separated into a vapor component and a liquid component with heating (thermostatic flash) or without heat (adiabatic flash), or the reaction mixture can be separated by the combination of these flash conditions. Flash distillation can be carried out, for example, at a temperature of the reaction mixture of about 80 to 200 ° C under a pressure (absolute pressure) of about 50 to 1,000 kPa (for example, about 100 to 1,000 kPa) , preferably about 100 to 500 kPa, and more preferably about 100 to 300 kPa. The formation of by-product (s) or the decrease in catalyst activity can additionally be inhibited (inhibited) by lowering the internal temperature and / or pressure of the flash evaporator compared to those of the reactor 1.
Petition 870190088814, of 09/09/2019, p. 49/77 / 56 [00083] In addition, a portion of the volatile phase component can be recycled to a reactor (for example, as described above, a portion of the volatile phase component has its heat removed and is condensed into a condenser or a heat exchanger and is then recycled to the reactor).
[00084] The volatile phase component contains product acetic acid, in addition, hydrogen iodide, a cocatalyst (such as methyl iodide), methyl acetate, water, by-product (s) (eg, an aldehyde compound such as acetaldehyde or an aldehyde condensation product, a C3-12 alkane carboxylic acid as propionic acid, and a C6-12 alkyl iodide as hexyl iodide), and is fed to a distillation column (separator column) to collect acetic acid. The highest boiling point catalyst component (metal catalyst component or low volatile phase component) is usually recycled to the reaction system. [First distillation] [00085] The following mode explains the distillation of the mixture and the removal of hydrogen iodide in the first distillation column (distillation in the first distillation column). Insofar as distillation is carried out or by adjusting the water concentration and the concentration of methyl acetate in the mixture to predetermined concentrations, this modality is also applicable to other distillations (the subsequent distillation in the second or third distillation column).
[00086] The volatile phase component (mixture) contains hydrogen iodide, water, methyl iodide, acetic acid, and methyl acetate. The water content of the mixture cannot be less than an effective amount to form a high concentration water cone in the distillation column and not more than 5% by weight. When the water content exceeds 5% by weight, a condensed zone of hydrogen iodide is moved downwardly to a position to feed the mixture (volatile phase component) to the distillation column, and thus hydrogen iodide cannot be removed from
Petition 870190088814, of 09/09/2019, p. 50/77 / 56 effectively. The zone having a high concentration of water in the distillation column is moved upwardly towards the top of the column, and hydrogen iodide cannot be removed effectively. According to the present invention, the condensed zone of hydrogen iodide can be formed above the feed position by adjusting the water concentration in the fed mixture to no more than 5% by weight, and hydrogen iodide can be effectively removed due to the methyl acetate (which is concentrated above the feed position) in the mixture, so that corrosion can be inhibited. In addition, even if the condensed zone of hydrogen iodide is not formed in the distillation column, hydrogen iodide in the distillation column according to the equilibrium reaction is converted by methyl acetate, so that corrosion can be inhibited .
[00087] The water content of the mixture can usually be about 0.5 to 4.5% by weight (for example, about 1 to 4.3% by weight) and preferably about 1.2 to 4% by weight. weight (for example, about 1.5 to 3.5% by weight). According to the present invention, a zone of high water concentration within the distillation column can be formed above the position for feeding the mixture (volatile phase component) to the distillation column. In this way, hydrogen iodide is allowed to react with methyl acetate (and also methanol in the mixture and methanol by-product) in the zone of high water concentration to produce methyl iodide and acetic acid.
[00088] The concentration of methyl acetate in the mixture can be selected in the range of no less than an effective amount to convert hydrogen iodide to methyl iodide in the distillation column to no more than 9% by weight (0.5 to 9 % by weight). When the concentration of methyl acetate exceeds 9% by weight, the condensate of the top product shows a low liquid-liquid separation. The concentration of methyl acetate in the mixture can usually be about 0.5 to 8% by weight (for example,
Petition 870190088814, of 09/09/2019, p. 51/77 / 56 about 0.5 to 7.5% by weight), preferably about 0.7 to 6.5% by weight (e.g., about 1 to 5.5% by weight), and more preferably 1.5 to 5% by weight (for example, about 2 to 4.5% by weight), or it can be about 0.5 to 7.2% by weight. The mixture representatively contains about 1 to 4.3% by weight (for example, about 1.3 to 3.7% by weight) of water; and about 0.5 to 7.5% by weight (for example, about 0.8 to 7.5% by weight), preferably about 1.2 to 5% by weight (for example, about 1, 7 to 4.5% by weight) of methyl acetate.
[00089] The methyl iodide content of the mixture can be for example about 25 to 50% by weight (for example, about 27 to 48% by weight), preferably about 30 to 45% by weight (for example, about 32 to 43% by weight), and more preferably about 35 to 40% by weight (for example, about 36 to 39% by weight).
[00090] When distillation is carried out continuously, the concentration of methyl acetate in the mixture can usually be about 0.07 to 1.2 mol / L (about 0.5 to 9% by weight), preferably about 0 , 1 to 1.0 mol / L, and more preferably about 0.3 to 0.8 mol / L. In addition, the water concentration in the mixture can be about 0.28 to 2.8 mol / L (about 0.5 to 5% by weight), preferably about 0.56 to 2.5 mol / L ( about 1 to 4.5% by weight), and more preferably about 0.83 to 2.2 mol / L (about
1.5 to 4% by weight).
[00091] According to the present invention, since the hydrogen iodide can be removed efficiently, the hydrogen iodide content of the mixture is not particularly limited to a specific content. For example, the hydrogen iodide content can be about 10 to 30,000 ppm. The hydrogen iodide content of the mixture (volatile phase component) produced by the methanol carbonylation reaction can be about 100 to 10,000 ppm, preferably about 200 to 7,500 ppm, and most preferably about 300 to 6,000 ppm (for example , about 500 to 5,000 ppm) based on the
Petition 870190088814, of 09/09/2019, p. 52/77 / 56 weight. In addition, the acetic acid content of the mixture is not particularly limited to a specific content, and can be for example about 30 to 70% by weight (for example, about 35 to 75% by weight), preferably about 40 to 65% by weight (for example, about 45 to 62% by weight), and more preferably about 50 to 60% by weight (for example, about 54 to 58% by weight).
[00092] The mixture (volatile phase component) may additionally contain dimethyl ether. The concentration of dimethyl ether can for example be selected within the range of 0.15 to 3% by weight, and can usually be about 0.15 to 2.5% by weight (for example, about 0.17 to 2 , 3 wt%), preferably about 0.2 to 2 wt% (for example, about 0.3 to 1.7 wt%), and more preferably about 0.5 to 1.5 wt% Weight. Most of the rest (residual component) of the mixture is often methanol. As described above, the mixture (volatile phase component) produced by the methanol carbonylation reaction practically contains a minute amount of an impurity (eg acetaldehyde, an aldehyde condensation product, a higher boiling point carboxylic acid such as propionic acid, and a C6-12 alkyl iodide) · [00093] The total amount of each component in the mixture (volatile phase component) is 100% by weight. In addition, although the mixture (volatile phase component) may form a vapor phase (or distillation atmosphere), the amount and concentration of each component mentioned above indicates those of the mixture (volatile phase component) in the form of a liquid. , for example, a condensate (for example, a liquefied condensate formed by cooling to 20 to 25 ° C) obtained by cooling and condensing a vapor phase mixture (a volatile phase component that forms a vapor phase).
[00094] The concentration of water and the concentration of methyl acetate
Petition 870190088814, of 09/09/2019, p. 53/77 / 56 in the mixture can be adjusted by feeding (or supplying) water and / or methyl acetate. The mixture containing a predetermined concentration of water and that of methyl acetate can be directly distilled without adjusting the water concentration and the concentration of methyl acetate. In addition, water and / or methyl acetate can be fed (or supplied or added) to the mixture (volatile phase component) or to the distillation atmosphere (the distillation atmosphere in the distillation column) of the volatile phase component (mixture) to adjust a water concentration to not greater than 5% by weight and a concentration of methyl acetate to 0.5 to 9% by weight to distill the volatile phase component. The water and / or methyl acetate can be fed (or supplied) to the feed line 22 or the first distillation column by using several lines connected to the first distillation column or to a new line.
[00095] The adjustment (or control) of the water concentration and of the methyl acetate concentration can be conducted by analyzing or detecting the concentrations of water and methyl acetate in the mixture (volatile phase component) introduced in the distillation column, and based on the results, and by adjusting the ratio between the components of the mixture in the distillation column, or of a unit or line (which is to supply a fluid to the distillation column) by using a controller (control unit); or it can also be conducted by supplying or adding water and / or methyl acetate. The unit for supplying the fluid to the distillation column can include the reactor or flash apparatus that is located before the distillation column, a decanter to feed condensate to the distillation column, and others.
[00096] The distillation atmosphere (the distillation atmosphere in the distillation column) of the mixture (volatile phase component) can be formed at an appropriate location within the distillation column. In order to convert hydrogen iodide effectively, it is preferred to form the atmosphere
Petition 870190088814, of 09/09/2019, p. 54/77 / 56 distillation at the same height as at or above the feeding site of the volatile phase component.
[00097] In addition, to the volatile phase component as the mixture, or to the distillation atmosphere of the volatile phase component as the mixture, at least one member of the group consisting of methyl acetate, methanol and dimethyl ether (a source of methanol) and if necessary water can be added to form a volatile phase component (mixture) having the concentrations of water and methyl acetate adjusted to distill the volatile phase component (mixture). The amounts of methyl acetate and water to be added are as described above. In addition, the amount of methanol to be added can be for example about 0.01 to 3.8 parts by weight (for example, about 0.1 to 3 parts by weight), preferably about 0.1 to 2 parts , 5 parts by weight (for example, about 0.2 to 2 parts by weight), and more preferably about 0.2 to 1.5 parts by weight (for example, about 0.5 to 1.5 parts by weight) with respect to 100 parts by weight of the mixture (volatile phase component). The amount of dimethyl ether to be added is an amount to form the concentration of dimethyl ether in the mixture as described above. The amount of dimethyl ether to be added can be for example about 0.01 to 2.7 parts by weight (for example, about 0.03 to 2 parts by weight), preferably about 0.05 to 1.5 parts by weight (for example, about 0.07 to 1.3 parts by weight), and more preferably about 0.1 to 1 parts by weight (for example, about 0.2 to 0.8 parts by weight ) with respect to 100 parts by weight of the mixture (volatile phase component).
[00098] In the separator column (first distillation column), the mixture (volatile phase component) is distilled (in particular, continuously distilled) and separated into a top product containing a lower boiling component such as methyl iodide (including methyl iodide produced by a methyl acetate reaction
Petition 870190088814, of 09/09/2019, p. 55/77 / 56 with methanol), and a side cut or bottom chain containing acetic acid, and acetic acid is collected. In the distillation column, usually a volatile phase component is separated as a vapor top product (usually containing methyl iodide, methyl acetate, acetaldehyde, water, and others); a side cut chain (side chain) containing acetic acid is separated as a liquid form by the side cut; and the bottom stream (bottom liquid stream or higher boiling point component, containing acetic acid, water, propionic acid, entrained metal catalyst component, a metal halide, and others) is separated as a liquid form.
[00099] This distillation can significantly reduce the concentration of hydrogen iodide in the second top product and a side cut current. In particular, a side cut-off stream (crude acetic acid stream) having a significantly decreased concentration of hydrogen iodide can be obtained. The concentration of hydrogen iodide in a side shear stream can be for example about 1 to 350 ppm, preferably about 2 to 300 ppm, and more preferably about 3 to 250 ppm.
[000100] The position of the feed line 22 connected (or joined) to the first distillation column 3 (the feeding site of the volatile phase component) is not particularly limited to a specific content. For example, the position of the supply line can be at an upper part, an intermediate part, or a lower part of the distillation column. The mixture is partially fed to the distillation column from an intermediate or lower portion of the distillation column in relation to height. Specifically, the connection (or union) position of the feed line 22 (the feed site of the volatile phase component) is practically located in an intermediate or lower position of the first distillation column 3. Since the mixture feed in a such a way can
Petition 870190088814, of 09/09/2019, p. 56/77 / 56 form a zone of high water concentration between or above an intermediate position of the distillation column and below the reflux line 42, thus the efficient contact of hydrogen iodide with methyl acetate (and methanol) can be increased, which can improve the efficiency of removing hydrogen iodide. In addition, a side cut stream (crude acetic acid stream) of the first distillation column 3 can be removed from either an upper part, an intermediate part, and a lower part of the distillation column, for example, a chain side cut can be removed from the same height as the position (feed site) of the feed line 22 attached to the first distillation column 3 or above or below its position (feed site). A side cutting chain is usually removed from an intermediate part or a lower part (bottom to the middle part) of the distillation column, for example, a place below the connection position of the supply line 22 (the feed site of the volatile phase component) (for example, a place between above the bottom of the column and below the connection position (supply site) of the supply line 22).
[000101] Furthermore, as shown in Fig. 2, the supply line 35b connected to the first distillation column 3 can be located at the same height position as that of the supply site of the volatile phase component of the supply line 22, or it may be located below or above the feeding site of the volatile phase component. The supply line 35b is usually located at the same height position as that of the feeding site of the volatile phase component or above the feeding site of the volatile phase component.
[000102] The bottom chain can be removed (discharged) from the bottom or bottom of the distillation column. Since the bottom stream contains a component useful as a metal catalyst or acetic acid component, the bottom stream can be recycled to the reactor (or step
Petition 870190088814, of 09/09/2019, p. 57/77 / 56 reaction) or the Flash Evaporation step, as described above. In addition, the bottom stream can be recycled to the reaction system or others via a storage vessel having a temporary storage function. The bottom stream can be fed to the second distillation column 5 to remove a high boiling point impurity like propionic acid.
[000103] As the separating column (distillation column), a conventional distillation column can be used, for example, a plate column, a filled column, and a flash distillation column. The distillation column such as a plate column or a filled column can usually be used. The material of (or to form the) distillation column is not limited to a specific material, and a glass material, a metallic material, a ceramic material or other materials can be used. Typically, a distillation column made of metal is used in practice.
[000104] For the column of plates, the theoretical number of plates is not particularly limited to a specific number, and, depending on the species of the component to be separated, it is about 5 to 50, preferably about 7 to 35, and more preferably about 8 to 30. Furthermore, for the purpose of separating acetaldehyde in the distillation column, the theoretical number of dishes can be about 10 to 80, preferably about 20 to 60, and more preferably about 25 to 50. In addition , in the distillation column, the reflux ratio can be selected from, for example, about 0.5 to 3,000, and preferably about 0.8 to 2,000 depending on the number of theoretical dishes mentioned above, or can be reduced by increasing of the theoretical number of dishes.
[000105] The distillation temperature and pressure in the separator column (distillation column) can be appropriately selected. For example, in the distillation column, the internal temperature of the column (usually the
Petition 870190088814, of 09/09/2019, p. 58/77 / 56 temperature at the top of the column) can be adjusted by adjusting the internal pressure of the column, and can be, for example, about 20 to 180 ° C, preferably about 50 to 150 ° C, and more preferably about from 100 to 140 ° C. The temperature of the top of the column can be adjusted to a temperature below the boiling point of acetic acid depending on the internal pressure of the column (for example, below 118 ° C, preferably not above 117 ° C). The temperature of the bottom of the column can be adjusted to a temperature above the boiling point of acetic acid depending on the internal pressure of the column (for example, not below 130 ° C, preferably not below 135 ° C).
[000106] The top product of the first distillation column contains methyl iodide, acetaldehyde, and in addition, methyl acetate, water, methanol, acetic acid, an aldehyde or a carbonyl impurity (such as crotonaldehyde or butyraldehyde), an iodide of C2-12 alkyl, a C3-12 alkane-carboxylic acid, and others.
[Condensation and liquid-liquid separation] [000107] The top product of the first distillation column is cooled and condensed in a cooling unit (condenser), and the resulting condensate from the top product can be clearly separated into an aqueous phase. (light phase, upper phase) and an organic phase (heavy phase, lower phase) in a liquid separation unit (decanter). In this way, the separability of the top product in the aqueous phase (light phase) and the organic phase (heavy phase) can be improved.
[000108] As described above, methyl acetate has a miscibility with both the aqueous phase (light phase) and the organic phase (heavy phase). The liquid-liquid separation decreases at a higher concentration of methyl acetate. Thus, the concentration of methyl acetate in the separated organic phase (heavy phase, lower phase) can be about 0.5 to 15% by weight (for example, about 1 to 15% by weight), preferably about
Petition 870190088814, of 09/09/2019, p. 59/77 / 56 from 1.5 to 14% by weight (for example, about 2 to 10% by weight), and more preferably about 2 to 8% by weight (for example, about 2.5 to 7 % by weight); and the concentration of methyl acetate in the aqueous phase (light phase, upper phase) can be about 0.2 to 8.5% by weight (about 0.4 to 8% by weight), preferably about 0.5 to 7.5% by weight (for example, about 0.6 to 6% by weight), and more preferably about 0.7 to 5% by weight (for example, about 0.8 to 4.5% by weight) or can be about 0.4 to 8% by weight (for example, about 1 to 5% by weight).
[000109] In addition, the liquid-liquid separation in the aqueous phase and the organic phase is sometimes influenced by the other components. In the separated organic phase (heavy phase), the concentration of methyl iodide can be for example about 75 to 98% by weight (for example, about 76 to 98% by weight) and preferably about 78 to 97% by weight (for example, about 80 to 96% by weight), and the acetic acid concentration can be about 1 to 10% by weight (for example, about 2 to 8% by weight) and preferably about 2.5 to 7.5% by weight (for example, about 3 to 7.5% by weight). The concentration of water in the organic phase (heavy phase) is usually not more than 1% by weight. In addition, in the aqueous phase (light phase), the water concentration can be about 50 to 90% by weight (for example, about 55 to 90% by weight) and preferably about 60 to 85% by weight (eg example, about 65 to 80% by weight), and the concentration of acetic acid can be about 10 to 40% by weight (e.g., 12 to 35% by weight) and preferably about 13 to 30% by weight. The percentage sum of all components in the organic phase (heavy phase) is 100% by weight, and the percentage sum of all components in the aqueous phase (light phase) is 100% by weight.
[000110] The concentration of hydrogen iodide in the aqueous phase (light phase) is greater than the concentration of hydrogen iodide in the organic phase (heavy phase). For example, the concentration of hydrogen iodide in the
Petition 870190088814, of 09/09/2019, p. 60/77 / 56 organic (heavy phase) is about no greater than 70 ppm (for example, minute quantity at 60 ppm), while the hydrogen iodide concentration in the aqueous phase (light phase) is about 10 to 1,000 ppm (for example, about 50 to 800 ppm). For this reason, feeding the aqueous phase (light phase) to the third distillation column can improve the efficiency of removing hydrogen iodide. In addition, feeding both the aqueous phase (light phase) and the organic phase (heavy phase) to the third distillation column can additionally improve the efficiency of removing hydrogen iodide.
[000111] In an example shown in the figure, the organic phase (heavy phase) is recycled to reactor 1, and the aqueous phase (light phase) is recycled to the first distillation column 3 to reflux. The organic phase (heavy phase) and / or the aqueous phase (light phase) can be recycled to reactor 1 or it can be recycled to the first distillation column 3.
[Second distillation] [000112] The first side-cut stream (crude liquid acetic acid) usually contains acetic acid, and other components (eg, methyl iodide, methyl acetate, water, and hydrogen iodide) that remain without separation in the first distillation column. A side cut stream (crude liquid acetic acid) of the first distillation column is usually additionally distilled (or dehydrated) in the second distillation column, and separated into a top product (low boiling content) from the top of the column, a stream bottom (high boiling component like a C3-12-alkane-carboxylic acid including propionic acid) from the bottom of the column, and a side shear current (purified acetic acid) from the side of the column, and product acetic acid can be obtained as a side cutting chain.
[000113] In the second distillation column, the removal of hydrogen iodide by an alkaline component is not necessarily necessary.
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As described above, water and hydrogen iodide usually remain in the first side shear stream (crude liquid acetic acid). The distillation of the first side cutting stream (crude liquid acetic acid) condenses hydrogen iodide in the second distillation column. In addition, hydrogen iodide is also produced by a reaction of methyl iodide with water as shown in equation (3) above. In this way, not only is hydrogen iodide together with water concentrated at the top of the second distillation column, but also hydrogen iodide is capable of being produced by a reaction of methyl iodide with water at the top of the second distillation column. Consequently, it is preferable to add an alkaline component to remove hydrogen iodide and to obtain higher purity acetic acid. Specifically, in the second distillation column, the first side cutting stream can be distilled in the presence of an alkali component (for example, an alkali metal hydroxide such as potassium hydroxide), or the mixture containing the first side cutting stream and the alkaline component can be distilled.
[000114] The alkaline component (aqueous alkaline solution) can be added to a side cutting current or to the distillation column by using several routes connected to the distillation column or a new route. In the example shown in the figure, the alkaline component can be added via at least one line from addition lines 57a and 57b. In addition, the position of the feed line 36 (or addition part) and that of an addition line 57b to the second distillation column 5 are not particularly limited. Each position can be located in the middle part of the second distillation column 5 or below or above the middle part of it. Usually, the addition position by the feed line 36 is practically located at or below the intermediate part of the second distillation column 5; the addition position by the addition line 57b is
Petition 870190088814, of 09/09/2019, p. 62/77 / 56 practically located in or above the intermediate part of the second distillation column 5. The addition of the alkaline component according to such a modality allows hydrogen iodide to be efficiently removed before moving or migrating hydrogen iodide to the column top of the second distillation column, even if the alkaline component (non-volatile alkaline component) is easily removed to the bottom of the distillation column. In this way, the concentration of hydrogen iodide in the entire distillation column including not only the bottom of the distillation column but also the top of the distillation column can be efficiently inhibited.
[000115] In the second distillation column, the first side cutting stream can be distilled in the presence of a reactive component having a boiling point less than the boiling point of acetic acid and converting hydrogen iodide to methyl iodide (at least a methanol or a derivative thereof, selected from the group consisting of methanol, dimethyl ether and methyl acetate, particularly methyl acetate) in addition to the alkaline component. Methanol or its derivative (particularly, methyl acetate) can be contained in the first side shear stream, and is preferably added via (through) addition lines 57a, 57b, and other routes. As described above, the reaction of methyl iodide with water occurs easily at the top of the distillation column, while the alkaline component is easily moved to the bottom of the distillation column. Thus, the amount of the alkaline component existing at the top of the distillation column sometimes decreases. The addition of methanol or its derivative, which has a low boiling point, in combination with the alkaline component can more effectively inhibit the hydrogen iodide concentration at the top of the distillation column, and can remove hydrogen iodide by conversion of hydrogen iodide to a metal iodide or methyl iodide.
Petition 870190088814, of 09/09/2019, p. 63/77 / 56 [000116] The water content of the first side cutting stream (crude liquid acetic acid) is usually about 0.3 to 5% by weight (for example, about 0.5 to 4% by weight , preferably about 0.7 to 3.5% by weight, and more preferably about 1 to 3% by weight), and the methyl acetate content thereof is about 0.1 to 3% by weight (e.g. example, about 0.2 to 2.5% by weight, preferably about 0.5 to 2% by weight, and more preferably about 0.7 to 1.5% by weight). The water concentration and methyl acetate concentration of the first side shear stream (crude liquid acetic acid) can also be used to remove hydrogen iodide. Specifically, water and / or acetic acid can be supplied to a side cutting stream or to the second distillation column, together with the addition of the alkaline component or instead of the addition of the alkaline component, to adjust the water concentration and concentration methyl acetate, to convert hydrogen iodide to methyl iodide and to remove hydrogen iodide in the same way as the first distillation. In this case, in order to increase the efficiency of dehydration, it is advantageous to supply methyl acetate without the addition of water.
[000117] The top product of the top of the column or the top of the second distillation column 5 is usually condensed in condenser C4, and the resulting condensate can be returned to reactor 1 and / or the second distillation column 5. When the condensate has a predetermined amount of water and can form separate liquid phases, the condensate can be separated into an aqueous phase and an organic phase in the same way as described above and recycled to reactor 1, the first distillation column 3 and / or the second distillation column 5. Water can be separated as a low boiling component in the second distillation column 5, and the separated water can be fed to reactor 1 or a water extractor 7. The highest boiling point fraction ( second highest boiling point component) as a
Petition 870190088814, of 09/09/2019, p. 64/77 / 56 high boiling (eg propionic acid) can be removed from the bottom of the column or from the bottom of the column, and if necessary can be returned to reactor 1 or discharged from the system. In addition, if necessary, the second side cutting stream (purified acetic acid stream) can additionally be subjected to a purification step such as distillation. [Separation and removal of impurity] [000118] The mode of Fig. 1 shows a process provided with a separation and removal system to remove an impurity (a third distillation column 6, a water extraction column (water extractor) 7 and a fourth distillation column 8). These separation and removal systems are not necessarily necessary. In addition, for the separation and removal of impurity, it is sufficient that the condensate in the decanter 4 is subjected to the separation and removal system. In the case where the condensate is separated into two layers (two liquid phases), the aqueous phase (light phase) and / or the organic phase (heavy phase) can be subjected to the separation and removal system. In addition, the separation and removal system can adopt various separation and removal processes without limiting the process mentioned above.
[Exhaust gas] [000119] The non-condensing component (exhaust gas component) of the condenser can be released from the system. If necessary, the non-condensing component can be recycled to reactor 1 directly, or it can be fed to the scrubber system to separate and collect a useful component (such as methyl iodide or acetic acid) from the non-condensed component, and the useful component can be optionally recycled for reactor 1. For the scrubber system, various separation and purification processes can be used, such as the PSA method (pressure swing adsorption).
EXAMPLES
Petition 870190088814, of 09/09/2019, p. 65/77 / 56 [000120] The following examples are intended to describe this invention in more detail and in no way should it be interpreted as defining the scope of the invention.
(Comparative Example 1) [000121] In a continuous acetic acid production process shown in Fig. 2, methanol was allowed to react with carbon monoxide in a carbonylation reactor, the reaction mixture obtained from the reactor was continuously fed to an apparatus flash and separated into a low volatile phase component (a background component at least containing a rhodium catalyst, lithium iodide, acetic acid, methyl acetate, methyl iodide, water and hydrogen iodide) and a phase component volatile (a liquefied gas component, liquid temperature: 135 ° C) by flash distillation. The volatile phase component was fed to a first distillation column. Supply lines 34b and 35b were not used. In addition, the volatile phase component included 38.2% by weight of methyl iodide (MeI), 0.3% by weight of methyl acetate (MA), 6.5% by weight of water (H2O), 5,000 ppm (based on weight) of hydrogen iodide (HI), and 54.5% by weight of acetic acid (where the acetic acid content was calculated by subtracting the total sum of different components of 100% acetic acid in weight, the same applies below).
[000122] At the first distillation column (number of plates: 20, loading plate: 2nd plate from the bottom), 100 parts by weight of the volatile phase component were fed, distilled at a head pressure of 150 KPA, one column bottom temperature of 140 ° C, column top temperature of 115 ° C and a light phase reflux ratio of 3, and liquid-liquid separated by cooling and decanting to form an aqueous phase and an organic phase. The aqueous phase (light phase, 5 parts by weight) and the organic phase (heavy phase, 38 parts by weight) were recycled to the reactor. The composition (formulation) of the top of the
Petition 870190088814, of 09/09/2019, p. 66/77 / 56 first distillation column (the composition of the top product) was as follows: 63.8% by weight of methyl iodide (Mel), 0.6% by weight of methyl acetate (MA), 23 , 3% by weight of water (H2O), 440 ppm of hydrogen iodide (HI), and 12.3% by weight of acetic acid. The composition of the aqueous phase (light phase) was as follows: 2.6% by weight of methyl iodide (MeI), 0.3% by weight of methyl acetate (MA), 67.0% by weight of water ( H2O), 900 ppm of hydrogen iodide (HI), and 30.0% by weight of acetic acid. The composition of the organic phase (heavy phase) was as follows: 96% by weight of methyl iodide (MeI), 0.7% by weight of methyl acetate (MA), 0.3% by weight of water (H2O) , 200 ppm of hydrogen iodide (HI), and 3.0% by weight of acetic acid.
[000123] From the side cut of the first distillation column (side cut plate: 4 ^a from the bottom) and the bottom of the column, a side cut chain containing acetic acid and a bottom chain containing a entrained catalyst were removed in a proportion of 54 parts by weight and a proportion of 3 parts by weight, respectively. The bottom stream was recycled to the reaction system. A side-cut stream was fed to a second distillation column for dehydration and purification. The composition of a side cut current was as follows: 2.9% by weight of MeI, 0.03% by weight of MA, 5.3% by weight of H2O, 970 ppm of HI, and 90.8% in weight of acetic acid.
[000124] The terms "parts by weight" of a fluid (for example, a volatile phase component, an aqueous phase (light phase) and an organic phase (heavy phase), a side cut current and a bottom current) indicates an hourly flow rate (the same applies below).
[000125] In the continuous reaction process, the following test pieces were placed on the 3rd plate from the bottom (which was the first plate above the loading plate of the first distillation column), the lowest plate of the column (which was the first dish below the dish of
Petition 870190088814, of 09/09/2019, p. 67/77 / 56 loading), and 19th plate from the bottom (which was the top of the column). After being left for 100 hours, each test piece was examined by a corrosion test. The weight of each part before and after the corrosion test was measured to determine an amount of corrosion. Based on the measured amount of corrosion (decrease in weight) and the test piece area, the corrosion rate (decrease in thickness) of the test piece per year has been converted into a thickness (mm) and shown with the unit “mm /THE".
[Test piece]
HB2: manufactured by Oda Koki Co., Ltd, HASTELLOY B2 (nickel based alloy)
HC: manufactured by Oda Koki Co., Ltd, HASTELLOY C (nickel based alloy)
SUS316L: manufactured by Umetoku Inc., SUS 316 Low Carbon (stainless steel) (Comparative Example 2) [000126] The corrosion test was carried out in the same way as in Comparative Example 1 except that the loading mixture (volatile phase component) was adjusted to a water concentration of 4% by weight and then fed to the first distillation column and that the reflux ratio in the first distillation column and the quantities of the light phase and the heavy phase recycled to the reaction system were modified depending on the water concentration.
The composition of the volatile phase component was as follows: 38.5 wt% MeI, 0.3 wt% MA, 4.0 wt% H2O, 5,000 ppm HI, and 56.7 wt% of acetic acid. In addition, the distillation was carried out at a light phase reflux ratio of 5, and the light phase (3.3 parts by weight) and the heavy phase (38.5 parts by weight) were recycled to the reaction system. The column top composition of the first distillation column (the composition of the top product) was as follows: 64.3% by weight of MeI,
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0.6 wt% MA, 23.3 wt% H2O, 470 ppm HI, and 11.8 wt% acetic acid. The composition of the aqueous phase (light phase) was as follows: 2.6% by weight of MeI, 0.3% by weight of MA, 68.0% by weight of H2O, 1200 ppm of HI, and 29.0% by weight of acetic acid. The composition of the organic phase (heavy phase) was as follows: 96% by weight of MeI, 0.7% by weight of MA, 0.3% by weight of H2O, 90 ppm of HI, and 3.0% by weight of acetic acid. From the first distillation column, a side cut stream containing acetic acid and the bottom stream were removed in a proportion of 55.2 parts by weight and a proportion of 3 parts by weight, respectively. The composition of a side cut current was as follows: 2.6% by weight of MeI, 0.04% by weight of MA, 2.8% by weight of H2O, 820 ppm of HI, and 93.6% in weight of acetic acid. The composition of the bottom stream was as follows: 0 wt% MeI, 0.03 wt% MA, 2.6 wt% H2O, 800 ppm HI, and 97.1 wt% acetic acid . The column top temperature of the first distillation column was 115 ° C, and the column bottom temperature of the same was the same as in Comparative Example 1.
(Comparative Example 3) [000128] The corrosion test was performed in the same way as in Comparative Example 2 except that the loading mixture (volatile phase component) was adjusted to a 10% by weight methyl acetate concentration and then fed to the first distillation column and that the reflux ratio in the first distillation column and the quantities of the light phase and heavy phase recycled to the reaction system were modified depending on the concentration of methyl acetate. However, the loading mixture (volatile phase component) had an unsatisfactory liquid-liquid separation in the light phase and the heavy phase. These phases formed a mixed phase or a phase, and the results made the operation unstable after several hours. Thus it was impossible to operate the process operation
Petition 870190088814, of 09/09/2019, p. 69/77 / 56 over a long period of time.
(Examples 1 to 4) [000129] The corrosion test was carried out in the same manner as in Comparative Example 1 except that the loading mixture (volatile phase component) having appropriate concentrations of methyl acetate and water in each Example is fed to first distillation column and that the reflux ratio in the first distillation column and the amounts of the light phase and heavy phase recycled to the reaction system were modified depending on the concentrations of methyl acetate and water.
[000130] The operating conditions in each of the Examples and Comparative Examples are shown in Table 1. The results of the corrosion test are shown in Table 2. The unit of the numerical values in Table 2 is the corrosion rate “mm / A ”.
Table 1
Parts by weight (ppm for HI) Comparative Examples Examples 1 2 3 1 2 3 4 food Flow rate 100 100 100 100 100 100 100 MeI 38.2 38.5 38 38 38.5 37 36 BAD 0.3 0.3 10 0.5 1 4.2 7.2 Water 6.5 4 4 4 4 1.2 2 HI 5,000 5,000 200 4,000 2,000 600 300 B.C 54.5 56.7 47.6 57.1 56.3 57.4 54.7 Side cut Flow rate 54 55.2 43.5 55.2 55.2 54.2 51.6 MeI 2.9 2.6 2.3 1.7 4.0 3.1 2.3 BAD 0.03 0.04 2.6 0.06 0.21 1.26 1.6 Water 5.3 2.8 2.8 2.8 2.7 0.7 1.2 HI 970 820 Traces 290 90 20 5 B.C 90.8 93.6 91.5 94.7 92.7 94.5 94.8 Top of column Flow rate 58 58.3 68.5 58.3 58.3 49.2 62.2 MeI 63.8 64.3 54.9 64.3 63.3 72.2 57.4 BAD 0.56 0.56 14.79 0.93 1.76 7.63 12.36 Water 23.3 23.3 22.6 23.3 23.4 11.9 20.9 HI 440 470 Traces 240 70 70 7 B.C 12.3 11.8 7.8 11.5 11.5 8.2 9.4 Column bottom Flow rate 3 3 3 3 3 3 3 MeI 0.0 0.0 0.0 0.0 0.2 0.1 0.0 BAD 0.03 0.03 0.17 0.17 0.17 1.20 1.18 Water 5.3 2.6 2.6 2.6 2.6 0.6 1.14 HI 440 470 300 290 90 20 5 B.C 94.6 97.3 96.3 97.2 97.0 98.1 97.7 Reflux Flow rate 15 16.5 15 16.5 16.5 6.4 16.8 MeI 2.6 2.6 4 2.6 3.5 3.5 5.1 BAD 0.3 0.3 8.3 0.5 0.9 4.3 7.9 Water 67 68 85 68 68.2 79 69.1 HI 900 1,200 Traces 710 250 70 20 B.C 30.01 28.98 2.7 28.83 27.4 13.18 17.9 Upper phase Flow rate 5 3.3 3.0 3.3 3.3 0.80 1.40
Petition 870190088814, of 09/09/2019, p. 70/77 / 56
(light phase) Parts by weight (ppm for HI) Comparative Examples Examples 1 2 3 1 2 3 4 MeI 2.6 2.6 4 2.6 3.5 3.5 5.1 BAD 0.3 0.3 8.3 0.5 0.9 4.3 7.9 Water 67 68 85 68 68.2 79 69.1 HI 900 1,200 Traces 710 250 70 20 B.C 30.0 29.0 2.7 28.8 27.4 13.2 17.9 Lower phase (heavy phase) Flow rate 38 38.5 50.5 38.5 38.5 42 44 MeI 96 96 73 96 94 84 79 BAD 0.7 0.7 17.1 1.15 2.2 8.2 14.2 Water 0.3 0.3 0.3 0.3 0.4 0.4 0.9 HI 110 90 Traces 50 40 Traces Traces B.C 3.0 3.0 9.6 2.5 3.4 7.4 5.9
Table 2
Test piece position Piece oftest Comparative Examples Examples 1 2 3 1 2 3 4 Top of column (19th plate) Zr 0.00 0.000.00 0.00 0.00 0.00 HB2 0.1 0.090.06 0.05 0.02 0.01 HC 0.22 0.180.12 0.09 0.05 0.02 SUS 316L 0.54 0.30.23 0.18 0.06 0.03 Plate ofupload + 1 Zr 0.00 0.000.00 0.00 0.00 0.00 HB2 0.23 0.180.07 0.05 0.01 0.01 HC 0.51 0.420.18 0.09 0.04 0.02 SUS 316L Not tested Not tested - 0.51 0.22 0.06 0.04 Bottom (Loading plate - 1) Zr 0.00 0.00 - 0.00 0.00 0.00 0.00 HB2 0.27 0.09 - 0.06 0.06 0.04 0.02 HC 0.6 0.21 - 0.11 0.1 0.05 0.03 SUS 316L Not tested 0.6 - 0.4 0.24 0.08 0.05
[000131] Comparative Example 3 failed to operate the device steadily, and corrosion could not be assessed.
[000132] As evidenced in Table 1 and Table 2, in Comparative Example 1, corrosion developed throughout the distillation column. In Comparative Example 2, since a concentrated zone of hydrogen iodide was transferred above the loading plate due to a lower concentration of water in the loading mixture (volatile phase component), the corrosion of the bottom was decreased; although due to a low concentration of methyl acetate in the loading mixture (volatile phase component), corrosion has developed above the loading plate. In Comparative Example 3, although the corrosivity of the entire column was improved, the condensate (liquid removed) of the top product from the top of the column had a very low liquid-liquid separation, so that the distillation column could not be operated stably during
Petition 870190088814, of 09/09/2019, p. 71/77 / 56 a long time. In Example 1, due to a high concentration of methyl acetate in the loading mixture (volatile phase component), methyl acetate was allowed to effectively react with hydrogen iodide. In particular, the test piece “HB2” showed relatively excellent corrosion resistance on the entire column. In Example 2, due to a higher concentration of methyl acetate in the loading mixture (volatile phase component), the test piece “HB2” showed a substantially complete level of corrosion resistance (corrosion rate: no greater than 0 , 05 mm / H). In Examples 3 and 4, due to an even higher concentration of methyl acetate in the loading mixture (volatile phase component), each of the “HB2”, “HC” and “SUS316L” test pieces showed corrosion resistance complete regardless of the change in water concentration.
INDUSTRIAL APPLICABILITY [000133] According to the present invention, since the water concentration and the methyl acetate concentration in the distillation column are adjusted or controlled, the top product of the distillation column can be condensed to form an aqueous phase and an organic phase while preventing corrosion of the distillation column due to hydrogen iodide. Accordingly, the present invention advantageously allows for continuous industrial production of acetic acid.
DESCRIPTION OF REFERENCE NUMBERS ··· Reactor ··· Flash evaporator ··· First distillation column (separating column) ··· Decanter ··· Second distillation column
34a, 34b, 35a, 35b ··· Supply line

权利要求:
Claims (15)
[1]
1. A process for producing acetic acid, comprising:
continuously feed the reaction mixture into the flash evaporator apparatus for flash distillation to form a volatile phase component as a mixture, continuously distill the mixture containing hydrogen iodide, water, methyl iodide, acetic acid, and methyl acetate to form a top vapor containing a lower boiling point component, and condensing the top vapor to form separate liquid phases, characterized by the fact that the mixture contains an effective amount of water in a concentration of no more than 5% by weight and methyl acetate in a concentration of 0.5 to 9% by weight, and is continuously separated, in the distillation step, in the top vapor containing methyl iodide, a liquid side cutting stream containing acetic acid, and a liquid stream of bottom containing acetic acid.
[2]
2. Process according to claim 1, characterized by the fact that the mixture has a concentration of methyl acetate from 0.07 to
1.2 mol / L and a water concentration of 0.28 to 2.8 mol / L, and is continuously distilled.
[3]
Process according to claim 1 or 2, characterized by the fact that the mixture contains 0.5 to 4.5% by weight of water and 0.5 to 8% by weight of methyl acetate, and is subjected to distillation step.
[4]
Process according to any one of claims 1 to 3, characterized in that the mixture additionally contains dimethyl ether.
[5]
Process according to any one of claims 1 to 4, characterized in that the mixture is fed to a column of
Petition 870190088814, of 09/09/2019, p. 73/77
2/4 distillation from an intermediate or lower portion of the tall distillation column.
[6]
Process according to any one of claims 1 to 5, characterized by the fact that a zone that has a high concentration of water is formed within the distillation column in a position higher than the position in which the mixture is fed to the column of distillation. Distillation, in the zone having a high concentration of water, hydrogen iodide is allowed to react with methyl acetate to produce methyl iodide and acetic acid, and the distillation provides the top vapor containing the resulting methyl iodide.
[7]
Process for producing acetic acid according to any one of claims 1 to 6, characterized in that:
methanol is allowed to continuously react with carbon monoxide by using a catalyst containing a group 8 metal from the Periodic Table, an ionic iodide (such as lithium iodide), and methyl iodide in the presence of water, the reaction product is separated into a low volatile phase component and a volatile phase component by flash distillation, the volatile phase component as the mixture is distilled to form the top vapor containing methyl iodide, the side-cut liquid stream and the bottom liquid stream containing acetic acid, and the top vapor is condensed to form an aqueous phase and an organic phase, and the volatile phase component is distilled while being adjusted to a water concentration of an effective amount and not greater than 5% by weight and a concentration of methyl acetate from 0.5 to 9% by weight in an atmosphere of distillation of the volatile phase component in terms of a liquid or condensed form.
Petition 870190088814, of 09/09/2019, p. 74/77
3/4
[8]
Process according to any one of claims 1 to 7, characterized in that at least one member of the group consisting of methyl acetate, methanol and dimethyl ether, and if necessary water, is added to the volatile phase component such as mixture or a distillation atmosphere of the same as the mixture to adjust the concentrations of water and methyl acetate, and the resulting volatile phase component is distilled.
[9]
Process according to any one of claims 1 to 8, characterized in that a distillation atmosphere of a volatile phase component is formed in the distillation column at a height equal to or greater than the height of a feed site of the volatile phase component.
[10]
Process according to any one of claims 1 to 9, characterized in that the mixture contains 1 to 4.3% by weight of water and 0.8 to 7.5% by weight of methyl acetate, and is subjected to distillation step.
[11]
Process according to any one of claims 1 to 10, characterized in that the mixture has a hydrogen iodide concentration of 100 to 10,000 ppm, and is subjected to a distillation to form the side cutting current having a concentration of hydrogen iodide from 1 to 350 ppm.
[12]
Process according to any one of claims 1 to 11, characterized in that the separated liquid phases are a lower phase and an upper phase, the lower phase has a concentration of methyl acetate from 1 to 15% by weight, and the upper phase has a concentration of methyl acetate from 0.4 to 8% by weight.
[13]
13. Method for improving liquid-liquid separation of a condensate while reducing a concentration of hydrogen iodide in a top product and a side shear, comprising:
continuously feed the reaction mixture into the device
Petition 870190088814, of 09/09/2019, p. 75/77
4/4 flash evaporator for flash distillation to form a volatile phase component as a mixture, continuously distill the mixture containing hydrogen iodide, water, methyl iodide, acetic acid, and methyl acetate to form a top vapor containing a lower boiling point component, and condensing the top vapor to give a condensate containing separate liquid phases, characterized by the fact that the mixture contains an effective amount of water in a concentration not greater than 5% by weight and methyl acetate at a concentration of 0.5 to 9% by weight, and is continuously separated, in the distillation step, in the top vapor containing methyl iodide, a liquid side cut stream containing acetic acid and a liquid bottom stream containing acetic acid .
[14]
14. Method according to claim 13, characterized in that the concentration of hydrogen iodide in the top vapor and the side shear current is reduced by adjusting a concentration of methyl acetate in the mixture to 0.5 to 8 % by weight.
[15]
15. Method according to claim 13 or 14, which improves liquid-liquid separation of condensate, characterized by the fact that the concentrations of methyl iodide and methyl acetate in the lower phase are adjusted to 76 to 98% by weight and 1 to 15% by weight, respectively (with the proviso that the total of components in the lower phase is 100% by weight), and the concentrations of water and methyl acetate in the upper phase are adjusted to 50 to 90% by weight and 0.4 to 8% by weight, respectively (with the proviso that the total of components in the upper phase is 100% by weight).

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WO2019229857A1|2018-05-29|2019-12-05|株式会社ダイセル|Acetic acid production method|

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US10752572B2|2018-05-29|2020-08-25|Daicel Corporation|Method for producing acetic acid|

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US10807935B2|2018-11-02|2020-10-20|Celanese International Corporation|Process for continuous acetic acid production|

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KR102357192B1|2019-08-28|2022-02-07|한국과학기술원|Complex Heat Exchange Type Fractionation Distillation Device of Multi-Component Azeotropic Mixture and Fractionation Distillation Method Using the Same|

法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-09| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-03-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-04-14| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2012057570|2012-03-14|

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PCT/JP2013/056766|WO2013137236A1|2012-03-14|2013-03-12|Acetic acid production method|

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