process to produce acetic acid

专利摘要:
A process for producing acetic acid Acetic acid is produced while efficiently inhibiting the condensation of hydrogen iodide on a distillation column (second distillation column) to purify crude acetic acid by further distillation. A process for producing acetic acid comprises an acetic acid collection step for feeding a first distillation column with a volatile component containing at least acetic acid, methyl acetate, methyl iodide, water, and hydrogen iodide, separating a first lower boiling component as a supernatant, and collect a first stream of liquid containing mainly acetic acid, and an acetic acid purification step to feed a second distillation column with the first stream of liquid, separate a second lower component boiling point as a supernatant, and collect a second stream of acetic acid-containing liquid, wherein an alkaline component is added or mixed with the first stream of liquid in modes (1) and / or (2), to distill a liquid object to be treated containing the first stream of liquid and the alkaline component in the second distillation column: (1) oc The alkaline component is added or mixed with the first liquid stream, before the first liquid stream is fed into the second distillation column, (2) the second distillation column, the alkaline component is added or mixed at the same height level or a height level greater than a height level at which the first stream of liquid is fed.
公开号:BR112013014814B1
申请号:R112013014814
申请日:2011-12-01
公开日:2019-09-03
发明作者:Miura Hiroyuki；Shimizu Masahiko；Saito Ryuji；Ueno Takashi
申请人:Daicel Corp；
IPC主号:

专利说明:

PROCESS TO PRODUCE ACETIC ACID
Technical Area [0001] The present invention relates to a process to produce acetic acid, while efficiently inhibiting the increase in the concentration of hydrogen iodide (or condensation of hydrogen iodide) in a distillation column (second distillation column), to purify crude acetic acid by further distillation.
Prior Art [0002] Various industrial processes for the production of acetic acid are known. Among others, an industrially excellent process includes a process, which comprises continuously allowing methanol to react with carbon monoxide, using a metal catalyst (such as a rhodium catalyst), an ionic iodide (for example, lithium iodide ), and methyl iodide in the presence of water, to provide acetic acid. In addition, recently, an improvement in reaction conditions and catalysts has been investigated, and an industrial process to produce acetic acid with highly efficient production has been developed, through the addition of a catalyst stabilizer (such as an iodide salt) and reaction under a low water content condition compared to the conventional system.
[0003]
Examples of the acetic acid production process include a process for producing purified acetic acid, which comprises allowing methanol to be reacted with carbon monoxide, subjecting the resulting reaction mixture containing acetic acid to distillation (instant distillation) in an instant evaporator, submitting a component vaporized by distillation
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2/81 to a first distillation column, to separate a stream of liquid containing acetic acid, as a main component and water, and others, subject the stream containing acetic acid to a second distillation column, to remove water and others, and separate a stream of acetic acid, like a stream of liquid. In this process, condensation of hydrogen iodide, on the first distillation column or on the second distillation column, can precipitate corrosion of the distillation column. Since it is preferable that the increase in the concentration of hydrogen iodide in the distillation column is inhibited, the decrease in the concentration of hydrogen iodide in the distillation column is being attempted.
[0004] For example, Published Japanese Patent Application No. 2006-160645 (JP-2006-160645A, Patent Document 1) describes a process for distilling a mixture containing hydrogen iodide and water, which comprises distilling the mixture with a water content of not more than 5% by weight, in a system distillation to prevent condensation of hydrogen iodide in the distillation system. With respect to a mixture applying the process, the document reveals that the process can be applied to a light component, which is separated from the reaction mixture by a first distillation (distillation by an instant evaporator or the like), and is rich in a component with a low boiling point (for example, water, an alcohol, an alkyl iodide, a carboxylic acid or an acid anhydride thereof, a carboxylic ester, and hydrogen iodide). In the process described in the document, however, the hydrogen iodide concentration is reduced by adjusting the water concentration based on the equilibrium theory, and there are limitations to decreasing the
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3/81 concentration of hydrogen iodide. Thus, it is difficult to lower the hydrogen iodide concentration to a high level. In addition, since the process described in this document is applied to a light component obtained by instant distillation, the condensation of hydrogen iodide in a distillation column, to further purify the acetic acid separated from the light component, does not can be inhibited.
[0005] In addition, Published Japanese Patent Application No. 2009-501129 (JP-2009-501129A, Patent Document 2) describes a process for producing purified acetic acid, which comprises feeding a stream of acetic acid containing acetic acid, a hydrogen halide, a lower boiling component and a highest boiling component, to a first distillation column, separate a part containing the lowest boiling current from the lowest boiling component, and a portion containing the highest boiling current from the highest boiling component boiling, in the first distillation column, extract a side stream containing at least acetic acid by side cutting, feed the side stream to a second distillation column, separate a part containing the lowest boiling current from the lowest point component boiling point, and a part containing the current with the highest boiling point of the component with the highest boiling point, in the second column of distillation, and extract a side stream containing acetic acid by side cutting to collect (or recover) acetic acid; which further comprises feeding (i) the first distillation column with water, or water and at least one first component (A) selected from the group consisting of an alcohol corresponding to the carboxylic acid and having n
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4/81 carbon atom (s), and an alcohol ester with carboxylic acid, or (ii) the first distillation column with the first component (A) with a height (position) level less than an opening side chain to conduct side cut of the side chain containing the carboxylic acid with n + 1 carbon atoms.
[0006] This document reveals that at least one second component (B), selected from the group consisting of (b1) methanol, (b-2) methyl acetate, (b-3) an alkali metal hydroxide (for example, potassium hydroxide), (b-4), an alkali metal acetate (eg, potassium acetate), and (b-5) a hypophosphorous acid, can generally be fed into the second distillation column, from at least a higher or lower position than a side opening by side cutting (side chain opening), to conduct side cutting of the acetic acid stream, in order to reduce the concentration of hydrogen iodide contained in the side cut extracted acetic acid stream , and avoid condensation of hydrogen iodide in the distillation column. In the Examples of that document, potassium hydroxide is fed to the second distillation column, at a height level (or plate) less than the side chain opening, or at a height level (or plate), which is higher than the side and bottom chain opening than a feed opening to feed the acetic acid chain to the second distillation column.
[0007] The process described in the document conducts, to a certain extent, the condensation of hydrogen iodide in the second distillation column. However, hydrogen iodide is contained in the acetic acid stream, to be fed into the second column
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5/81 distillation, and is moved together with water to an upper (or top) part of the second distillation column, by distillation, while potassium hydroxide, or the like, is moved downwards. Therefore, when potassium hydroxide is fed into the second distillation column, at a height level lower than an opening to feed the acetic acid stream in the second distillation column, as described in the document, it is difficult to effectively inhibit condensation of hydrogen iodide at the top (or top) of the second distillation column. In addition, in the process described in the document, although the second component (B) is fed, in order to decrease hydrogen iodide contained in the side stream by lateral cut fed from the first distillation column, in a real system, not only iodide of hydrogen contained in the side stream by side cut, but also hydrogen iodide recently produced by a reaction of methyl iodide in water, and other reactions at the top of the second distillation column, exist in the second distillation column. Condensation of hydrogen iodide at the top of the distillation column cannot be inhibited efficiently using potassium hydroxide or the like. According to the process described in the document, even if the quality of acetic acid can be improved, by reducing the concentration of hydrogen iodide (HI) contained in the side stream by side cutting, it is difficult to reduce the concentration of hydrogen iodide to a high level throughout the second distillation column. In addition, the hydrogen iodide concentration in the entire second distillation column can be reduced by feeding an alkali metal hydroxide (for example,
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6/81 potassium) at a height level less than the feeding opening of the second distillation column, and feeding an alcohol (eg methanol) at the same time (or in the same position) as the alkali metal hydroxide, or at a lower position than the alkali metal hydroxide feed position. In this case, however, a distillation column with a large diameter column is required, and the process is inefficient.
[0008] Incidentally, Japanese Patent Application Published N °. 4861414 (JP-48-61414A, Patent Document 3) describes a method for extracting (or separating) iodine from acetic acid, which comprises introducing a stream of acetic acid, containing iodine as an impurity, into a part of the medium of both ends of a first distillation column, introduce an alkali metal or alkaline earth metal compound (an oxide, hydroxide, carbonate, bicarbonate or weak organic acid salt of an alkali metal or alkaline earth metal) into the middle of the two ends of the first distillation column, extract a supernatant product stream from the first distillation column, introduce the product stream into a middle part of both ends of a second distillation column, and extract a stream of substantially acetic acid iodine-free from the bottom of the second distillation column, and extract a fraction of supernatant containing iodine from the second distillation column will.
[0009] According to the method described in the document, the alkali metal, or alkaline earth metal compound, is fed to the product stream from the first distillation column, or the second distillation column. However, currents of
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7/81 product are supernatants in the first and second distillation columns, and this method is quite different, in the acetic acid production process, from the aforementioned process for separating the acetic acid stream as a liquid component. For example, the method described in the document is intended to decrease hydrogen iodide contained in a stream of purified product, and the method is quite different in the liquid to be treated, from the above mentioned process.
Summary of the Invention
Problems to be solved by the invention [00010] It is, therefore, an object of the present invention to provide a process to produce acetic acid, while effectively inhibiting (or preventing) the increase in the concentration of hydrogen iodide (or condensation of iodide) hydrogen), in a distillation column (second distillation column), to purify crude acetic acid, from which a component with a lower boiling point was removed by distillation, by further distillation.
[00011] Another object of the present invention provides a process for producing acetic acid, the process preventing corrosion of a second distillation column.
Means to solve the problems [00012] The inventors of the present invention carried out intensive studies to reach the above objects and, finally, they discovered that, in a process to produce acetic acid, which comprises separating a component with a lower boiling point, from a volatile component containing at least acetic acid, methyl acetate, methyl iodide, and hydrogen iodide, by distillation, feeding a second column of
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8/81 distillation (dehydration column) with the resulting crude acetic acid, and separate water and other elements, to obtain purified acetic acid, condensation of hydrogen iodide throughout the second distillation column can be inhibited (or prevented ) at a high level, by adding an alkaline component to the crude acetic acid in a specific embodiment, and subjecting the mixture to distillation; and that the inhibition of condensation can inhibit corrosion of the entire second distillation column. The present invention was carried out based on the above conclusions.
[00013] That is, the process of the present invention includes a process for producing acetic acid, which comprises a step of collecting acetic acid to feed a first distillation column with a volatile component, containing at least acetic acid, methyl acetate, methyl iodide, water and hydrogen iodide, separate a lower boiling first component as a supernatant (volatile component or vaporized component), and collect a first liquid stream (crude acetic acid liquid stream, first liquid component) , containing mainly acetic acid, and an acetic acid purification step to feed a second distillation column with the first liquid stream, additionally separate a second low-boiling component as a supernatant, and collect a second liquid stream ( liquid stream of purified acetic acid, the second liquid component) containing acid of the acetic; wherein an alkaline component is added or mixed in the following ways (1) and / or (2) to distill a liquid object to be treated (or a liquid object) containing the first stream of liquid and the alkaline component in the second
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9/81 distillation column (or the first stream of liquid to be subjected to distillation in the presence of the alkaline component):
(1) the alkaline component is added or mixed with the first liquid stream, before the first liquid stream is fed into the second distillation column, (2) in the second distillation column, the alkaline component is added or mixed at the same level the height (or position) than a height level (or position), at which the first stream of liquid is fed, or at a height level (or position) greater than the height level (or position), at which the first liquid stream is fed.
[00014] Incidentally, in mode (2), the feed position of the first liquid component is generally located in a position higher than a position, in which the second liquid component is collected (extracted as a bottom fraction or as a lateral fraction by cutting side) of the second distillation column.
[00015] To this end, probably due to the fact that hydrogen iodide, in the first liquid component, is easily allowed to contact or react with the alkaline component (neutralization) in the second distillation column, before the alkaline component is moved to the bottom from the second distillation column, condensation of hydrogen iodide across the second distillation column can be effectively inhibited.
[00016] According to the process of the present invention, the first component with the lowest boiling point is separated by the first distillation column. For example, in the first liquid component, the concentration of methyl iodide can be from about 10 ppm to 8% by weight, [for example, less than 4% in
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10/81 weight (for example, from about 10 ppm to 3.5% by weight)], the concentration of methyl acetate can be about 0.1 to 8% by weight, the concentration of water can be about 0.2 to 20% by weight (in particular, not more than 3% by weight), and the hydrogen iodide concentration can be not more than 1000 ppm based on weight (for example, not more than 100 ppm, preferably from about 1 to 30 ppm). In addition, the amount to be added of the alkaline component can be, for example, from about 1 to 2000 molar equivalents to 1 mol of hydrogen iodide in the first stream of liquid, and the alkaline component can be added in order to that the concentration of the alkaline component in the liquid object may not exceed 100,000 ppm based on weight.
[00017] In mode (1), the contact temperature of the first liquid stream (or component) and the alkaline component can be from about 100 to 170 ° C, and the time, from when the first liquid stream (or component) and the alkaline component are mixed, even when the mixture is fed into the second distillation column, it can be no longer than 5 minutes.
[00018] According to the present invention, once the alkaline component is added in a specific way, the alkaline component can be used for neutralizing hydrogen iodide, certainly, so that the amount to be added of the alkaline component can be reduced.
Therefore, the condensation or accumulation of an excessive amount of the alkaline component in the second distillation column (for example, a lower part of the distillation column) can be effectively inhibited. For example, in the process, the amount to be added of the alkaline component
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11/81 can be no more than 85 molar equivalents (for example, no more than 80 molar equivalents) relative to 1 mol of hydrogen iodide in the first stream of liquid, and the alkaline component can be added in order that the concentration of the alkaline component in the liquid object may not be greater than 1000 ppm (for example, not greater than 800 ppm), based on weight.
[00019] According to the present invention, a second distillation can be carried out in the presence of the added alkaline component and at least one component (A) having a lower boiling point than the boiling point of acetic acid and being selected from the group consisting of an alcohol, an ether, and an ethyl ester. Since component (A) tends to exist in an upper part of the distillation column, the tendency and neutralization with the alkaline component are combined to efficiently inhibit the production of hydrogen iodide, due to a reaction of methyl iodide with water at the top of the second distillation column. In this way, for example, the liquid object, in which component (A) exists at a concentration of not less than 0.2% by weight (for example, not less than 1% by weight), can be distilled in the second column of distillation.
[00020] Representatively, component (A) can be a component containing at least one member selected from the group consisting of methanol, dimethyl ether, and methyl acetate.
[00021] Component (A) can be contained in the first stream of liquid (for example, when methyl acetate is contained in a sufficient concentration, in the first stream of liquid), or it can be recently (or
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12/81 separately) added. That is, component (A) can be allowed to exist in the liquid object, by adding component (A) to the first liquid stream. Representatively, component (A) can be allowed to exist in the liquid object, by (i) adding component (A) to the first liquid stream, before the first liquid stream is fed into the second distillation column and / or (ii), in the second distillation column, the addition of component (A) to the first liquid stream, at the same height (or position) level as a height (or position) level, in which the first liquid stream is fed (for example, a plate to be fed or supplied), or at a height (or position) level higher than the height level, where the first stream of liquid is fed [for example, a plate higher than ( for example, the first top plate) a plate, into which the first stream of liquid is fed].
[00022] In the process of the present invention, the material of (or to form the) second distillation column can comprise an alloy (e.g., a nickel-based alloy). The present invention achieves corrosion inhibition, and even a second distillation column made of such a relatively corrosive material can preferably be used.
[00023] The process of the present invention further generally comprises a reaction step, to allow methanol to continuously react with carbon monoxide in the presence of a catalyst system, comprising a metal catalyst, an ionic iodide (for example, a metal iodide alkaline, such as lithium iodide), and methyl iodide in a carbonylation reactor, and an instant distillation step for continuous supply to a vaporizer (instant evaporator)
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13/81 with a reaction mixture from the reactor, and evaporation of a volatile component containing at least the acetic acid product, methyl acetate, methyl iodide, water and hydrogen iodide by instant distillation, and the volatile component obtained through these steps it is fed to the first distillation column.
[00024] For the process to comprise the instant distillation step, in the instant distillation step, the reaction mixture can be separated into the volatile component and a liquid catalyst mixture containing at least the metal catalyst and ionic iodide, the instant distillation can be conducted, provided that the concentration of methyl acetate is not less than
0.6% by weight. Probably because of the instant distillation under the condition that it can inhibit an increase in the concentration of hydrogen iodide in the instant evaporator and, in addition, it can efficiently increase the concentration of methyl acetate in the second distillation column, increase in the concentration of hydrogen iodide in the second distillation column can still be efficiently inhibited.
[00025] The concentration of methyl acetate in the liquid catalyst mixture can be not less than
1% by weight (in particular, not less than 1.5% by weight).
In addition, the water concentration in the liquid catalyst mixture can be no more than 15% by weight. The concentration of the metal catalyst in the liquid catalyst mixture can be not less than
300 ppm, based on weight. In addition, the concentration of acetic acid in the 40% by weight liquid catalyst mixture.
[00026] Representatively, it cannot be less than with respect to
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14/81 concentration of each component in the liquid catalyst mixture, the ionic iodide concentration may not be greater than 50% by weight, the concentration of methyl iodide may not be greater than 5% by weight, the concentration of acetic acid may be about 45 to 90% by weight, and the water concentration can be no more than 10% by weight. In particular, with regard to the concentration of each component in the liquid catalyst mixture, the concentration of ionic iodide can be not more than 40% by weight, the concentration of methyl iodide can be about 0.01 to 4% by weight, the concentration of acetic acid can be about 50 to 85% by weight, the concentration of methyl acetate can be about 0.7 to 5% by weight, and the concentration of water can be about 0.8 to 8% by weight.
[00027] In the instant distillation step, the instant distillation can be conducted at an absolute pressure of about 0.1 to 0.5 MPa, and the temperature of the liquid catalyst mixture (or the instant distillation temperature) can be about 100 to 170 ° C.
[00028] In the process of the present invention, the concentration of each component in the flash evaporator can be adjusted by adding each component or component (s) to produce each component. For example, the concentration of methyl acetate in the liquid catalyst mixture can be adjusted (for example, adjusted to not less than 0.6% by weight), by adding or mixing methyl acetate and / or a production component of methyl acetate to the reaction mixture and / or to the instant evaporator.
[00029] Throughout the description, the total part (s) of any / any component (s) existing in the same mixing system (such as the first fraction of liquid) is not
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15/81 greater than 100% by weight, and the proportions of all components is 100% by weight, in total.
Effects of the Invention [00030] According to the process of the present invention, acetic acid can be produced, while efficiently inhibiting (or preventing) an increase in the concentration of hydrogen iodide in a distillation column (second column of distillation), to purify crude acetic acid, from which a lower boiling component was removed by distillation, by further distillation. In addition, according to the present invention, corrosion of the second distillation column can be inhibited. Thus, distillation can be carried out efficiently, without forming the second distillation column, with a high quality material having a high resistance to corrosion. Thus, according to the present invention, the second distillation column can be made of a cheap or low quality material, so that the cost of the acetic acid production process can be reduced efficiently.
Brief Description of the Drawings [00031] Fig. 1 is a diagram for explaining an acetic acid production process (or production apparatus), in accordance with an embodiment of the present invention.
Description of Embodiments [00032] Hereinafter, the present invention will be explained in detail with reference to the drawings. FIG. 1 is a diagram (a flow chart, a schematic process drawing, or a schematic plan drawing) to explain an acetic acid production process (or production apparatus), according
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16/81 with an embodiment of the present invention.
[00033] The embodiment of Fig. 1 shows a continuous process (or apparatus) for producing acetic acid from a liquid reaction medium (or reaction mixture), generated by a continuous carbonyl reaction of methanol with carbon monoxide carbon in the presence of a catalyst system comprising a rhodium catalyst, as a metal catalyst, and a cocatalyst [lithium iodide as an ionic iodide (or iodide salt) and methyl iodide], as well as acetic acid, methyl acetate, and a finite amount of water.
[00034] The process (or production apparatus) comprises a reactor (reaction system) 1 to perform the aforementioned methanol carbonylation reaction; a vaporizer or evaporator (instant evaporator) 2 to separate a volatile component or a stream of acetic acid (a fraction of the lowest boiling point) containing at least the acetic acid product, methyl acetate, methyl iodide, water, and the by-product hydrogen iodide, and a mixture of liquid catalyst (a low volatility component or a higher boiling fraction) containing mainly a catalyst component (a higher boiling component) (for example, a rhodium catalyst and lithium iodide) from a liquid reaction medium (or a reaction mixture, or a reaction solution), which is introduced from reactor 1, via a feed line 14, and contains acetic acid generated by the reaction ; a first distillation column (dividing column) 3 for separating or extracting at least part of a lower boiling fraction (first lower boiling fraction) containing a lower boiling component (eg methyl iodide, acetate
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17/81 methyl, and acetaldehyde) out of the volatile component introduced from vaporizer 2, through a supply line 15, as a supernatant from an upper part of its column, and extract or discharge a first stream of liquid containing acetic acid (a stream of acetic acid, a stream of crude acetic acid), as a side stream by side cutting; a second distillation column 4 to extract at least part of a lower boiling fraction (second lower boiling fraction) containing a lower boiling component (such as water), as a supernatant over an upper part of its column out of the acetic acid stream introduced from the first distillation column 3, through a feed line 23, by side cut, separate at least part of a component with a higher boiling point (impurities with a higher boiling point ) (containing, for example, water and propionic acid), from a lower part of the column, and obtain a second stream of liquid containing acetic acid (a stream of acetic acid, purified stream of acetic acid), by means of a power line 29, as a side chain by side cut.
[00035] This process is equipped with a condenser or a heat exchanger to condense a component introduced through each line. Specifically, the reactor 1 is equipped with a condenser 5 to condense a condensable component in a flue gas (vapor) discharged through a discharge line 11; a recycling line 12 for recycling a liquid component condensed by the condenser 5 to the reactor 1; and a discharge line 13 for discharging a gaseous component, which is a non-condensing component in condenser 5. [00036] In addition, vaporizer 2 is equipped with a
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18/81 heat exchanger 6 to cool a mixture of liquid catalyst (or lower fraction) separated by vaporizer 2 and discharged from the bottom of vaporizer 2, through a discharge line 18; a recycling line 19 for recycling the liquid catalyst mixture cooled by the heat exchanger 6 to reactor 1; a heat exchanger 7 for condensing a condensable component in part of the volatile component (or volatile phase) discharged as a supernatant by the vaporizer 2 and introduced through a supply line 15a; a discharge line 16 for discharging a gaseous component, which is a non-condensable component in the heat exchanger 7; and a recycling line 17 for recycling a liquid (or liquefied) component containing acetic acid condensed by heat exchanger 7 to reactor 1.
[00037] In addition, the first distillation column 3 is equipped with a condenser 8 to condense a condensable component in the fraction with the lowest boiling point or supernatant discharged through a discharge line 20; a recirculation line 22 for recycling a liquid component condensed by the condenser 8 to the reactor 1; a recycling line 22a for recycling (or refluxing) part of the liquid component condensed by the condenser 8, to the first distillation column 3; a discharge line 21 for discharging a gaseous component, which is a non-condensable component in the condenser 8; and a line 24 to discharge a higher boiling fraction to the first distillation column 3 and recycle the higher boiling fraction to reactor 1. In this context, the liquid component recycled to the first distillation column 3 is used to reflux in the first distillation column 3.
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19/81 [00038] The second distillation column 4 is equipped with a condenser 9 to condense a condensable component in the fraction with the lowest boiling point or supernatant discharged through a discharge line 25; a recycling line 27 for recycling (or refluxing) a liquid component or lower boiling fraction condensed by the condenser 9 to the second distillation column 4; a discharge line (recycling line) 26 to separate part or all of the liquid component or lower boiling point condensed by condenser 9 from line 27 and recycle the separate component or fraction to reactor 1 ; and a line 28 for feeding a separate gas in the condenser 9 to a washer 10, through a line 13.
[00039] This process shown in FIG. 1 further comprises a scrubber or scrubber system 10 for recovering gaseous components (or non-condensing components) or other more discharged by the condenser 5, the heat exchanger 7, and the condenser 8, and abandoning the components and / or recycling the components for the reaction system (for example, reactor 1). In this context, a line for recycling the gaseous component, or others, from the washing system 10 to the reaction system (for example, reactor 1) is omitted in FIG. 1.
[00040] Hereinafter, the process shown in FIG. 1 will be explained in more detail.
[00041] Methanol as a liquid component, and carbon monoxide as a gaseous reagent, can be continuously fed to reactor 1 at a predetermined speed, and a catalyst mixture (a liquid catalyst mixture) containing a carbonylation catalyst system [ a catalyst system comprising a catalyst component
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20/81 main (for example, a rhodium catalyst), and a cocatalyst (for example, lithium iodide and methyl iodide)] and water can be continuously fed to reactor 1. In addition, fraction (s) (for example , in the form of a liquid) containing the lowest boiling point fraction (s) and / or the highest boiling point fraction (s) of the next step (s) (for example, vaporizer 2, the first and second distillation columns 3 and 4, the heat exchanger 7, and the washing system 10) can also be fed to reactor 1. Then, inside the reactor 1, a liquid phase reaction system containing the reagent and the component with the highest boiling point, such as the metal catalyst component (for example, a rhodium catalyst), and the ionic iodide (for example, lithium iodide) is in equilibrium with a vapor-phase system containing carbon, by-products by reaction (hydrogen, methane, carbon dioxide), and a compone vaporized from a lower boiling point (eg, methyl iodide, acetic acid as a product, and methyl acetate), and a carbonylation reaction of the methanol product occurs under agitation by a stirrer or other means.
[00042] The internal pressure of reactor 1 (for example, reaction pressure, partial pressure of carbon monoxide, partial pressure of hydrogen, partial pressure of methane, and partial pressure of nitrogen) can be maintained at a constant pressure, removing steam through the top of the column and introducing the extracted steam into condenser 5. The extracted steam is cooled by condenser 5, to provide a liquid component (containing acetic acid, methyl acetate, methyl iodide, acetaldehyde, water, and others) and a component gaseous (containing carbon monoxide, hydrogen, and others). The component
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21/81 The resulting liquid is recycled to reactor 1, and the resulting gaseous component (waste gases) is discharged to the washing system 10 and, if necessary, recycled to reactor 1. In particular, the reaction system is a system exothermic reaction, which accompanies heat generation, and part of the amount of heat generated in the reactor can be removed by cooling part of the reaction heat transferred from the steam reaction solution with the condenser 5.
[00043] If necessary, hydrogen can be fed to reactor 1 in order to increase catalytic activity. In addition, since the reaction system is an exothermic reaction system that accompanies heat generation, reactor 1 can be equipped with a removable heating (or heat extraction) or cooling unit (for example, a jacket ), to control a reaction temperature. In this context, as described later, the process of Fig. 1 equipped with a heat exchanger 7 to extract heat from part of a volatile component of the instant evaporator
2.
Thus, even when the reactor is not equipped with the removable heating or cooling unit, heat can be removed.
[00044] Components contained in the reaction mixture (crude reaction solution) generated in reactor 1 may include acetic acid, hydrogen iodide, a component with a lower boiling point, or impurity having a lower boiling point than that of the acid acetic (for example, methyl iodide, as a co-catalyst, methyl acetate, as a reaction product of acetic acid with methanol, and acetaldehyde, crotonaldehyde, 2-ethylcrotonaldehyde, and a higher iodide (such as hexyl iodide or iodide of decila), in the form of by-products), and a
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22/81 higher boiling point component, or higher boiling point impurity with a higher boiling point than acetic acid [a metal catalyst component (a rhodium catalyst, and lithium iodide as a co-catalyst), propionic acid, and water].
[00045] In order to mainly separate the highest boiling point component (such as the metal catalyst component) from the reaction mixture, the reaction mixture (or part of the reaction mixture) is continuously extracted from reactor 1, and introduced or fed into the vaporizer (evaporator) 2. In vaporizer 2, a volatile component or a fraction with a lower boiling point (containing mainly acetic acid, which is a product and also works as a reaction solvent, methyl acetate, iodide of methyl, water, hydrogen iodide, and others), is evaporated by instant distillation, to separate a mixture of liquid catalyst, or a higher boiling fraction (containing mainly a metal catalyst component, for example, a catalyst rhodium, lithium iodide, and others), of the reaction mixture.
In this context, in the liquid catalyst mixture, the metal catalyst component and, in addition, the remaining components without evaporation (for example, acetic acid, methyl iodide, water and methyl acetate) are also contained.
[00046]
Within vaporizer 2, instant distillation can be carried out, so that at least methyl acetate in the liquid catalyst mixture can be maintained at a predetermined concentration (for example, not less than 0.1% by weight, particularly, not less to 0.6% by weight). Instant distillation under the condition prevents elevation of
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23/81 concentration of hydrogen iodide in the instant evaporator. Thus, corrosion of the instant evaporator is markedly prevented. In addition, adjusting the concentration of methyl acetate allows the concentration of hydrogen iodide to be reduced efficiently, while increasing the concentration of methyl acetate in the first stream of liquid.
As a result, a more effective reduction of the hydrogen iodide concentration in the second distillation column is achieved. In this context, the concentration of methyl acetate can be adjusted, for example, by increasing the concentration of methanol in the reaction mixture, and allowing the reaction of methanol with acetic acid to occur predominantly, and others. If necessary, the concentration of methyl acetate can be adjusted by feeding methyl acetate and / or a component to produce methyl acetate (for example, methanol and dimethyl ether) to the instant evaporator 2. In the embodiment of the figure, a line 30, which joins line 14, is provided. If necessary, the concentration of methyl acetate in the instant evaporator can also be adjusted, by mixing methyl acetate and / or a component of methyl acetate production, through line 30 with the reaction mixture of reactor 1.
[00047] The liquid catalyst mixture is continuously discharged from the bottom of the column. The discharged liquid catalyst mixture can be directly recycled to reactor 1. In the embodiment shown in the figure, the discharged liquid catalyst mixture has its heat removed (it is cooled) in heat exchanger 6 and then recycled to the reactor 1.
[00048] On the other hand, the volatile component, or fraction of
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24/81 lowest boiling point (acetic acid stream) is extracted from the top of the column or top of the vaporizer 2, and fed or introduced into the first distillation column 3, and part of the volatile component is introduced into the heat exchanger 7, to be condensed. The volatile component cooled by the heat exchanger 7 produces a liquid component (containing acetic acid, methanol, methyl iodide, methyl acetate, water, propionic acid, acetaldehyde and others) and a gaseous component (containing carbon monoxide, hydrogen, and others). The resulting liquid component is recycled to reactor 1. The resulting gaseous component (waste gases) is fed to the washing system 10 and, if necessary, carbon monoxide is obtained without purifying the gaseous component, or by purifying it by a method of PSA (Pressure Swing Adsorption), and recycled to reactor 1. The lowest boiling point fraction is extracted from the vaporizer for introduction into the heat exchanger, and part of the reaction heat transferred from the instant steam reaction solution is cooled by heat exchanger. Thus, the heat can be removed efficiently. Thus, since the subsequent distillation column or condenser can be reduced (or miniaturized), even for a large plant, acetic acid can be produced with high purity and high performance in a resource and energy saving equipment. In addition, heat can be removed without installing an external circulation refrigeration unit in the reactor, which leads to the prevention of the loss of carbon monoxide and to improving the efficiency of the reaction, or to reducing the cost of the equipment.
[00049] Incidentally, making (maintaining) the temperature and / or the internal pressure of vaporizer 2 lower than that of the reactor
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25/81
1, further generation of by-products or deterioration of catalytic activity can be inhibited.
[00050] In the first distillation column 3, usually the lowest boiling point component (or fraction) containing the lowest boiling point component (containing methyl iodide, methyl acetate, acetaldehyde, water, and others) as a supernatant from the top or top of the column and fed to condenser 8, and a fraction with the highest boiling point (a first component with the highest boiling point) containing the component with the highest boiling point (eg propionic acid, a dragged catalyst, and lithium iodide) is separated by the bottom or bottom of the column, through a bottom line 24, and recycled to reactor 1.
(fraction
The first component with the lowest boiling point or supernatant with the lowest boiling point) extracted from the top or top of the first distillation column contains acetic acid and others, and is fed to condenser 8. The fraction with the lowest boiling point extracted of the first distillation column can be condensed by the condenser 8, to cool part of the reaction heat transferred from the reaction solution to the fraction with the lowest boiling point, through the instant steam with the condenser 8 and, thus, part of the reaction heat can be removed.
In condenser 8, the lowest boiling point fraction is condensed to separate a gaseous component containing mainly carbon monoxide, hydrogen and others, and a liquid component containing methyl iodide, methyl acetate, acetic acid, acetaldehyde and others. The gaseous component separated in the condenser 8 is fed to the washing system 10 and, if necessary, carbon monoxide is obtained without purifying the
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26/81 gaseous component, or with its purification, by the PSA (Pressure Swing Adsorption) method, and the gaseous component is recycled to the reaction system (for example, reactor 1) (not shown). The liquid component separated in the condenser 8 can be recycled to the first distillation column 3, via line 22a. In this context, the liquid component can be a
solution uniform or a solution separated (per example, a solution biphasic) of system. Per example, for the component liquid containing an amount predetermined of water, the
liquid component can be separated into two phases composed of an aqueous phase (aqueous layer or water phase) and an oil phase (organic layer or organic phase), where the aqueous phase contains acetic acid, acetaldehyde, and others, and the phase oily contains methyl iodide and others. In addition, the oil phase can be recycled to reactor 1 and / or the first distillation column 3, and the water phase (aqueous phase) can be recycled to reactor 1 and / or the first distillation column 3.
[00052] In addition, the first fraction (or component) with the highest boiling point contains the component with the highest boiling point, as well as the component with the lowest boiling point, which remains without evaporation, acetic acid, and others. Part of the fraction with the highest boiling point discharged through line 24 can be recycled to vaporizer 2 via line 24a, if necessary.
[00053] In addition, the first liquid stream (side stream, acetic acid stream), containing mainly acetic acid, is extracted from the first distillation column 3, and is fed or introduced into the second distillation column 4. From the stream of acetic acid (first stream of
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27/81 liquid), which is obtained by lateral cutting of the first distillation column 3 and is fed into the second distillation column 4, a component with a lower boiling point (eg water), which remains in the acetic acid stream, it is further separated in the second distillation column 4, and a stream of higher purity acetic acid (purified stream of acetic acid) is extracted as a side stream.
[00054] The first stream of liquid generally contains acetic acid and, in addition, components (eg, methyl iodide, methyl acetate, water, and hydrogen iodide), which continue without separation in the first distillation column. When the first stream of liquid containing these components is subjected to distillation, hydrogen iodide is condensed on the second distillation column. Hydrogen iodide is contained in the first liquid component and is also produced by a reaction of methyl iodide in water, and condensed in the second distillation column. In particular, hydrogen iodide is easily displaced together with water to the top (or top) of the second distillation column and is condensed. In addition, the reaction of methyl iodide with water tends to occur at the top of the second distillation column.
[00055] Thus, in the second distillation column, the first stream of liquid is subjected to distillation in the presence of the alkali component (for example, an alkali metal hydroxide, such as potassium hydroxide). That is, the alkaline component is added or mixed with the first liquid component, through a line 40 and / or a line 41, and the liquid object containing the first liquid component and the alkaline component is subjected to distillation in the second column of
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28/81 distillation. Specifically, the alkaline component is added to the first liquid component, before the first liquid component is fed into the second distillation column via line 40, which joins line 23, and / or the alkaline component is added to the first liquid component in the second distillation column 4, so that the alkaline component is introduced at a height level (or a plate) higher or higher than the feed line 23. The addition of the alkaline component, in this way, allows the neutralization of iodide of hydrogen, before hydrogen iodide is moved to the top of the second distillation column, even if an alkaline component, which is easily transferred to the bottom of the distillation column, is used. Thus, condensation of hydrogen iodide throughout the distillation column, including not only the lower part of the distillation column, but also its upper part, can be effectively inhibited.
[00056]
In addition, in the second distillation column, the first liquid component can be subjected to distillation in the presence of the alkaline component and at least one component (A) having a lower boiling point than the boiling point of acetic acid, and be selected from the group consisting of an alcohol (for example, methanol), an ether (for example, dimethyl ether), and an ethyl ester (for example, methyl acetate). In this context, component (A) can be contained in the first liquid component, or can be added in line 40 and / or line 41. In order to allow component (A) to exist in a sufficient concentration in the first liquid component, it is preferable that component (D) is added in line 40 and / or line 41. As described above, the alkaline component
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29/81 can be easily transferred to the bottom of the distillation column, and the reaction of methyl iodide with water tends to occur at the top of the distillation column. Therefore, the alkaline component at the top of the distillation column sometimes decreases, depending on the addition position (or height level). Component (A) has a lower boiling point, is easily transferred to the top of the distillation column, and can consume hydrogen iodide (or can inhibit the production of hydrogen iodide) through the reaction, and the addition of Component (A) in combination with the alkaline component allows the condensation of hydrogen iodide to be inhibited at the top of the distillation column, with more certainty.
[00057] In the second distillation column 4, a second component with the lowest boiling point (fraction of the lowest boiling point) containing the component with the lowest boiling point is fed, as a supernatant, through the top or top of the column to the condenser (holding tank) 9, and a second liquid stream (side stream, acetic acid stream), rich in acetic acid, is distilled through a side cut. If necessary, the fraction with the lowest boiling point, discharged from the top or top of the column, can be recycled to the second distillation column 4 and / or to the reaction system 1. Water can be separated, as a lower component boiling point, in the second distillation column 4, or can be separated, mainly, in the first distillation column, 3 and further separated in the second distillation column 4 for purification. In this context, a fraction with the highest boiling point (a second component with the highest boiling point), as a component with the highest boiling point (for example,
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30/81 propionic acid), can be discharged from the bottom or bottom of the column, and, if necessary, can be recycled to reactor 1, or can be discharged from the system (not shown). In addition, the second stream of liquid can be further subjected to distillation for purification.
[00058] The lowest boiling point fraction extracted from the top or top of the second distillation column 4 contains methyl iodide, methyl acetate, water, acetaldehyde, and others, and is condensed by condenser 9. Then, fraction of lowest boiling point condensed in condenser 9 can be recycled to reactor 1, via line 26, or recycled to the second distillation column 4, via line 27. In addition, the gas separated in condenser 9 can be fed to the washer 10, via line 13. In addition, for the liquid component containing a predetermined amount of water, in the same way as before, the liquid component can be separated into an aqueous phase and an oil phase, and these phases can be recycled. The fraction with the lowest boiling point extracted from the second distillation column 4 is condensed by the condenser 9, to cool part of the reaction heat transferred from the reaction solution to the fraction with the lowest boiling point, through the instantaneous steam with the condenser 9.
(Reaction step) [00059] In the reaction step (carbonyl reaction step), methanol is carbonylated with carbon monoxide in the presence of the catalyst system. In this context, fresh methanol can be fed to the reaction system, directly or indirectly, or methanol and / or its derivative, removed by several distillation steps, can be recycled and fed to the reaction system.
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31/81 [00060] The catalyst system can normally comprise a metal catalyst, a co-catalyst, and an accelerator.
Examples of the metal catalyst may include a transition metal catalyst, in particular,
catalyst in metal containing group metals 8 of the Table Periodic (per example, a catalyst cobalt, one catalyst in rhodium, and a catalyst iridium). O catalyst can be a metal, like a substance simple, or
can be used in the form of an oxide (including a complex metal oxide), a hydroxide, a halide (for example, a chloride, a bromide, and an iodide), a carboxylate (for example, an acetate), a salt an inorganic acid (for example, a sulfate, a nitrate, and a phosphate), a complex, and others. These metal catalysts can be used alone or in combination. The preferred metal catalyst includes a rhodium catalyst and an iridium catalyst (in particular, a rhodium catalyst).
[00061] Furthermore, it is preferred to use the metal catalyst in the form dissolved in a reaction solution. In this context, since rhodium generally exists as a complex in the reaction solution, the shape of the rhodium catalyst is not particularly limited to a specific shape, since the catalyst can change to a complex in the reaction solution.
reaction, and can be u catalyst rhodium example, RHI3, [RHI2 carbonyl in rhodium preferred Beyond of this
a complex of r
r r
solution used in various forms. As such, a rhodium iodide [by (CO) 4] ^- , and [Rh (CO) 2I2 ^- ], or the like, the catalyst can be a particularly stabilized complex in the reaction by adding a halide salt (for example , an iodide salt) and / or water.
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[00062] The concentration of catalyst in metal is, for example, of fence from 10 to 5000 ppm (based on in weight, the even if applying here the follow) , in preferably, in fence from 100 to
and,
200 to 3000 ppm,
4000 ppm, more preferably, from about particularly, from about 300 to 2000 ppm (for example, from about 500 to 1500 ppm), throughout the liquid phase in the reactor.
For the co-catalyst or accelerator contained in the catalyst system, an ionic iodide (an iodide salt) is used. The added iodide salt in order to stabilize rhodium catalyst inhibit secondary reactions, in particular, in a low water content. The iodide salt is not particularly limited to a specific item, as the iodide salt produces an iodide ion in the reaction solution. The iodide salt can include, for example, a metal halide, [for example, a metal iodide, such as an alkali metal iodide (for example, lithium iodide, sodium iodide, potassium iodide, rubidium iodide , and cesium iodide), an alkaline earth metal iodide (for example, beryllium iodide, magnesium iodide, and calcium iodide), or a metal iodide in the group
3B of the Periodic Table (for example, boron iodide and aluminum iodide)], an organic halide, [for example, an organic iodide, such as a phosphonic salt of an iodide (phosphonium iodide) (for example, a salt with triphenylphosphine and tributylphosphine), or an ammonium salt of an iodide (an ammonium iodide) (for example, a tertiary amine salt, a pyridine compound, an imidazole compound, an imide compound, or the like, with an iodide ), a bromide corresponding to iodide, and a chloride corresponding to iodide]. In this context, alkali metal iodide (eg lithium iodide) also functions as a
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33/81 stabilizer for the carbonylation catalyst (for example, a rhodium catalyst). These iodide salts can be used alone or in combination. Among such iodide salts, an alkali metal iodide (such as lithium iodide) is preferred.
[00064] In the reactor (liquid reaction mixture), the concentration of the ionic iodide is, for example, from about 1 to 25% by weight, preferably from about 2 to 22% by weight and, more preferably, from about 3 to 20% by weight, throughout the liquid phase (or liquid reaction mixture) in the reactor. In addition, the concentration of the iodide ion in the reactor can be, for example, from about 0.07 to 2.5 mol / liter and, preferably, from about 0.25 to 1.5 mol / liter.
[00065] For the accelerator contained in the catalyst system an alkyl iodide is used (for example, a C1-4 alkyl iodide, such as methyl iodide, ethyl iodide, or propyl iodide), in particular, iodide methyl. Thus, the accelerator may contain at least methyl iodide. Once the reaction is promoted at higher concentrations of the accelerator, an economically advantageous concentration can be appropriately selected, taking into account the recovery of the accelerator, the plant size of one step to circulate the recovered accelerator to the reactor, the amount of energy necessary for recovery or circulation, among others.
In the reaction system, the concentration of the alkyl iodide (in particular, methyl iodide) is, for example, from about 1 to
25% by weight, preferably from about 5 to 20% by weight and, more preferably, from about 6 to 16% by weight (e.g., from about 12 to 15% by weight) throughout the liquid phase in the reactor.
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34/81 [00066] The reaction is a continuous reaction, and the reaction solution can normally contain methyl acetate. The proportion of methyl acetate can be from about 0.1 to 30% by weight, preferably from about 0.3 to 20% by weight and, more preferably, from about 0.5 to 10% by weight (for example, from about 0.5 to 6% by weight) throughout the reaction solution.
[00067] The carbon monoxide to be fed to the reaction system can be used as a pure gas, or it can be used as a gas diluted with an inactive gas (for example, nitrogen, helium, and carbon dioxide). On the other hand, discharged gas component (s) containing carbon monoxide obtained in the next step (s) can be recycled to the reaction system. The partial pressure of the carbon monoxide in the reactor can be, for example, from about 2 to 30 atmospheres and, preferably, from about 4 to 15 atmospheres.
[00068] In the carbonylation reaction, hydrogen is formed (or generated) by a displacement reaction between carbon monoxide and water. Hydrogen can be fed to the reaction system. Hydrogen can be fed as a gas mixture of carbon monoxide, as a raw material, to the reaction system. In addition, hydrogen can be fed to the reaction system by recycling gaseous component (s) (including hydrogen, carbon monoxide, and others) discharged in the next distillation step (s) ( s) (distillation column), if necessary, after adequately purifying the gaseous component (s). The partial pressure of hydrogen in the reaction system can be, for example, from about 0.5 to 200 kPa, preferably from about 1 to 150 kPa and, more preferably, from about 5 to 100 kPa (for example , from about 10 to 50 kPa), in terms of absolute pressure.
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35/81 [00069] The partial pressure of carbon monoxide or the partial pressure of hydrogen in the reaction system can be adjusted, for example, through an appropriate adjustment of the amount of carbon monoxide and hydrogen fed and / or recycled to the reaction system, the amount of raw materials (for example, methanol) fed to the reaction system, the reaction temperature, the reaction pressure, and others.
[00070] In the carbonylation reaction, the reaction temperature can be, for example, from about 150 to 250 ° C, preferably from about 160 to 230 ° C and, more preferably, from about 180 to 220 ° C . In addition, the reaction pressure (the total pressure of the reactor) can, for example, be about 15 to 40 atmospheres.
[00071] The reaction can be carried out in the presence or absence of a solvent. The reaction solvent is not limited to a specific type, since the reactivity, or the separation or purification efficiency does not decrease, and a variety of solvents can be used. In normal cases, acetic acid, as a product, can practically be used as a solvent.
[00072] The concentration of water in the reaction system is not limited to a specific value, and can be a low concentration. The water concentration in the reaction system is, for example, not more than 15% by weight (for example, from about 0.1 to 12% by weight), preferably not more than 10% by weight (for example , from about 0.1 to 6% by weight) and, more preferably, from about 0.1 to 5% by weight, and can generally be from about 1 to 15% by weight (e.g., from about 2 to 10% by weight) throughout the liquid phase of the reaction system. The solubility of carbon monoxide in the solution
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36/81 fed to the vaporizer is reduced by carrying out the reaction, maintaining a specific concentration of each component [articularly, an iodide salt (lithium iodide) and water] in the reaction system, and the loss of carbon monoxide can be reduced.
[00073] In the previous carbonylation reaction, the production of acetic acid is accompanied by the production of an ester of acetic acid produced with methanol (methyl acetate), the water generated with the esterification reaction, additionally propionic acid, acetaldehyde and others.
[00074] In the reaction system, the generation of aldehydes can be reduced or inhibited by extracting the aldehyde in the recycling stream, from the next step (s) (for example, distillation column), or modifying the reaction conditions, for example, reducing the proportion of the co-catalyst, such as an alkyl iodide and / or the partial pressure of hydrogen. In addition, hydrogen generation in the reaction system can be reduced or inhibited by adjusting the water concentration.
[00075] The time-space yield of the target acetic acid in the reaction system can be, for example, from about 5 mol / Lh to 50 mol / Lh, preferably from about 8 mol / Lh to 40 mol / Lh and, more preferably, from about 10 mol / Lh to 30 mol / Lh.
[00076] The steam component extracted from the top of the reactor for the purpose of reactor pressure control, or others, is preferably cooled with a condenser, a heat exchanger or other means, to remove part of the reaction heat . It is preferable that the cooled vapor component is separated into a liquid component (containing acetic acid, methyl acetate, methyl iodide, acetaldehyde, water, and others) and a gaseous component (containing carbon monoxide, hydrogen, and
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37/81 others), the liquid component is recycled to the reactor, and the gaseous component is introduced into the washing system.
[00077] In addition, the reaction system (or the reaction mixture) may also contain methanol (unreacted methanol). The methanol concentration in the reaction system can be, for example, not more than 1% by weight (for example, from about 0 to 0.8% by weight), preferably not more than 0.5% by weight (for example, from about 0 to 0.3% by weight), more preferably, not more than 0.3% by weight (for example, from about 0 to 0.2% by weight) and usually not above the detection limit (less than 0.1% by weight). In this context, the concentration of methyl acetate also depends on the concentration of methanol in the system. Thus, the amount of methanol to be fed to the reaction system can be adjusted in association with the concentration referred to below of methyl acetate in the vaporizer.
(Instant distillation step or catalyst separation step) [00078] In the instant distillation step (vaporizer), from the reaction mixture fed through the reaction step, or from the reactor, to the vaporizer (evaporator or instant evaporator) , a low volatility component or liquid catalyst mixture (a higher boiling fraction) containing at least one higher boiling catalyst component (a metal catalyst component, for example, a rhodium catalyst and a salt ionic iodide) is separated as a liquid (component), and a volatile component or volatile phase (a fraction of the lowest boiling point) containing acetic acid is separated as a vapor (component).
[00079] In the stage of instant distillation (stage of
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38/81 instant evaporation), the reaction mixture can be separated into the vapor component (or vaporized stream) and the liquid component (or liquid stream), with or without heating. For example, in adiabatic instantaneous vaporization, the reaction mixture can be separated into the vapor component and the liquid component, without heating and under reduced pressure, and in thermostatic instantaneous vaporization, the reaction mixture can be separated into the vapor component and the heated (and reduced pressure) liquid component. The reaction mixture can be separated into the vapor component and the liquid component, combining these instantaneous conditions.
[00080] In instant distillation, the distillation temperature (or reaction temperature) can, for example, be about 100 to 260 ° C (for example, about 110 to 250 ° C), preferably about from 120 to 240 ° C (for example, from about 140 to 230 ° C), more preferably, from about 150 to 220 ° C (for example, from about 160 to 210 ° C) and, particularly, from about from 170 to 200 ° C. In addition, in instant distillation, the temperature of the liquid catalyst mixture (or the temperature of the liquid of the reaction mixture) can be, for example, about 80 to 200 ° C (for example, about 90 to 180 ° C), preferably, from about 100 to 170 ° C (for example, from about 120 to 160 ° C) and, more preferably, from about 130 to 160 ° C. In addition, in instant distillation, the absolute pressure can be about 0.03 to 1 MPa (for example, about 0.05 to 1 MPa), preferably about 0.07 to 0.7 MPa and, more preferably, from about 0.1 to 0.5 MPa (for example, from about 0.15 to 0.4 MPa). Hydrogen iodide can be easily produced (or the concentration of hydrogen iodide tends to increase), under a condition of temperature (and pressure)
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39/81 relatively high. According to the present invention, however, even under such a condition, the production or increase of hydrogen iodide concentration in the instant evaporator can be efficiently inhibited.
[00081] The separation (instant distillation) of the metal catalyst component can generally be carried out using a distillation column (an instant evaporator). In addition, the metal catalyst component can be separated by instant distillation, in combination with a mist collection method or a solids collection method, which is widely used in industrial applications.
[00082] The material of (or for forming) the vaporizer is not particularly limited to a specific type and can be a metal, ceramic, glass, or others. Practically, a vaporizer made of a metal is used. In particular, the hydrogen iodide concentration within the flash evaporator can be significantly inhibited, and the corrosion of the flash evaporator can also be inhibited to a high degree. Thus, like an instant evaporator in the present invention, not only can an instant evaporator made of an expensive material, having a high corrosion resistance (such as zirconium), but also an instant evaporator made of a relatively cheap material having a resistance to not very high corrosion, for example, a metal as a simple substance (such as titanium or aluminum) and an alloy [for example, a transition metal based alloy, such as an iron based alloy (or an alloy containing iron as the main component, for example, a stainless steel (including a stainless steel containing chromium, nickel, molybdenum and others), a nickel-based alloy (or an alloy
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40/81 containing nickel as the main component, for example, HASTELLOY (trade name) and INCONEL (trade mark)), a cobalt based alloy (or a cobalt containing alloy as the main component), or a titanium alloy; and an aluminum alloy].
[00083] The step of separating the liquid catalyst mixture can consist of a single step, or it can be composed of a plurality of steps in combination. The mixture of liquid catalyst or higher boiling catalyst component (metal catalyst component), separated by such step (s), can normally be recycled to the reaction system, as illustrated in the figure embodiment . In addition, the liquid catalyst mixture can be cooled (or removed from heat) by the heat exchanger, and recirculated to the reactor, as shown in the example in the figure. Cooling can improve efficiency
extracting heat from the entire system. [00084] A mixture of the catalyst liquid separate (or O component low volatility or highest point fraction in boiling) contains the catalyst in metal (for example, one
rhodium catalyst), ionic iodide (eg, an alkali metal iodide, such as lithium iodide) and, in addition, remaining components without evaporation (eg, acetic acid, methyl iodide, water, methyl acetate and hydrogen iodide).
[00085] In instant distillation (or instant evaporator), the ratio (weight ratio) of the volatile component to be separated in relation to the liquid catalyst mixture (or the low volatility component) can be about 10/90 to 50 / 50, preferably from about 15/85 to 40/60 and, more
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41/81 preferably, from about 20/80 to 35/65 in a proportion of the previous / last.
[00086] According to the present invention, among the components in the liquid catalyst mixture, the concentration of methyl acetate can be adjusted (or regulated). Adjusting the concentration allows the production or increase of the hydrogen iodide concentration in the flash evaporator to be effectively inhibited in a wide range of flash distillation conditions. Multiple factors are involved in the reason why increasing the concentration of hydrogen iodide is avoided by adjusting the concentration of methyl acetate, and one of the factors includes the consumption of hydrogen iodide by the next equilibrium reaction.
CH ₃ I + CH ₃ COOH CH ₃ COOCH ₃ + HI [00087] The concentration of methyl acetate in the liquid catalyst mixture can be selected from the range of at least 0.05% by weight (for example, 0.1 to 20% by weight) and may, for example, be not less than 0.2% by weight (for example, from about 0.3 to 15% by weight), preferably not less than 0.5% by weight (for example, from about 0.6 to 10% by weight) and, usually, from about 0.8 to 5% by weight (for example, 1 to 4% by weight). In particular, the concentration of methyl acetate in the liquid catalyst mixture can be not less than 0.6% by weight (for example, from about 0.6 to 20% by weight), preferably not less than 0, 7% by weight (for example, from about 0.7 to 15% by weight), more preferably, not less than 0.8% by weight (for example, from about 0.8 to 10% by weight) and usually from about 0.7 to 5% by weight (e.g., from 0.7 to 3% by weight, preferably from about 0.8 to 2% by weight and, more preferably, from about 0.9 to
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1.5% by weight). The concentration of methyl acetate is adjusted
for the break, from mode that production or increase of iodide concentration in hydrogen can to be further efficiently inhibited. [00088] The concentration in water in the mixture in catalyst
liquid can be, for example, selected from the range not exceeding 15% by weight (for example, 0.1 to 12% by weight), and can be, for example, not exceeding 10% by weight (for example, from about 0.5 to 10% by weight), preferably not more than 8% by weight (for example, from about 0.8 to 8% by weight) and, more preferably, not more than 5% by weight weight (for example,
about 1 to 4% by weight). [00089] Besides that, the concentration of acid acetic in mixture of catalyst liquid can be, per example, no bottom to 30% by weight (for example, about 35 to 95% in
weight), preferably not less than 40% by weight (for example, from about 45 to 90% by weight) and, more preferably, not less than 50% by weight (for example, from about 50 to 85% by weight) weight) and can generally be from about 60 to 90% by weight (for example, from about 70 to 90% by weight and, preferably, from about 75 to 85% by weight).
[00090] In addition, the concentration of methyl iodide in the liquid catalyst mixture can be selected from the range not exceeding 10% by weight (for example, from 0.001 to 8% by weight), and can be, for example, not more than 7% by weight (for example, from about 0.005 to 6% by weight), preferably not more than 5% by weight (for example, from about 0.01 to 4% by weight), more preferably not more than 3% by weight (for example, from about 0.05 to 2.5% by weight), especially not more than 2% by weight (for example, from about 0.1 to 1.8 % in
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43/81 by weight), and can generally be from about 0.1 to 3% by weight (for example, from about 0.3 to 2.5% by weight, preferably from about 0.5 to 2 % by weight and, more preferably, of about
1 to 1.5% by weight). [00091] Besides that, the concentration ionic iodide at mixture in catalyst liquid can be, for example, no higher The 60% by weight (for example, from about 1 to 55% in
weight), preferably not more than 50% by weight (for example, from about 2 to 45% by weight), more preferably, not more than 40% by weight (for example, from about 3 to 37% by weight) weight) and, in particular, not exceeding 36% by weight (for example, from about 5 to 35% by weight). Multiple factors are also involved in the reason why increasing the concentration of hydrogen iodide is avoided by adjusting the concentration of ionic iodide, and one of the factors includes the consumption of hydrogen iodide by the next equilibrium reaction. By the way, the same equilibrium reaction is equally applicable to hydrogen iodide in the reaction mixture.
MI + CH ₃ COOH CH ₃ COOM + HI [In the formula, the symbol M represents a residue of an ionic iodide (or cationic group, for example, an alkali metal, such as lithium)] [00092] By the way, the concentration of metal catalyst in the liquid catalyst mixture can be, for example, not less than 100 ppm (for example, from about 150 to 10,000 ppm), preferably not less than 200 ppm (for example, from about 250 to 5000 ppm) and, more preferably, not less than 300 ppm (for example, from about 350 to 3000 ppm), based on weight. [00093] In addition, the concentration of methanol in the liquid catalyst mixture can be, for example, not more than 1% in
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44/81 weight (for example, from about 0 to 0.8% by weight), preferably not more than 0.5% by weight (for example, from about 0 to 0.3% by weight) and , more preferably, not more than 0.3% by weight (for example, from about 0 to 0.2% by weight). As described later, when the concentration of methanol is higher, the concentration of methyl acetate in the liquid catalyst mixture is easily and efficiently increased.
[00094] For example, the concentration of methyl acetate in the liquid catalyst mixture can be efficiently increased by increasing the concentration of methanol in the reaction mixture (or a mixture of liquid catalyst). That is, as represented by the following general formula, methanol is allowed to react with acetic acid to produce methyl acetate (equilibrium reaction). Thus, the reaction of methyl acetate production occurs easily, when the concentration of methanol increases. As a result, the concentration of methyl acetate in the liquid catalyst mixture can be increased. By the way, the same equilibrium reaction is equally applicable to hydrogen iodide in the reaction mixture.
CH ₃ OH + CH ₃ COOH CH ₃ COOCH ₃ + H ₂ O [00095] In the interval that the efficiency of acetic acid production is sufficiently guaranteed, the concentration of methanol can be increased, increasing the concentration of methanol to be fed in the reaction , or by slowing down the reaction speed to inhibit methanol consumption. The reaction speed can be adjusted by appropriately selecting the reaction temperature, the concentration of the catalyst (for example, concentration of methyl iodide and the concentration of the metal catalyst), the concentration of carbon monoxide (or the partial pressure of monoxide carbon), and others. THE
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45/81 methanol concentration can be adjusted, by adding methanol directly, as described later.
[00096] In addition, the concentration of methyl acetate in the liquid catalyst mixture can be adjusted, by adding methyl acetate and / or a component to produce methyl acetate (eg, methanol and dimethyl ether). In this context, as described above, methanol is allowed to react with acetic acid to produce methyl acetate, and dimethyl ether is allowed to react with hydrogen iodide or the like, to provide methanol, which is allowed to react with acetic acid to produce methyl acetate. If necessary, a component to increase or decrease the concentration of each component can be added or mixed in the form of a mixture containing a solvent.
[00097] When the elevator or reducer component is added to the reaction mixture, the position (or time) of addition is not particularly limited to a specific parameter, as the elevator or reducer component is added, before the mixture of reaction to be fed to the instant evaporator. The elevator or reducer component can be fed to the reactor. In terms of process efficiency, the elevator or reducer component can be fed to the reaction mixture, after the reaction mixture is discharged from the reactor, and before the reaction mixture is fed to the instant evaporator (for example, as shown in the figure, the elevator or reducer component can be fed to a line to supply the instant evaporator with the reaction mixture discharged from the reactor).
[00098] On the other hand, when the elevator or reducer component is added to the instant evaporator (or the component
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46/81 elevator or reducer is mixed with the reaction mixture in the instant evaporator), the position (height level) of addition is not particularly limited to a specific parameter. The lifting or reducing component can be added to the portion of the liquid phase, or to the portion of the gas phase in the instant evaporator, or both. The elevator or reducer component can be added to the process solution, to be recycled from the next step (s) to the instant evaporator.
[00099] The volatile component (acetic acid stream), separated in the vaporizer, contains the acetic acid product and, in addition, methyl iodide, an ester of the acetic acid product with methanol (for example, methyl acetate), water, a small amount of by-product (s) (eg acetaldehyde and propionic acid) and others. The volatile component can be distilled in the first distillation column and the second distillation column to produce purified acetic acid.
[000100] As described above, the production or increase of the hydrogen iodide concentration in the vaporizer can be inhibited. Thus, the concentration of hydrogen iodide in the volatile component can, for example, be adjusted to not exceed 1% by weight (for example, about 0, or the detection limit at 8000 ppm), preferably not greater than 5000 ppm (for example, from about 1 to 4000% by weight) and, more preferably not more than 3000 ppm (for example, from about 10 to 2000% by weight). In addition, the hydrogen iodide concentration in the liquid catalyst mixture can, for example, be adjusted to not exceed 1% by weight (for example, from about 0 to 8000 ppm), preferably not more than 5000 ppm (for example, from about 1 to 4000 ppm) and, more preferably, not more than 3000 ppm (for example, from
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47/81 about 10 to 2000 ppm).
[000101] The hydrogen iodide concentration can be measured directly, or measured (or calculated) indirectly. For example, the concentration of the iodide ion derived from the iodide salt [e.g., an iodide derived from the co-catalyst, such as LiI, and a metal iodide (e.g., a corroded metal iodide (such as Fe, Ni, Cr, Mo or Zn) produced in the acetic acid production process)], can be subtracted from the total concentration of iodide ions (I ^- ), to determine (or calculate) the concentration of hydrogen iodide.
[000102] Part of the separate volatile component (acetic acid stream) can be introduced into a condenser or heat exchanger for cooling, or heat extraction, as shown in the figure. Since the reaction heat transferred from the instant steam reaction solution can be partially cooled by heat extraction, the efficiency of heat extraction can be improved, and acetic acid with a high degree of purity can be produced without the installation of an external circulation refrigeration unit in the reactor. In addition, the cooled volatile component can be recycled to the reaction system, just like the embodiment illustrated in the figure. On the other hand, the gaseous component in the cooled volatile component can be introduced into the washing system.
(Acetic acid collection stage) [000103] In the acetic acid collection stage (distillation stage), the volatile component is fed to the first distillation column, a first component with the lowest boiling point (a fraction of the lowest boiling containing methyl iodide, acetic acid, methyl acetate, by-product
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48/81 acetaldehyde, and others) is separated as a supernatant (volatile component or vaporized component) from the volatile component by distillation (first distillation), and a stream containing mainly acetic acid is collected as a liquid component (first liquid component) . The volatile component to be subjected to the first distillation can be a reaction mixture, which in turn is obtained from the reactor, and is usually a volatile component obtained, subjecting the reaction mixture to additional instant distillation and separation of the catalyst mixture. liquid.
[000104]
That is, the separate volatile component is fed to the first distillation column (dividing column), and separated into a fraction with a lower boiling point (supernatant) containing a component with a lower boiling point and a stream containing acetic acid (acetic acid stream). ) by distillation.
[000105] Every volatile component can be fed to the first distillation column or, as described above, part of the volatile component can be introduced into the heat exchanger, and the remaining (residual) current can be fed to the first distillation column. In the first distillation column, the first lowest boiling component (fraction of lowest boiling point) containing at least part of the lowest boiling component (for example, methyl iodide, methyl acetate, acetaldehyde, and iodide of hydrogen) is separated, and the lowest boiling point fraction containing acetic acid is discharged as a liquid stream. In this context, in the first distillation column, as described in the figure embodiment, each one of the first component with the lowest boiling point and the first component with the highest point
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49/81 boiling point (fraction with the highest boiling point, bottom fraction) containing at least part of the component with the highest boiling point (such as propionic acid or water) can be separated. In addition, in the embodiment of Fig. 1, the first stream of liquid is withdrawn (or extracted or collected) as a side stream by side cutting. The first stream of liquid can be extracted from the bottom of the column or removed (or collected), together with the fraction with the highest boiling point.
[000106] As described above, the acetic acid stream fed to the first distillation column is not limited to an acetic acid stream obtained by extracting the rhodium catalyst component from the reaction mixture from the reaction system. The acetic acid stream can contain at least acetic acid, the lowest boiling component, the highest boiling component, and others (for example, it may contain acetic acid, methyl acetate, methyl iodide, water , and hydrogen iodide); or it can simply be a mixture of these components.
[000107] For the first distillation column, for example, a conventional distillation column, for example, a distillation column, such as a plate column or a filling column. The material of the (or former) of the first distillation column may include the same material as that of the vaporizer. For the first distillation column, a distillation column made of the same material, which is a relatively cheap material (for example, an alloy), such as that of the instant evaporator, can be used.
[000108] The distillation temperature and pressure in the first distillation column can be appropriately selected,
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50/81 depending on the condition, such as the type of the distillation column, or the main object (target) for extraction selected from the component with the lowest boiling point and the component with the highest boiling point. For example, for plate column, the internal pressure of the column (in general, the pressure of the
top gives column) can be about from 0.01 to 1 MPa, from preferably, in fence in 0.01 to 0 , 7 MPa and, more preferably ^, of about 0.05 to 0.5 MPa, in terms of manometer. [000109] In addition addition, in first column in distillation,
internal column temperature (in general, the top column temperature) can be adjusted by adjusting the internal column pressure, and can be, for example, from about 20 to 180 ° C, preferably from about 50 to 150 ° C and, more preferably, from about 100 to 140 ° C.
[000110] Furthermore, for the plate column, the theoretical number of plates is not particularly limited to a specific value 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, from about 8 to 30. In addition, in order to separate highly acetaldehyde (or with a high precision) in the first distillation column, the theoretical number of plates can be about 10 to 80 preferably from about 12 to 60, and more preferably from about 15 to 40.
[000111] In the first distillation column, the reflux ratio can be selected, for example, from about 0.5 to 3000 and, preferably, from about 0.8 to 2000, depending on the aforementioned theoretical number of plates, or it can be reduced by increasing the theoretical number of plates. In this context, in the first distillation column, distillation can be carried out without reflux.
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51/81 [000112] Since the lowest boiling fraction (first lowest boiling component) separated from the first distillation column contains a useful component (for example, methyl iodide and methyl acetate), the fraction lower boiling point can be directly recycled to the reaction system (or reactor) and / or the first distillation column, or it can be liquefied by extracting heat from part of the reaction heat in the reaction system (for example, the reactor) with a condenser, a heat exchanger, or other medium and then recycled to the reactor and / or the first distillation column. For example, the lowest boiling point fraction extracted from the first distillation column is not required to be recycled to the first distillation column, after condensation by the condenser as the embodiment of Fig. 1. The lowest point fraction extracted boiling water can be recycled directly, or simply cooled to remove a flue gas component (eg, carbon monoxide and hydrogen), and then the remaining (residual) liquid component can be recycled. In addition, among the components with the lowest boiling point in the fraction with the lowest boiling point, acetaldehyde deteriorates the quality of acetic acid as a final product. Thus, if necessary, after acetaldehyde extraction (for example, after acetaldehyde extraction, submitting the fraction containing the lowest boiling point impurities to the acetaldehyde separation step mentioned later (acetaldehyde separation column)), (s) remaining component (s) can be recycled to the reaction system and / or the first distillation column. In this context, the flue gas component can be introduced into the washing system.
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52/81 [000113] fraction with the highest boiling point (bottom fraction) separated in the first distillation column contains water, acetic acid, a dragged rhodium catalyst, lithium iodide and, in addition, remaining acetic acid without being evaporated, the lowest boiling point impurities, others. Thus, if necessary, the fraction with the highest boiling point can be recycled to the reaction system (reactor) and / or the vaporizer.
In fact, before recycling, propionic acid, which deteriorates the quality of acetic acid as a final product, can be removed.
(Acetic acid purification step) [000114]
In the purification step of acetic acid, hydrogen iodide, a component with the lowest boiling point, and a component with the highest boiling point, each remaining undisturbed in the first distillation column, are removed from the first liquid stream by distillation with higher precision, and purified acetic acid is collected. That is, in the acetic acid purification step, the first liquid stream is fed to the second distillation column, and the second lowest boiling component is further separated as a supernatant, and the second liquid stream containing acetic acid is collected.
[000115] The first liquid stream separated or collected in the first distillation column and fed to the second distillation column is a liquid composition, containing mainly acetic acid. The first stream of liquid contains other components (for example, methyl iodide, methyl acetate, water, and hydrogen iodide), in addition to acetic acid. In the first stream of liquid, the concentrations of these other components can be selected, depending on the setting, or
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53/81 lack of adjustment, concentration of each component in the instant evaporator, distillation conditions in the first distillation column, and others.
[000116] For example, concentration in iodide in methyl at first liquid stream can to be in fence in 0 to 10% in weight (for example, about 10 ppm to 8% in Weight), in
preferably, from about 0.1 to 8% by weight, more preferably, from about 0.2 to 7% by weight and particularly, from about 0.3 to 6% by weight (e.g., from about 0, 5 to 5% by weight, preferably from about 0.7 to 4% by weight and, more preferably, from about 1 to 3% by weight), and can generally be no more than 4% by weight (e.g. example, from about 0 to 4% by weight, preferably from about 10 ppm to 3.5% by weight, more preferably, from about 1 to 3.3% by weight, and particularly from about 1 , 5 to 3.2% by weight).
[000117] Incidentally, when the methyl iodide concentration is low, the hydrogen iodide of the condensation derived from methyl iodide can be inhibited at the top of the second distillation column. Furthermore, according to the present invention, even when the concentration of methyl iodide is high, the condensation of hydrogen iodide can be inhibited throughout the second distillation column.
[000118] Furthermore, the concentration of methyl acetate in the first stream of liquid can be from about 0 to 10% by weight, preferably from about 0.1 to 8% by weight and, more preferably, from about from 0.2 to 7% by weight, and can generally be from about 0.2 to 6% by weight, [for example, from about 0.3 to 5% by weight, preferably from about 0, 4 to 4% by weight, more preferably, from about 0.5 to 3% by weight, in particular, from about 0.7 to 2.5% by weight (e.g.
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54/81 about 1 to 2% by weight)].
[000119] Incidentally, when the concentration of methyl acetate is high, condensation of hydrogen iodide is more easily inhibited at the top of the second distillation column, probably due to the consumption of hydrogen iodide by the reaction of hydrogen iodide with methyl acetate. Furthermore, according to the present invention, even when the concentration of methyl acetate is low, condensation of hydrogen iodide can be inhibited throughout the second distillation column. The concentration of methyl acetate can be increased, efficiently, by adjusting the concentration of methyl acetate in the liquid catalyst mixture in the instant distillation, as described above. The concentration of methyl acetate in the first stream of liquid can be increased by adding methyl acetate to the first distillation column.
[000120] Furthermore, the concentration of water in the first stream of liquid can be from about 0.1 to 25% by weight, preferably from about 0.2 to 20% by weight, more preferably, from about 0.3 to 15% by weight and, in particular, from about 0.5 to 12% by weight (for example, from about 0.7 to 10% by weight and preferably from about 1 to 8% by weight), and can generally be less than 5% by weight, [for example, not more than 4% by weight, for example, from about 0.1 to 4% by weight, preferably from about 0, 3 to 3.5% by weight, more preferably, not more than 3% by weight (for example, from about 0.5 to 3% by weight) and, especially, from about 1 to 2.5% by weight (for example, about 1 to 2% by weight)].
[000121] Indeed, when the water concentration is low, the
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55/81 condensation of hydrogen iodide can still be easily inhibited at the top of the second distillation column. In particular, as the concentration of water in the first stream of liquid (or liquid object) and that of water in the column are lower, the corrosion rate of the second distillation column decreases. The corrosion rate can decrease significantly at a water concentration of less than 5% by weight, particularly less than 3% by weight. Thus, the combination of the water concentration and the below mentioned addition of the alkaline component can further inhibit the condensation of hydrogen iodide in the second distillation and the corrosion of the second distillation column even more effectively. Furthermore, according to the present invention, even when the water concentration is high, the condensation of hydrogen iodide can be inhibited throughout the second distillation column. In this context, as described in Japanese Patent Application initialed no. 2009-501129, adding water to the first distillation column sometimes increases the water concentration in the first liquid stream.
[000122] The hydrogen iodide concentration in the first liquid stream can be, for example, not more than 2000 ppm (for example, from about 0 to 1800 ppm), preferably not more than 1500 ppm (for example, from about 1 to 1200 ppm), more preferably, not more than 1000 ppm (for example, from about 2 to 900 ppm) and, generally, not more than 800 ppm (for example, from about 3 to 700 ppm) weight-based. For a relatively low concentration, the hydrogen iodide concentration in the first liquid component can be no more than 500 ppm (for example, from about 0 to 300 ppm), preferably no more than 100 ppm (for example, about
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56/81 from 0.1 to 50 ppm), more preferably, not more than 30 ppm (for example, from about 0.3 to 25 ppm) and generally about 1 to 30 ppm (for example, from about 2 to 25 ppm) based on weight. If necessary, the concentration of hydrogen iodide in the first liquid component can be decreased, using the method described in Published Japanese Patent Application No. 2009-501129, or other methods.
[000123] Incidentally, the concentration of acetic acid in the first stream of liquid can be, for example, not less than 50% by weight (for example, from about 55 to 99.5% by weight), preferably not less to 60% by weight (for example, from about 65 to 99% by weight), more preferably, not less than 70% by weight (for example, from about 75 to 98.5% by weight) and, in particular , not less than 80% by weight (for example, from about 85 to 98% by weight) and usually from about 80 to 99.5% by weight (for example, from about 85 to 99% by weight , preferably, from about 90 to 98% by weight and, more preferably, from about 92 to 97% by weight).
[000124] In this way, the first stream of liquid contains hydrogen iodide or a component of hydrogen iodide production, in the second distillation column. When the first stream of liquid is directly subjected to the second distillation, hydrogen iodide is condensed through continuous reactions in the second distillation column (in particular, the upper part or the gas phase part of the distillation column). Thus, according to the present invention, the alkaline component is added (or fed or mixed) in the first stream of liquid, in the following modes or embodiments (1) and / or (2), and the liquid object containing the first liquid stream and the alkaline component is
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57/81 subjected to distillation in the second distillation column:
(1) the alkaline component is added or mixed with the first liquid stream, before the first liquid stream is fed into the second distillation column, (2) in the second distillation column, the alkaline component is added or mixed at the same level in height (or in the same position or plate) as a height level (or plate or position), into which the first stream of liquid is fed, or at a level of height or position higher (or greater) than the level of height (or position) at which the first stream of liquid is fed.
[000125] In mode (1), it is sufficient that the mixing position (addition position) of the alkaline component for the first liquid stream is located before feeding to the second distillation column. For example, the alkaline component can be fed to a line to feed the first liquid component, from the first distillation column to the second distillation column. In this context, the alkaline component is normally fed, after the first stream of liquid is discharged from the first distillation column.
[000126] Incidentally, in mode (1), the time, from when the first liquid component and the alkaline component are mixed until when the mixture is fed into the second distillation column (retention time, contact time), can not more than 5 minutes (for example, about 1 second and 4 minutes), preferably not more than 4 minutes (for example, about 3 seconds to 3 minutes), more preferably, not more than 3 minutes (for example, about 5 seconds to 2 minutes). When the retention time
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58/81 is too long, the alkaline component is consumed by methyl iodide in the first stream of liquid, so that the selective neutralization of hydrogen iodide sometimes decreases.
[000127] Furthermore, in mode (2), it is sufficient that the alkaline component is added in the same position as a position, in which the first stream of liquid is fed into the second distillation column, or in a position higher than the position in which the first stream of liquid is fed into the second distillation column. When the position of addition of the alkaline component is greater than the position of addition of the first liquid stream, for example, in the second distillation column, the plate, in which the alkaline component is added, can be the first or highest plate (for example, example, the first plate 30, preferably, the first plate 20 and, more preferably, to the first plate 10a) above the plate in which the first liquid stream is fed. In addition, the position of addition of the first liquid stream is usually located higher, or higher, than the collection position of the second liquid stream (for example, by side cut).
[000128] The contact temperature of the first liquid component and the alkaline component [the temperature (liquid temperature) of the liquid object containing the first liquid component and the alkaline component] can be, for example, from about 50 to 190 ° C , preferably, from about 70 to 180 ° C (for example, from about 90 to 175 ° C) and, more preferably, from about 100 to 170 ° C. In particular, the range above the liquid temperature is combined with mode (1) to achieve efficient progress in neutralizing hydrogen iodide
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59/81 (HI) and the alkaline component, while inhibiting the consumption of the alkaline component by methyl iodide in the first stream of liquid.
[000129] The alkaline component can include a metal hydroxide [for example, an alkali metal hydroxide (for example, lithium hydroxide, sodium hydroxide and potassium hydroxide), an alkaline earth metal hydroxide (for example, hydroxide calcium), and metal hydroxides from Groups 3 to 12 of the Periodic Table (for example, iron (II) hydroxide, zinc hydroxide, and copper (II) hydroxide)], a metal oxide [for example, a metal oxide corresponding to metal hydroxide, such as an alkali metal oxide (eg sodium oxide)], an inorganic acid salt (eg, a weak acid metal salt, such as a carbonate of alkali metal or an alkali metal bicarbonate (hydrogen carbonate)), a salt of an organic acid [for example, an acetate salt, such as an acetic acid metal salt (for example, an alkali metal acetate, such as like lithium acetate, potassium acetate, or sodium acetate an alkaline earth metal acetate, such as calcium acetate; or a salt of acetic acid with any of the metals in groups 3 to 12 of the Periodic Table, such as iron (II) acetate, zinc acetate, or copper (II) acetate], an amine, ammonia and others. The alkaline components can be used separately or in combination.
[000130] Among them, the preferred alkaline component includes an alkali metal hydroxide, an alkaline earth metal hydroxide, an acetate salt (for example, an alkali metal acetate salt, an alkaline earth metal acetate salt), in particular an alkali metal hydroxide.
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60/81 [000131] The amount to be added of the alkaline component can be appropriately selected, depending on the liquid (formulation) composition of the first liquid stream. For example, the concentration of the alkaline component in the liquid object (or the proportion of the alkaline component in the total amount of the first stream of liquid and the alkaline component) can be selected from the range not exceeding 100000 ppm (eg from about 1 to 70,000 ppm) based on weight, and the alkaline component can be added to the first stream of liquid, so that the concentration of the alkaline component can be no more than 50,000 ppm (for example, from about 3 to 30,000 ppm ), preferably not more than 20000 ppm (for example, from about 5 to 15000 ppm) and, more preferably, not more than 10,000 ppm (for example, from about 10 to 7000 ppm). In particular, the alkaline component can be added to the first stream of liquid, so that the concentration of the alkaline component in the liquid object can be no more than 5000 ppm (for example, from about 1 to 3000 ppm), preferably not greater than 2000 ppm (for example, from about 5 to 1500 ppm) and, more preferably, not more than 1000 ppm (for example, between 10 and
900 ppm), based on weight, or so that the concentration of the alkaline component may not exceed 800 ppm [for example, from about 5 to 750 ppm, preferably not more than 500 ppm (for example, from about 10 to 400 ppm)], generally about 10 to 1500 ppm (for example, preferably about 20 to 1200 ppm, preferably about 30 to 1000 ppm, and particularly about 40 to 800 ppm), based on weight.
[000132] In addition, the amount to be added of the alkaline component in relation to 1 mol of hydrogen iodide
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61/81 in the first stream of liquid (or liquid object to be treated) can be selected, from the range of no less than 1 molar equivalent, and can be, for example, from about 1 to 2000 molar equivalents (for example, from about 1.5 to 1500 molar equivalents), preferably from about 2 to 1000 molar equivalents (for example, from about 2.5 to 800 molar equivalents), more preferably, from about 3 to
600 molar equivalents (for example, from about 5 to 500 molar equivalents) and, in particular, from about 10 to 300 molar equivalents. In particular, the amount to be added of the alkaline component in relation to 1 mol of hydrogen iodide in the first stream of liquid (or object
liquid to be treated) can to be no higher to 200 equivalents molars (per example of fence from 1 to 150 equivalents molars) , in preferably, no superior than 100 equivalents molars (per example of fence from 1.5 to 90 equivalents molars) , more preferably no higher to 85 equivalents
from 2 to 83 molar equivalents) about molars (for example, and especially not more than 80 molar equivalents (for example, about 3 to 78 molar equivalents), and can generally be about 1 to 85 molar equivalents (for example, from about 1 to 82 molar equivalents, preferably from about 3 to 80 molar equivalents and, more preferably, from about 5 to 78 molar equivalents).
[000133] According to the present invention, even if the amount of the alkaline component is small, sufficiently effective extraction of hydrogen iodide (HI) can be achieved. In this context, an unconsumed alkaline component (for example, an alkali metal hydroxide) is accumulated in the
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62/81 bottom of the second distillation column and finally extracted from the bottom, or others, of the second distillation column. Therefore, when the alkaline component is accumulated in a large amount, it is necessary to extract a large amount of the lower fraction containing acetic acid, in order to prevent the alkaline component from being mixed in purified acetic acid. In addition, when the alkaline component is accumulated in large quantities, the entrainment of the alkaline component causes an increase in the concentration of a component (eg, a potassium component) derived from the alkaline component in purified acetic acid, or corrosion of the Distillation tends to accelerate, due to an increase in the boiling point. In addition, when the temperature of the second distillation column is equal to the ambient temperature, the alkaline component is sometimes solidified (or crystallized), due to saturation, thus deteriorating its handling properties. Therefore, the process of the present invention, in which a small amount of the alkaline component is allowed to react with hydrogen iodide, is extremely advantageous in terms of the efficiency of the process.
[000134] According to the present invention, the second distillation can be carried out in the presence of component (A), which has a relatively low boiling point and is capable of consuming hydrogen iodide, by a reaction with hydrogen iodide (reaction equilibrium), or inhibit the production of hydrogen iodide in the equilibrium reaction (for example, inhibit a reaction of methyl iodide with water). The second distillation in the presence of component (A) in combination with the alkaline component can inhibit the condensation of hydrogen iodide at the top of the second distillation column in
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63/81 a higher level. In this context, as component (A), a component having a lower boiling point than the boiling point of acetic acid (ie less than 118 ° C) is practically used in terms of the separability of purified acetic acid, or the decreased hydrogen iodide concentration at the top of the distillation column.
[000135] Component (A) can include an alcohol (for example, a C _1-4 alkanol, such as methanol, ethanol, propanol, isopropanol, or 2-butanol), an ether (for example, a C ₁ dialkyl ether _-3 , such as dimethyl ether, methyl ethyl ether, diethyl ether, dipropyl ether, or diisopropyl ether), and an ethyl ester [for example, an alkyl acetate (for example, a C1-3 alkyl acetate, such as such as methyl acetate, ethyl acetate, propyl acetate or isopropyl acetate)]. These components (A) can be used separately or in combination.
[000136] The preferred component (A) can include methanol, dimethyl ether, methyl acetate, and the like.
[000137] The concentration of component (A) in the liquid object can be selected from the range of not less than 0.1% by weight (for example, from about 0.15 to 15% by weight) and can be, for example , not less than 0.2% by weight (for example, from about 0.25 to 12% by weight), preferably not less than 0.3% by weight (for example, from about 0.35 to 10% by weight), more preferably, not less than 0.4% by weight (for example, from about 0.45 to 8% by weight), especially, not less than 1% by weight (for example, about from 1 to 5% by weight) and generally not less than 0.5% by weight [for example, from about 0.6 to 10% by weight, preferably from about 0.7 to 8% by weight weight, more preferably, from about 0.8 to 6% by weight (eg
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64/81 (for example, from about 1 to 4% by weight) and, especially, from about 1 to 2% by weight].
[000138] Incidentally, in the gaseous phase (or portion of gaseous phase or top part of the column), inside the second distillation column, the concentration of component (A) can be not less than 1% by weight (for for example, from about 1.5 to 20% by weight), preferably not less than 2% by weight (for example, from about 2.5 to 15% by weight) and, more preferably, not less than 3 % by weight (for example, from about 3 to 12% by weight).
[000139] In addition, in the gas phase within the second distillation column, the proportion of methyl iodide in relation to component (A) [the previous / last] (weight ratio) can be about 0.01 to 10 and, preferably, from about 0.1 to 5.
[000140] O component (THE) may be contained in the first chain in liquid (per example, the case in that one concentration enough in acetate methyl is contained in first current liquid), or Can be added
recently (or especially). That is, component (A) can be added to the first stream of liquid (or to the second distillation column). The way to add (or mix) component (A) is not particularly limited to a specific type, as long as component (A) is allowed to exist in the liquid object, in the second distillation column, and can comprise the following modes (a) and / or (b):
(a) Component (A) is added or mixed with the first liquid stream, before the first liquid stream is fed into the second distillation column, (b) Component (A) is added or mixed with the
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65/81 first liquid stream in the second distillation column.
[000141] In mode (b), as is the case with the alkaline component, in the second distillation column, component (A) can be added or mixed in the same position (or same plate) as a position (or plate), in that the first liquid stream is fed, or in the position (or plate) higher than that position, in which the first liquid stream is fed. In particular, it is preferable that component (A) is fed in the same position as a position, in which the first stream of liquid is fed (a plate to be fed) or in an upper position (or plate) (eg, the first top plate) to the position where the first liquid stream is fed (the plate to be fed). In addition, component (A) can be added together with the alkaline component, or component (A) and the alkaline component can be added separately.
[000142] Incidentally, for component (A), the time (retention time, contact time), from when the first liquid component and component (A) are mixed until the mixture is fed into the second column of distillation can be, for example, not less than 1 second (for example, from about 2 seconds to 20 minutes), preferably not less than 5 seconds (for example, from about 5 seconds to 15 minutes), more preferably, about 10 seconds to 10 minutes (for example, about 20 seconds to 7 minutes), and it can generally be about 10 seconds to 5 minutes [for example, about 10 seconds to 3 minutes (for example example, about 10 seconds to 1 minute)]. In addition, the contact temperature of the first liquid component and component (A) [the temperature (temperature of the
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66/81 liquid) of the liquid object containing the first liquid component and component (A)] can be, for example, from about 20 to 190 ° C, preferably from about 50 to 180 ° C (for example, from about 70 to 175 ° C) and, more preferably, from about 100 to 170 ° C. Probably, due to the retention time or the temperature of the liquid within the aforementioned range, the reaction of the component (A) with hydrogen iodide accelerates or the reaction progresses in the second distillation column, to some extent, the increase the concentration of hydrogen iodide in the second distillation column tends to be even more efficiently inhibited.
[000143] For the second distillation column, a conventional distillation column, for example, a plate column, a filling column, and other columns can be used. The material of (or to form) the second distillation column can include the same material as that of the first distillation column. According to the present invention, since the condensation of hydrogen iodide inside the second distillation column can be significantly inhibited, not only a distillation column made of an expensive material having a high resistance to corrosion ( as a zirconium), but also a distillation column made of a relatively cheap material having a not very high resistance to corrosion, for example an alloy [for example, a transition metal based alloy, such as an iron based alloy (or an alloy containing iron as the main component, for example, a stainless steel (including stainless steel containing chromium, nickel, molybdenum and others)), a nickel-based alloy (or an alloy containing nickel as the main component, for example, HASTELLOY (trade name) and INCONEL
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67/81 (trade name)), a cobalt based alloy (or a cobalt alloy as the main component)]. Among others, an iron-based alloy or a nickel-based alloy is preferred.
[000144] The distillation temperature and pressure in the second distillation column can be appropriately selected, depending on the condition, such as the species of the distillation column, or the main object (target) for extraction, selected from the component with the lowest boiling point and the component with the highest boiling point. For example, the internal pressure of the column (in general, the pressure of the top of the column) can be from about 0.01 to 1 MPa, preferably from about 0.01 to 0.7 MPa, and more preferably , from about 0.05 to 0.5 MPa, in terms of gauge pressure.
[000145] In the second distillation column, the internal temperature of the column can be, for example, from about 30 to 200 ° C, preferably from about 80 to 180 ° C and, more preferably, from about 100 to 170 ° C, depending on the internal pressure of the column. The temperature at the top of the column (or the temperature of the gaseous phase) can be, for example, from about 30 to 180 ° C, preferably from about 50 to 150 ° C and, more preferably, from about 70 to 120 ° C. In addition, the temperature at the bottom of the column can be, for example, from about 80 to 200 ° C, preferably from about 100 to 190 ° C (for example, from about 120 to 185 ° C) and, more preferably, from about 130 to 180 ° C (for example, from about 140 to 170 ° C).
[000146] Furthermore, the theoretical number of plates of the second distillation column is not particularly limited to a specific value and, depending on the species of the component to be separated, it can be from about 5 to 1500, preferably from
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68/81 about 10 to 120, and more preferably, about 20 to 100, and can generally be about 30 to 120 (e.g., about 40 to 100). In addition, in the second distillation column, the reflux ratio can be selected from, for example, about 0.1 to 100, preferably from about 0.3 to 50 and, more preferably, from about 0, 5 to 30 (for example, from about 0.5 to 20), according to the theoretical number of plates mentioned above. In this context, in the first distillation column, distillation can be carried out without reflux.
[000147] According to the present invention, as described above, distillation in the presence of the alkaline component (and component (A)) can inhibit the increase in the concentration of hydrogen iodide in the second distillation column. In particular, according to the present invention, condensation of hydrogen iodide can be significantly inhibited, even at the top (gas phase portion) of the second distillation column. For example, in the continuous reaction, the concentration of hydrogen iodide in the second component with the lowest boiling point (distillate) is less than 40 ppm (for example, from about 0 or detection limit to 38 ppm), preferably not greater than 36 ppm (for example, from about 0 or detection limit to 35 ppm), more preferably, not more than 33 ppm (for example, from about 0 or detection limit to 32 ppm) and, in particular, not more than 30 ppm (for example, from about 0 or detection limit to 25 ppm).
[000148] Since the fraction with the lowest boiling point (second component with the lowest boiling point) separated by the second distillation column contains a useful component, such as methyl iodide or methyl acetate, the fraction with the lowest boiling point can be directly recycled to the system
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69/81 reaction (for example, the reactor) and / or the second distillation column. In order to remove part of the reaction heat, in the same way as the lowest boiling point fraction extracted by the first distillation column, the lowest boiling point fraction can be liquefied by a condenser, a heat exchanger, or other means and then recycled. In addition, since the lowest boiling fraction sometimes contains acetaldehyde, the lowest boiling fraction can be recycled, for example, after extraction of acetaldehyde with the aldehyde separation column below, if necessary. In this context, the flue gas component can be introduced into the washing system.
[000149] In the embodiment of Fig. 1, the purified acetic acid stream (second stream of liquid) is extracted (or collected) by side cutting, and the position of the side chain opening is generally in a medium or lower position of the second distillation column. As described above, generally, the side chain opening for extracting the second liquid stream is practically situated at a lower position than the position (the position of the feed opening) for feeding the first liquid stream.
[000150] In addition, in the second distillation column, each of the second lowest boiling component and second highest boiling component (fraction of highest boiling point, bottom fraction) containing at least part of the higher boiling point (such as propionic acid or water), can be separated. In addition, in the embodiment of Fig. 1, the second stream of liquid is extracted (or removed or collected) as a stream by side cutting. The second stream of liquid can be extracted by
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70/81 bottom of the column, or removed (or collected) together with the fraction with the highest boiling point (second component with the highest boiling point).
[000151] In fact, the second component with the highest boiling point can be discharged from the bottom or bottom of the column. Since the component with the highest boiling point separated by the second distillation column contains propionic acid and others, the fraction with the highest boiling point can be directly discarded (or removed). In addition, since the second highest boiling component sometimes still contains acetic acid, if necessary, the highest boiling fraction, from which propionic acid is removed and / or recovered, can be recycled for the reaction system (for example, the reactor). In fact, through the extraction of the acetic acid stream (second liquid fraction) through the side current opening at a higher position in relation to the lower opening to extract the second highest boiling point component, the side current and the highest point component boiling point (highest boiling point fraction) can be efficiently separated.
(Iodide extraction step) [000152] Purified acetic acid (second stream of liquid) and recovered is usually introduced into a column for acetic acid product and obtained as an acetic acid product. Before or after introduction into the column for the acetic acid product, the purified acetic acid can be further subjected to an iodide extraction step to remove an iodide (for example, a C1-15 alkyl iodide, such as hexyl iodide or decyl iodide).
[000153] In the iodide extraction step, the acid stream
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71/81 acetic acid can be contacted with a remover (material or removing agent) having an iodide removal capacity or iodide adsorption capacity (for example, a zeolite, an activated carbon, and an ion exchange resin). In order to efficiently remove iodide from the acetic acid stream, which is continuously obtained (in a continuous system), an ion exchange resin, with iodide removal capacity or iodide adsorption capacity, in particular, an extraction column of iodide with ion exchange resin inside, is advantageously used.
[000154] The ion exchange resin to be used is generally an ion exchange resin (usually a cation exchange resin), in which at least part of the active region (for example, usually an acid group, such as a sulfone group , a carboxyl group, a phenolic hydroxyl group, or a phosphone group) is replaced or exchanged for a metal. The metal can include, for example, at least one member selected from the group consisting of silver (Ag), mercury (Hg) and copper (Cu). The cation exchange resin, as a base (substrate), can be any one of a strong acid cation exchange resin and a weak (soft) cation exchange resin, and the preferred one includes an acid cation exchange resin strong, for example, a macroreticular ion exchange resin, and the like.
[000155] In ion exchange resin, the proportion of the active region exchanged with the metal (or replaced by the metal) can be, for example, from about 10 to 80 mol%, preferably from about 25 to 75% per mol and, more preferably, from about 30 to 70 mol%.
[000156] At least the contact of the acetic acid stream in the
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72/81 second distillation column with the ion exchange resin (preferably passing the acetic acid stream through the ion exchange resin) performs the iodide extraction. During contact with (or passing through) the ion exchange resin, if necessary, the temperature of the acetic acid stream can be gradually increased (or raised). The temperature rise in stages ensures the inhibition of the discharge or flow of the metal from the ion exchange resin, as well as removal of the iodide, efficiently.
[000157] Examples of iodide extraction column may include a filling column, having within it at least the ion exchange resin that is exchanged with a metal, a column equipped with a bed of an ion exchange resin ( for example, a bed containing particulate resin) (a protective bed) and the like. The iodide extraction column can be provided with ion exchange resin exchanged with metal and, in addition, another ion exchange resin (for example, a cation exchange resin, an anion exchange resin, and a non- ionic) inside. Even when the metal is emanating from the ion exchange resin exchanged with metal, the disposition of the cation exchange resin on the downstream side of the ion exchange resin exchanged with metal (for example, arrangement of the cation exchange resin by filling, or arrangement of the cation exchange resin such as a resin bed) allows the effluent metal to be captured with the cation exchange resin, and to be removed from the carboxylic acid stream.
[000158] The temperature of the iodide extraction column can be, for example, from about 18 to 100 ° C, preferably from about 30 to 70 ° C and, more preferably, from about 40 to 60 ° C.
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73/81 [000159] The speed of the acetic acid stream to be passed through the array is not limited to a specific value, and can be, for example, in an iodide extraction column using a protective bed, for example, about 3 to 15 BV / h (bed volume per hour), preferably about 5 to 12 BV / h and more preferably about 6 to 10 BV / h.
[000160] In the iodide extraction step, the acetic acid stream can be at least contacted with the ion exchange resin, exchanged for metal. For example, the iodide extraction column may comprise a column with ion exchange resin, exchanged for metal, and a column with another ion exchange resin. For example, the iodide extraction column may comprise an anion exchange resin column, and an ion exchange resin column, exchanged for metal, on the downstream side of the anion exchange resin column, or it may comprise an anion exchange resin column. ion exchange, exchanged for metal, and a column of cation exchange resin on the downstream side of the column of ion exchange resin, exchanged for metal. The details of the previous example can be found in WO02 / 062740, and others.
(Acetaldehyde separation step) [000161] When the fraction containing acetaldehyde generated by the reaction is recycled and distributed to the reaction system or others, the amount of by-product (s), such as propionic acid, an unsaturated aldehyde, or an iodide alkyl increases. Thus, it is preferred to remove acetaldehyde in the solution to be recycled. In particular, extraction of acetaldehyde is preferred, as it is unnecessary to separate and remove propionic acid, which makes the acetic acid sub-standard in the second distillation column. The method for separating acetaldehyde can
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74/81 comprise feeding a recycling solution (a solution to be recycled) to the acetaldehyde separation column, to separate a fraction of the lowest boiling point containing acetaldehyde and a fraction of the highest boiling point containing methyl iodide, acetate of methyl, water, and others and then separate acetaldehyde from the top or top of the aldehyde separation column, with the flue gas component (for example, carbon monoxide and hydrogen). In addition, the flue gas component can be removed previously with a condenser, or a cooling unit, before the separation of acetaldehyde. In addition, since the highest boiling point fraction, obtained by extracting acetaldehyde as the lowest boiling point fraction, contains methyl iodide, water, methyl acetate, acetic acid, and the like, the highest point fraction boiling water can be recycled to the reaction system.
[000162] For the aldehyde separation column, for example, a conventional distillation column can be used, for example, a plate column, a filling column, an instant evaporator, and others.
[000163] The temperature (the temperature at the top of the column), and the pressure (the pressure at the top of the column)), in the acetaldehyde separation column, can be selected, depending on the type of the distillation column and others, and are not particularly limited to a specific value, insofar as at least acetaldehyde is separable as a lower-boiling fraction from the recycling solution [for example, the lower-fraction (s) boiling obtained in the first and / or second distillation column (s)], using the difference between acetaldehyde and other components
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75/81 (in particular, methyl iodide) at the boiling point. For example, for the plate column, the pressure can be from about 0.01 to 1 MPa, preferably from about 0.01 to 0.7 MPa and, more preferably, from about 0.05 to 0 , 5 MPa as a gauge pressure. The internal temperature of the column is, for example, from about 10 to 150 ° C, preferably from about 20 to 130 ° C and, more preferably, from about 40 to 120 ° C. The theoretical number of plates can be, for example, from about 5 to 150, preferably from about 8 to 120 and, more preferably, from about 10 to 100.
[000164] In the acetaldehyde separation column, the reflux ratio can be selected from about 1 to 1000, preferably from about 10 to 800 and preferably from about 50 to 600 (e.g. approximately 70 to 400), depending on the theoretical number of plates mentioned above.
EXAMPLES [000165] The following examples are intended to describe the present invention in greater detail and should in no way be construed as defining the scope of the invention.
(Comparative Example 1) [000166] In a continuous reaction process to produce acetic acid, methanol was allowed to react with carbon monoxide in a carbonylation reactor, the reaction mixture obtained in the reactor was fed continuously to a vaporizer and subjected to instant distillation. The resulting volatile component, containing at least the acetic acid product, methyl acetate, methyl iodide, water, and hydrogen iodide, was fed to a first distillation column, and a first component with the lowest boiling point was
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76/81 separated as a supernatant. For a second distillation column (number of plates: 50, loading plate: 30 ^the plate from the bottom), 100 parts of a first stream of liquid having a composition of 3.0% by weight of methyl iodide (Honey ), 2.0% by weight of methyl acetate (MA), 2.0% by weight of water (H ₂ O), 20 ppm (based on weight) of hydrogen iodide (HI), and 93.0% by weight of acetic acid (the liquid temperature of the first liquid stream: 130 ° C) was fed; and a lower boiling point impurity (second lowest boiling component) was distilled and removed at a head pressure of 150 kPa, a column bottom temperature of 160 ° C, a column top temperature of 145 ° C , and a reflux ratio of 2, in a proportion of 26 parts of a second component with a lower boiling point (distillate) and 74 parts of a second stream of liquid containing acetic acid (background fraction). The second component with the lowest boiling point (distillate) was distributed to the reaction system, and the crude acetic acid (second stream of liquid) as the background fraction, after purification, was subjected to further purification in the next column of distillation. The composition (formulation) of the second component with the lowest boiling point (distillate) was as follows: 11.4% by weight of MeI, 7.7% by weight of MA, 7.6% by weight of H2O, 40 ppm of HI, and 75.1% by weight of acetic acid (Ac).
[000167] In the continuous reaction process, specimens were added at the top of the second distillation column. After remaining there for 100 hours, each specimen was examined by a corrosion test, and the corrosion of each specimen was observed, before and after the corrosion test.
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77/81 [000168] The corrosion test was evaluated based on the following criteria in Comparative Examples 1 and 3 and Examples 1 to 3, and evaluated for the amount of corrosion observed in Comparative Example 2 and Examples 4 to 6.
A: specimen not corroded at all. B: specimen severely corroded. C: slightly corroded specimen. D: specimen significantly corroded. (Example 1) [000169] The process was carried out in the same way as in Comparative Example 1, with the exception that potassium hydroxide (KOH) was then added to the first stream of liquid, to have a ratio of 0.07% by weight in the resulting mixture (liquid object), and where the mixture was fed (loaded) to the second distillation column, and the corrosion test was carried out. The liquid temperature of the first liquid stream did not change after the addition of potassium hydroxide. The time, from when potassium hydroxide was added to the first stream of liquid to when the mixture was fed to the second distillation column, was 30 seconds. The composition of the distillate did not change, except that the HI concentration was 5 ppm.
(Example 2) [000170] The process was carried out in the same way as in Comparative Example 1, with the exception that potassium hydroxide (KOH) was then added to the first stream of liquid, to have a ratio of 0.02% by weight in the resulting mixture (liquid object), and where the mixture was fed (loaded) to the second distillation column, and the corrosion test was carried out. THE
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The liquid temperature of the first liquid stream did not change after the addition of potassium hydroxide. The time, from when potassium hydroxide was added to the first stream of liquid to when the mixture was fed to the second distillation column, was 30 seconds. The composition of the distillate did not change, except that the HI concentration was 10 ppm.
(Example 3) [000171] The process was carried out in the same way as in Comparative Example 1, with the exception that potassium hydroxide (KOH) was then added to the first stream of liquid, to have a ratio of 0.04% by weight in the resulting mixture (liquid object), and where the mixture was fed (loaded) to the second distillation column, and the corrosion test was carried out. The liquid temperature of the first liquid stream did not change after the addition of potassium hydroxide. The time, from when potassium hydroxide was added to the first stream of liquid to when the mixture was fed to the second distillation column, was 30 seconds. The composition of the distillate did not change, except that the HI concentration was 20 ppm.
(Comparative Example 2) [000172] The process was carried out in the same way as in Comparative Example 1, except that 100 parts of the first stream of liquid having a composition of 3.0% by weight of MeI, 2.0% in MA weight, 0.6 wt% H ₂ O, 20 ppm HI (based on weight), and 94.4 wt% acetic acid was used, and the corrosion test was performed. The composition of the second component with the lowest boiling point (distillate) was
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Following 79/81: 11.0 wt% Honey, 7.9 wt% MA, 2.1 wt%, H ₂ O, and 42 ppm HI; and the rest was acetic acid.
(Example 4) [000173] The process was carried out in the same way as in Comparative Example 2, with the exception that potassium hydroxide (KOH) was then added to the first stream of liquid, to have a ratio of 0.07% by weight in the resulting mixture (liquid object), and where the mixture was fed (loaded) to the second distillation column, and the corrosion test was carried out. The liquid temperature of the first liquid stream did not change after the addition of potassium hydroxide. The time, from when potassium hydroxide was added to the first stream of liquid to when the mixture was fed to the second distillation column, was 30 seconds. The composition of the distillate was as follows: 11.5% by weight of MeI, 7.2% by weight of MA, 2% by weight of H2O, and less than 5 ppm of HI; and the rest was acetic acid.
(Example 5) [000174] The process was carried out in the same way as in Comparative Example 2, with the exception that potassium hydroxide (KOH) was then added to the first stream of liquid, to have a ratio of 0.02% by weight in the resulting mixture (liquid object), and where the mixture was fed (loaded) to the second distillation column, and the corrosion test was carried out. The liquid temperature of the first liquid stream did not change after the addition of potassium hydroxide. The time, from when potassium hydroxide was added to the first stream of liquid to when the mixture was fed to the second distillation column, was 30 seconds.
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80/81
The composition of the distillate was as follows: 11.7% by weight of honey, 7.4% by weight of MA, 2.2% by weight of H ₂ O, and 11 ppm of HI, and the rest was acid acetic.
(Example 6) [000175] The process was carried out in the same way as in Comparative Example 2, with the exception that potassium hydroxide (KOH) was then added to the first stream of liquid, to have a ratio of 0.04 % by weight in the resulting mixture (liquid object), and where the mixture was fed (loaded) to the second distillation column, and the corrosion test was carried out. The liquid temperature of the first liquid stream did not change after the addition of potassium hydroxide. The time, from when potassium hydroxide was added to the first stream of liquid to when the mixture was fed to the second distillation column, was 30 seconds. The distillate composition was as follows: 11.1 wt% MeI, 7.0 wt% MA, 2.1 wt% H ₂ O, and 19 ppm HI; and the rest was acetic acid.
[000176] The composition of the distillate and the results of the corrosion test are shown in the Table. The details of the materials described in the Table are as follows. The mm / Y unit means the corrosion rate of the specimen per year (the reduced thickness (mm) of the specimen per year).
HB2: HASTELLOY B2 (nickel-based alloy), manufactured by Oda Koki Co., Ltd.
HC: HASTELLOY C (nickel-based alloy), manufactured by Oda Koki Co., Ltd.
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81/81 [Table 1]
Composition of distilled ConditionKOH charge Corrosion testing MeI BAD H2O HI B.C KOH KOH / HI HB2 HC Weight Weight Weight ppm % Weight % Weight molar ratio mm / Y mm / Y Example1Comparative 11.4 7.7 7.6 40 remaining 0 0 B D Example 111.4 7.7 7.6 5 remaining 0.07 76 THE B Example 211.4 7.7 7.6 10 remaining 0.02 22 THE Ç Example 311.4 7.7 7.6 20 remaining 0.04 22 THE Ç Example2Comparative 11.0 7, 9 2.1 42 remaining 0 0 0.09 0.15 Example 411.5 7.2 2 bottomto 5 remaining 0.07 76 bottomto 0.03 0.05 Example 511.7 7, 4 2.2 11 remaining 0.02 23 0.04 0, 08 Example 611, 1 7, 0 2.1 19 remaining 0.04 21 0.05 0.1
Industrial Applicability [000177] The production process of the present invention is extremely useful as a process for producing acetic acid, while efficiently inhibiting the increase in the concentration (or condensation) of hydrogen iodide in the second distillation column.
Description of Reference Numbers
Reactor
Vaporizer (evaporator)
First distillation column
Second distillation column
5, 6, 7, 8, 9 Condenser or heat exchanger
Washing system

权利要求:
Claims (11)
[1]
- CLAIMS -
1. PROCESS TO PRODUCE ACETIC ACID, characterized by the fact that it comprises an instant evaporation step to separate a reaction mixture into a volatile component and a liquid component;
acetic acid collection step to feed a first distillation column with the volatile component, containing at least acetic acid, methyl acetate, methyl iodide, water, and hydrogen iodide, separate a lower boiling point first component as a supernatant, and collect a first stream of liquid containing mainly acetic acid, purification step of acetic acid to feed a second distillation column with the first stream of liquid, separate a second low boiling component as a supernatant, and collect a second stream of liquid containing acetic acid, where the first stream of liquid additionally contains methyl iodide in a concentration of 10 ppm at 8% by weight, methyl acetate at a concentration of 0.1 to 8% by weight, water at a concentration of 0.2 to 20% by weight, hydrogen iodide at a concentration not exceeding 1000 ppm based on weight, in which a component Alkaline is added or mixed in the following ways (1) and / or (2), to distill a liquid object to be treated containing the first liquid stream and the alkaline component in the second distillation column:
(1) the alkaline component is added or mixed
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[2]
2/4 with the first liquid stream, before the first liquid stream is fed into the second distillation column, (2) the second distillation column, the alkaline component is added or mixed at the same height level as a height level , in which the first liquid stream is fed, or at a height level higher than the height level, in which the first liquid stream is fed.
2. PROCESS, according to claim 1, characterized in that the amount to be added of the alkaline component is from 1 to 2000 molar equivalents in relation to 1 mol of hydrogen iodide in the first liquid stream, and the alkaline component is added, so that the concentration of the alkaline component in the liquid object can be no more than 100,000 ppm based on weight.
[3]
3. PROCESS, according to claim 2, characterized by the fact that, in the first stream of liquid, the concentration of methyl iodide is less than 4% by weight.
[4]
4. PROCESS, according to claim 2 or 3, characterized by the fact that, in the first stream of liquid, the
concentration of methyl iodide is 10 ppm to 3.5% in weight.one of 5. PROCESS , according with any claims 2 to 4, featured fur fact that first net current liquid, the concentration of water is not more than 3% by weight. 6. PROCESS , according with any one of claims 2 to 5, featured fur fact that first liquid stream, the concentration of hydrogen iodide be not more than 100 ppm weight-based.7. PROCESS , according with any one of claims 2 to 6, featured fur fact that first
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3/4 stream of liquid, the hydrogen iodide concentration should be 1 to 30 ppm based on weight.
[5]
8. PROCESS, according to any one of claims 1 to 7, characterized by the fact that, in mode (1), the contact temperature of the first liquid stream and the alkaline component is from 100 to 170 ° C, and the time, at from when the first stream of liquid and the alkaline component are mixed until when the mixture is fed into the second distillation column, it should not exceed 5 minutes.
[6]
9. PROCESS, according to any one of claims 1 to 8, characterized in that the amount to be added of the alkaline component is not more than 85 molar equivalents in relation to 1 mol of hydrogen iodide in the first liquid stream, and the alkaline component to be added, so that the concentration of the alkaline component in the liquid object can be no more than 1000 ppm based on weight.
[7]
10. PROCESS according to any one of claims 1 to 9, characterized in that the amount to be added of the alkaline component is not more than 80 molar equivalents in relation to 1 mol of hydrogen iodide in the first liquid stream, and the alkaline component to be added, so that the concentration of the alkaline component in the liquid object can be not more than 800 ppm, based on weight.
[8]
11. PROCESS according to any one of claims 1 to 10, characterized in that, in the second distillation column, at least one component (A) having a lower boiling point than a boiling point of acetic acid, and being selected from the group consisting of a
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4/4 alcohol, an ether, and an ethyl ester, exist in a concentration of not less than 0.2% by weight in the liquid object.
[9]
12. PROCESS, according to claim 11, characterized by the fact that component (A) exists at a concentration of not less than 1% by weight in the liquid object.
[10]
13. PROCESS, according to claim 11 or 12, characterized by the fact that component (A) is allowed to exist in the liquid object, by adding the first component of liquid stream.
(A-N-A
[11]
14. PROCESS, according to any one of claims 11 to 13, characterized in that component (A) is allowed to exist in the liquid object, through (i) adding component (A) in the first liquid stream, before the first liquid stream is fed into the second distillation column and / or (ii), in the second distillation column, add component (A) to the first liquid stream, at the same height level as a height level, at which the first liquid stream is fed, or at a height level higher than the height level, at which the first liquid stream is fed.
15. Process of wake up with any an of claims 1 to 14, featured fur fact of material gives second column distillation understand an turns on the base in
nickel.

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同族专利:

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EP2657220B1|2016-08-31|

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法律状态:
2018-12-04| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2019-08-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-09-03| 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 01/12/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 01/12/2011, 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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JP2010288523|2010-12-24|

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PCT/JP2011/077847|WO2012086386A1|2010-12-24|2011-12-01|Acetic acid production method|

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