process for producing acetic acid, method for inhibiting hydrogen iodide production, or increasing t

专利摘要:
process for producing acetic acid, method for inhibiting hydrogen iodide production, or increase in the concentration of hydrogen iodide in a vaporizer in an acetic acid production process, and acetic acid process or method is produced, while inhibiting an increase in concentration or production of hydrogen iodide in an instant evaporator. A process for producing acetic acid comprises a series of steps: a reaction step for allowing methanol to continuously react with carbon monoxide in the presence of a catalyst system comprising a metal catalyst, an ionic iodide, and methyl iodide in a carbonylation reactor. means an instant distillation step for continuously feeding a vaporizer with a reactor reaction mixture and evaporating a volatile component containing at least the acetic acid, methyl acetate and methyl iodide product by instant distillation to separate the volatile component. and a liquid catalyst mixture containing at least the metal catalyst and ionic iodide, and an acetic acid collection step for separating an acetic acid-containing stream from the volatile component to collect acetic acid; wherein, in the instant distillation step, instant distillation is performed, provided that the concentration of methyl acetate in the liquid catalyst mixture is not less than 0.6% by weight.
公开号:BR112013014804B1
申请号:R112013014804
申请日:2011-12-01
公开日:2019-08-13
发明作者:Nakajima Hidehiko；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, METHOD FOR INHIBITING THE PRODUCTION OF HYDROGEN IODIDE, OR INCREASING THE CONCENTRATION OF HYDROGEN IODIDE IN A VAPORIZER, IN A PROCESS OF PRODUCTION OF ACETIC ACID, AND PROCESS OR METHOD
Technical Area [0001]
The present invention relates to a process for producing acetic acid, while efficiently inhibiting the increase in the concentration of hydrogen iodide in an instant evaporator (vaporizer) to distill a reaction mixture from a reactor.
Prior Art [0002] Various industrial processes for the production of acetic acid are known. Among others, an industrially excellent process includes a process that comprises continuously allowing methanol to react with carbon monoxide with the use of 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, improved reaction conditions and catalysts have been investigated, and an industrial process for producing highly efficient acetic acid has been developed, through the addition of a catalyst stabilizer (such as an iodide salt), and the reaction under a low water condition compared to the conventional system.
[0003] According to the process, in general, acetic acid is produced, allowing methanol to react with carbon monoxide, by subjecting the resulting reaction mixture containing acetic acid to distillation (instant distillation) in a
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2/57 vaporizer (instant evaporator), subject a vaporized component by distillation to additional distillation, and separate (further purification) a component containing acetic acid. The reaction mixture contains the product acetic acid, methyl iodide, and others. When the hydrogen iodide concentration in the flash evaporator is increased, in response to the distillation conditions (for example, a change in composition (formulation), a change in pressure, and a change in temperature), the corrosion of the flash evaporator can be hasty. That is, since instant distillation is a single continuous distillation, usually hydrogen iodide is not condensed in the instant evaporator (or the condensation effect is hardly revealed). However, in addition to hydrogen iodide contained in the reaction mixture, there is hydrogen iodide recently produced in the instant evaporator (for example, hydrogen iodide is produced by a reaction of methyl iodide with acetic acid, due to a reduction in the concentration of methyl acetate, or produced by a reaction of lithium iodide with acetic acid, due to an increase in lithium iodide). When a component containing hydrogen iodide is subjected to a distillation column for separation of acetic acid, or when a residue (liquid residue or lower fraction), after separation of the vaporized component, is recycled to the reactor, the reaction system can be adversely affected, and in addition corrosion of the peripheral device (s) may be precipitated. Therefore, it is preferable that the increase in the hydrogen iodide concentration in the instant evaporator is avoided. Although a technique for inhibiting hydrogen iodide condensation in a distillation column, such as plate column,
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3/57 filling is already known, a technique closely focused on hydrogen iodide in an instant distillation for the reaction mixture is not known.
[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 reaction mixture (or liquid reaction composition) or to a light component, which is separated from the reaction mixture by a first distillation and it is rich in a low boiling component (for example, water, an alcohol, an alkyl iodide, a carboxylic acid, or such an acid anhydride, a carboxylate ester, and hydrogen iodide). In the Examples in this document, a process solution (specifically, a volatile component separated by an instant distillation of a reaction mixture), free of an ionic iodide (such as lithium iodide), is examined for the effect of water concentration on condensation of hydrogen iodide. As described above, the purpose of Patent Document 1 is to condense hydrogen iodide in distillation, and the reduction of hydrogen iodide in an instant evaporator has not been examined.
[0005] Published Japanese Patent Application No. 6-40998 (JP-6-40998A, Patent Document 2) describes a process for producing acetic acid, allowing methanol to react with carbon monoxide in the presence of a rhodium catalyst and
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4/57 methyl iodide, the process comprising a step to continuously carry out the reaction to a water concentration not exceeding 10% by weight in the reaction solution, to continuously extract the reaction solution to introduce an evaporation step, in which the pressure is less than the reaction condition, and separate a vaporizing component and a non-vaporizing component containing rhodium; and, in step, (a) hydrogen is introduced and evaporation is conducted on the condition that the partial pressure of hydrogen is at least not less than 0.1 atmospheres, and / or (b) the non-vaporizing component containing the separate rhodium is treated with at least hydrogen having a partial pressure of hydrogen of at least 0.1 atmospheres, and not less than 0.1 atmospheres of carbon monoxide and then returned to the reactor for recycling. The document describes in the Examples, that the reaction solution is subjected to instant distillation at a bottom liquid temperature of 120 to 138 ° C to evaporate half of that volume, a condensed solution containing 0.5% by weight of methyl iodide , 0.2% by weight of ethyl methyl, and others, is obtained. However, no consideration is given to hydrogen iodide in instant distillation.
Summary of the Invention
Problems to be solved by the invention [0006] It is, therefore, an object of the present invention to provide a process to produce acetic acid, while effectively inhibiting (or avoiding) the increase in a concentration of hydrogen iodide in an instant evaporator.
[0007] It is another object of the present invention to provide a process for producing acetic acid, the
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5/57 process preventing corrosion of an instant evaporator.
Means to solve problems [0008] Basically, the composition (formulation) of the reaction solution (or reaction mixture), theoretically, depends on a reaction temperature, a pressure in an instant distillation, and others, under one condition adiabatic. Based on information from equilibrium theory, the inventors of the present invention examined a method to inhibit an increase in the concentration of hydrogen iodide in an instant evaporator, in an instant distillation step of a reaction mixture obtained by a methanol carbonylation reaction using a catalyst system containing a metal catalyst, an ionic iodide (for example, an alkali metal iodide), and methyl iodide. However, temperature, pressure, and composition can be determined arbitrarily, and their combination varies, in a variable way, the conditions of instant distillation. In addition, there are a variety of reactions involved in the production of hydrogen iodide in the instant evaporator, and these reactions are complicated. Therefore, it was really difficult to steadily inhibit the production of hydrogen iodide and the increase in the concentration of hydrogen iodide, while maintaining sufficiently efficient production of acetic acid, based on a simple equilibrium theory.
[0009] The inventors of the present invention carried out intense studies to reach the above objects and, finally, found that the increase in the concentration of hydrogen iodide in the instant evaporator is inhibited by carrying out a distillation, while adjusting a composition of a specific component. residual liquid component (mixture
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6/57 of liquid catalyst), which is separated from a volatile component in instant distillation; that inhibiting the increase in the concentration of hydrogen iodide prevents corrosion of the instantaneous evaporator and furthermore reduces the adverse effects (eg corrosion) caused by hydrogen iodide on the entire process, to which the volatile component, or the liquid catalyst mixture of the instant evaporator, is fed [for example, a distillation column to subject a volatile component to further distillation, or its accessory facilities (or apparatus) (for example, a heat exchanger, such as a pump circulation system, a condenser, or a cooler); accessory installations (or apparatus) for recycling a mixture of liquid catalyst to a reactor (for example, a heat exchanger and a circulation pump); and power lines for this distillation column and ancillary facilities]. The present invention was carried out based on the above conclusions.
[00010] That is, the process of the present invention includes a process for producing acetic acid, which comprises a reaction step to allow methanol to continuously react with carbon monoxide in the presence of a catalyst system, comprising a metal catalyst (e.g. example, a rhodium catalyst), an ionic iodide (for example, an alkali metal iodide, such as lithium iodide), and methyl iodide in a carbonylation reactor, an instant distillation step to continuously feed a vaporizer with a mixture reactor and separate a volatile component containing at least acetic acid product, methyl acetate, and methyl iodide by instant distillation to separate the volatile component and a mixture of liquid catalyst
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7/57 containing at least the metal catalyst and ionic iodide, and an acetic acid collection step to separate a stream containing acetic acid from the volatile component, to collect acetic acid; wherein, in the instant distillation step, the instant distillation is carried out on the condition that the concentration of methyl acetate in the liquid catalyst mixture is not less than 0.6% by weight.
[00011] 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 liquid catalyst mixture can be not less than 40% by weight. According to the present invention, the increase in the concentration of hydrogen iodide in the vaporizer can be inhibited, while ensuring a sufficiently efficient production (or reaction rate) of acetic acid.
[00012] Representatively, with regard to the concentration of each component in the liquid catalyst mixture, the concentration of ionic iodide can be not more than 50% by weight, the concentration of methyl iodide can be not more than 5% by weight, the concentration of acetic acid can be from about 45 to 90% by weight, and the water concentration can be not 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
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8/57 can be about 50 to 85% by weight, the concentration of methyl acetate can be about 0.7 to 5% by weight, and the water concentration can be about 0.8 to 8 % by weight.
[00013] In the instant distillation step, the instant distillation can be conducted at an absolute pressure of 0.1 to 0.5 MPa, while maintaining the temperature of the liquid catalyst mixture (the instant distillation temperature) of about 100 at 170 ° C.
[00014] 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.
[00015] According to the present invention, condensation or hydrogen iodide production in the instant evaporator can be inhibited by adjusting (or controlling) the concentration of methyl acetate, or others, and then corrosion of the instant evaporator can be inhibited.
[00016] Thus, the present invention also includes a method for inhibiting the production or increase in the concentration of hydrogen iodide in a vaporizer [in a liquid phase portion in a vaporizer (in a liquid catalyst mixture) and / or in a portion gas phase in a vaporizer] (or to inhibit corrosion of a vaporizer) in an acetic acid production process, the production process comprising a reaction step to allow methanol to react continuously with
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9/57 carbon monoxide in the presence of a catalyst system comprising a metal catalyst, an ionic iodide, and methyl iodide in a carbonylation reactor, an instant distillation step to continuously feed a vaporizer (instant evaporator) with a reaction mixture from the reactor and separate a volatile component containing at least the acetic acid product, methyl acetate, and methyl iodide by instant distillation, to separate the volatile component and a mixture of liquid catalyst, containing at least the metal catalyst and the ionic iodide , and an acetic acid collection step to separate a stream containing acetic acid from the volatile component to collect acetic acid; wherein, in the instant distillation step, the instant distillation is carried out on the condition that the concentration of methyl acetate in the liquid catalyst mixture is not less than 0.6% by weight.
[00017] In the method, the concentration of hydrogen iodide in the liquid catalyst mixture can, for example, be maintained at a temperature not exceeding 1% by weight.
[00018] In the process or method of the present invention, the vaporizer material may comprise an alloy (e.g., a nickel-based alloy). The present invention achieves corrosion inhibition, and even a vaporizer made of such a relatively corrosive material can preferably be used. [00019] Throughout the description, the total proportion (s) of any / any component (s) existing in the same mixing system (such as the liquid catalyst mixture) does not exceed 100% in Weight; and the proportions of all components are 100% by weight, in total.
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10/57
Effects of the Invention [00020] According to the process of the present invention, acetic acid can be produced, while efficiently inhibiting (or avoiding) the increase in the hydrogen iodide concentration in the instant evaporator. In addition, according to the present invention, corrosion of the instant evaporator can be inhibited. Therefore, instant distillation can be carried out efficiently, without manufacturing the instant evaporator with a high quality material having a high resistance against corrosion. Thus, according to the present invention, an instantaneous evaporator [in addition, first and second distillation columns, or its accessory installations (or apparatus) (for example, a condenser)] can be made from 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 [00021] Fig. 1 is a diagram for explaining an acetic acid production process (or production apparatus), according to an embodiment of the present invention.
Description of Embodiments [00022] 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) for explaining a production process (or production apparatus) for acetic acid, according to an embodiment of the present invention.
[00023] The embodiment of Fig. 1 shows a continuous process (or apparatus) for producing acetic acid (CH3COOH), at
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11/57 from a liquid reaction medium (or reaction mixture), generated by a continuous carbonyl reaction of methanol (MeOH) with carbon monoxide (CO) in the presence of a catalyst system comprising a rhodium catalyst, such as a metal catalyst, and a co-catalyst [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.
[00024] 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 a lower boiling point) containing at least the acetic acid product, methyl acetate, and methyl iodide, and a mixture of liquid catalyst (a low volatility component or a higher boiling fraction) containing essentially a catalyst component (a higher boiling component) (for example, a rhodium and lithium iodide catalyst) from a medium liquid reaction (or a reaction mixture, or a reaction solution), which is introduced from reactor 1, through a feed line 14, and contains acetic acid generated by the reaction; a first distillation column (dividing column) 3, to separate or extract at least part of a lower boiling fraction containing a lower boiling component (eg, methyl iodide, methyl acetate, and acetaldehyde) from volatile component introduced from vaporizer 2, through a supply line 15, as a supernatant from an upper part of its column, and extract a stream containing acid
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12/57 acetic (a stream of acetic acid) in the form of a side stream by side cut; a second distillation column 4 to extract at least part of a lower boiling fraction containing a lower boiling component as a supernatant from a top column from the acetic acid stream introduced from the first column of distillation 3, through a feed line 23, by lateral 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 stream of acetic acid, through a feed line 29, as a side stream by side cut.
[00025] In addition, 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 one of the discharge line 13 for discharging a gaseous component, which is a non-condensing component in the condenser 5.
[00026] In addition, vaporizer 2 is equipped with a 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, via 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
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13/57 condensing a condensable component, part of the volatile component (or volatile phase) discharged as a supernatant from 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.
[00027] 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.
[00028] In addition, 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 fraction of a lower
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14/57 boiling condensed by the condenser 9 for the second distillation column 4; a discharge line (recycling line) 26 for separating part or all of the liquid component or fraction of the lowest boiling point condensed by the condenser 9, from line 27, and recycling the separate component or fraction to the reactor 1; and a line 28 for feeding a separate gas in the condenser 9 to a washer 10 through a line 13.
[00029] This process shown in FIG. 1 further comprises a scrubber or scrubber system 10 for recovering gaseous components (or non-condensing components) or others discharged by condenser 5, heat exchanger 7, and 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.
[00030] Hereinafter, the process shown in FIG. 1 will be explained in more detail.
[00031] 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 catalyst system carbonylation [a catalyst system comprising a major catalyst component (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 liquid form) containing fraction (s) with the lowest boiling point and / or fraction (s) with the highest boiling point from the next step (s)
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15/57 (eg vaporizer 2, first and second distillation columns 3 and 4, heat exchanger 7, and washing system 10) can also be fed to reactor 1. In Next, 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 ionic iodide (for example , lithium iodide) is in equilibrium with a vapor phase system containing carbon monoxide, by-products by the reaction (hydrogen, methane, carbon dioxide), and a vaporized lower boiling point component (eg methyl iodide, acetic acid as a product, and methyl acetate), and a methanol carbonylation reaction occurs under agitation by a stirrer or other means.
[00032]
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, drawing steam from the top from 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 gaseous component ( containing carbon monoxide, hydrogen, and others). The resulting liquid component is recycled to reactor 1, and the resulting gaseous component (waste gases) is discharged to the washing system 10 and, if necessary, recycled to the reactor.
1. In particular, the reaction system is an exothermic reaction system that accompanies heat generation, and part of the amount of heat generated in the reactor can be removed by
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16/57 cooling part of the reaction heat transferred from the steam reaction solution with the condenser 5.
[00033] For reactor 1, if necessary, hydrogen can be fed, in order to increase catalytic activity. In addition, since the reaction system is an exothermic reaction system that accompanies heat generation, the reactor 1 can be equipped with a heat removal (or heat extraction) unit or a cooling unit (for example, a shirt) to control a reaction temperature. In this context, as described later, the process of Fig. 1 is 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 removal unit heat or cooling, heat can be removed.
[00034] The 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 with a lower boiling point having a lower boiling to that of acetic acid (eg, methyl iodide, as a co-catalyst, methyl acetate, as a reaction product of acetic acid with methanol, and acetaldehyde, crotonaldehyde, 2-ethylcrotonaldehyde, and an upper iodide (such as hexyl iodide or decyl iodide), in the form of by-products), and a component with a higher boiling point, or impurity with a higher boiling point with a higher boiling point than that of acetic acid [a metal catalyst component (a catalyst rhodium, and lithium iodide as a cocatalyst), propionic acid, and water].
[00035] In order to essentially separate the component of
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17/57 higher boiling point (such as the metal catalyst component) of the reaction mixture, the reaction mixture (or part of the reaction mixture) is continuously extracted from reactor 1 introduced or fed to the vaporizer (evaporator)
In the vaporizer
2, a volatile component or a fraction with a lower boiling point (containing essentially acetic acid, which is a product and also works as a reaction solvent, methyl acetate, methyl iodide, water, hydrogen iodide, and others) is evaporated by instant distillation to separate a mixture of liquid catalyst or a higher boiling fraction (essentially containing a metal catalyst component, for example, a rhodium catalyst, lithium iodide, and others) from the reaction mixture.
In this context, in the liquid catalyst mixture, the metal catalyst component and, in addition, remaining components without evaporation (for example, acetic acid, methyl iodide, water and methyl acetate) are also contained.
[00036] Within vaporizer 2, instant distillation is 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 0.6% by weight) . Instant distillation under the condition prevents the hydrogen iodide concentration from rising in the instant evaporator. Thus, corrosion of the instant evaporator is markedly prevented. In this context, the concentration of methyl acetate can, for example, be adjusted by increasing the concentration of methanol in the reaction mixture, and allows the reaction of methanol with acetic acid to occur predominantly, and others. If necessary, the methyl acetate concentration can be adjusted by feeding methyl acetate and / or a
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18/57 component to produce methyl acetate (for example, methanol and dimethyl ether) for the instant evaporator 2. In the figure embodiment, a line 30 is provided, which joins line 14. If necessary, the concentration of Methyl acetate in the instant evaporator can also be adjusted by mixing methyl acetate and / or a methyl acetate production component, through line 30, with the reaction mixture from reactor 1.
[00037] 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.
[00038] On the other hand, the volatile component, or fraction with the 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 into 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
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19/57
Swing Adsorption), and recycled to reactor 1. The fraction with the lowest boiling point is extracted from the vaporizer to be introduced into the heat exchanger, and part of the reaction heat transferred from the reaction solution to the instant steam is cooled by the heat exchanger. heat. 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 the installation of a refrigeration unit with external circulation in the reactor, which leads to the avoidance of loss of carbon monoxide and to improve the efficiency of the reaction, or to reduce the cost of the equipment.
[00039] By the way, by making (maintaining) the temperature and / or internal pressure of vaporizer 2 lower than that of reactor 1, a greater generation of by-products or deterioration of catalytic activity can be inhibited.
[00040] In the first distillation column 3, usually the fraction with the lowest boiling point (or supernatant) containing the component with the lowest boiling point (containing methyl iodide, methanol, methyl acetate, acetaldehyde, water, and others) , is separated by the top or top of the column and fed to condenser 8, and a fraction with the highest boiling point containing the component with the highest boiling point (for example, water, propionic acid, a entrained catalyst, and lithium iodide) , is separated by the bottom or bottom of the column through a bottom line 24 and recycled to reactor 1. The fraction with the highest boiling point (first fraction
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20/57 with higher 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 via line 24, can be recycled to vaporizer 2 via line 24a, if necessary. A side stream (acetic acid stream, or crude acetic acid stream) containing essentially acetic acid is extracted from the first distillation column 3 by a side cut and is fed or introduced into the second distillation column 4.
[00041] The lowest boiling point fraction (supernatant, or first supernatant, or first lowest boiling fraction), extracted from the top or top of the first distillation column 3, contains acetic acid and others, and is fed to the condenser 8. The lowest boiling point fraction, extracted from the first distillation column 3, can be condensed by the condenser 8 to cool some of the reaction heat transferred from the reaction solution to the lowest boiling point fraction, through steam. instantaneous with condenser 8 so that part of the reaction heat can be removed. In condenser 8, the lowest boiling point fraction is condensed, to separate a gaseous component containing essentially 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, 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
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21/57 liquid component can be a uniform solution or a separate solution (for example, a biphasic solution). For example, for the liquid component containing a predetermined amount 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 the aqueous phase contains acetic acid, acetaldehyde, and others, and the oil phase 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 aqueous phase can be recycled to reactor 1 and / or the first distillation column 3.
[00042] In the acetic acid stream, which is obtained by lateral cutting from the first distillation column 3 and is fed to the second distillation column 4, a component with the lowest boiling point (eg water), which remains in the the acetic acid stream is further separated in the second distillation column 4, and a higher purity acetic acid stream (purified acetic acid stream) is extracted as a side stream. In the second distillation column 4, a fraction with the lowest boiling point containing the component with the lowest boiling point is fed from the top or top of the column to condenser 9, and a side stream (acetic acid stream), rich in acetic acid, is distilled by lateral cut. If necessary, the fraction with the lowest boiling point (supernatant, or second supernatant, or the second 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 the system. reaction 1. Water can be separated as a component with a lower boiling point in the second distillation column 4, or
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22/57 can be separated, essentially, in the first distillation column 3 and further separated in the second distillation column 4 for purification. In this context, a fraction with a higher boiling point (a second fraction with a higher boiling point), as a component with a higher boiling point (eg propionic acid), can be discharged from the bottom or bottom of the column and, if necessary, it can be recycled to reactor 1, or it can be discharged from the system (not shown).
[00043] The lowest boiling point fraction extracted by 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 in the first distillation column, the liquid component can be separated into an aqueous phase and an oil phase, and these phases can be recycled . The lowest boiling point fraction 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 lower boiling point fraction via instantaneous steam with the condenser 9.
(Reaction step) [00044] In the reaction step (carbonylation reaction step), methanol is carbonylated with carbon monoxide in the presence of the catalyst system. In this context, fresh methanol can be
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23/57 fed to the reaction system directly or indirectly, or methanol and / or one of its derivatives, removed through distillation steps, can be recycled and fed to the reaction system.
[00045] 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, a metal catalyst containing the group 8 metal from the Periodic Table (for example, a cobalt catalyst, a rhodium catalyst, and an iridium catalyst) . The catalyst can be a metal, as a simple substance, or it 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 of 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).
[00046] In addition, 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 type, since the catalyst can change to a complex in the reaction solution, and can be used in various ways. As such, an example catalyst, RHI ₃ , rhodium, a rhodium iodide complex [by [RhI ₂ (CO) ₄ ], and [Rh (CO) ₂ I ₂ ]], a complex
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Rhodium carbonyl, or the like, is particularly preferred. In addition, the catalyst can be stabilized in the reaction solution by adding an ionic iodide (for example, an iodide salt) and / or water.
[00047] 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
4000 ppm, more preferably, from about 200 to 3000 ppm and, in particular, from about 300 to 2000 ppm (for example, from about 500 to 1500 ppm), throughout the liquid phase in the reactor.
[00048] For the co-catalyst or accelerator contained in the catalyst system, an ionic iodide (an iodide salt) is used. The iodide salt is added in order to stabilize the rhodium catalyst and inhibit side reactions, in particular, in a low water content. The iodide salt is not particularly limited to a specific type, 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, cesium iodide), an alkaline earth metal iodide (for example, beryllium iodide, magnesium iodide, and calcium iodide), or a metal iodide of group 3B in the Periodic Table (for example, boron iodide and iodide of aluminum)], an organic halide [for example, an organic iodide, such as a phosphonium iodide salt (a phosphonium iodide) (for example, a triphenylphosphine and tributylphosphine salt) or an iodide ammonium salt (a ammonium iodide) (for example, a tertiary amine salt, a pyridine compound, an imidazole compound, a
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25/57 composed of imide, or the like, with an iodide), a bromide corresponding to the iodide, and a chloride corresponding to the iodide]. In this context, alkali metal iodide (for example, lithium iodide) also functions as a stabilizer for the carbonylation catalyst (for example, a rhodium catalyst). These iodide salts can be used alone, or in combination. Among these iodide salts, an alkali metal iodide (such as lithium iodide) is preferred.
[00049] In the reactor (liquid reaction mixture), the ionic iodide concentration 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.
[00050] For the accelerator contained in the catalyst system, an alkyl iodide (for example, a C1-4 alkyl iodide, such as methyl iodide, ethyl iodide or propyl iodide), in particular, methyl iodide, Is it used. 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 size of the one-step plant for the circulation of the recovered accelerator to the reactor, the amount of energy needed 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 (for example, from about 12 to 15% by weight) throughout
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26/57 liquid phase in the reactor.
[00051] 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.
[00052] 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 from 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.
[00053] 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 , in
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27/57 about 10 to 50 kPa), in terms of absolute pressure.
[00054] The partial pressure of carbon monoxide, or 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 system reaction time, the amount of raw materials (for example, methanol) fed into the reaction system, the reaction temperature, the reaction pressure, and others.
[00055] 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 (total reactor pressure) can be, for example, about 15 to 40 atmospheres.
[00056] 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 be used in a practical way as a solvent.
[00057] 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. fence
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28/57 from 2 to 10% by weight) in the entire liquid phase of the reaction system. The solubility of carbon monoxide in the solution fed to the vaporizer is reduced by carrying out the reaction, while maintaining a specific concentration of each component [articularly, an iodide salt (lithium iodide) and water] in the reaction system, and the loss of carbon carbon monoxide can be reduced.
[00058] In the previous carbonylation reaction, acetic acid production is accompanied by the production of an acetic acid ester produced with methanol (methyl acetate), water generated with the esterification reaction, in addition to propionic acid, acetaldehyde and others .
[00059] 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.
[00060] The space / time yield (production rate or formation rate) of 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.
[00061] The vapor component extracted from the top of the reactor, for the purpose of controlling the pressure of the reactor, or others, is preferably cooled with a condenser, a heat exchanger, or other means to remove some of the heat in
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Reaction. 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 others), the liquid component is recycled to the reactor and the gaseous component is introduced into the washing system.
[00062] 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 of methyl acetate, after mentioned, in the vaporizer.
(Instant distillation step or catalyst separation step) [00063] In the instant distillation step (vaporizer), from the reaction mixture fed by the reaction step or from the reactor to the vaporizer (instant evaporator or instant distillation column) , a low volatility component or liquid catalyst mixture (a higher boiling fraction) containing at least one higher boiling catalyst component (a metal catalyst component,
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30/57 for example, a rhodium catalyst and an ionic iodide salt) is separated as a liquid (component), and a volatile component or volatile phase (a fraction of lower boiling point) containing acetic acid is separated as a vapor (component). [00064] In the instant distillation step (instant evaporation step), 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, adiabatic vaporization, the reaction mixture can be separated into the vapor component and the liquid component, without heating and under reduced pressure, and in thermostatic vaporization, the reaction mixture can be separated into the vapor component and the liquid component. with heating (and reduced pressure). The reaction mixture can be separated into the vapor component and the liquid component, combining these instantaneous conditions.
[00065] In instant distillation, the reaction temperature can be, for example, from about 100 to 260 ° C (for example, from about 110 to 250 ° C), preferably from about 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 170 to 200 ° C . In addition, in instant distillation, the temperature of the liquid catalyst mixture (or the temperature of the lower solution of the flash distillation column) can be, for example, from about 80 to 200 ° C (for example, from 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), from
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Preferably from 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 relatively high temperature (high pressure). 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.
[00066] The separation (instant distillation) of the metal catalyst component can generally be carried out with the use of 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 by a solid collection method, which is widely used in industrial applications.
[00067] The material of (or to form) the vaporizer is not particularly limited to a specific type, and can be a metal, a ceramic, a glass, or others. In a practical way, a vaporizer made of a metal is used. In particular, according to the present invention, since the concentration of hydrogen iodide within the flash evaporator can be significantly inhibited, and others, the corrosion of the flash evaporator can also be inhibited to a high degree. Thus, for an instantaneous evaporator in the present invention, not only can an instantaneous evaporator made of an expensive material having a high corrosion resistance (such as zirconium), but also an instantaneous evaporator made of a relatively inexpensive material having not much resistance high to corrosion, for
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32/57 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 a nickel-containing alloy as the main component, for example, HASTELLOY (trade name) and INCONEL (trade name)), a cobalt based alloy (or an alloy containing cobalt as the main component), or a titanium alloy; and an aluminum alloy].
[00068] 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 the efficiency of extracting heat from the entire system.
[00069] The separate liquid catalyst mixture (or low volatility component, or higher boiling fraction) contains the metal catalyst (for example, a rhodium catalyst), the ionic iodide (for example, a metal iodide alkali, such as lithium iodide) and, in addition, remaining components without evaporation (for example, acetic acid, methyl iodide, water, methyl acetate, and iodide
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33/57 hydrogen).
[00070] In instant distillation (or instant evaporator), the ratio (weight ratio) of the volatile component to be separated in relation to the mixture of liquid catalyst (or low volatility component) can be about 10/90 to 50 / 50, preferably, from about 15/85 to 40/60 and, more preferably, from about 20/80 to 35/65 in a proportion of the anterior / posterior.
[00071] According to the present invention, among the components in the liquid catalyst mixture, the concentration of at least methyl acetate is adjusted (or regulated). Adjusting the concentration allows the production or increase in the concentration of hydrogen iodide in the instant evaporator to be effectively inhibited in a wide range of instant distillation conditions. Multiple factors are involved in the reason why the increase in 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 [00072] The concentration of methyl acetate in the liquid catalyst mixture can be selected from the range of not less than 0.6% by weight (for example, 0, 6 to 20% by weight), which may be, for example, not less than 0.7% by weight (for example, from about 0.7 to 15% by weight), preferably not less than 0.8% by weight (for example, from about 0.8 to 10% by weight), more preferably, from about 0.9 to 5% by weight and, normally, from about 0.7 to 5% by weight (eg example, from about 0.7 to 3% by weight, preferably from about 0.8 to 2% by weight and, more preferably, from about 0.9 to 1.5% by weight
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34/57
Weight). In addition concentration of acetate in methyl on mixture in catalyst liquid can be so high how much not less than 1% by weight (for example, about 1, 2 to 10% in Weight), in preference , not inferior to 1.3% in weight (for
example, from about 1.4 to 8% by weight), more preferably, not less than 1.5% by weight (for example, from about 1.7 to 7% by weight) and, in particular, not less to 2% by weight (for example, from about 2.2 to 5% by weight).
[00073] By the way, when the concentration of methyl acetate in the vaporizer is excessively high, the production or increase in the concentration of hydrogen iodide can be inhibited, while the subsequent steps are prevented by the reduced separation of the organic phase and the aqueous phase , or others. Therefore, there are some cases, in which the process may not be carried out in a stable manner.
[00074] The water concentration in the liquid catalyst mixture can be, for example, selected from the range not exceeding 15% by weight (for example, from 0.1 to 12% by weight) and can be, for example, not more than 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) , more preferably, not more than 4% by weight (for example, from about 0.8 to 4% by weight), and especially not more than 2% by weight (for example, from about 0.8 to 2 % by weight).
[00075] Furthermore, the concentration of acetic acid in the liquid catalyst mixture can be, for example, not less than 30% by weight (for example, from about 35 to 95% by 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)
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35/57
weight) and can generally be fence in 60 to 90% by weight. [00076] In addition, the concentration in iodide methyl at mixture of liquid catalyst can to be selected among The range not exceeding 10% by weight (per example, from 0.001 to 8% in
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, about from 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% by weight) and can generally be from about 0.1 to 3% by weight (for example, from about 0.3 to 2.5% in weight) weight and preferably about 0.5 to 2% by weight).
[00077] Furthermore, the concentration of ionic iodide in the liquid catalyst mixture can be, for example, not more than 60% by weight (for example, from about 1 to 55% by 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) and, especially, not more than 36% by weight (for example, from about 5 to 35% by weight) and can generally be from about 5 to 25% by weight (for example, from about 8 to 20% by weight). Multiple factors are also involved in the reason why the increase in hydrogen iodide concentration is avoided by adjusting the ionic iodide concentration, and one of the factors includes the consumption of hydrogen iodide by the next equilibrium reaction.
MI + CH ₃ COOH CH ₃ COOM + HI [00078] In the formula, the symbol M represents a residue of an ionic iodide (or cationic group, for example, a metal
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36/57 alkaline, such as lithium] [00079] By the way, in terms of corrosion inhibition, it is preferable that the amount of the component (such as methyl iodide or lithium iodide) producing hydrogen iodide in an equilibrium reaction is small .
[00080] By the way, the concentration of the metal catalyst in the liquid catalyst mixture can be, for example, not less than 100 ppm (for example, from about 150 to 10000 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.
[00081] Furthermore, the concentration of methanol in the liquid catalyst mixture can be, for example, not more than 1% by weight (for example, from about 0 to 0.8% by weight), preferably not more than to 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.
[00082] The adjustment of the concentrations of the constituents in the liquid catalyst mixture (increase or decrease in concentration) is not particularly limited to a specific value, and the concentrations can be adjusted by the condition of instant distillation, the amount of the process solution to be recycled from the next reaction (step (s)), and others. If necessary, in order to adjust the concentration of each component, a component to increase or decrease the concentration of each component [for example, a
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37/57 ester (for example, an ethyl ester), an alcohol, and an ether] can be added to the reaction mixture and / or the instant evaporator. Such a component can be a component (a basic component) reactive to hydrogen iodide.
[00083] 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 liquid catalyst mixture). 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.
CH ₃ OH + CH ₃ COOH CH ₃ COOCH ₃ + H ₂ O [00084] In the interval, where the efficiency of acetic acid production is sufficiently guaranteed, the methanol concentration can be increased by increasing the methanol concentration to be fed to the reaction, or slowing down the reaction to inhibit methanol consumption. The reaction speed can be adjusted by appropriately selecting the reaction temperature, the concentration of the catalyst (for example, the concentration of methyl iodide and the concentration of the metal catalyst), the concentration of carbon monoxide (or partial pressure of monoxide carbon), and others. The methanol concentration can be adjusted by directly adding methanol, as described later.
[00085] By the way, when the concentration of methanol or methyl acetate in the reaction solution is higher, the amount of acetic acid production can be increased, and the
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38/57 concentration of hydrogen iodide in the vaporizer can be easily reduced. However, there are some cases, where the reaction is unstable, and it is difficult to control the temperature or pressure. Therefore, it is preferable that the concentration of methyl acetate or methanol, as a source of methyl acetate, is reduced in the reaction solution, and that the concentration of methyl acetate in the vaporizer (or the liquid catalyst mixture) is adjusted to the aforementioned concentration.
[00086] 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 (for example, 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.
[00087] 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 value, 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 evaporator
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39/57 instantaneous (for example, as shown in the figure, the elevator or reducer component can be fed to a line, to supply the instantaneous evaporator with the reaction mixture discharged from the reactor).
[00088] On the other hand, when the elevator or reducer component is added to the instant evaporator (or the elevator or reducer component is mixed with the reaction mixture in the instant evaporator), the position (height level) of addition is not particularly limited to a specific value. The elevator or reducer component can be added to any liquid phase portion or gas phase portion 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.
[00089] The volatile component (acetic acid stream) separated in the vaporizer contains the acetic acid product, in addition to methyl iodide, an ester of the acetic acid product with methanol (eg 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.
[00090] According to the present invention, as described above, the production or increase in the concentration of hydrogen iodide in the vaporizer can be inhibited. Thus, the concentration of hydrogen iodide in the volatile component can, for example, be adjusted to no more than 1% by weight (for example, from about 0 or detection limit to 0.8% by weight), preferably not more than 0.6% by weight (for example, from about 0.001 to 0.5% by weight), more preferably, not more than 0.3%
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40/57 by weight (for example, from about 0.01 to 0.2% by weight) and, especially, not more than 0.1% by weight (for example, from about 0.02 to 0.09 % by weight). In addition, the hydrogen iodide concentration in the liquid catalyst mixture can, for example, be set to no more than 1% by weight (for example, from about 0 or detection limit to 0.8% by weight), preferably not more than 0.6% by weight (for example, from about 0.001 to 0.5% by weight), more preferably, not more than 0.3% by weight (for example, about 0, 01 to 0.2% by weight) and, in particular, not more than 0.1% by weight (for example, from about 0.02 to 0.09% by weight).
[00091] 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 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 hydrogen iodide concentration.
[00092] Part of the separate volatile component (acetic acid stream) can be introduced in a condenser or in a heat exchanger for cooling or extraction of heat, just like the embodiment illustrated in the figure. Since the reaction heat transferred from the reaction solution to the instant steam 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 installation of a refrigeration unit with external circulation in the reactor. In addition, the cooled volatile component
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41/57 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) [00093] In the acetic acid collection stage (distillation stage), acetic acid is collected by separating a stream containing acetic acid from the volatile component. The method of separation is not particularly limited to a specific type. Typically, the separated volatile component is fed to the distillation column (dividing column), and separated into a lower boiling fraction (supernatant) containing a lower boiling component (eg methyl iodide, acetic acid, acetate) methyl, acetaldehyde by-product) and a stream containing acetic acid (acetic acid stream) by distillation. The acetic acid collection step is not necessarily the embodiment shown in the figure, and can be a step, in which a treatment to remove the lowest boiling component and a treatment to extract water are carried out on a single column distillation process (for example, a step using a distillation column described in Japanese Patent Publication No. 3616400), or a step, in which a treatment to remove the lowest boiling component and a treatment to extract water from a The first distillation column is followed by a purification step on a second distillation column.
Considering the efficiency of the purification, others, preferably, a usable step includes a distillation step, in which the treatment for extracting the component with the lowest boiling point is carried out, essentially, in
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42/57 first distillation column, and the treatment to extract water is carried out, essentially, in the second distillation column.
(First distillation column) [00094] Part of the acetic acid stream (lowest boiling point fraction), fed from the vaporizer, is introduced into the heat exchanger, and the remaining (residual) acetic acid stream is fed to the first distillation column. In the first distillation column, a fraction with the lowest boiling point (or the fraction with the lowest boiling point, or first supernatant) containing at least part of a component with the lowest boiling point (eg methyl iodide, methyl, and acetaldehyde) and a higher boiling fraction (or bottom fraction) containing at least part of a higher boiling component (eg, propionic acid and water) are separated from the acetic acid stream, and a stream containing at least acetic acid is extracted. In the embodiment of Fig. 1, the chain containing acetic acid is extracted as a side chain by side cutting. The current containing acetic acid can be extracted from the bottom of the column.
[00095] 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 component with the lowest boiling point, the component with the highest boiling point, and others; or it may simply be a mixture of these components.
[00096] For the first distillation column, it can be
Petition 870190021485, from 03/01/2019, p. 57/77
43/57, for example, a conventional distillation column, for example, a distillation column, such as a plate column, or a filling column. The material of (or to form the) first distillation column can include the same material as that of the vaporizer. According to the present invention, the production or increase in the concentration of hydrogen iodide in the instant distillation step can be inhibited. Thus, 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.
[00097] The distillation temperature and pressure in the first 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 lowest point component boiling point and the component with the highest boiling point. For example, for the plate column, the internal pressure of the column (in general, the
pressure at the top column) may be about 0, 01 to 1 MPa, preferably of fence 0.01 to 0, 7 MPa and more preferably about 0.05 to 0.5 MPa, in terms in manometric pressure.[00098] Furthermore, in first column in distillation, The
internal column temperature (in general, the temperature at the top of the column) can be adjusted by adjusting the internal pressure of the column, 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.
[00099] Furthermore, for the plate column, the theoretical number of plates is not particularly limited to a specific value
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44/57 and, depending on the species of the component to be separated, it is from about 5 to 50, preferably from 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 from about 10 to 80, preferably from about 12 to 60 and, more preferably, from about 15 to 40.
[000100] 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 theoretical number of plates mentioned above, 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.
[000101] Since the lowest boiling point fraction, separated from the first distillation column, contains a useful component (eg methyl iodide and methyl acetate), the lowest boiling point fraction 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 (eg the reactor) with a condenser, an exchanger heat, or other medium and then recycled to the reactor and / or the first distillation column. For example, the fraction with the lowest boiling point extracted from the first distillation column does not need to be recycled to the first distillation column, after condensation by the condenser, as the embodiment of Fig. 1. The fraction of the lowest extracted boiling point can be recycled directly, or simply cooled to remove a flue gas component (for example,
Petition 870190021485, from 03/01/2019, p. 59/77
45/57 carbon 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 the extraction of acetaldehyde (for example, after the extraction of acetaldehyde, submitting the fraction containing the lowest boiling impurities to the acetaldehyde separation step mentioned below (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.
[000102] The fraction with the highest boiling point (lower fraction or first fraction with the highest boiling point), separated in the first distillation column, contains water, acetic acid, a dragged rhodium catalyst, lithium iodide, in addition to acetic acid remaining without being evaporated, impurities with a lower boiling point, and others. Thus, if necessary, the fraction with the highest boiling point can be recycled to the reaction system (reactor) and / or the vaporizer. By the way, before recycling, propionic acid, which deteriorates the quality of acetic acid as a final product, can be removed.
(Second distillation column) [000103] In the second distillation column, hydrogen iodide, a component with the lowest boiling point and a component with the highest boiling point, each of which remains undisturbed in the first distillation column, are removed with higher precision. For the second distillation column, a distillation column can be used
Petition 870190021485, from 03/01/2019, p. 60/77
Conventional 46/57, for example, a plate column, a filling column, and other columns. The material of (or to form) the second distillation column can include the same material as that of the first distillation column. In addition, the internal column temperature, the internal column pressure, the theoretical number of plates, and the reflux ratio in the second distillation column can be selected, depending on the species of the distillation column, for example, can be selected at from the same (similar) range as the range in the first distillation column above.
[000104] Since the lowest boiling fraction (second lowest boiling fraction or second supernatant) separated from the second distillation column contains a useful component, such as methyl iodide or methyl acetate, the lowest fraction boiling point can be directly recycled to the reaction system (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 from the first distillation column, the lowest boiling point fraction can be liquefied by a condenser, a heat exchanger, or another medium 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, referred to below , if necessary. In this context, the flue gas component can be introduced into the washing system.
[000105] In addition, the fraction with the highest boiling point (second fraction with the highest boiling point) can be
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47/57 discharged from the bottom or bottom of the column. Since the highest boiling fraction separated from the second distillation column contains propionic acid, and others, the highest boiling fraction can be discarded directly (or removed). In addition, since the highest boiling fraction 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).
[000106] In the second distillation column, the purified acetic acid stream is extracted by side cutting in the embodiment of Fig. 1. The position of the side stream opening can generally be in a middle or lower part of the distillation column, or the acetic acid stream can be extracted from the bottom of the column. By the way, by extracting the acetic acid stream from the side current opening in a position higher than the bottom opening to extract the fraction with the highest boiling point, the side current and the fraction with the highest boiling point can be efficiently separated.
(Iodide extraction step) [000107] Purified and recovered acetic acid is usually introduced into a column for the acetic acid product and obtained as the acetic acid product. Before or after the introduction of the acetic acid product in the column, 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 iodide decila).
[000108] In the iodide extraction step (or iodide removal step), the acetic acid stream can be contacted with
Petition 870190021485, from 03/01/2019, p. 62/77
48/57 a remover (material or removing agent) having an iodide removal or 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, having an iodide removal or adsorption capacity, in particular, an extraction column of iodide with ion exchange resin, is advantageously used.
[000109] 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 element 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 (mild) acid cation exchange resin, and the preferred one includes a strong acid cation exchange resin, for example. example, a macroreticular ion exchange resin, and the like.
[000110] In ion exchange resin, the proportion of the active region exchanged for metal, (or replaced by metal) can be, for example, from about 10 to 80 mol%, preferably from about 25 to 75% mol and more preferably about 70 to mol%.
[000111] At least the contact of the acetic acid stream from the second distillation column with the exchange resin
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49/57 ionic (preferably, passage of the acetic acid stream through the ion exchange resin) performs the extraction of the iodide. During contact with (or passing through) the ion exchange resin, if necessary, the temperature of the acetic acid stream can be increased (or raised) gradually. The temperature rise in stages ensures the inhibition of spillage or flow of the metal from the ion exchange resin, as well as the removal of the iodide, efficiently.
[000112] Examples of the iodide extraction column may include a filling column, filling its interior at least with ion exchange resin, which is exchanged with a metal, a column provided with a bed of an ion exchange resin (for example, a bed comprising a particulate resin) (a protective bed) and the like. The iodide extraction column can be provided with ion exchange resin, exchanged for metal and, in addition, another ion exchange resin (for example, a cation exchange resin, an anion exchange resin, and a non-exchange resin ionic) inside. Even when the metal is emanated from the ion exchange resin, exchanged for metal, the arrangement of the cation exchange resin on the downstream side of the ion exchange resin, exchanged for metal (for example, arrangement of the cation exchange resin by filling, or arrangement of the cation exchange resin as a resin bed) allows the effluent metal to be captured with cation exchange resin and removed from the carboxylic acid stream.
[000113] 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.
Petition 870190021485, from 03/01/2019, p. 64/77
50/57 [000114] The flow of the acetic acid stream to be passed is not limited to a specific value, and can be, for example, in an iodide extraction column, using a protection 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.
[000115] 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 ion exchange resin, exchanged for metal, and a column of cation exchange resin on the downstream side of the ion exchange resin column, exchanged for metal. The details of the previous example can be found in WO02 / 062740, and others.
(Acetaldehyde separation step) [000116] When the fraction containing acetaldehyde generated by the reaction is recycled and distributed to the reaction system, the amount of by-product (s), such as propionic acid, an unsaturated aldehyde, or an alkyl iodide, 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 comprise feeding
Petition 870190021485, from 03/01/2019, p. 65/77
51/57 of a recycling solution (a solution to be recycled) for the acetaldehyde separation column, to separate a lower boiling fraction containing acetaldehyde and a higher boiling fraction containing methyl iodide, methyl acetate , 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 fraction with the highest boiling point obtained by extracting acetaldehyde as the fraction with the lowest boiling point contains methyl iodide, water, methyl acetate, acetic acid, and the like, the fraction with the highest boiling point can be recycled to the reaction system. [000117] 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.
[000118] The temperature (the temperature at the top of the column), and the pressure (pressure at the top of the column)) in the acetaldehyde separation column can be selected, depending on the species 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 point fraction from the recycling solution [for example, the lower boiling point fraction (s) obtained ( s) in the first and / or second distillation column], using difference between acetaldehyde and other components (in particular, methyl iodide) at the boiling point. Per
Petition 870190021485, from 03/01/2019, p. 66/77
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 at 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.
[000119] 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 (for example, about 70 to 400), depending on the theoretical number of plates mentioned above.
EXAMPLES [000120] The following examples are intended to describe the present invention in greater detail, and should in no way be construed to define the scope of the invention.
[000121] When the acetic acid production process described in FIG. 1 was applied, the change in the corrosion state of the vaporizer, in the presence of methyl acetate, was observed. Specifically, methyl iodide, water, methyl acetate, acetic acid, lithium iodide, a rhodium catalyst were fed to reactor 1, and methanol was allowed to react with carbon monoxide to provide reaction solutions with different compositions. Each of the resulting reaction solutions was subjected to vaporizer 2 (pressure: 0.2 MPa, resulting (volatile component) distillation column 3 and instantaneous distillation at temperature: 140 ° C), the steam was fed the first of the distillation to provide
Petition 870190021485, from 03/01/2019, p. 67/77
53/57 crude acetic acid. With the exception of crude acetic acid, the other components were recycled to the reaction system. The concentration of the rhodium catalyst in the liquid catalyst mixture (the bottom fraction of the vaporizer) was 1200 ppm, and the lower fraction of the vaporizer was recycled to reactor 1.
[000122] Specimens of various materials were added to the vaporizer 2 liquid catalyst mixture, and the continuous acetic acid production process was carried out for 100 hours in a state, in which the specimens were left in the vaporizer. After the 100 hour continuous production process was completed, each specimen was examined by a corrosion test.
[000123] The corrosion test was evaluated based on the following criteria in Comparative Examples 1 to 2 and Examples 1 to 3, and evaluated about the amount of corrosion observed in Comparative Examples 3 to 5 and Examples 4 to 8.
A: specimen not corroded at all. B: specimen severely corroded. C: slightly corroded specimen.
D: specimen significantly corroded.
[000124] The composition of the liquid catalyst mixture and the results of the corrosion test are shown in Tables 1 and
2. In Tables 1 and 2,% by weight means% in weight, Ac represents acid acetic, BAD represents acetate in methyl, MeOH means methanol, MeI represents iodide in methyl, Zr represents zirconium, HB2 represents a league The basis of
nickel (HASTELLOY B2 manufactured by Oda Koki Co. Ltd.), HC represents a nickel-based alloy (HASTELLOY C manufactured by Oda Koki Co. Ltd.), and the unit mm / Y means the rate of
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54/57 specimen corrosion per year (the decreased thickness (mm) of the specimen per year). The concentration of the iodide ion derived from the iodide salt was subtracted from the total concentration of iodide ions (I ^- ) to calculate the concentration of hydrogen iodide (HI).
Petition 870190021485, from 03/01/2019, p. 69/77
Table 1
Mixture catalyst liquid Test of corrosion B.C% Weight BAD% Weight MeOH% Weight HI% Weight MeI% Weight H2O% Weight LiI% Weight Zr HB2 HC ExampleComparative 1 76, 5 0.1 bottom0.1 The 0.3 1 7 15 THE B D ExampleComparative 2 75, 4 0.1 bottom0.1 The 0.4 2 7 15 THE B D Example 1 75.7 0, 9 bottom0.1 The less than0.1 1 7 15 THE THE Ç Example 2 74, 8 0.9 bottom0.1 The less than0.1 2 7 15 THE THE Ç Example 3 74.7 1.9 bottom0.1 The less than0.1 1 7 15 THE THE B
55/57
Petition 870190021485, from 03/01/2019, p. 70/77
Table 2
Liquid catalyst mixture
Corrosion testing
MA MA MeOH
HI
Honey H2O LiI
Zr
HB2 HC
% Weight Weight % Weight% Weight Weight Weight % Weight mm / Ymm / Y mm / Y ExampleComparative 3 80, 9 0.1 bottom0.1 The 0.1 0.7 3.1 15.0 bottom0.03 The 0.1 0.52 ExampleComparative 4 76, 5 0.1 bottom0.1 The 0.2 5.0 3.0 15.0 bottom0.03 The 0.12 0.62 ExampleComparative 5 70.5 0.1 bottom0.1 The 0.2 5.0 9.0 15.0 bottom0.03 The 0.12 0.62 Example 480.3 0.9 bottom0.1 The bottom The 0.1 0.9 3.0 14.7 bottom0.03 The 0.04 0.16 Example 579.3 0.9 bottom0.1 The bottom The 0.1 1.6 3.0 15.0 bottom0.03 The 0.05 0.20 Example 679.3 1.9 bottom0.1 The bottom The 0.1 1.5 2.9 14.3 bottom0.03 The less than0.03 0.04 Example 782, 1 0.7 bottom0.1 The bottom The 0.1 1.2 1.0 14.8 bottom0.03 The 0.05 0.15 Example 880.8 1.8 bottom0.1 The bottom The 0.1 0.9 1.5 14.8 bottom0.03 The less than0.03 less than0.03
56/57
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57/57 [000125] As shown in the tables, the production and increase in the concentration of hydrogen iodide (Hl), and the corrosion of the specimens, were prevented by adjusting the composition of the liquid catalyst mixture in the vaporizer to specific components and specific proportions.
Industrial Applicability [000126] The production process of the present invention is extremely useful as a process for producing acetic acid, while efficiently inhibiting the production or increasing the concentration of hydrogen iodide in the instant evaporator to distill the reaction mixture obtained from the reactor.
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 (13)
[1]
- CLAIMS -
1. PROCESS TO PRODUCE ACETIC ACID, characterized by the fact that it 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, and methyl iodide, in a reactor carbonylation, instant distillation step for continuous feeding of a vaporizer with a reaction mixture from the reactor, and evaporation of a volatile component containing at least the acetic acid product, methyl acetate and methyl iodide, by instant distillation, to separate the volatile component and a mixture of liquid catalyst containing at least the metal catalyst and ionic iodide, and step of collecting acetic acid to separate a stream containing acetic acid from the volatile component, to collect acetic acid, in which the metal catalyst comprises a rhodium catalyst, and in the instant distillation step, the The sample is conducted, provided that the concentration of methyl acetate in the liquid catalyst mixture is not less than 0.6% by weight, and the concentration of water in the liquid catalyst mixture is not more than 8% by weight.
[2]
2. PROCESS, according to claim 1, characterized in that the concentration of methyl acetate in the liquid catalyst mixture is not less than 1% by weight.
[3]
3. PROCESS, according to claim 1 or 2, characterized by the fact that the concentration of methyl acetate in the liquid catalyst mixture is not less than 1.5% by weight.
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2/4
[4]
4. PROCESS, according to any one of claims 1 to 3, characterized in that the water concentration in the liquid catalyst mixture is 0.8 to 8% by weight.
[5]
PROCESS according to any one of claims 1 to 4, characterized in that the ionic iodide comprises an alkali metal iodide, and the concentration of the metal catalyst in the liquid catalyst mixture is not less than 300 ppm based on weight.
[6]
6. PROCESS according to any one of claims 1 to 5, characterized in that the concentration of acetic acid in the liquid catalyst mixture is not less than 40% by weight.
[7]
7. PROCESS, according to any one of claims 1 to 6, characterized in that, in the liquid catalyst mixture, the ionic iodide concentration is not greater than 50% by weight, the methyl iodide concentration is not greater than 5% by weight, the concentration of acetic acid is 45 to 90% by weight, the concentration of methyl acetate is 0.6 to 3% by weight, and the concentration of water is 0.8 to 8% in Weight.
[8]
8. PROCESS, according to any one of claims 1 and 4 to 7, characterized by the fact that, in the liquid catalyst mixture, the ionic iodide concentration is not greater than 40% by weight, the methyl iodide concentration is of 0.01 to 4% by weight, the concentration of acetic acid is 50 to 85% by weight, the concentration of methyl acetate is 0.6 to 2% by weight, and the concentration of water is 0.8 to 4% by weight.
[9]
9. PROCESS, according to any one of claims 1 to 8, characterized by the fact that, in the instant distillation step, the instant distillation is carried out
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3/4 at an absolute pressure of 0.1 to 0.5 MPa, maintaining the temperature of the liquid catalyst mixture from 100 to 170 ° C.
[10]
10. PROCESS according to any one of claims 1 to 9, characterized in that the concentration of methyl acetate in the liquid catalyst mixture is adjusted, by adding methyl acetate and / or a component of methyl acetate production for the reaction mixture and / or the vaporizer.
[11]
11. PROCESS according to any one of claims 1 to 10, characterized in that the vaporizer material comprises a nickel-based alloy.
[12]
12. METHOD FOR INHIBITING THE PRODUCTION OF HYDROGEN IODIDE, OR INCREASING THE CONCENTRATION OF HYDROGEN IODIDE IN A VAPORIZER, IN AN ACETIC ACID PRODUCTION PROCESS, characterized by the fact that the production process 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, and methyl iodide in a carbonylation reactor, instant distillation step for continuous supply of a vaporizer with a reactor reaction mixture, and evaporation of a volatile component containing at least the acetic acid product, methyl acetate and methyl iodide by instant distillation to separate the volatile component and a mixture of liquid catalyst containing at least the metal catalyst and ionic iodide, and acid collection step acetic acid to separate a current containing acetic acid from the compone volatile, to collect acetic acid,
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4/4 where the metal catalyst comprises a rhodium catalyst, and in the instant distillation step, instant distillation is carried out, provided that the concentration of methyl acetate in the liquid catalyst mixture is not less than 0, 6% by weight, and the water concentration in the liquid catalyst mixture does not exceed 8% by weight
[13]
13. METHOD, according to claim 12, characterized in that the vaporizer material comprises a nickel-based alloy.

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法律状态:
2018-12-04| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2019-07-09| B09A| Decision: intention to grant|

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2019-08-13| B16A| Patent or certificate of addition of invention granted|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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JP2010279798|2010-12-15|

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PCT/JP2011/077845|WO2012081417A1|2010-12-15|2011-12-01|Acetic acid production method|

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