process to produce acetic acid

专利摘要:
PROCESS TO PRODUCE ACETIC ACID Acetic acid is produced, while inhibiting the increase in the concentrations of hydrogen iodide and acetic acid in an acetaldehyde distillation column. A process for producing acetic acid comprises a step to allow methanol to react with carbon monoxide; a step for feeding a vaporizer with a reaction mixture, to separate a volatile component (2A) and a low volatility component (2B); a step to feed a distillation column with the volatile component (2A), and separate a supernatant (3A) containing methyl iodide, acetic acid, methyl acetate, water, acetaldehyde, and hydrogen iodide, and a stream (3B) containing acetic acid to collect acetic acid; and a separation step to feed an acetaldehyde distillation column with at least part of the supernatant (3A), and separate a liquid object to be treated containing the supernatant (3A) and a lower boiling point component (4A) containing acetaldehyde and a component with the highest boiling point (4B); on what; in the separation step, the liquid object containing methanol and / or dimethyl ether, in a concentration of 0.1 to 50% by weight, is subjected to distillation.
公开号:BR112013014808B1
申请号:R112013014808-0
申请日:2011-12-01
公开日:2021-03-02
发明作者:Masahiko Shimizu；Ryuji Saito；Hiroyuki Miura
申请人:Daicel Corporation；
IPC主号:

专利说明:

Technical area
The present invention relates to a process for producing acetic acid, while efficiently inhibiting the increase in the concentration of hydrogen iodide (in particular, hydrogen iodide and acetic acid) in an acetaldehyde distillation column. Prior Art
Various industrial processes for producing acetic acid are known. Among others, an industrially excellent process includes a process, which comprises continuously allowing methanol to react with carbon monoxide, with the use of a metal catalyst (such as a rhodium catalyst) and methyl iodide; 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 content condition, compared to the conventional condition.
In this process, a volatile component is separated, when acetic acid is separated from a liquid reaction mixture by distillation. The volatile component contains a useful component, such as methyl iodide, while the component is a liquid component containing acetaldehyde. Therefore, the volatile component is collected or recycled to the reaction system, after acetaldehyde is separated by distillation (or condensation). The volatile component contains an acidic component (such as hydrogen iodide or acetic acid), in addition to methyl iodide, acetaldehyde, water and methyl acetate. When hydrogen iodide or acetic acid is condensed (or produced) on an acetaldehyde distillation column under a distillation condition (for example, applied pressure or at an elevated temperature), corrosion of the acetaldehyde distillation column can be precipitated . In addition, when the solution containing methyl iodide is subjected to distillation and then the fraction and / or the separated residue is recycled to the reaction system, corrosion from a recycling pump or a recycling line can be hasty. Therefore, it is preferable that the concentration of the acid component (such as hydrogen iodide or acetic acid), in the distillation column to separate acetaldehyde, is reduced.
Japanese Patent No. 3581725 (JP-3581725B, Patent Document 1) describes a recycling process, which comprises the carbonylation of methanol and / or methyl acetate in a reaction medium containing a Group 8 metal catalyst from the Periodic Table and methyl iodide ; separate a volatile phase and a low volatility phase from the carbonylation product, where the volatile phase contains the unreacted product, methanol and / or methyl acetate, and methyl iodide, and the low volatility phase contains the metal catalyst of the group 8; distill the volatile phase, to provide a supernatant containing the product, unreacted methanol and / or methyl acetate, and methyl iodide; and recycling the supernatant to the carbonylation reactor; where the supernatant is a mixture containing acetaldehyde and methyl iodide, the supernatant is recycled to the reactor after distillation of the supernatant in the presence of methanol, at a column top temperature below 55 ° C and a reflux tank temperature below 25 ° C and dissolving acetaldehyde produced in a form of paraldehyde or metaldehyde in a mixed solution containing methyl iodide and methanol, in a weight ratio (methyl iodide / methanol) of 5/4 to 1/2, as a composition of a bottom fraction of the distillation column for extraction or separation.
In fact, according to the process described in the document, the use of methanol in the distillation column aims at dissolving the paraldehyde or metaldehyde, and is not intended to inhibit the production of hydrogen iodide. In addition, the process described in the document requires methanol, from 0.8 to 2 times more than the weight of highly rich methyl iodide contained in the supernatant, and it is necessary to treat a large quantity of a liquid object to be treated, composed of the total amount of supernatant and methanol. Thus, it is necessary to use a distillation column having a large diameter, which is not economical.
International publication W02008 / 016502 (W02008 / 016502, Patent Document 2) discloses a process for decreasing the aldehyde impurity of an acetic acid stream, which comprises allowing an acetic acid stream containing an aldehyde impurity to react with a compound hydroxyl (such as glycol, polyol, or a C4-io alcohol) to convert the aldehyde impurity into an acetal, and separate the acetal. Specifically, the document describes the following recycling technique: a supernatant containing methyl iodide, methyl acetate, acetic acid, water, and an aldehyde impurity is liquefied in a decanter, from 5 to 50% of the resulting heavy phase (organic phase) , which contains methyl iodide and the aldehyde impurity, is treated with a hydroxyl compound, in a ratio of 1 to 10 equivalents of the hydroxy compound in relation to the aldehyde impurity and then distilled to separate a fraction of acetal and a fraction of methyl iodide, and the acetal fraction is discharged, and methyl iodide is recycled to the heavy phase in the decanter, or in the carbonylation reaction. The document also describes that methyl iodide, to be used for the reaction, can be produced by adding hydrogen iodide to a carbonyl reactor. Thus, the document proposes that hydroxyl compound be used for converting an aldehyde to an acetal, and an acidic ion exchange resin be used for acetalation, and the document is not intended to decrease hydrogen iodide or acetic acid.
Published Japanese Patent Application No. 2007- 526308 (JP-2007-526308A, Patent Document 3) describes a process for producing acetic acid, which comprises the steps of: (a) reacting carbon monoxide with at least one reagent chosen from the group consisting of methanol , methyl acetate, methyl formate, dimethyl ether and mixtures thereof, in a reaction medium comprising water, methyl iodide, and a catalyst to produce a reaction product comprising acetic acid; (b) performing a vapor-liquid separation in the reaction product to provide a volatile phase comprising acetic acid, water, and methyl iodide and a less volatile phase comprising the catalyst; (c) distilling said volatile phase to produce a purified product of acetic acid and a first supernatant comprising water, methyl acetate, and methyl iodide; (d) phase out the first supernatant, to provide a first liquid phase comprising water and a second liquid phase comprising methyl iodide; (e) adding dimethyl ether to the process in an amount effective to improve the separation of the first supernatant, to form the first and second liquid phases; and removing acetaldehyde from at least one of the first and second liquid phases, in which the dimethyl ether is added to a stream associated with the acetaldehyde extraction step. According to the document, dimethyl ether is used as a component to easily separate the first and second liquid phases, and the decrease in hydrogen iodide or acetic acid is not intended. In addition, the document is silent on an amount to be added of dimethyl ether.
Published Japanese Patent Application No. 2000-72712 (JP-2000-72712A, Patent Document 4) discloses a process for producing acetic acid, which comprises a first step to allow carbon monoxide to react with methanol, dimethyl ether, or methyl acetate in the presence of a rhodium catalyst, an iodide salt, and methyl iodide; a second step to distill the liquid reaction mixture obtained in the first step, to separate a high volatility phase containing a carbonyl compound and a low volatility phase; and a third step to distill the high volatility phase containing the carbonyl compound obtained in the second step, to separate a product containing acetic acid and an impurity containing the carbonyl compound; a fourth step to allow the impurity containing the carbonyl compound obtained in the third step to contact water to separate an organic phase containing an alkyl iodide and an aqueous phase containing the carbonyl compound; and a fifth step to send back the organic phase obtained in the fourth step to the reaction step; in which the contact of the impurity containing the carbonyl compound with water in the fourth stage is carried out at 30 to 60 ° C. The document reveals that the process can comprise a step 3b, between the third step and the fourth step, to distill the impurity containing the carbonyl compound obtained in the third step by a multi-stage distillation column, and that methanol with 0.1 at 55 mol times more than the iodide ion in the column of 10 {multistage distillation, can be fed into the distillation.
In addition, the document reveals that (i) in step 3b, hydrogen iodide produced by the reaction of methyl iodide in water sometimes causes corrosion of a metal 15 used for the distillation column, (ii) since the reaction is an equilibrium reaction, the addition of methanol to the distillation column inhibits the production of hydrogen iodide and then corrosion of the metal, and (iii) since methanol is a minor point component of 20 boiling and the azeotropic temperature of hydrogen iodide and water is 127 ° C, methanol is added, preferably, to the bottom or its surroundings, of the distillation column. In addition, the document describes in the Examples that, in step 3b, methanol with 10 mol times 25 more than the iodide ion concentration in an 80-plate distillation column is added at 10 g / ha to a lower gas phase in the distillation, and the distillation is continued at 82 ° C and, consequently, the concentration of the iodide ion in the multi-stage distillation column is not more than 1 ppm; and that the addition of a predetermined amount of methanol to a liquid mixture as a model solution containing methyl iodide, water, and hydrogen iodide, reduced the concentration of the iodide ion.
In the process described in the document, however, a liquid mixture containing only methyl iodide, water, and hydrogen iodide is used as a model solution, and the effect of methanol added to a model solution containing acetic acid and methyl acetate is not investigated. . In addition, feeding methanol, about 0.1 to 55 mol times more than the amount of the iodide ion is insufficient to decrease the acid concentration in a real process solution containing not only hydrogen iodide, but also acetic acid or methyl acetate and having a complicated composition. In addition, according to the process described in the document, since methanol is added to the bottom gas phase, it is difficult to effectively inhibit corrosion of the entire distillation column. Thus, the process is not efficient. Summary of the Invention
Problems to be solved by the invention It is, therefore, an object of the present invention to provide a process for producing acetic acid, while effectively inhibiting (or preventing) an increase in the concentration of hydrogen iodide (in particular, hydrogen iodide) and acetic acid) on a 5 J acetaldehyde distillation column. It is another object of the present invention to provide a process for producing acetic acid, the process inhibiting (or preventing) the corrosion of an acetaldehyde distillation column. 10- It is yet another object of the present invention to provide a process for producing acetic acid, the process efficiently separating acetaldehyde, even using an acetaldehyde distillation column made of a cheap material.
It is yet another object of the present invention to provide a process for producing, in a stable manner, acetic acid (acetic acid with a high degree of purity), while extracting acetaldehyde efficiently.
It is another object of the present invention to provide a process for producing acetic acid, while recycling methyl iodide as a catalyst with high efficiency. Means for solving problems
The inventors of the present invention have investigated a method for reducing a concentration of hydrogen iodide in an acetaldehyde distillation column, with respect to a process comprising subjecting methanol to a carbonylation reaction with a catalyst system containing a metal catalyst , an ionic iodide, and methyl iodide, separate a stream containing an acetic acid product from the resulting volatile component, and remove acetaldehyde from the resulting lowest boiling component (supernatant) containing methyl iodide and acetaldehyde (and collect more efficiently a useful component, such as methyl iodide, to recycle the useful component to the reaction system); and found that the hydrogen iodide concentration cannot be sufficiently reduced by simply adding methanol to the acetaldehyde distillation column, which is made according to the unique concentration of the iodide ion, as described in Japanese patent JP-2000 -72712A.
More specifically, according to Japanese patent JP-2000-72712A, hydrogen iodide can be reduced by adding methanol in consideration of the following equilibrium reaction (1), in which hydrogen iodide is involved: CH3I + H20 <=> CH3OH + Hl (1)
However, since the supernatant contains acetic acid, methyl acetate, and water, in addition to methyl iodide and hydrogen iodide, a plurality of equilibrium reactions, including the following reactions, in which methanol participates, occurs in addition to reaction (1). Thus, the reaction system is highly complicated. CH3COOH + CH3OH <=> CH3COOCH3 + H20 CH3I + CH3COOH <z> CH3COOCH3 + Hl in the system containing acetic acid, methyl acetate, and others, it is difficult to reduce the hydrogen iodide concentration, even if the reaction (1) 10! is simply noticed. In addition, not only hydrogen iodide, but also acetic acid, is also an acidic component, and it is preferable that acetic acid is reduced, because acetic acid is a corrosive factor of the acetaldehyde distillation column. From 15 points of view of reducing the concentration of hydrogen iodide (below, the reduction of the concentration of acetic acid) and an efficient collection of methyl iodide, it is further verified that considering only the reaction (1) will not very far. In addition, the use of a large 20; methanol amount not only requires a large acetaldehyde distillation column, but also significantly reduces the efficiency of the process, due to a large amount of a process solution to be distilled.
Therefore, the inventors of the present invention carried out intensive studies to achieve the aforementioned objectives and finally found that, in an acetaldehyde distillation column, the distillation of a process solution, which comprises a supernatant containing acetic acid and methyl acetate, in addition to methyl iodide, acetaldehyde, and hydrogen iodide, and a specific amount of methanol and / or dimethyl ether added to the supernatant, effectively inhibits or prevents an increase in a concentration of hydrogen iodide (additionally a concentration of acetic acid) in the column distillation of acetaldehyde; that corrosion of the acetaldehyde distillation column is prevented or inhibited, and the use of an inexpensive material for the acetaldehyde distillation column reduces the cost of the acetic acid production process; and that the separation of acetaldehyde (and collection of methyl iodide) is efficiently retained, while inhibiting an increase in the concentration of hydrogen iodide (and acetic acid). The present invention was carried out on the basis of the above conclusions.
That is, the process of the present invention includes a process for producing acetic acid, the process comprising 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 iodide methyl in a carbonylation reactor; an instant evaporation step for continuous supply of a vaporizer with a reaction mixture from the reactor to separate a volatile component (2A) containing the acetic acid product, methyl acetate, methyl iodide and water, and a low volatility component (2B ) containing the metal catalyst and ionic iodide; a step of collecting acetic acid to feed a distillation column with the volatile component (2A), and separate a supernatant (3A) containing methyl iodide, acetic acid, methyl acetate, water, acetaldehyde by-product, and hydrogen iodide, and a stream (3B) containing acetic acid to collect acetic acid; and an acetaldehyde separation step to feed an acetaldehyde distillation column (extraction column or separation column) with the condensed supernatant (3A) (part or all of the supernatant (3A)), and distill a liquid object to be treated containing the supernatant (3A) (or a condensed or condensed component in the supernatant (3A)), to separate a lower boiling point component (4A) containing acetaldehyde and a higher boiling point component (4B); in which, in the acetaldehyde separation step, the liquid object containing at least one source of methanol selected from the group consisting of methanol and dimethyl ether, in a concentration of 0.1 to 50% by weight, is subjected to distillation.
In the process, in the liquid object, the proportion of methyl iodide can be from about 1 to 98% by weight (for example, from about 1 to 95% by weight), the proportion of methyl acetate can be about 0.5 to 50% by weight (for example, from about 0.5 to 30% by weight), the proportion of acetic acid can be about 0.2 to 50% by weight, the proportion of water can be from about 0.1 to 90% by weight, and the proportion of hydrogen iodide can be from about 1 to 1000 ppm (for example, from about 1 to 300 ppm) based on weight.
In the process, the concentration of the methanol source in the liquid object can be from about 0.1 to 50% by weight (for example, from about 0.2 to 50% by weight), and can be from about 1 to 30% by weight (for example, from about 2 to 25% by weight). In addition, in the process, in the liquid object, the concentration of acetic acid can be about 0.3 to 50% by weight, the proportion of the methanol source (in terms of methanol) can be about 0.1 to 40 mol relative to 1 mol of a total amount of acetic acid and hydrogen iodide. In addition, in the process, the relationship between the methanol source (in terms of methanol) and the liquid object can be not less than 80 mol (for example, not less than 20 0 mol) with respect to 1 mol of hydrogen iodide . Representatively, in the process, in the liquid object, the concentration of acetic acid can be from about 0.5 to 50% by weight (for example, from about 0.5 to 40% by weight), the concentration of iodide of hydrogen can be from about 5 to 1000 ppm (for example, from about 5 to 200 ppm), the ratio of the methanol source (in terms of methanol) can be about 1 to 20 mol (for example, from about 1 to 5 mol) in relation to 1 mol of a total amount of acetic acid and hydrogen iodide.
In the process of the present invention, the concentration of the methanol source in the liquid object can be adjusted with the reaction conditions, or the amount of pre-feed. The concentration of the methanol source in the liquid object is generally adjusted by adding or mixing the methanol and / or methyl acetate source to the supernatant (3A) inside or outside the acetaldehyde distillation column (for example, the concentration of the methanol source in the liquid object is adjusted from 0.1 to 50% by weight). In fact, although methyl acetate is not a source of methanol, methyl acetate can produce methanol by chemical equilibrium. Thus, the concentration of the methanol source in the liquid object can be adjusted by adding methyl acetate. Representatively, the concentration of the methanol source in the liquid object can be adjusted by adding or mixing the methanol source and / or methyl acetate, as follows (A) and / or mode (B): (A) a source of methanol and / or methyl acetate is added or mixed with the supernatant (3A), before the supernatant (3A) is fed to the acetaldehyde distillation column [i.e., the source of methanol and / or methyl acetate is added or mixed with the supernatant (3A), from the feed to the acetaldehyde distillation column], (B) in the acetaldehyde distillation column, the source of methanol and / or methyl acetate is added or mixed with the supernatant (3A), at the same height level (or in the same position, for example, in the distillation column, on the same plate) as a height level (or a position or a plate), where the supernatant (3A) is fed or at a level height (for example, in the distillation column, a plate) higher than the height level (for example, in the column in the distillation, a plate), in which the supernatant (3A) is fed.
In mode (A), a temperature of a mixture containing the supernatant (3A) and the source of methanol and / or methyl acetate can be regulated from 20 to 100 ° C, and a time, from when the supernatant (3A) ) and the source of methanol and / or methyl acetate are mixed until the mixture is fed to the acetaldehyde distillation column, it can be set for no less than 5 seconds; and the concentration of the methanol source can be adjusted, at least, in mode (A). Representatively, in mode (A), a temperature of a mixture containing the supernatant (3A) and the source of methanol and / or methyl acetate can be regulated from 30 to 85 ° C, and a time, from when the supernatant (3A) and the source of methanol and / or methyl acetate are mixed until when the mixture is fed to the acetaldehyde distillation column, it can be set for no less than 10 seconds; and the concentration of the methanol source can be adjusted, at least, in mode (A). Feeding the acetaldehyde distillation column with the supernatant (3A), to which the source of methanol and / or methyl acetate is added under such a condition can further efficiently inhibit the increase in the concentration of hydrogen iodide or acetic acid in the column. distillation of acetaldehyde.
According to the process of the present invention, the supernatant (3A) can be fed directly to the acetaldehyde separation step (or acetaldehyde distillation column), and the supernatant (3A) can generally be retained (or maintained) in a decanter and then discharged to be fed to the acetaldehyde separation step. That is, the process of the present invention may further comprise a condensation step to temporarily retain the supernatant (3A) in a decanter (or storage tank), with condensation, and discharge the supernatant (3A) from the decanter. The supernatant (3A) discharged from the decanter in the condensation step can be fed to the acetaldehyde distillation column. When the process comprises the condensation step, in mode (A), the methanol source is usually added or mixed with the supernatant (3A) at a time, from when the supernatant (3A) is discharged from the decanter until when the supernatant (3A) is fed to the acetaldehyde distillation column.
In the condensation step, the amount to be maintained of the supernatant (3A) can be adjusted or controlled based on a floating (or changeable or variable) flow rate of the supernatant (3A) to be fed to the decanter. That is, according to the acetic acid production process, the amount of the supernatant (3A) to be fed to the decanter varies significantly throughout the process. Such flow control allows the process to be carried out in a stable and efficient manner. Thus, a combination of such a process with the adjustment of the concentration of the methanol source effectively ensures both the stable functioning of the process and the inhibition of an increase in the concentration of hydrogen iodide or acetic acid in the acetaldehyde distillation column. With respect to variation (or change), for example, assuming that the average flow rate of the lowest boiling point component (3A) to be fed to the decanter is 100 in terms of liquid volume, the flow rate of the smallest component boiling point (3A) to be fed to the decanter can be about 80 to 120 throughout the entire process.
A concrete method for adjusting (or controlling) the amount of the supernatant (3A) to be retained includes, for example, (1) a method, in which the supernatant (3A) is discharged, so that the variation in the amount or the level of supernatant liquid (3A) to be retained in the decanter can be inhibited (or kept substantially constant), and / or (2) a method, in which a decanter having a buffering function, is used as the decanter to relieve (or diffuse) the variation in the amount of the supernatant (3A) fed into the decanter.
According to method (1), for example, in the condensation step, assuming that the average liquid level J (or average value) and / or the level of the supernatant interface (3A) maintained in the decanter is 100, the level (or average amount) and / or the supernatant interface level (3A) maintained in the decanter can be adjusted (specifically, the supernatant (3A) can be discharged to adjust the liquid level) from about 95 to 105 throughout the process. The liquid level means a height level of the contact surface of the condensed supernatant (3A) with gas (gas phase), in the decanter. When the supernatant (3A) is separated into two phases (upper phase and lower phase), the interface level means a height level of the boundary between two phases (or a height level of the lower phase). Thus, the concept of the interface level is used for condensed supernatant, separated into layers (separated into phases) (3A).
In addition, according to the regulation method (2), in the condensation step, a decanter having a buffering function can be used as the decanter. In particular, the retention time (or maintenance time) of the supernatant (3A) in such a decanter can be regulated, so as to be not less than 6 minutes. The use of the decanter, which allows such sufficient retention time, can efficiently decrease the variation of the supernatant (3A) in the decanter.
According to the present invention, in order to carry out the whole process in a stable manner, in the condensation step, the amount of the supernatant (3A) to be retained can normally be adjusted or controlled based on the variation of the flow rate of the supernatant ( 3A) to be fed to the decanter and, in addition, the amount of the supernatant (3A) to be fed to the separation step: acetaldehyde can be adjusted. Specifically, in the condensation step, the amount of the supernatant (3A) to be fed to the acetaldehyde separation step can be adjusted to be constant or almost constant (or to be kept substantially constant) [for example, assuming the flow rate mean of the supernatant (3A) is 100, the flow rate of the supernatant (3A) to be fed to the acetaldehyde separation step can be adjusted from 95 to 105 throughout the entire process].
Representative examples of the method for adjusting or controlling the amount of the supernatant (3A) to be fed to the acetaldehyde separation step (or acetaldehyde distillation column) include at least one of the following methods (a), (b) and (c) selected: (a) a method for circulating part of the supernatant Ç3A) discharged from the decanter to a stage other than the acetaldehyde separation step [for example, at least one item selected from the group consisting of the reaction system (reactor or stage reaction phase) and the acetic acid collection step (or distillation column), in particular, at least the reaction system (or reactor) or reaction step]; (b) a method for feeding the acetaldehyde separation step with the supernatant (3A) discharged from the decanter, through a storage vessel with a buffering function; and (c) a method to adjust the amount of the supernatant (3A) to be discharged from the decanter, to keep constant (or almost constant, for example, assuming that the average flow rate of the supernatant (3A) to be discharged from the decanter is 100 , the amount of the lowest boiling point component (3A) to be discharged from the decanter throughout the entire process is adjusted from 95 to 105).
For method (a), in the condensation step, the amount (or flow rate) of the supernatant (3A) to be fed to the acetaldehyde separation step can be adjusted by circulating part of the supernatant (3A) discharged from the decanter to a stage different from the acetaldehyde separation step. In method (a), not less than 20% (for example, from about 20 to 90%) of the average flow rate of the supernatant (3A) to be fed to the decanter can be distributed, in particular, from about 40 to 90% of the average flow can be circulated. In addition, in method (a), the supernatant (3A) can be separated into an upper layer and a lower layer in the decanter, and the upper layer and the lower layer can be circulated.
For method (b), the retention time of the supernatant (3A) in the storage vessel with a buffering function can be not less than 1 minute (for example, not less than 2 minutes). In addition, in method (b), the total supernatant retention time (3A) in the decanter and the supernatant retention time (3A) in the storage vessel with a buffering function can be no less than 3 minutes (for example , not less than 4 minutes).
For method (c), normally, a decanter having a buffering function is used as the decanter, and the supernatant retention time (3A) in the decanter can be not less than 3 minutes.
Methods (a) to (c) can be performed alone or in combination (for example, at least method (a) or method (b)).
According to the present invention, not only the extraction of acetaldehyde, but also the collection (recycling) of methyl iodide, are efficiently achieved. For example, the present invention may further comprise a recycling step to feed the acetaldehyde distillation column with the supernatant (3A), separate a lower boiling component (4A) containing acetaldehyde and a higher boiling component ( 4B) containing methyl iodide by distillation, recycle the component with the highest boiling point (4B), as a separate solution (or a solution) [for example, recycle the component to a reaction system step (or reactor or step reaction), for the separation of acetaldehyde (for example, at least one element selected from the group consisting of the reaction system 10 (reactor or reaction step), the acetic acid collection step (or distillation column), and the acetaldehyde removal column; particularly, at least, the reactor or reaction step)].
In addition, according to the present invention, in the recycling step, the separated solution can be recycled, reducing the flow variation of the separated solution. Specifically, in the recycling step, the separate solution can be recycled via a storage vessel having a buffering function.
The lowest boiling point component (4A) sometimes contains methyl iodide, due to insufficient separation. Thus, according to the present invention, when the lowest boiling point component (4A) contains methyl iodide, in the recycling step, methyl iodide 25 collected from the lowest boiling point component (4A) can be recycled [recycled to a reaction system step for acetaldehyde separation, for example, recycled to at least one element selected from the group consisting of the reaction system (reactor or reaction step), the acetic acid collection step ( or distillation column), and the acetaldehyde distillation column].
In the process of the present invention, the material of (or to form the) acetaldehyde distillation column may comprise an alloy [for example, a nickel-based alloy, an iron-based alloy (for example, a stainless steel and a alloy based on biphasic iron (for example, a biphasic stainless steel))]. The present invention achieves corrosion inhibition, and even an acetaldehyde distillation column made of a relatively corrosive material can preferably be used.
In fact, throughout this description, the term "liquid object to be treated" (or "liquid object") means a process solution, before being distilled in the acetaldehyde distillation column, unless otherwise indicated. Throughout the description, the total part (s) of any / any component (s) existing in the same mixing system (such as the liquid object to be treated) is not more than 100% by weight, - and the proportions of all components are 100% by weight, in total. Effects of the Invention
According to the process of the present invention, acetic acid can be produced, efficiently inhibiting (or preventing) an increase in the concentration of hydrogen iodide (in particular, hydrogen iodide and acetic acid) in the acetaldehyde distillation column. In addition, according to the process of the present invention, corrosion of the acetaldehyde distillation column can be inhibited (or prevented). In addition, according to process 10 of the present invention, acetaldehyde can be efficiently removed, even if the acetaldehyde distillation column is not made of a high quality material with a high resistance to corrosion. Thus, according to the process of the present invention, acetaldehyde can be efficiently separated, even using an acetaldehyde distillation column made from a low quality or inexpensive material. Thus, the present invention allows the use of a cheap or low quality material to produce the acetaldehyde distillation column, so that the cost of the acetic acid production process can be reduced efficiently.
In addition, according to the present invention, acetic acid (acetic acid with a high degree of purity) can be produced in a stable manner, while inhibiting an increase in the concentration of hydrogen iodide or acetic acid in the acetaldehyde distillation column , adjusting the amount of the supernatant to be stored in the decanter, in response to the variation in the amount of supernatant feed containing methyl iodide, and acetaldehyde, while removing acetaldehyde efficiently.
In addition, according to the present invention, since acetaldehyde can be efficiently and reliably separated from the supernatant, acetic acid can be produced, while at the same time, highly efficient recycling of the methyl iodide from the catalyst separated from the 10 supernatant. Brief Description of Drawings
Fig. 1 is a diagram for explaining a production process (or production apparatus) for acetic acid, according to an embodiment of the present invention. Fig. 2 is a diagram for explaining a production process (or production apparatus) for acetic acid, according to another embodiment of the present invention. Description of the Forms of Realization
Hereinafter, the present invention will be explained in detail 20 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.
The embodiment of Fig. 1 shows a continuous process (or apparatus) for producing acetic acid from a liquid reaction medium (or reaction mixture), generated by a continuous carbonyl reaction of methanol with 5 carbon monoxide in the presence of a catalyst system comprising a rhodium catalyst as a metal catalyst, and a co-catalyst [lithium iodide as a halide salt and methyl iodide], as well as acetic acid, methyl acetate, and a finite amount of water .
The process (or production apparatus) comprises a reactor (reaction system) 1 to carry out the methanol carbonylation reaction; a vaporizer 2 to separate a volatile component or volatile phase (2A) containing acetic acid product, methyl iodide, methyl acetate, and water 15 and a low volatility component or low volatility phase (2B) containing the catalyst rhodium and lithium iodide from a liquid reaction medium (or a reaction mixture, or a reaction solution), containing acetic acid generated by the reaction; a dividing column 3 20 to separate a supernatant (a first supernatant) (3A) containing methyl iodide, acetic acid, methyl acetate, water, acetaldehyde by-product, hydrogen iodide, and others, a current phase or acetic acid (3B ) containing acetic acid as a side current, and a current with a higher boiling point or component with a higher boiling point (3C) containing acetic acid, water, propionic acid, and others, from the volatile component (2A) fed to the vaporizer 2; a decanter 4 for temporarily retaining or storing the condensed supernatant (3A); a buffer tank 5 for temporarily storing (or retaining) the supernatant (3A) fed or discharged from the decanter 4; an acetaldehyde distillation column (separation column or extraction column) 6 to separate the supernatant (3A) fed or discharged from the decanter 4 from the buffer tank 5 to a lower boiling component (4A) containing acetaldehyde and iodide methyl, and a component with a higher boiling point (4B) containing methyl iodide, methyl acetate, water, acetic acid, and others; a buffer tank 7 for temporarily storing (or retaining) the component with the highest boiling point (4B), separated in the distillation column 6; an extraction apparatus or extractor 8 for separating acetaldehyde from the lowest boiling point component (4A) by extraction to recycle methyl iodide; lines 51 and 52 to feed methanol and / or dimethyl ether; several lines to feed or circulate each component to that device.
Hereinafter, the process shown in FIG. 1 will be explained in more detail. For reactor 1, methanol as a liquid component is fed continuously at a predetermined speed, and carbon monoxide as a gaseous reagent is fed continuously. In addition, for reactor 1, a catalyst mixture (liquid catalyst mixture) containing a carbonylation catalyst system [a catalyst system comprising a main metal catalyst component (for example, a rhodium catalyst), and a co- catalyst (for example, lithium iodide and methyl iodide)] and water can be fed. In addition, a stream (for example, in liquid form) containing the lowest boiling point component (s) or the highest boiling point component (s) from the next step (s) is fed to reactor 1 via line 13 and / or line 40.
Next, inside the reactor 1, a liquid phase reaction system containing the reagent and the highest boiling component, such as the metal catalyst component, (for example, a rhodium catalyst and lithium iodide) is in equilibrium with a vapor-phase system containing carbon monoxide, by-products from 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. In order to maintain the internal pressure of the reactor 1; (eg reaction pressure, partial pressure of carbon monoxide, partial pressure of hydrogen, partial pressure of methane and partial pressure of nitrogen) constant, steam can be extracted and discharged from the top of reactor 1. In addition, the extracted steam of reactor 1 can be cooled by a heat exchanger, to obtain 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 can be recycled to reactor 1 (not shown), and the resulting gaseous component (waste gas) can be discharged.
For reactor 1, if necessary, hydrogen can be fed, in order to increase catalytic activity. Hydrogen can be fed together with carbon monoxide, or it can be fed separately. In addition, since the reaction system is an exothermic reaction system that accompanies heat generation, 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.
Components contained in the reaction mixture (crude reaction solution) generated in reactor 1 may include acetic acid, a component with a lower boiling point, or impurity with a lower boiling point with a lower boiling point than that of acetic acid (for example, example, 25 methyl iodide as a co-catalyst, methyl acetate as a reaction product of acetic acid with methanol, water, and acetaldehyde, a superior iodide (such as hexyl iodide) in the form of by-products), and a component higher boiling point or a higher boiling point impurity with a higher boiling point than that of acetic acid [eg a metal catalyst component (eg a rhodium catalyst), lithium iodide as a co- catalyst, propionic acid, and water].
In order to essentially separate the component with the highest boiling point (such as the metal catalyst component) from the reaction mixture, part of the reaction mixture is continuously extracted from reactor 1 and introduced or fed into the vaporizer (column of distillation or catalyst separation column) 2 through a feed line 11.
The amount of the reaction mixture to be fed from the reactor 1 to the vaporizer 2 is not constant and varies in the continuous process, due to the pressure variation caused by the spraying of carbon monoxide to be fed to the liquid phase and others. For example, assuming that the average flow rate of the reaction mixture to be fed to the vaporizer 2 is 100, the flow rate (or flow rate, the same applies to the flow rate) of the reaction mixture to be fed to the vaporizer 2 is about 98 to 102 throughout the process. As described later, for a closed process, the variation in the amount of feed affects the next step (s) and can sometimes be a factor that causes a change in the amount of feed of the supernatant to be fed to the decanter.
In the vaporizer (flash distillation column) 5 2, from the reaction mixture, a low volatility component (2B) (essentially containing the metal catalyst component, such as rhodium or lithium iodide catalyst, and others) and a lower boiling current or volatile component (2A) (containing 10 essentially acetic acid, which is a product and also works as a reaction solvent, methyl acetate, methyl iodide, water, acetaldehyde and others) are separated, and the low volatility component (2B) is extracted from the bottom of the vaporizer, through a line of 15 bottom 13, and recycled to reactor 1 and the volatile component (2A) (acetic acid stream) is extracted by the top of the column or upper part of the vaporizer 2, through a feed line 12, and fed or introduced into the dividing column (or distillation column) 3. In this context, the low volatility component (2B) also contains a catalyst of metal (the catalis rhodic acid), and ionic iodide (lithium iodide) and, in addition, remaining components without evaporation (for example, methyl iodide, methyl acetate, water, and traces of acetic acid). The volume ratio of the volatile component (2A) to be separated in the vaporizer 2 is about 20 to 40% throughout the reaction mixture.
Part of the component with the lowest boiling point (2A) may have its heat removed, and recycled to the reactor. In an embodiment of Fig. 1, part of the vaporized lower-boiling component (2A) (for example, from about 10 to 30% by volume) is fed to a storage vessel (containment tank) and / or to the heat exchanger 9 by means of a line 12a, and condensed by heat extraction, and recycled to the reactor 1 by means of a line 12b. In this way, the extraction of heat from part of the component with the lowest boiling point (2A) and circulation of the component to the reactor allows an apparatus, such as a distillation column (for example, a dividing column), to be reduced (or miniaturized), even for a large plant. Thus, acetic acid can be produced with high purity and high performance in a resource and energy saving equipment.
The quantity (quantity of feed) of the volatile component (2A) to be fed from the vaporizer 2 to 20 dividing column 3 also fluctuates in the continuous process, with the variation of the quantity (quantity of feed) of the reaction mixture to be fed to the vaporizer 2. For example, supposing that the average flow rate of volatile component (2A) to be fed to the dividing column 3 is 100, the flow rate of the volatile component (2A) to be fed to the dividing column 3 is about 98 to 102 during the entire process.
In the dividing column 3, generally, a supernatant (or component with the lowest boiling point) (3A) (containing methyl iodide, methyl acetate, acetaldehyde, water, acetic acid, hydrogen iodide, and others) is separated by the top of the column or upper part of the column, through an extraction line 14, and a stream with a higher boiling point or component with a higher boiling point (3C) (a component containing water, propionic acid, and others) is separated (or removed ) through the bottom or bottom of the column, via a bottom line 16. The separate highest boiling point component (3C) can be discharged via line 16, or can be partially or totally recycled to reactor 1 , through a line 40. A side stream or stream of the acetic acid phase (3B) (acetic acid stream), containing essentially acetic acid, is collected from the dividing column 3, through a feed line 15 by cut side. In this context, the stream (3B) containing acetic acid collected by side cutting can generally be fed to the other distillation column i (not shown) via line 15 and then distilled for purification (not shown). The proportion of the supernatant (3A) separated in the dividing column 3 is about 35 to 50% by weight over the entire volatile component (2A). As described later, when a process solution, from the next step (s) is circulated or recycled to the dividing column 3, the total amount of the component to be fed from the vaporizer 2 and the component recycled from the next step (s) is subjected to distillation on dividing column 3, to separate the supernatant (3A).
The amount of the supernatant (3A) to be fed from the dividing column 3 to the decanter 4 is affected by the variation in the amount of the reaction mixture to be fed to the vaporizer 2 and the variation in the amount of the volatile component (2A) to be fed. from vaporizer 2 to dividing column 3, and floats in the continuous process. For example, assuming the average flow rate of the supernatant (3A) to be fed to the decanter 4 is 100, the flow rate of the supernatant (3A) to be fed to the decanter 4 is about 90 to 110 over the entire process. (that is, the flow rate of the supernatant (3A) fluctuates within the range of about 0 to + 10% by volume). The supernatant (3A) is fed to the decanter 4, with a relatively large number of fluctuations. The supernatant (3A), separated via line 14, is condensed, fed continuously to the decanter (storage vessel) 4, and kept (stored) temporarily in the decanter 4. Inside the decanter 4, the condensed supernatant (3A) is separated in an upper layer and a lower layer, the upper layer (water layer or aqueous phase) essentially contains water, acetic acid, methyl acetate, and others, and the lower layer (organic layer or organic phase) contains essentially methyl iodide , methyl acetate, and others. Acetaldehyde, methyl iodide, and hydrogen iodide are contained in the two layers. A greater amount of acetaldehyde is contained in the upper layer (water layer), compared to the lower layer. Hydrogen iodide is contained essentially in the upper layer, in many cases. In the supernatant (3A) to be fed to the decanter 4, the volume ratio of the upper layer (or upper layer component) to the lower layer (or lower layer component) [the first / last] is, for example, from about 0.5 / 1 to 1.5 / 1 (for example, from about 0.7 / 1 to 1.3 / 1). The variation in the amount of feed in the upper layer and the lower layer is within the same range, as mentioned above.
The supernatant (3A), kept in the decanter 4, is fed to the acetaldehyde distillation column 6, via a feed line 17 and / or a 20 feed line 18. In the embodiment of Fig. 1, the storage of the supernatant (3A) to be kept in decanter 4, (or the variation of the liquid level), is significantly prevented from floating, through the circulation (or recycling) of part of the supernatant (3A) 25 to the reaction system, or others , via a line 17a (underlines 17a) branched from line 17, or a line 18a (underlines 18a) branched from line 18, based on the flow rate of the supernatant (3A) to be fed to the decanter 4 .
That is, the amount of the supernatant (3A) to be continuously fed to the decanter 4 (for example, the amount to be fed per unit of time) is not constant in the continuous reaction and, as described above, the amount fluctuates through the reaction. carbonylation, instant distillation, and recycling of methyl iodide (for example, the amount of supernatant (3A) to be fed per unit time is increased or decreased). Therefore, the direct feeding of the supernatant (3A) to the decanter 4 causes great variation in the liquid level of the supernatant (3A) condensed and stored in the decanter 4 and, sometimes, the process cannot be operated, depending on the variation. In order to alleviate (or decrease) the variation, the supernatant (3A) can be fed from decanter 4 to the acetaldehyde distillation column; 6, with a sufficient flow to alleviate the variation of the flow. However, such feeding causes an insufficient process in the aldehyde distillation column 6.
Then, in the embodiment of Fig. 1, the amount of the supernatant (3A) to be kept in the decanter 4 is adjusted or controlled by recycling part of the supernatant (3A) in one step (in the embodiment of Fig. 1 , the reactor 1 and / or the dividing column 3) different from the acetaldehyde separation step, without feeding the decanter 4 to the distillation column 6, based on the variation in the flow rate of the supernatant (3A) to be fed to the decanter 4 .
Specifically, in the embodiment of Fig. 1, the supernatant (3A) is discharged from the top layer and the bottom layer into the decanter 4, via line 17 and line 18, respectively. The flow rate of the supernatant (3A) to be discharged from the decanter 10 4 is regulated, so that each of the liquid levels of the upper layer and the lower layer can be constant (or almost constant), even under the variation of the flow rate. of supernatant (3A) to be fed to the decanter 4. That is, the decanter 4 is equipped with liquid level sensors for detecting variation of the liquid level (not shown), and one of the sensors detects the variation of the level of liquid in the upper layer, and the other sensor detects that of the lower layer. The amount of the supernatant (3A) to be discharged from the top layer and the bottom layer 20 into the decanter 4 is regulated based on the liquid level information detected by the sensors, so that predetermined levels of liquid from these layers can be maintained. More specifically, based on the information obtained by the liquid level sensors, when the flow rate at 25 is fed to the decanter is large, the flow rate of the supernatant (3A) to be discharged is increased, to prevent the liquid level from increasing; when the flow rate to be fed to the decanter is small, the flow rate of the supernatant (3A) to be discharged is decreased. In such a way, the liquid level (or the liquid level of the upper layer) of the supernatant (3A) in the decanter 4 (the liquid level of the upper layer and that of the lower layer) is kept constant or almost constant, adjusting (controlling ) the flow rate throughout the process [for example, assuming that the average liquid level is 100, each of the liquid level of the upper layer and that of the lower layer is regulated (or adjusted) from about 99 to 101 throughout the process, that is, the variation in the liquid level is adjusted to a maximum of about 1% in the entire process].
In addition, a portion of the supernatant (3A) discharged through line 17 and line 18 is fed to line 19, through line 17b and line 18b. The flow rate of the supernatant (3A) to be fed to line 19 is adjusted (controlled), to be kept constant or almost constant, adjusting the amount of the supernatant (3A) to be distributed through line 17a and / or line 18a. That is, in the embodiment of Fig. 1, as described above, the amount of the supernatant (3A) discharged from each one between the upper layer and the lower layer in the decanter 4 oscillates, so that the liquid level in the decanter 4 can be constant or almost constant. When changing the amount of the supernatant (3A) to be distributed through line 17a and / or line 18a, in response to the variation, the flow rate of the supernatant (3A) to be fed to line 19 is regulated, to avoid (or almost 5 avoidance), variation [for example, assuming that the average flow rate of the supernatant (3A) to be fed to line 19 is 100, in terms of liquid volume, the flow rate of the supernatant (3A) is regulated (or adjusted) by about 98 to 102 throughout the process, that is, the flow variation is adjusted up to 10, a maximum of about 2% in the entire process]. By the way, in the embodiment of Fig. 1, the flow variation of the component with the lowest boiling point (3A) to be fed to line 19 can be essentially controlled by varying the amount of the supernatant (3A) to be distributed and, 15 additionally, it can be further controlled by regulating the retention time of the supernatant (3A) in the decanter 4.
Indeed, it is sufficient that the flow rate of the supernatant (3A) to be fed to line 19 is regulated by the variation of the 20 flow rate of the supernatant (3A) to be distributed to line 17a and / or to line 18a. As long as a large variation in the flow to be fed to line 19 is not caused, the flow of the supernatant (3A) to be distributed to line 17a or line 18a can be kept constant (in other words, the flow 25 of the supernatant ( 3A) to be fed to line 17b or line 18b may vary).
In addition, in the embodiment of Fig. 1, the supernatant (3A) is discharged via line 17 and line 18. The flow rate of the supernatant (3A) to be fed to line 19 can be regulated by the discharge of supernatant 5 ( 3A) through only one of lines 17 and 18, and circulation of part of the supernatant (3A). Furthermore, without reference to the top layer and the bottom layer, the supernatant (3A) can be fed or discharged via a single line.
The supernatant (3A) to be fed to line 17a can be fed to a line 30 through a line 17al and circulated to the dividing column 3, it can be fed to a line 40 through a line 17a2 and recycled (or returned) to reactor 1, or it can be recycled via both lines 17al and 17a2. In addition, the supernatant (3A) to be fed to line 18a is fed to line 40 and recycled to reactor 1.
Since the variation in the flow rate of the supernatant (3A) to be fed to line 19 is significantly inhibited, as described above, the supernatant (3A) can be directly fed to the distillation column 6. In the embodiment of Fig. 1 in order to further decrease the flow variation, the supernatant (3A) is fed to the distillation column 6, through a buffer tank storage vessel 5 having a buffering function. That is, the buffer tank 5 and then fed to the distillation column 6, through a line 20. By temporarily retaining the supernatant (3A) in the buffer tank 5, even when the quantity to be fed from from buffer tank 5 to line 20 is kept constant (or almost constant), the variation in the flow rate of the supernatant (3A) fed from line 19 in buffer tank 5 can be efficiently reduced.
For the supernatant (3A) to be distilled on the distillation column 6, a predetermined amount of a methanol source (methanol and / or dimethyl ether) is added or mixed via a line 51 and / or a line 52. This is , the predetermined amount of the methanol source (methanol and / or dimethyl ether) can be added 15 or mixed in line 19, through line 51.
Specifically, the supernatant (3A) containing acetic acid, methyl acetate, water, and hydrogen iodide, in addition to methyl iodide and acetaldehyde, is fed as a mixture (liquid object to be treated, process solution 20) containing the methanol source for the buffer tank 5 and then the distillation column 6, through line 20. In the embodiment of Fig. 1, the methanol source is added in line 19, before feeding to the buffer tank 5. The methanol source can be added in line 20 through line 51, just before feeding to the distillation column 6.
In addition, the methanol source is fed through line 52, on the same plate (or level of height or position) as a plate (or level of height or position), in which the supernatant (3A) is fed to the distillation column 6, through line 20, or on an upper plate (or level of height or position) in relation to that plate (or level or height of position); and a mixture containing the methanol source and the supernatant (3A) can be subjected to distillation. Feeding the methanol source to the distillation column 6 in that relative position can also reliably inhibit the increase in the concentration of hydrogen iodide (and acetic acid) in the plate (or height or position level) that feeds the supernatant (3A) or a plate (or level of height or position) above it. Thus, the corrosion of the entire distillation column 6 can also be efficiently inhibited.
For line 51 and / or line 52, methyl acetate can be added, instead of the methanol source, or added together with the methanol source.
Taking into account the concentration of the methanol source in the distillation column 6, the amount of the methanol source (and / or methyl acetate, the same applies to others) to be added in each of line 51 and / or line 52 can be regulated so that the methanol source can have a predetermined concentration in an appropriate proportion.
The mixture, containing the supernatant (3A) fed to the distillation column 6, is separated into a stream with a lower boiling point or component with a lower boiling point (or a second supernatant) (4A) and a stream with a higher boiling point or highest boiling point component 5 (4B), in the distillation column 6, by means of distillation; where the lowest boiling current (4A) contains a trace of methyl iodide, carbon monoxide, hydrogen, and others, in addition to acetaldehyde, and the highest boiling current (4B) contains methyl acetate, water , and others, 10 in addition to methyl iodide. The increase in the concentration of hydrogen iodide and acetic acid in the distillation column 6 is significantly inhibited by distillation of the supernatant (3A) together with the methanol source. Due to the addition of dimethyl ether, the increase in the concentration of hydrogen iodide appears to be inhibited, in association with a plurality of reactions including the following reaction. CH3OCH3 + 2HI <=> 2CH3I + H20
The separate lowest boiling point component (4A) is fed from the top or top of the column 20 to an acetaldehyde extraction apparatus (water extraction column) 8, through a line (discharge line) 21, and acetaldehyde is extracted from the lowest boiling point component (4A) using water. The extracted acetaldehyde (aqueous solution of aldehyde) is discharged through 25 of a line 21b. In this context, part of the component with the lowest boiling point (4A) can be returned to the distillation column 6, via a line 21a. In addition, the refine containing a trace of methyl iodide, and others, can be discharged out of the system. In the embodiment of Fig. 1, the refined discharged 5 through a line 24 is fed to the distillation column 6, through a line 24a, and / or is fed to a line 40, through a line 24b, to be recycled to the reactor 1. In such a way, the distillation or recycling of the refine can further improve a percentage of methyl iodide recovery.
In addition, the component with the highest separate boiling point (4B) is introduced as a separate solution (bottom fraction or lower column fraction) via line 22 to line 40, which leads to reactor 1, 15 or the dividing column 3. In such a way, the useful component containing methyl iodide is circulated (recycled) to the reaction system and others. The component with the highest boiling point (4B) can be fed directly to line 40, through line 22. In the embodiment of Fig. 1, the component with the highest boiling point (4B) is fed to buffer tank 7 and then to line 40 through line 23. That is, although the flow variation of the component with the highest boiling point (4B) to be fed through line 22 is inhibited with the highly controlled flow of the supernatant (3A ) to be fed to the distillation column 6, as described above, recycling the refine after the extraction of acetaldehyde mentioned above, and other factors sometimes cause the flow rate of the highest boiling component (4B) to vary. However, even if the flow of the highest boiling point component (4B) 5 fluctuates, the temporary retention of the highest boiling point component (4B), to be fed through line 22 in buffer tank 7, allows variation in buffer tank 7 is reduced. Thus, the component with the highest boiling point (4B) can be fed to line 40, keeping 10 constant (or almost constant) the flow of the component with the highest boiling point (4B) to be fed to line 23. Therefore, the variation the flow of the component with the highest boiling point (4B) to be recycled can be inhibited (or reduced).
The component with the highest boiling point (4B) fed to line 40 can be totally or partially recycled to the dividing column 3, through a line 40a. The component with the highest boiling point (4B) fed to line 40a can be partially or totally fed to the distillation column 6, through a line 40al, insofar as the stable operation of the distillation column 6 can be assured. Fig. 2 is a diagram for explaining a production process (or production apparatus) for acetic acid, in accordance with another embodiment of the present invention. The process (or apparatus) of Fig. 2 is the same as that of Fig. 1, except that a decanter 4A having a buffering function is used, instead of decanter 4 of Fig. <1, and the supernatant (3A ) is directly fed to the distillation column 6, through line 17. 5 That is, as in the embodiment of Fig. 1, the decanter cannot generally completely relieve the variation in the flow rate of the supernatant (3A) to be fed to from the dividing column 3. In contrast, in an embodiment of Fig. 2, the decanter 4A having a large capacity sufficient to alleviate (reduce) the flow variation is used, and the flow to be discharged in line 17 can be kept constant or almost constant, alleviating the flow variation inside the decanter 4A (for example, assuming that the average flow rate of the supernatant (3A) to 15 be fed through line 14 is 100, in terms of liquid volume, the flow rate of the supernatant (3A) to be discharged or fed to line 1 7 throughout the process it can be regulated (or adjusted) from about 98.5 to 101.5, that is, the flow variation can be adjusted up to 20 in a maximum of about 1.5%).
In the embodiment of Fig. 2, the supernatant (3A) is fed as the top layer to the distillation column 6, via line 17. The supernatant (3A) can be fed as the bottom layer via line 18, 25 as shown in the embodiment of Fig. 1, or it can be fed via line 17 and line 18 (are shown). In addition, without reference to the top layer and the bottom layer, the supernatant (3A) can be fed through a single line. (Reaction step)
In the reaction step (carbonyl reaction step), methanol is carbonylated with carbon monoxide in the presence of the catalyst system. In this context, fresh methanol can be fed to the reaction system directly or indirectly, or methanol and / or a derivative of it taken from various distillation steps can be recycled and fed to the reaction system.
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 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 a metal 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).
In addition, it is preferable 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, a rhodium catalyst, a rhodium iodide complex [for example, Rhl3 / [Rhl2 (CO) 4] 'and [Rh (CO) 2 I2'], a rhodium carbonyl complex, 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.
The concentration of the metal catalyst is, for example, from about 10 to 5000 ppm (based on weight, the same applies hereinafter), preferably from about 100 to 4000 ppm, more preferably, from about 200 at 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.
As the co-catalyst or accelerator contained in the catalyst system, an ionic iodide (for example, 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 may include, for example, a metal halide [for example, ■ a metal iodide, such as an alkali metal iodide (for example, lithium iodide, sodium iodide, 10-potassium iodide, iodide of rubidium, and cesium iodide), an alkaline earth metal iodide (for example, beryllium iodide, magnesium iodide, and calcium iodide), or a group 3B metal iodide in the Periodic Table (for example, boron iodide and aluminum iodide), a bromide corresponding to the iodide, and a chloride corresponding to the iodide], an organic halide [for example, an organic iodide, such as a phosphonium salt of an iodide (phosphonium iodide) (for example, a salt with triphenylphosphine and tributylphosphine) or an ammonium salt of an iodide (an ammonium iodide) (for example, a tertiary amine salt, a pyridine compound, an imidazole compound, an imide compound, or the like , with an iodide), a bromide corresponding to the iodide, and a chloride corresponding to the io deto]. 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 halide salts can be used alone or in combination. Among these halide salts, an alkali metal iodide (such as lithium iodide) is preferred.
In the reaction system (liquid reaction mixture) in the reactor, the concentration of the ionic iodide (for example, an iodide salt) 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 in the reactor. In addition, the concentration of the iodide ion in the reaction system can be, for example, from about 0.07 to 2.5 mol / liter and preferably from about 0.25 to 1.5 mol / liter .
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 used . 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 to circulate 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 20% by weight, preferably from about 5 to 20% by weight and, more preferably , from about 6 to 16% by weight (for example, from about 8 to 14% by weight) throughout the liquid phase in the reactor.
The reaction is a continuous reaction, and the reaction solution contains 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.
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.
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 mixed with carbon monoxide as a raw material for the reaction system. In addition, hydrogen can be fed to the reaction system by recycling the gaseous component (s) (including hydrogen, carbon monoxide, and others) discharged in step (s): distillation process (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 250 kPa, preferably from about 1 to 200 kPa and, more preferably, from about 5 to 150 kPa (for example , from about 10 to 100 kPa), in terms of absolute pressure.
The partial pressure of carbon monoxide or the partial pressure of hydrogen in the reaction system can be adjusted, for example, through an appropriate adjustment of the amount of carbon monoxide and hydrogen fed and / or recycled to the reaction system, of the amount of raw materials (for example, methanol) fed to the reaction system, the reaction temperature, the reaction pressure, and others.
In the carbonylation reaction, the reaction temperature can be, for example, from about 150 to 250 ° C, preferably from about 160 to 230 ° C and, more preferably, from about 180 to 220 ° C. In addition, the reaction pressure (the total pressure of the reactor), including partial pressures of by-products, can be, for example, about 15 to 40 atmospheres.
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 efficiency of separation or purification does not decrease, and a variety of solvents can be used. In normal cases, acetic acid as a product can practically be used as a solvent. That is, in the reaction solution, the remaining main component can be acetic acid, which is a reaction product and serves as a reaction solvent.
The water concentration 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 (by example, from about 0.1 to 8% 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. of about 2 to 10% by weight) throughout the liquid phase of the reaction system. The solubility of carbon monoxide: in the solution fed to the vaporizer, it is reduced by carrying out the reaction, maintaining a specific concentration of each component [articularly, an iodide salt (lithium iodide) and water] in the reaction system, and the 25 loss of carbon monoxide can be reduced.
In the previous carbonylation reaction, the production of acetic acid is accompanied by the production of an ester of acetic acid produced with methanol (methyl acetate), water generated with the esterification reaction, in addition to propionic acid, acetaldehyde and others.
In fact, since acetaldehyde is separated by the acetaldehyde separation step mentioned below, the concentration of acetaldehyde in the reactor is kept low and is relatively low, despite the continuous reaction. For example, the concentration of acetaldehyde in the reactor (or 10; reaction system) can be, based on weight, not exceeding 1000 ppm (for example, 0 or detection limit at 700 ppm) and, preferably, not exceeding at 400 ppm (for example, from 5 to 300 ppm) in the liquid phase in the reactor throughout the process.
In addition, inside the reactor, by-products derived from acetaldehyde are also produced (for example, crotonaldehyde, which is a reducing substance, produced by condensation of acetaldehyde aldol; 2-ethylcrotonaldehyde produced by condensation of 20 acetaldehyde and hydrogenated crotonaldehyde aldol and hexyl iodide produced by the aldol condensation of three acetaldehyde molecules, hydrogenation and iodization). According to the present invention, since the variation in the concentration of acetaldehyde in the reactor is also inhibited, the combination of ■ the inhibition and the low concentration of acetaldehyde mentioned above can significantly decrease by-products derived from acetaldehyde. That is, these by-products are often produced in proportion to the second to the third potency of the acetaldehyde concentration, and the inhibited (or decreased) concentration and variation of acetaldehyde can efficiently induce the inhibition of underproduction. The time-space yield of objective acetic acid in the reaction system can be, for example, from about 5 mol / Lh to 50 mol / Lh, preferably from about 10 8 mol / Lh to 40 mol / Lh and , more preferably, from about 10 mol / Lh to 30 mol / Lh. The steam component can be removed from the top of the reactor, for pressure control purposes of the reactor, or others, and the extracted steam component can be cooled with a condenser, a heat exchanger or other means to remove part of the reaction heat. The cooled vapor component can be separated into a liquid component (containing acetic acid, methyl acetate, methyl iodide, acetaldehyde, water, and others) and 20 into a gaseous component (containing carbon monoxide, hydrogen, and others), and the liquid component can be recycled to the reactor. (Instant evaporation step)
In the instant distillation step (vaporizer), from the reaction mixture fed by the reaction step by the reactor to the vaporizer (evaporator or instant distillation column), a low volatility component or low volatility phase (2B) containing, at least one boiling point catalyst component (a metal catalyst component, for example, a rhodium catalyst and an ionic iodide) is separated as a liquid (component), and a volatile component or volatile phase (2A) containing acetic acid and methyl iodide is separated as a vapor (component).
As described above, the amount of feed from the reaction mixture to the vaporizer varies. With respect to the degree of variation, assuming that the average flow rate (in terms of liquid volume; the same applies to others, unless otherwise stated) of the reaction mixture to be fed to the vaporizer is 100, the flow rate the reaction mixture to be fed to the vaporizer is about 90 to 110 (for example, about - 93 to 107), preferably about 95 to 105 (for example, about 97 to 103) and, more preferably, from about 98 to 102 (e.g., from about 98.5 to 101.5) throughout the entire process.
The separation (instant distillation) of the metal catalyst component can be conducted by a conventional separation method, or a conventional separation apparatus, and can generally be carried out using an instant distillation column. In addition, the metal catalyst component can be separated by means of instant distillation in combination with a mist collection method or a solids collection method, which is widely used in industrial applications.
In the rapid evaporation phase, the reaction mixture can be separated into the vapor component (or vaporized stream) and the liquid component (or liquid stream), with or without heating. For example, in adiabatic 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 water component. heated liquid (and reduced pressure). The reaction mixture can be separated into the vapor component and the liquid component, combining these vaporization conditions. These instant distillation steps can be carried out, for example, at a temperature of about 80 to 200 ° C under a pressure (absolute pressure) of about 50 to 1000 kPa (for example, from about 100 to 1000 kPa), preferably, from about 100 to 500 kPa and, more preferably, from about 100 to 300 kPa.
The step of separating the liquid catalyst mixture can be made up of a single step, or it can be made up 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, part of the volatile component (2A) can be recycled to the reactor or reaction system, as described above. The volatile component (2A) to be recycled can have its heat removed and condensed in a suitable method, to be recycled to the reactor. The proportion of the volatile component (2A) to be recycled, for example, can be from about 1 to 50% by volume (for example, from about 5 to 45% by volume), preferably from about 10 to 40% by volume, more preferably, from about 10 to 30% by volume. The separate volatile component (2A) contains the product acetic acid, and in addition, hydrogen iodide, a co-catalyst (such as methyl iodide), methyl acetate, water, by-product (s) (for example, an aldehyde , such as acetaldehyde, and propionic acid) and others, and is fed to a distillation column to collect acetic acid. The proportion of the volatile component (2A) to be fed to the acetic acid collection step in the entire reaction mixture can be, for example, from about 5 to 50% by weight, preferably from about 8 to 40% by weight and, more preferably, from about 10 to 35% by weight (for example, from about 12 to 30% by weight). (Acetic acid collection step)
In the acetic acid collection step, the volatile component (2A) is fed to the distillation column (dividing column) and separated into a supernatant (3A) containing 5 methyl iodide, acetic acid, methyl acetate, acetaldehyde by-product, and iodide of hydrogen and a stream (3B) containing acetic acid to collect acetic acid. Specifically, in the distillation column, the supernatant (3A) containing methyl iodide, 10 methyl acetate, acetic acid, acetaldehyde, hydrogen iodide, water, and others, is separated in the form of vapor from the volatile component (2A) (current acetic acid), powered by the vaporizer; and the liquid stream (3B) (side cut stream, side stream) containing acetic acid is extracted. The liquid stream (3B) containing acetic acid can be extracted by lateral cutting, or extracted from the bottom of the distillation column. In this context, in the distillation column, a component with a higher boiling point (3C) containing water, propionic acid, a component of entrained metal catalyst, ionic iodide, and others, can be separated. The component with the highest boiling point (3C) can be removed (discharged) from the bottom of the distillation column. Since the highest boiling point component (3C) contains a useful component, such as the remaining metal catalyst or acetic acid component, without being evaporated, and the component (3C) can be recycled to the reactor (or step reaction stage), the rapid evaporation step (or column distillation), or others, as the embodiment of the figure. In fact, before recycling, propionic acid, which deteriorates the quality of acetic acid as a final product, can be removed. The acetic acid stream (crude acetic acid solution) is generally dehydrated in the next distillation column and then introduced into an acetic acid purification column, in order to separate components of higher and lower boiling points by means of distillation to obtain the acetic acid product.
In addition, as described later, the component with the highest boiling point (3C), to be recycled, can be recycled to the reaction system, or others, through a storage vessel having a buffering function.
As described above, the amount of the lowest boiling point component (2A) to be fed to the distillation column is also affected by the variation in the amount fed from the reactor, and varies in many cases. With respect to the degree of variation, for example, assuming that the average flow rate of the volatile component (2A) to be fed to the distillation column 100, the flow rate of the volatile component (2A) to be fed to the distillation column (2A ) is about 90 to 110 (for example, about 93 to 107), preferably, about 95 to 105 (for example, about 97 to 103) and, more preferably, about 98 to 102 (for example, from about 98.5 to 101.5) throughout the process.
In the distillation column (dividing column), the position of a feed opening to feed the component with the lowest boiling point (2A) is not particularly limited to a specific point. For example, the position of the feed opening may be in an upper part, in a middle part, or in a lower part of the distillation column. In addition, in the distillation column, the component with the lowest boiling point (2A) can be fed in a higher position or in a lower position in relation to a side chain opening, for lateral cutting of the acetic acid chain. In addition, the position of the side chain opening for lateral cutting of the acetic acid stream can be in an upper part, in a middle part, or in a lower part of the distillation column and, normally, the position of the side chain opening is, preferably, in a part of the medium or a bottom part of the distillation column.
For the distillation column, a conventional distillation column can be used, for example, a plate column, a fill column, and an instant distillation column. A distillation column, such as a plate column, or a fill column, can generally be employed. In fact, the material of (or to form the) distillation column is not limited to a specific type, and glass, metal, ceramics, or others, can be used. Typically, a distillation column made of metal is used in practice.
The temperature and pressure in the distillation column can be appropriately selected, depending on the condition, such as the species of the distillation column, oü of the main object (target) for extraction selected from the component with the lowest boiling point and the component with the highest point boiling. For example, in the distillation column, the internal temperature of the column (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.
In addition, for the plate column, the theoretical number of plates is not particularly limited to a specific value and, depending on the species of the component to be separated, it is about 5 to 50, preferably about 7 to 3 5 and, more preferably, from about 8 to 30. In addition, in order to separate highly acetaldehyde (or with a high precision) in the distillation column, the theoretical number of plates can be about 10 to 80, preferably , from about 12 to 60 and, more preferably, from about 15 to 40. In addition, in the 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 can be reduced by increasing the theoretical number of plates.
The separated supernatant (3A) practically contains methyl iodide, acetaldehyde, hydrogen iodide and, in addition, acetic acid, methyl acetate, water, and others. The proportion of the supernatant (3A) to be fed to the condensation phase (or decanter), or to the acetaldehyde extraction step (or acetaldehyde extraction column), can be, for example, from about 5 to 70% in preferably from about 10 to 65% by volume and more preferably from about 12 to 60% by volume (e.g., from about 15 to 50% by volume) in the entire volatile component (2A ). (Condensation and discharge stage)
According to the process of the present invention, the supernatant (3A) can be fed directly to the acetaldehyde separation step (4) (or acetaldehyde distillation column). The supernatant (3A) can generally be condensed and then fed to the acetaldehyde separation step. Typically, the process of the present invention may further comprise a condensation and discharge step to temporarily retain the supernatant (3A) in a decanter (or storage tank) and discharge the supernatant (3A) from the decanter (the step can simply be referred to as a condensation step, or the like).
In the condensation step, the separate lowest boiling point component (3A) is kept (or stored) temporarily in the decanter (or storage tank) during condensation and then discharged, to be subjected to at least the acetaldehyde separation. In particular, according to the present invention, the amount of the supernatant (3A) to be retained (or the amount of the supernatant (3A) to be discharged) in the condensation and discharge step can be regulated (or controlled) throughout the process, based on the variation of the flow rate of the supernatant (3A) to be fed to the decanter.
That is, as described above, the amount of the supernatant (3A) to be fed to the decanter often varies widely, through a series of steps. To alleviate the flow variation, the amount of the supernatant (3A) to be retained in the decanter can be adjusted.
Concrete examples of the method, to adapt (or control) the amount of the supernatant (3A) to be retained, may include (1) a method, in which the supernatant (3A) is discharged, so that the variation of the amount or level of supernatant liquid (3A) to be retained in the decanter can be reduced (for example, a method shown in Fig. 1), and (2) a method, in which a decanter decants to alleviate the variation in the quantity; feeding the supernatant (3A) into the decanter (for example, a method shown in Fig. 2). These methods can be combined.
The supernatant (3A) discharged from the decanter is fed to the acetaldehyde separation step (or acetaldehyde distillation column). When the supernatant (3A) is fed directly without adjusting the flow, the separation of stabilized acetaldehyde is sometimes inhibited under the influence of the variation in the amount of the supernatant (3A) to be fed to the decanter. Thus, according to the present invention, the amount of the supernatant (3A) to be fed to the acetaldehyde separation step (the total amount of the supernatant (3A) and the methanol source) can be adjusted. As described later, when the supernatant (3A) and the methanol source are mixed and then fed to the acetaldehyde separation step, strictly speaking, the total amount of the supernatant (3A) and the methanol source is, sometimes adjusted. However, since the amount of feed from the methanol source is easily corrected (or kept constant), the controlled variation in the amount of the supernatant (3A) leads to a controlled change in the amount of the liquid object to be fed to the distillation column. acetaldehyde. Therefore, also in this way, it is sufficient that the amount of the supernatant (3A) be adjusted. Thus, even if the total amount of the supernatant (3A) and the methanol source is adjusted, the total of the supernatant (3A) and the methanol source is sometimes referred to as the supernatant (3A).
The method for adjusting or controlling the amount of supernatant (3A) to be fed to the acetaldehyde separation step may include, for example, (a) a method for circulating part of the supernatant (3A) (or the total amount of the supernatant (3A ) and the methanol source) discharged from the decanter to a step other than the acetaldehyde separation step (in particular, at least the reactor or reaction step) (for example, the embodiment shown in Fig. 1), ( b) a method of feeding the acetaldehyde separation step with the supernatant (3A) (or the total amount of the supernatant (3A) and the source; methanol) discharged from the decanter through a storage vessel with a buffering function ( for example, the embodiment shown in Fig. 1), and (c) a method for adjusting the amount of the supernatant (3A) to be discharged from the decanter (or the total amount of the supernatant (3A) and the methanol source) , to remain constant (or almost constant) (eg example, the embodiment shown in Fig. 2). These methods can be combined. (Liquid object to be treated (or liquid object) to be subjected to the acetaldehyde separation step)
As described later, in the acetaldehyde separation step (or acetaldehyde distillation column), the liquid object to be treated (or liquid object) containing the supernatant (3A) is subjected to distillation. In the present invention, the liquid object to be subjected to distillation contains a predetermined concentration of the methanol source.
The distillation of the liquid object under the condition allows the increase in the concentration of hydrogen iodide (and acetic acid) in the acetaldehyde distillation column to be efficiently inhibited.
In effect, it is sufficient that the liquid object contains at least the supernatant (3A) (as described above, part of the supernatant (3A), when the supernatant (3A) is circulated). As described later, the methanol source can be added to the supernatant (3A). The liquid target may contain a liquid component circulated or recycled after the acetaldehyde separation step (for example, a lower boiling point component (4A), a lower boiling point component (4A) after acetaldehyde extraction, and a highest boiling point component (4B), and others.
Typically, the liquid object essentially comprises the supernatant (3A) and contains a variety of components, such as methyl iodide and methyl acetate, in addition to acetic acid and acetaldehyde.
The concentration of methyl iodide in the liquid object can be, for example, from about 1 to 98% by weight (for example, from about 1 to 95% by weight), preferably from about 1.5 to 95 % by weight (for example, from about 10 to 90% by weight) and, more preferably, from about 20 to 80% by weight (for example, from about 30 to 70% by weight). In addition, the concentration of methyl iodide can be, for example, not less than about 60% by weight (for example, from about 70 to 98% by weight), preferably not less than 70% by weight ( for example, from about 80 to 97% by weight) and, more preferably, not less than 85% by weight (for example, from about 87 to 95% by weight). When the lower layer portion of the supernatant (3A) is used essentially as the liquid object, the methyl iodide concentration is generally within such a range.
In addition, the methyl iodide concentration can be, for example, not more than 20% by weight (for example, from about 0.1 to 15% by weight), preferably not more than 15% by weight ( for example, from about 0.5 to 10% by weight) and, more preferably, not more than 10% by weight (for example, from about 1 to 6% by weight). When the upper layer part of the supernatant (3A) is used essentially as the liquid object, the concentration of methyl iodide is generally within such a range.
In addition, in terms of corrosion inhibition, it is preferable that the concentration of the component (eg, methyl iodide) producing hydrogen iodide in an equilibrium reaction in the acetaldehyde distillation column, is low.
The concentration of methyl acetate in the liquid object can be selected from the range of 0.5 to 50% by weight, and can be, for example, from about 0.5 to 30% by weight (for example, from about 1 to 25% by weight), preferably from about 2 to 25% by weight (for example; from about 3 to 20% by weight) and, more preferably, from about 3 to 15% by weight (for example example, from about 4 to 10% by weight). In addition, the concentration of methyl acetate can be, for example, not more than 30% by weight (for example, from about 0.1 to 25% by weight), preferably not more than 20% by weight ( for example, from about 0.5 to 18% by weight) and, more preferably, not more than 15% by weight (for example, from about 3 to 13% by weight). When the bottom layer portion of the supernatant (3A) is used essentially as the liquid object, the methyl acetate concentration is generally within such a range.
In addition, the concentration of methyl acetate can be, for example, not more than 20% by weight (for example, from about 0.1 to 15% by weight), preferably not more than 15% by weight ( for example, from about 0.5 to 10% by weight) and, more preferably, not more than 10% by weight (for example, from about 1 to 8% by weight). When that of the upper layer of the supernatant (3A) is used essentially as a liquid object, the concentration of methyl acetate is generally within such a range.
The concentration of acetic acid in the liquid object can be selected from the range of 0.1 to 50% by weight (for example, from 0.2 to 50% by weight and preferably from 0.3 to 50% by weight ), and can be, for example, from about 0.2 to 40% by weight, preferably from about 0.5 to 30% by weight (for example, from about 0.8 to 25% by weight) and, more preferably, from about 1 to 20% by weight (for example, from about 3 to 15% by weight). In addition, the concentration of acetic acid can be, for example, not more than 20% by weight (for example, from about 0.1 to 15% by weight), preferably not more than 10% by weight (for example, for example, from about 0.3 to 8% by weight) and, more preferably, not more than 8% by weight (for example, from about 0.5 to 5% by weight). When the bottom layer portion of the supernatant (3A) is used essentially as a liquid object, the concentration of acetic acid is generally within such a range.
In addition, the concentration of acetic acid can be, for example, not more than 50% by weight (for example, from about 1 to 45% by weight), preferably not more than 40% by weight (for example, from about 5 to 35% by weight) and, more preferably, not more than 30% by weight (for example, from about 8 to 25% by weight). When the part of the upper layer of the supernatant (3A) is used essentially as a liquid object, the concentration of acetic acid is generally within such a range.
The water concentration in the liquid object can be selected from the range of 0.05 to 95% by weight, and can be, for example, from about 0.1 to 90% by weight (for example, from about 0 , 2 to 80% by weight), preferably from about 0.5 to 80% by weight (e.g., from about 0.8 to 75% by weight), and more preferably, from about 1 to 75 % by weight (for example, from about 1.5 to 70% by weight). In addition, the water concentration can be, for example, not more than 5% by weight (for example, from about 0.01 to 3% by weight), preferably not more than 3% by weight (for example , from about 0.05 to 2% by weight) and, more preferably, not more than 2% by weight (for example, from about 0.1 to 1% by weight). When the portion of the bottom layer of the supernatant (3A) is used essentially as the liquid object, the water concentration is generally within such a range.
In addition, the water concentration can be, for example, not less than 40% by weight (for example, from about 45 to 95% by weight), preferably not less than 50% by weight (for example, from about 55 to 90% by weight) and, more preferably, not less than 60% by weight (for example, from about 65 to 80% by weight). When the part of the upper layer 25 of the supernatant (3A) is used essentially as the liquid object, the water concentration is generally within such a range.
The concentration of hydrogen iodide in the liquid object can be selected from the range of 1 to 2000 ppm (for example, from 1 to 1000 ppm and, preferably, from 5 to 1000 ppm), based on weight, and can be, for example, example, from about 3 to 1500 ppm, preferably from about 4 to 1000 ppm and, more preferably, from about 5 to 800 ppm (for example, from about 7 to 600 ppm) and can generally be from about 1 to 500 ppm [for example, from about 1 to 3 00 10 ppm, preferably from about 5 to 200 ppm (for example, from about 5 to 150 ppm), more preferably, from about 10 to 120 ppm and, in particular, from about 15 to 100 ppm]. In this context, the concentration of hydrogen iodide in the liquid object can be, for example,; from about 3 to 100 ppm and preferably from about 5 to 80 ppm (for example, from about 5 to 50 ppm), based on weight. When the bottom layer portion of the condensed supernatant (3A) is essentially subjected to the acetaldehyde separation step, the hydrogen iodide concentration is generally within such a range. In addition, the concentration of hydrogen iodide in the liquid object can be, for example, from about 30 to 150 ppm and, preferably, from about 50 to 100 ppm based on weight. When the top layer portion of the condensed supernatant 25 (3A) is essentially subjected to the acetaldehyde separation step, the hydrogen iodide concentration is generally within such a range.
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 [for example, an iodide derived from the co-catalyst, such as Lil, and a metal iodide (for example, 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 iodide ion concentration (! ') To determine (or calculate) the hydrogen iodide concentration.
The concentration of acetaldehyde in the liquid object can be, for example, from about 0.001 to 5% by weight, preferably from about 0.005 to 3% by weight and, more preferably, from about 0.01 to 1% by weight. weight, and can generally be from about 0.02 to 0.7% by weight (for example, from about 0.03 to 0.6% by weight). In this context, the concentration of acetaldehyde in the liquid object can be, for example, from 200 to 6000 ppm and, preferably, from about 400 to 4000 ppm, based on weight. When the bottom layer portion of the condensed supernatant (3A) is subjected, essentially to the acetaldehyde separation step, the acetaldehyde concentration is generally within such a range. In addition, the concentration of acetaldehyde in the liquid object can be, for example, from about 500 to 20000 ppm and, preferably, from about 1000 to 16000 ppm based on weight. When the portion of the top layer of the condensed supernatant (3A) is essentially subjected to the acetaldehyde separation step, the acetaldehyde concentration is generally within such a range.
The liquid object contains at least one source of methanol selected from the group consisting of methanol and dimethyl ether. The source of methanol can be methanol alone, dimethyl ether alone, or a combination of methanol and dimethyl ether. In this context, the methanol source also includes methanol obtained by hydrolysis of methyl acetate. For the combination of methanol and dimethyl ether, the ratio (weight ratio) of methanol to dimethyl ether [first / last] can be about 99.9 / 0.1 to 0.1 / 99.9 ( for example, from about 99/1 to 1/99), preferably from about 95/5 to 5/95 and, more preferably, from about 90/10 to 10/90 (for example, about 85/15 to 15/85). In this context, when the methanol source contains a component (methanol or dimethyl ether) in a relatively large amount, the ratio (weight ratio) of one component to the other component [the first / last] can be about 99 , 9 / 0.1 to 30/70 (for example, about 99.5 /, 5 to 40/60), preferably, about 99/1 to 45/55 (for example, about 98 , 5 / 1.5 to 50/50), more preferably, from about 98/2 to 55/45 (e.g., from about 97/3 to 60/40) and, in particular, from about 96 / 4 to 65/35 (for example, from about 95/5 to 70/30).
The concentration of the methanol source in the liquid object can be selected from the range of 0.1 to 5 50% by weight (for example, from 0.2 to 50% by weight), and can be, for example, from about 0 , 1 to 40% by weight (for example, from about 0.2 to 30% by weight), preferably from about 0.2 to 25% by weight, more preferably, from about 0.2 to 20% by weight (for example, from about 0.5 to 18% by weight) and, especially about 0.7 to 17% by weight (for example, from about 1 to 15% by weight, and preferably , from about 2 to 15% by weight), and can generally be from about 1 to 30% by weight (for example, from about 2 to 25% by weight).
In addition, the concentration of the methanol source in the liquid object can be from about 0.1 to 35% by weight (for example, from about 0.1 to 28% by weight), preferably from about 0.15 to 21% by weight, more preferably, from about 0.2 to 17% by weight (for example, from about 0.5 to 13% by weight) and, especially, from about 0.6 to 12% by weight weight (for example, from about 0.7 to 10% by weight). This concentration is preferable, in particular, when the methanol source contains dimethyl ether in large quantities, or in other cases.
Furthermore, the concentration of the methanol source in the liquid object can be, for example, from about 0.1 to 20% by weight and, preferably, from about 0.2 to 15% by weight (for example, from about 0.5 to 13% by weight). When the bottom layer portion of the condensed supernatant (3A) is essentially subjected to the acetaldehyde separation step, the concentration of the methanol source is generally within such a range. In addition, the concentration of the methanol source in the liquid object can be, for example, from about 0.3 to 50% by weight (for example, from about 0.5 to 40% by weight), and preferably , from about 1 to 30% by weight. When the part of the upper layer •; of the condensed supernatant (3A) is essentially subjected to the acetaldehyde separation step, the concentration of the methanol source is generally within such a range.
In addition, in the liquid object, the ratio of the methanol source (in terms of methanol) to 1 mol of the total amount of acetic acid and hydrogen iodide in the liquid object (or the supernatant (3A)) can be selected within the range of about 0.1 to 40 mol, and can be, for example, about 0.1 to 20 mol (for example, about 0.3 to 15 mol), preferably, about 0.4 to 10 mol (for example, about 0.5 to 10 mol), more preferably, about 0.7 to 7 mol (for example, about 1 to 5 mol) and, particularly, about from 1.1 and 4 mol (for example, from about 1.2 to 3 mol) and can generally be from about 1 to 20 mol (for example, from about 1.5 to 5 mol). In this context, the proportion mentioned above is expressed in terms of methanol. That is, for the use of dimethyl ether as the source of methanol, since 2 mol of methanol are produced by hydrolysis of 1 mol of dimethyl ether, the ratio is calculated as 2 mol of methanol per mol of dimethyl ether.
In addition, in the liquid object, the ratio of the methanol source (in terms of methanol) to 1 mol of hydrogen iodide in the liquid object can be at least not less than 70 mol [for example, not less than 80 mol (for example, from about 100 to 300000 mol)],) preferably not less than 200 mol (for example, from about 300 to 200000 mol), more preferably, not less than 50 0 mol (for example , from about 700 to 100000 mol), in particular not less than 1000 mol (for example, from about 1500 to 80000 mol) and, generally, from about 3 00 to 100000 mol (for example, from about 500 to 70000 mol and preferably about 1000 and 50000 mol).
In addition, in the liquid object, the ratio of the methanol source (in terms of methanol) to 1 mol of acetic acid in the liquid object can be selected from the range of about 0.1 to 40 mol, and can be , for example, from about 0.1 to 20 mol (for example, from about 0.3 to 15 mol), preferably from about 0.4 to 10 mol (for example, from about 0, 5 to 10 mol), more preferably, from about 0.7 to 7 mol (for example from about 1 to 5 mol) and, in particular, from about 1.1 to 4 mol (for example, from about 1 , 2 to 3 mol), and can generally be about 1 to 20 mol (e.g., about 1.5 to 5 mol).
In addition, the relationship between the methanol source (in terms of methanol) in relation to 1 mol of acetic acid; in the liquid object can be from about 0.1 to 40 mol (for example, from about 0.3 to 35 mol), preferably from about 0.4 to 30 mol (for example, from about 0.5 to 25 mol), more preferably, from about 0.7 to 20 mol (for example, from about 1 to 15 mol) and, in particular, from about 1.1 to 10 mol (for example, about 1.2 to 7 mol). When the bottom layer portion of the condensed supernatant (3A) is essentially subjected to the acetaldehyde separation step, the concentration of the methanol source is generally within such a range. In addition, the ratio of the methanol source (in terms of methanol) to 1 mol of acetic acid in the liquid object can be from about 0.05 to 20 mol (for example, from about 0.1 to 15 mol), preferably from about 0.2 to 10 mol (for example, from about 0.3 to 8 mol), more preferably, from about 0.5 to 6 mol (for example, from about 1 to 5 mol) and, in particular, from about 1.1 to 4 mol (for example, from about 1.2 to 3 mol). When the portion of the top layer of the condensed supernatant (3A) is essentially subjected to the acetaldehyde separation step, the concentration of the methanol source is generally within such a range.
The concentration of the methanol source in the liquid object can be adjusted with the reaction, or the amount of feed. The concentration of the methanol source can be generally adjusted by adding or mixing the methanol and / or methyl acetate source to the supernatant (3A) inside or outside the acetaldehyde distillation column. Typically, the process of the present invention may comprise a step (sometimes referred to as an addition step or a mixing step), for adding or mixing the source of methanol (methanol and / or dimethyl ether) and / or methyl acetate to the supernatant (3A) to be fed to the acetaldehyde distillation column. As described above, since methanol can be produced from methyl acetate, methyl acetate can also be added or mixed with the supernatant (3A), (insofar as the concentration of the methanol source in the distillation column of acetaldehyde can be adjusted, in particular at least the methanol source can be added to the supernatant (3A).
The methanol source can be mixed with the supernatant (3A), at any stage of the reaction system, as the methanol source can be distilled through the acetaldehyde distillation column, 25 together with the supernatant (3A) separated in acetic acid collection step. The methanol source can be mixed with the supernatant (3A) in the acetaldehyde distillation column. In particular, from the point of view that the increase in hydrogen iodide concentration (and acetic acid concentration) in the acetaldehyde distillation column is effectively inhibited, the source of methanol and / or methyl acetate can be added or mixed in the mode (A) and / or mode (B) as follows: (A) the methanol source is added or mixed with the supernatant (3A), before the supernatant (3A) is fed to the acetaldehyde distillation column (for example, the embodiment of Fig. 1), (B) in the acetaldehyde distillation column, the source of methanol and / or methyl acetate is added or mixed with the supernatant (3A), at the same level of height or position [by example, on the same plate (or location)] as a level of height or position, at which the supernatant (3A) is fed, or at a level or height [for example, a plate (or location)] higher than the level in height, at which the supernatant (3A) is fed (for example, the form; embodiment of Fig. 1, and the embodiment d Fig. 2).
In mode (A), the mixing position of the methanol source to the supernatant (3A) is not particularly limited to a specific location, as the methanol source is mixed with the supernatant (3A), before the supernatant (3A ) be fed to the acetaldehyde distillation column. For example, the methanol source can be mixed with the supernatant (3A), before feeding to the decanter, after discharging the decanter, or after discharging from the buffer tank (for example, embodiments of FIGs. Fig. 1 and 2). The source of methanol and / or methyl acetate can be mixed in a plurality of positions. Representatively, the source of methanol and / or methyl acetate is usually added after the decanter is discharged (when part of the supernatant (3A) is distributed after circulation). In particular, it is preferable that the source of methanol and / or methyl acetate is mixed with the supernatant (3A), in a discharge line from the decanter to feed the acetaldehyde distillation column [a decanter line (if necessary , by means of a storage vessel with a buffering function) to the acetaldehyde elimination column)].
The time, from when the supernatant (3A) and the source of methanol and / or methyl acetate are mixed until when the mixture is fed to the acetaldehyde distillation column (the retention time of the source of methanol and / or 20 methyl acetate), can be selected from the interval of not less than 1 second (for example, from 3 seconds to 40 minutes) and can be, for example, not less than 5 seconds (for example, from about 7 seconds to 35 minutes), preferably not less than 10 seconds (for example, from about 10 seconds to 30 minutes) and, more preferably, from about 15 seconds to 20 minutes (for example, from about 20 seconds to 10 minutes), and can generally be about 10 seconds to 5 minutes [for example, about 10 seconds to 3 minutes (for example, about 10 seconds to 1 minute)]. The increase in the concentration of hydrogen iodide or acetic acid in the acetaldehyde distillation column is more easily inhibited by regulating the retention time in such a range (in particular, in combination with the liquid temperature mentioned below).
In addition, in mode (B), the source of methanol and / or methyl acetate can be mixed in the same position as a plate, into which the supernatant (3A) is fed, or: a plate higher than that plate, and is generally mixed in a lower position than the top of the column (in a position other than the top of the column).
For the combination of mode (A) with mode (B), it is sufficient that the total amount of the source of methanol and / or methyl acetate to be mixed is adjusted in each mixing position, so that the total amount can be in the aforementioned interval, in the acetaldehyde distillation column.
The temperature (liquid temperature) of the supernatant (3A) to be fed to the acetaldehyde distillation column (the mixture of the supernatant (3A) and the methanol source, when the methanol and / or methyl acetate source is added to the supernatant (3A)), it can be, for example, from about 10 to 100 ° C, preferably from about 15 to 95 ° C (for example, from about 20 to 90 ° C) and, more preferably, from about 25 to 85 ° C (for example, about 30 to 80 ° C), and can generally be about 20 to 100 ° C (for example, about 30 to 85 ° C).
In particular, since such a range of liquid temperature (i.e., the liquid temperature of the mixture of the supernatant (3A) and the methanol source) in combination with mode (A), probably allows the reaction of the source of methanol with hydrogen iodide or acetic acid occurs, to some extent, before feeding the supernatant (3A) to the acetaldehyde distillation column, or probably promotes this reaction in the acetaldehyde distillation column, the increase in the hydrogen iodide concentration or acetic acid in the acetaldehyde distillation column can be more effectively inhibited. (Acetaldehyde separation step)
In the acetaldehyde separation step, the liquid object containing the supernatant (3A) fed to the acetaldehyde distillation column (extraction column or separation column) is separated into a lower boiling point component (4A) containing acetaldehyde and a component of highest boiling point (4B), by distillation. As described above, the liquid object is subjected to distillation as a liquid object to be treated containing a predetermined concentration of the methanol source. That is, in the stage: of acetaldehyde separation, the liquid object is distilled and separated into the component with the lowest boiling point (4A) and the component with the highest boiling point (4B). Before the separation of acetaldehyde, a component of the flue gas 5 can be removed, in advance, from the supernatant (3A) by means of a condenser, a refrigerator, or others.
For the acetaldehyde distillation column, a conventional distillation column, for example, a plate column, a fill column, and an instant distillation column, can be used. A distillation column, such as a plate column or a fill column, can generally be employed. The material of (or to form the) acetaldehyde distillation column is not particularly limited to a specific type, 15 and can be a metal, a ceramic, and the like. In particular, according to the present invention, since the increase in the concentration of hydrogen iodide (and acetic acid) within the distillation column is significantly inhibited, the corrosion of the distillation column can also be inhibited at a high level . Thus, for the acetaldehyde distillation column, in the present invention, not only a distillation column made of an expensive material having a high corrosion resistance (such as zirconium), but also a distillation column made of A 25 relatively inexpensive material, for example, an alloy [for example, a transition metal-based alloy, such as an iron-based alloy (or an iron-containing alloy as a major component, for example, stainless steel (including steel stainless steel containing chromium, nickel, molybdenum and others)), a biphasic iron-based alloy 5 (for example, a biphasic (or duplex) stainless steel), a nickel-based alloy (or a nickel-containing alloy as the main component , for example, HASTELLOY (trade name) and INCONEL (trade name)), or a cobalt-based alloy (or an alloy containing cobalt as a major component)].
The temperature (the temperature at the top of the column) and the pressure (pressure at the top of the column)) in the acetaldehyde distillation column can be selected, depending on the type of the distillation column and others, and are not particularly limited to one specific value, insofar as the component with the lowest boiling point (4A) containing at least acetaldehyde and the component with the highest boiling point (4B) are separable from the supernatant (3A), or from the liquid object (or solution of process), 20 by using the difference between acetaldehyde and other components (essentially methyl iodide) at the boiling point.
For example, the pressure at the top of the column is about 10 to 1000 kPa, preferably about 10 to 700 kPa and, more preferably, about 100 to 500 kPa, in terms of absolute pressure.
The temperature inside the column can be, for example, from about 10 to 150 ° C, preferably from about 30 to 140 ° C and, more preferably, from about 40 to 130 ° C, and can be generally from about 30 to 100 ° C (for example, from about 50 to 90 ° C). In addition, the temperature at the top of the column can be, for example, from about 10 to 100 ° C, preferably from about 30 to 120 ° C and, more preferably, from about 40 to 100 ° C. In addition, the temperature at the bottom of the column can be, for example, from about 30 to 150 ° C, preferably from about 50 to 130 ° C and, more preferably, from about 60 to 120 ° C. The number (theoretical number) of distillation column plates can be, for example, from about 5 to 150, preferably from about 10 to 120 and, more preferably, from about 20 to 10 0, and can generally be from about 30 to 120 (for example, from about 40 to 100).
In the acetaldehyde distillation column, the reflux ratio can be selected from about 1 to 1000, preferably from about 10 to 800, more preferably, from about 50 to 600 (for example, from about 100 to 500) and, in particular, from about 150 to 400 (e.g., from about 200 to 350), depending on the theoretical number of plates mentioned above.
In this way, the increase in the concentration of hydrogen iodide or acetic acid in the acetaldehyde distillation column can be inhibited by distillation in the presence of the methanol source. For example, in the continuous reaction, the concentration of hydrogen iodide in the acetaldehyde distillation column (top of the column and / or: at the bottom of the column) is not more than 100 ppm (for example, about 0 or limit detection rate at 70 ppm), preferably not more than 50 ppm (for example, from about 0 or detection limit to 30 ppm), more preferably, no more than 10 ppm (for example, from about 0 or limit of detection at 5 ppm) and, in particular, not exceeding 3 ppm (for example, from about 0 or detection limit at 1 ppm).
In addition, in the continuous reaction, the concentration of acetic acid in the acetaldehyde distillation column (upper column and / or lower column) can be, for example, not more than 50% by weight (for example, 0 ( or not above the detection limit, the same applies to others) at 30% by weight), preferably from about 0 to 10% by weight (for example, from about 0.001 to 5% by weight), more preferably, from about 0 to 3% by weight (for example, from about 0.01 to 2% by weight) and, especially, from about 0.005 to 1% by weight.
In addition, the concentration of acetic acid in the acetaldehyde distillation column (upper part of the column and / or lower part of the column) may not exceed 10% by weight (for example, from about 0 to 7% by weight), preferably not more than 7% by weight (for example, from about 0 to 6% by weight) and, more preferably, not more than 5% by weight (for example, from about 0 to 4% by weight) . When the portion of the bottom layer of the condensed supernatant (3A) is essentially subjected to the acetaldehyde separation step, the concentration of acetic acid is generally within such a range. In addition, the concentration of acetic acid in the acetaldehyde distillation column (top of the column and / or bottom of the column) can be no more than 30% by weight (for example, from about 0 to 25% by weight ), preferably not more than 15% by weight (for example, from about 0 to 10% by weight) and, more preferably, not more than 8% by weight (for example, from about 0 to 5% by weight) Weight) . When the part of the top layer of the condensed supernatant (3A) is essentially subjected to the acetic acid separation step, the concentration of acetaldehyde is generally within such a range.
The highest boiling point component (4B) is separated as a separate solution (bottom fraction, or column bottom fraction) containing a useful methyl iodide component from the acetaldehyde distillation column. (Recycling step)
The component with the highest boiling point (4B) practically contains a useful component, such as methyl iodide. After separation, the component with the highest boiling point (4B) can be recovered, that is, recycled to a step, from the reaction system for the separation of acetaldehyde. That is, the process of the present invention may further comprise a recycling step, to recycle the component with the highest boiling point (4B), as a separate solution, for one step, from the acetaldehyde separation reaction system.
In the recycling phase, the component with the highest boiling point (4B), as a separate solution, is recycled. The recycling of the separated solution (or component with the highest boiling point (4B)) is not particularly limited to a specific type, as the recycling step is applied from the acetaldehyde separation reaction system. The step can be any one of the reaction step (or reactor), the instant distillation step (or instant distillation column), and the acetic acid collection step (or distillation column). As the embodiment of the figure, the component with the highest boiling point (4B) can be recycled to the acetaldehyde distillation column, or it can be recycled to a combination of these steps. The separated solution (or component with the highest boiling point (4B)), after the separation of acetaldehyde, is generally recycled, at least, to the reactor.
The separate solution (or component with the highest boiling point (4B)) can be recycled directly, or recycled via a storage vessel having a buffering function (for example, a buffer tank). The use of the storage vessel with a buffer function relieves the flow variation in the storage vessel, and allows easy recycling of the separated solution at a constant or almost constant flow, even if the flow of the separated solution varies. Thus, the storage vessel can reduce the influence of the flow variation in the recycling step.
The storage vessel with a buffering function can be selected based on the degree of flow variation, in the same way as in the condensation step, and can be selected based on the desired retention time of the separate solution. In the storage vessel, the retention time of the separated solution f is not particularly limited to a specific value, and can be, for example, not less than 3 minutes (for example, from about 4 minutes to 3 hours), preferably not less than 6 minutes (e.g., about 8 to 60 minutes) and, more preferably, not less than 12 minutes (for example, about 15 to 40 minutes).
When the separated solution is recycled through the storage vessel with a buffering function, the flow variation of the separated solution (component with the highest boiling point (4B)) can be reduced.
The separate lowest boiling point component (4A) containing acetaldehyde can be discharged in its original state. Since the lowest boiling point component (4A) sometimes contains a useful component, such as methyl iodide, methyl iodide (or a component containing methyl iodide, for example, a component containing methyl iodide, methyl acetate, and others) it can be collected from the lowest boiling component (4A) and recycled.
The method for separating each of acetaldehyde and methyl iodide (or a component containing methyl iodide) from the lowest boiling point component (4A) is not particularly limited to a specific type, and may include a conventional method ( for example, extraction, distillation). Representative examples of the method may include (i) a method for separating each of methyl iodide and acetaldehyde by distilling the lowest boiling component (4A), (ii) a method for separating each of methyl iodide and acetaldehyde by water extraction, which takes advantage of the miscibility of acetaldehyde with water and the immiscibility of methyl iodide with water. From the point of view of inhibiting the production of metaldehyde or others, water extraction (ii) is preferred. According to the method, since the increase in the concentration of protons in the distillation solution, due to the degradation of the ester or others, inhibits the production of paraldehyde and metaldehyde, acetaldehyde can be efficiently condensed to a high level and removed.
The extraction temperature and extraction time are not particularly limited to specific values. For example, extraction can be carried out at a temperature of 0 ° C to 100 ° C for about 1 second to 1 hour. The extraction pressure is not particularly limited to a specific value, and an advantageous condition can be selected, because of costs and more. For the extractor, for example, a combination of a mixer with a decanter, a combination of a static mixer with a decanter, a RDC (column of rotating discs), a column Karr, a column of spray, a column of filling, a column of perforated plates, a partitioned column, a pulse column, and others.
The recycling of methyl iodide (or a component containing methyl iodide) is not particularly limited to a specific type, as the recycling step is applied from the acetaldehyde separation reaction system. Methyl iodide can be recycled to any of the reaction step (or reactor), the instant distillation step (or instant distillation column), and the collection and acetic acid step (or distillation column). As the embodiment of the figure, methyl iodide can be recycled (recycled as the highest boiling component (4B)) to the acetaldehyde separation column, or it can be recycled for a combination of these steps. EXAMPLES
The following examples are intended to describe the present invention in greater detail, and should in no way be interpreted as defining the scope of the invention. (Comparative Examples 1 to 4 and Examples 1 to 6)
When the acetic acid production process described in FIG. 1 was applied, the change of state: corrosion in the presence of methanol was observed. Specifically, methyl iodide, water, methyl acetate, acetic acid, lithium iodide, rhodium were fed to reactor 1, and methanol was allowed to react with carbon monoxide. The reaction solution was extracted from reactor 1 and fed to a vaporizer. In vaporizer 2, the volatile component (2A) was fed to the dividing column 3, and the low volatility component (2B) was directly recycled to reactor 1. In the dividing column 3, the volatile component (2A) was distilled off in the supernatant (3A), the current containing acetic acid, and the current with the highest boiling point (3C). The current containing acetic acid (3B) was extracted by side cutting, and the current with the highest boiling point (3C) was directly recycled to reactor 1. The supernatant (3A) was fed to decanter 4 and separated into an upper layer and a bottom layer, in decanter 4. In decanter 4, the liquid level of decanter 4 was kept constant by adjusting the amount of current for lines 17 and 18 and the retention time. Then, as a solution discharged from the decanter 4 and to be fed to the acetaldehyde extraction column 6, a liquid object to be treated having a composition shown in Table 1, was obtained. In Comparative Examples 1 and 3 and Examples 1, 3 and 5, a lower layer portion of the supernatant (3A) was used in the decanter 4; In Comparative Examples 2 and 4 and Examples 2, 4 and 6, a portion of the top layer of the supernatant (3A) was used in the decanter 4. In Examples 1 and 2, the concentration of methanol in the liquid object was adjusted by methanol feeding by middle of line 51.
The liquid object shown in Table 1 and specimens of different materials (each with size: 36 mm x 25 mm x 2.5 mm) were placed in a 500 ml autoclave [made of HASTELLOYB2 (HB2) manufactured by Oda Koki Co , Ltd.], and the autoclave was closed. The internal pressure of the autoclave was increased to 0.05 MPa, with N2 at room temperature, and then the internal temperature of the autoclave was raised to 85 ° C. Under this circumstance, the internal pressure of the autoclave was increased to 0.14 MPa. By keeping the autoclave for 100 hours in this state, the acetaldehyde separation step (the state in the acetaldehyde extraction column 6) in the continuous acetic acid production process was artificially reproduced. After that, the corrosion of each specimen was observed. The corrosion test was evaluated based on the following criteria, in Comparative Examples 1 to 2 and Examples 1 to 2, and evaluated about the amount of corrosion observed in Comparative Examples 3 to 4 and Examples 3 to 6. "A": body of proof not corroded at all. "B": specimen highly corroded. "C": specimen little corroded. "D": specimen significantly corroded.
The composition (formulation) of each liquid object is shown in Table 1, and the results are shown in Table 2. The composition (formulation) of each liquid object, after being maintained for 100 hours (after cooling), that is, treated liquid object is also shown in Table 2. In this context, when methanol was added, the liquid object sometimes contained a lower boiling component, such as dimethyl ether, or a hydrocarbon component (therefore, sum of the components described in the Tables was not 100% by weight). The concentration of dimethyl ether in the treated liquid object was about 0.5 to 2% by weight greater than that of the liquid object. In Tables 1 and 2, "ppm" represents a concentration based on weight, "% by weight" means% by weight, "t" represents less than 0.1% by weight, "ND" means not detectable (detection limit ); "Ac" stands for acetic acid, "MA" stands for methyl acetate, "MeOH" stands for methanol, "Honey" stands for methyl iodide, "AD" stands for acetaldehyde, "HC" stands for a nickel-based alloy (HASTELLOY C manufactured by Oda Koki Co., Ltd.), "SUS" represents stainless steel (SUS316 manufactured by Umetoku Inc.), "NAS64" represents two-phase stainless steel (NAS64 manufactured by Umetoku Inc.), and "NAS354N" represents stainless steel (NAS354N manufactured by Umetoku Inc.), and "mm / Y" means the corrosion rate of the specimen per year (the decreased thickness (mm) of the specimen per year). The iodide ion concentration derived from the iodide salt was subtracted from the total iodide ion concentration (I ') to calculate the hydrogen iodide concentration.


As evidenced by the tables, the production or high concentration of hydrogen iodide (HI) and the corrosion of the specimen were inhibited, adjusting the composition of the liquid in the acetaldehyde elimination column to specific components and specific proportions. Industrial Applicability
The production process of the present invention is extremely useful as a process for producing acetic acid, while efficiently inhibiting the increase in the concentration of hydrogen iodide (in particular, hydrogen iodide and acetic acid) in the acetaldehyde distillation column . Description of Reference Numbers 1 Reactor 2 Vaporizer (evaporator) 3 Divider column 4 Decanter 4A Decanter with buffering function 5, 7 Buffer tank 6 Acetaldehyde extraction column 8 Extraction apparatus 9 Containment tank 51, 52 Line to feed the methanol source (methanol and / or dimethyl ether)

权利要求:
Claims (11)
[0001]
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 evaporation step for continuous supply of a vaporizer with a reaction mixture from the reactor, to separate a volatile component (2A) containing the product acetic acid, methyl acetate, methyl iodide and water, and a low component volatility (2B) containing the metal catalyst and ionic iodide, step of collecting acetic acid to feed a distillation column with the volatile component (2A), and separate a supernatant (3A) containing methyl iodide, acetic acid, acetate of methyl, water, the by-product acetaldehyde and hydrogen iodide, and a stream (3B) containing acetic acid to collect acetic acid, and acetaldehyde separation step there add an acetaldehyde distillation column with at least part of the supernatant (3A), and distill a liquid object to be treated containing the supernatant (3A), to separate a lower boiling point component (4A) containing acetaldehyde and a component of highest boiling point (4B), in which, in the acetaldehyde separation step, the liquid object contains at least one source of methanol selected from the group consisting of methanol and dimethyl ether, in a concentration of 2 to 25% in weight.
[0002]
2. PROCESS, according to claim 1, characterized by the fact that, in the liquid object, the proportion of methyl iodide is from 1 to 98% by weight, the proportion of methyl acetate is from 0.5 to 50% in weight, the proportion of acetic acid is from 0.2 to 50% by weight, the proportion of water is from 0.05 to 95% by weight, and the proportion of hydrogen iodide is from 1 to 1000 ppm, based on weight .
[0003]
3. PROCESS, according to claim 1 or 2, characterized by the fact that the concentration of the methanol source in the liquid object is 2 to 20% by weight.
[0004]
4. PROCESS, according to any one of claims 1 to 3, characterized by the fact that, in the liquid object, the concentration of acetic acid is 0.3 to 50% by weight, the proportion of the methanol source (in terms of methanol) be 0.1 to 40 moles with respect to 1 mole of a total amount of acetic acid and hydrogen iodide.
[0005]
5. PROCESS, according to any one of claims 1 to 4, characterized by the fact that the ratio of the methanol source (in terms of methanol) in the liquid object is not less than 80 moles in relation to 1 mole of hydrogen iodide.
[0006]
6. PROCESS, according to any one of claims 1 to 5, characterized by the fact that, in the liquid object, the concentration of acetic acid is from 0.5 to 50% by weight, the concentration of hydrogen iodide is from 5 to 1000 ppm, and the proportion of the methanol source (in terms of methanol) is 1 to 20 moles to 1 mole of a total amount of acetic acid and hydrogen iodide.
[0007]
7. PROCESS, according to any one of claims 1 to 6, characterized by the fact that the concentration of the methanol source in the liquid object is adjusted, by adding or mixing the source of methanol and / or methyl acetate, in the manner (A ) and / or method (B) below: (A) the source of methanol and / or methyl acetate is added or mixed with the supernatant (3A), before the supernatant (3A) is fed to the acetaldehyde distillation column, (B) in the acetaldehyde distillation column, the source of methanol and / or methyl acetate is added or mixed with the supernatant (3A), at the same height level as a height level, at which the supernatant (3A) is fed, or at a height level higher than the height level, at which the supernatant (3A) is fed.
[0008]
8. PROCESS, according to claim 7, characterized by the fact that, in mode (A), a temperature of a mixture containing the supernatant (3A) and the source of methanol and / or methyl acetate is regulated from 20 to 100 ° C, and a time, from when the supernatant (3A) and the source of methanol and / or methyl acetate are mixed until when the mixture is fed to the acetaldehyde distillation column, be set to no less than 5 seconds; and that the concentration of the methanol source is adjusted at least in method (A).
[0009]
9. PROCESS, according to claim 7, characterized by the fact that, in mode (A), a temperature of a mixture containing the supernatant (3A) and the source of methanol and / or methyl acetate is regulated from 30 to 85 ° C, and a time, from when the supernatant (3A) and the source of methanol and / or methyl acetate are mixed until the mixture is fed to the acetaldehyde distillation column, to be set to no less than 10 seconds; and that the concentration of the methanol source is adjusted at least in method (A).
[0010]
10. PROCESS according to any one of claims 1 to 9, characterized in that the material of the acetaldehyde distillation column comprises an iron-based alloy.
[0011]
11. PROCESS according to any one of claims 1 to 10, characterized in that the material of the acetaldehyde distillation column comprises a stainless steel or a two-phase stainless steel.

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法律状态:
2020-08-25| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-09-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-01-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-02| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 01/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2010-279799|2010-12-15|

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JP2010279799|2010-12-15|

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PCT/JP2011/077846|WO2012081418A1|2010-12-15|2011-12-01|Process for producing acetic acid|

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