SA517381989B1 - Processes for producing acetic acid - Google Patents

Abstract

The disclosure is directed to a carbonylation process for producing acetic acid which includes separating a vapor product stream from a carbonylation reactor to produce a crude acid product comprising acetic acid comprising lithium cations and contacting the crude acetic acid product with a cationic exchanger in the acid form within a first treatment device to produce an intermediate acid product; and contacting the intermediate acetic acid product with a metal-exchanged ion exchange resin having acid cation exchange sites within a second treatment device to produce a purified acetic acid. Embodiments directed to operation of a treatment device comprising a plurality of sampling ports are also disclosed. Fig. 1.

Description

PROCESSES FOR PRODUCING ACETIC ACID FULL DESCRIPTION BACKGROUND The production of acetic acid by krylation involves the reaction of methanol and carbon monoxide continuously in the presence of a catalyst in a reactor. The Jeli mixture in the reactor includes a transition metal; which may be a group 9 metal which may be iridium and/or rhodium and may additionally include one or more solvents; cole various stabilizers; covalent catalysts; enhancers; etc. Reaction mixtures known in the art may include acetic acid; methyl acetate except 016; methyl iodide 06 hydrogen iodide chydrogen iodide booster hydrogen iodide etc. There is a complex network of interdependent equilibria comprising the components of the 0 liquid acetic acid reaction in the reactor; Which includes those related to the formation of acetic acid as well as those related to the formation of various impurities also produced in the reactor. Impurities present in acetic acid include permanganate reducing compounds (PRCs) compounds such as acetaldehyde accordingly; The acetic acid processes declared in Art. may additionally include various purification processes and control programs whereby the formation of impurities is reduced and/or impurities resulting from the process are removed or converted into an acetic acid product. It is difficult to remove the various impurities present in an acetic acid product. Control and control of purification systems is needed in various aspects of the acetic acid production process. Considerable documents important for understanding and evaluating the present disclosure include US Patent No. 6 US Patent No. 5,801,279; US Patent Application No. 0 067714/2012; and International Patent Application No. 02062740.

Acetic acid processes suitable for the purposes described herein to produce steam from the krill reactor which is subsequently distilled in a light terminals column to produce an acetic acid product as a bypass may vary in systems and processes; Le in that purification streams; recirculating streams; the type and number of distillation columns used; the various purification processes used; etc. Examples of suitable processes include those described in US Patent No.: 3,769,329; US Patent No.: 3,772,156; US Patent No.: 4,039,395; US Patent No.: 4,255,591; US Patent No.: 4,615,806; US Patent No.: 5001259; US Patent (ad) 8+ US Patent No.: 5144068; US Patent No.: 5,237,097; US Patent No.: 5,334,755; US Patent No.: 5,653,853; Patent 0 US: 5,683,492; US Patent No.: 5,831,120; US Patent No.: 0 US Patent No.: 5,416,237( US Patent No.: 5,731,252; US Patent No.: 5,916,422; US Patent No.: 6,143,930; US Patent No.: 6,225,498; US Patent No.: $6,255,527 US Patent ad) 1 US Patent No.: 6,657,078; US Patent No.: 7,208,624; 5 US Patent No.: 7,223,883; US Patent No.: 72023886; US Patent No.: 7,271,293 US Patent No.: 7,476,761 US Patent No.: 1 US Patent No.: 7,855,306; US Patent No.: 8076507) USPt Application No.: 20060247466; US Patent Application tay 2; USPt Application No.: 20110288333; USPt 0 Application No.: 20120090981; USPt Application No.: 20130078012; Application US Patent No.: 2012081418; US Patent Application No.: 4; US Patent Application No.: 2013281735; European Patent No.: 0161874; IL No: 9822420; IL No: 0216297; IL No: 2012137236; etc.; merge For reference, the entire contents and their detection are shown schematically in 5. Figure 1 shows a process for the production of acetic acid according to the detected embodiments (ls) generally indicated on

It's Operation 100.

General description of the invention in embodiments; The creel process includes at least one member selected from the group consisting of methanol, dimethyl ether, and methyl acetate in the presence of 0.1 to less than 14 cela/A) catalysts of rhodium methyl iodide and lithium dithium iodide to form an intermediate. Reaction (104) including acetic acid in a reactor; separation of reaction medium (104) into a liquid recycle stream (0 1 0) and a vapor product stream (1 22); separation of the vapor product stream (22 1) into distillation columns (124) and 130 ) in a prepurification series to produce a crude acid product (128) comprising an acetic acid comprising lithium cations; contact of the crude acetic acid product with a first purification resin (214) comprising a cation exchanger in the acid form within a pretreatment device (206) to produce an acid product 0 intermediate; contact of the acetic acid intermediate product with a second purification resin (216) comprising a metal exchange ion exchange resin having acid cation exchange sites within a second treatment tool (210) to produce a purified acetic acid stream (222) first treatment tool; second treatment tool; or Both of them separately include at least one sampling port (416; see Fig. 3) inserted through the (404) side of the processing tool (206) or (210); cobblestone l on a sample of the first purification resin (214)); purification resin 5 nd (216); a liquid sample of the acetic acid stream contained in the curing tool; or union thereof through the corresponding sampling port (416); Determination of impurity concentration in at least one due. This summary is provided to introduce a set of concepts described (Lilia) below in the detailed description. This summary does not mean to set out the essential or major features of the given topic; It is not meant to be used as an adjunct to limiting the scope of the given topic. 0 Brief Explanation of Drawings Figure 1: is a schematic diagram of a process for the production of acetic acid according to an embodiment; Figure 2: is a schematic diagram of a processing toolchain according to an embodiment; Figure 3 is a cross-sectional view of a processing tool according to an embodiment; And

Fig. 4 Cross-sectional view of the sampler according to an embodiment; And

Fig. 5 is an integrated schematic showing the step for charging a resin curing tool column according to embodiments. Detailed description:

In Dad) it should be noted that in the development of any incarnation of ad MATH must make several decisions

Pertains to implementation to achieve the specific objectives of the developer; For example, compliance with system-related restrictions

with the ¢ action that differs from the implementation of AY . Moreover it will be appreciated that the development effort is complex and time consuming but is nonetheless a routine project for those skilled in the art and has the benefit of this disclosure. Addendum (SIN) The processes detected herein may also include components other than those specifically mentioned or referred to; as is obvious to one with the slightest skill in the art.

In the summary and this detailed description; Each numeric value must be read once as modified by the term “about (also not already clearly modified)” and then read again as unmodified unless otherwise specified in the context. Also in the summary and this detailed description; It should be understood that the focus range listed or described as useful; Appropriate; etc; means taking into account any and all concentrations within the range; containing final points; As mentioned. on

5 way JE BURY from 1 to 10" is read as referring to any and every possible number along the string between about 1 and about 10. Therefore" even if particular data points are within range; or even data points that are not range; clearly defined or referring only to a few particular data points; it is understood that the inventors value sagas that any and all data points within the range are considered defined; and that the inventors have knowledge of the overall range and all points within the range.

by full description; Lo includes protection elements; The following terms shall have the meanings referred to unless otherwise specified.

As specified in the specification and claims; pall from near inclusive 'at the term Jat and/or 800/03 denotes the inclusive case 'and and the exclusive case 'or 'OF' and is used

Here for brevity. For example; A mixture containing acetic acid and/or methyl acetate may include acetic acid methyl acetate only or both acetic acid and methyl acetate. Chemical and Engineering News, 63(5), 27 (1985). 5 All molecular weights are weight averages unless otherwise noted. All percentages are shown as percentage by weight (wt7); based on the total weight of the selected fixture or existing current; Unless otherwise noted. The room temperature is 259°C and the Soll pressure is 25 1.3 0 1 kPa unless Lad otherwise.

For the purposes stated herein the percentage of exchangeable active sites for the resin is based on the total exchange capacity in milliequivalents per gram (mequivalents/g). For example; A cation exchange resin has a cation exchange capacity of 2 mEq/g; Substitution of 2 mEq/g with silver ion constitutes 7100 active sites to be substituted with silver; Substitution of 1 mEq/g constitutes 750 active sites to be replaced.

For the purposes mentioned here:

Acetic acid is abbreviated as “ACOH”; methyl acetate is abbreviated as ¢ “MeAc”; Jie iodide is abbreviated as “116/a”; sulfur monoxide is abbreviated as “SCO”

Permanganate Reducing Compounds (PRC) refer to oxidizable compounds that cause a failed determination of the permanganate test as readily understood by one skilled in the art; compare:

“A New System For Automatic Measurement of Permanganate Time,” Laboratory Automation and Information Management, 34, 1999, 57-67. Examples of PRCS include acetaldehyde; acetone methyl Ji) ketone cmethyl ethyl ketone cbutyraldehyde crotonald head 206a©0201008; 2- Jin) crotonaldehyde except2-61; 2- ethyl butyraldehyde except1©-2; etc; and aldol condensation products from that. For the purposes stated cla “overhead lef” denotes the lower boiling condensable fraction that exits at or near the top of the distillation column. Similarly, “overhead lef” denotes the higher boiling fraction that exits at or near the bottom of the distillation column 0 is understood to be retard only taken from the top of the very bottom outlet of a distillation column for example, where the very bottom of the column is an unusable tar; a solid waste product; or a trickle stream as is readily understood by one with the slightest skill in the art. Likewise, the upper stream may be taken only below the uppermost upper outlet of a distillation column, for example, where the lowest boiling fraction is a non-condensable stream or represents a trace stream, as is readily understood by one having the lowest 5 skill in the art. USED HERE The average retention time of a column feed stream within a column refers to the total flow rate available in a column divided by the total unoccupied volume contained in the column, unless otherwise specified. input 0 and output column input; denoted by Yeh here as an inner chamber; Suitable for filling with purifying resin. The terms tool and shaft processing are used interchangeably unless otherwise specified. For the purposes stated herein a tool and a processing column are used interchangeably other than a distillation column. As used herein, mass flow rate is indicated in kg/hr unless otherwise specified; It may be determined directly or calculated from volumetric measurements. When allocating the total mass flow rate or

Concentration of a component as present “if present” Cif ANY understands that the component may or may not be present in the stream above the detection limit of an appropriate analytical method as readily understood by one having minimal skill in the art. In" the flow rate ASH of a stream whether at the rate of

own flow or at a rate proportional to the mass flow rate of the stream “AT” it is understood that such control includes the directly specified process flow stream variation; or control the mass flow of a given stream by means of a variety of currents that directly affect the mass flow rate of the target stream; It is also easily understood by one who has skill in the art. All such ratios are expressed as mass-to-weight percentages by mass unless otherwise specified.

As used herein, a acrylate reactant is any substance that reacts with carbon monoxide under reaction conditions to produce [clin]acid or the product in question. The carbonizable reactants include methanol; methyl acetate; dimethyl ether; methyl formate etc.

According to f to use Hana a low water krill process shall have a limited concentration of water in 5 krill reactor less than or equal to about 14 wt 7. According to use Hana when at least part of the stream is recycled or reversed to another section of the process; It is understood that aud 001100" refers to a section of the total mass flow of the stream. The stream may be combined with other streams (ie, indirectly recycled); also all components originally present in the stream exist after Slay

For comparison; A stream 'derived from another stream' may include the total stream or may include less than all of the individual components initially present in the stream. Thus a 'derived' stream from a specific stream may include a stream subjected to further treatment or purification prior to deposition. For example; A stream that is distilled before being recycled is derived from the original stream.

according to usage here unless otherwise specified; Determinations based on a comparison of an effect observed in the presence of an ingredient relative to an effect observed in the absence of the same component refer to comparisons made under essentially identical conditions except for the presence or absence of the specified component (lie) in essentially the same combination”; essentially the same temperature; ceil and other conditions).

Impurities in acetic acid include several species containing iodine 06. Examples include alkyl iodides having from 1 to about 20 carbon atoms. Alkyl iodides having a higher molecular weight greater than sa 6 Cr atoms at parts per billion levels may be present in the final product. These impurities pose a problem for many end uses of acetic acid and require their removal according to various purity standards. Other impurities include many aldehydes

aldehydes 0 and corrosion metals. These contaminants may be removed by contact of acetic acid with a suitable purification resin at temperatures greater than about 0 °C (compare US Patent No. 8). The use of such purification resins, however, requires monitoring of both the final product and the resin itself to prevent impurities from building up. “breaking through” the purification resin layer during production. While samples of the final product are easily obtained, it is nearly impossible5 to obtain purification resin samples to be used in those purifications while the DAL system is in operation. However, closing these purification systems to obtain resin samples is uneconomical and often questionable.However, a sampler according to one or more embodiments of the present disclosure allows both a liquid sample and a solid purification resin sample to be obtained and analyzed at various points along resin layer The ability to obtain these samples 0 allows for improved monitoring and control of the process These sample ports further allow prediction of when the resin will become depleted before excessive amounts of impurities are introduced into the final product Embodiments of the method include the provision of a mesh column Has an inner chamber containing active purification resin located between column inlet and outlet cages Column additionally includes one or more sample ports arranged between column inlet and column outlet; dedi At least one sample port is a liquid sample port; solid sample port; or both; An acetic acid stream has an initial concentration of impurity from

through the column at a temperature and flow rate sufficient to produce a stream of pure acetic acid at the outlet of the column having a second concentration of impurities; If found; which is lower than the first concentration. accordingly; Acetic acid contacts with purification resin inside the column to remove impurities and purify acetic acid. in embodiments; The method additionally includes the opening of at least one sample port edd or simultaneous current flow of acetic acid through the column. in embodiments; The impurity includes iodine; Chromium, nickel, iron, cron, or a combination thereof. in embodiments; The iodide may be an alkyl iodide. in embodiments; The purification resin comprises a “strong latin acid” ion exchange resin having at least about 1 active sites in the form of silver or mercury” and/or a temperature of at least about 509°C. in embodiments; Opening of at least one sample port may include obtaining a sample of the 0 purification resin through at least one solid sample port; a liquid sample of the acetic acid stream contained in the column through at least one liquid die port; or union thereof; The method additionally involves determining the concentration of impurities in at least one sample. in embodiments; The concentration of one or more impurities is determined using a high-performance liquid chromatography gas chromatography; atomic absorption inductively coupled plasma spectrometer 5 mass spectrometer; a fluorescence spectrometer for; or a union thereof. in embodiments; The impurity concentration of one or more samples is compared with a predetermined impurity concentration value and it is determined whether or not the impurity concentration indicates depletion of the refining resin at a point in the column corresponding to the location of the sample port from which the sample is obtained. in embodiments; The method additionally involves stopping the flow of acetic acid through the column. in embodiments; 0 The acetic acid flow shall be stopped before substantially all of the active refining resin in the column has been depleted such that the concentration of impurities in the acetic acid product does not render the acetic acid unsuitable for a particular end use. in embodiments; A second column may be provided identical to the first and acetic acid flows through and subsequently into the second column while the flow through the first column is halted.

in embodiments; While the flow stops on the column at least a portion of the spent resin is regenerated before completing the acetic acid stream flow through the column to produce purified acetic acid HU. In Embodiments » Regeneration of the spent resin involves removing at least a portion of the spent resin from the column and refilling at least a portion of the column with the active refining resin. in embodiments; Section includes

At least of the active resin used to refill the column on previously spent resin regenerated to

Active purification resin. in embodiments»; and at least regenerates from the spent resin to the active purification resin within the column.

in embodiments»; The method includes the steps: (a) Provide a column comprising an inner chamber enclosed by many sides arranged radially around a central axis and having an entry end in a fluid connection

0 with; and longitudinally separated (oe) exit end through the inner chamber; (b) direct an amount of refining resin into the inner chamber sufficient to fill a section of the inner chamber; (c) flow of an aqueous wash fluid from the exit end through the inner chamber to the inlet end at a rate of a flow and for a period of time sufficient to wash and/or remove particulate matter from the refining resin; and (d) an acetic acid stream having an initial concentration of impurities flows through the column at a temperature and flow rate sufficient to produce a purified acetic acid stream at the outlet

5 the column having a second concentration of impurities; If found; which is lower than the first concentration.

in embodiments; The column includes one or more sample ports arranged between the column inlet and column outlet; The die port includes at least one liquid sample port; solid sample port; or both. The method involves additionally opening at least one sample port. in embodiments; Water washer fluid flows for at least 60 minutes.

in embodiments; After step (c) of the Sle scrubber flowing through the column an amount of inert gas is directed to the column inlet to remove a portion of the scrubber. in embodiments; The reverse thrust flow of acetic acid (outlet to inlet) is then flowed through the column at a flow rate and for a period of time sufficient to remove essentially all vapor from the inner chamber. in embodiments; Removing the vapor may involve opening one or more Ble samples. in embodiments; The reverse thrust flow rate is acid

clasts less than or equal to about 0.05 layer sizes per minute; The time period is less than or equal to about 30 minutes.

in embodiments; The purification resin is pneumatically directed to the inner chamber of the column by providing a fluid contact between the inner chamber and a bottom outlet from a containing slurry container

on purification resin; Followed by applying pressure to the upper space of the container in an amount sufficient to transfer the section over

Less slurry is pneumatically transferred from the container to the inner chamber.

in embodiments; The inner chamber of the column and/or the upper space of the container shall be purged with inert gas; For example, nitrogen” to remove oxygen from the space (Cl) so that the space includes less than 1 weight of 7 oxygen) before charging the column with purification resin.

in embodiments»; The creel process includes at least one selected member of the group formed by methanol » dimethyl ether; methyl acetate in the presence of 0.1 to less than 14 wt 7 water; rhodium catalysts; methyl iodide and lithium iodide; to form a reaction medium comprising acetic acid in a reactor; separation of the reaction medium into a liquid recycle stream and a vapor product stream; Separation of the vapor product stream in up to two distillation columns in a primary purification series to produce a crude acid product comprising acetic acid

5 includes lithium cations; contact of a crude acetic acid product with a first purification resin comprising a cation exchanger in the acid form within a pretreatment to produce an intermediate acid product; contact of the acetic acid intermediate product with a second purification resin comprising an exchange metal ion exchange resin having acid cation exchange sites within a second treatment tool to produce a purified acetic acid stream of the first treatment tool; second processing tool; or both individually include Mie sampling of at least one subject

0 .by the handler side; Obtain a sample of the first purification resin; second purification resin; liquid sample lad acetic acid contained in the curing tool; or union thereof through the corresponding sample port; Determine the impurity concentration in at least one sample.

in embodiments; The Lilia process involves comparing the impurity concentration of at least one sample with a specified cline impurity concentration value and determining if the impurity concentration from the sample indicates a resin depletion.

dul at a point in the process tool corresponding to the location of the dial port at which the die is sampled. in embodiments; The process additionally includes stopping the flow of acetic acid through the curing tool before essentially all of the active refining resin in the curing tool is used up; Regeneration of at least a section of the spent resin and completion of the acetic acid stream flow through the curing tool to produce purified acetic acid stream. in embodiments; This metal-exchange ion exchange resin includes at least 71 strong acid exchange sites occupied by silver. in embodiments; The raw acid product includes up to 10 ppm Lithium. in embodiments; Separation of the vapor product stream includes: distillation of the vapor product stream in column 0 first and bypass drawing to produce a distilled acetic acid product; and distillation of the distilled acetic acid product in a second distillation column to produce a crude acid product comprising acetic acid and lithium cations. in embodiments; The process additionally includes the step of adding potassium salt selected from the group consisting of potassium acetate, potassium carbonate and potassium hydroxide to the distilled acetic acid product before distillation 5 of the distilled acetic acid product in a second distillation column; At least part of the potassium is removed by the cation exchanger in the acid form. in embodiments; The crude acetic acid product contacts the cation exchanger at a temperature of 509°C to 120°C. in embodiments; The acetic acid intermediate product contacts the metal exchange ion exchange resin at a temperature of 09 °C to *85 °C; or a union thereof. in 0 embodiments; The acetic acid intermediate product has a lithium ion concentration of less than 50 parts per billion. in embodiments; The acid-form cation exchanger includes a large lattice resin to exchange a strong acid cation in the acid form; Large or medium pores. in embodiments; The process (Lilia) includes treatment of the purified acetic acid product with a cation exchange resin

to retrieve any silver; cg) palladium or rhodium. in embodiments; The concentration of water in the reaction medium is controlled from 0.1 to 5 wt7; Based on the total amount of reaction medium present. in embodiments; The process additionally includes introducing a lithium compound selected from the group consisting of dithium acetate, lithium carboxylates, lithium carbonates, lithium hydroxide, and mixtures thereof into the reactor to maintain the lithium acetate concentration. from 0.3 to 0.7 wt7 in the reaction medium.In embodiments; the process additionally includes maintaining a concentration of hydrogen iodide from 0.1 to 1.3 7055 in the reaction medium; maintaining a concentration of catalyst rhodium of 300 and 3000 w/ea per million in the reaction medium; maintaining a concentration of Water from 0.1 to 4.1 wt7# in the 0 reaction medium Maintaining a concentration of methyl acetate from 0.6 to 4.1 wt7 of the reaction medium, or a combination thereof In embodiments, the process additionally includes controlling the concentration of butyl acetate in the acetic acid product at 10 wppm or less without removing the butyl acetate directly from the acetic acid product In embodiments the concentration of the butyl acetate is controlled by maintaining the acetaldehyde concentration at 1500 ein per million or less in the reaction medium Temperature control in m active from 150 to 250 “Celsius; control the pressure of all hydrogen in the reactor from 3 to 2 atm; Controlling the concentration of rhodium catalyst from 100 to 3000 w/gpm in the reaction medium; or a union thereof. in embodiments; The process additionally includes controlling the concentration of ethyl iodide in the reaction medium at 0 less than or equal to 750 wpm sis. in embodiments; The concentration of propionic acid in the acetic acid product is less than 250 w/ppm; without directly removing the propionic acid from the acetic acid product; Wherein ethyl iodide is present in the reaction medium and propionic acid in the acetic acid product in a weight ratio of 1:3 to 2:1; where acetaldehyde and ethyl iodide are present in the reaction medium in a weight ratio of 1:2 to 1:20; where the concentration of ethanol 5 in the methanol feed in the reactor is less than 150 w/ppm; or a union thereof.

in embodiments; The concentration of ethyl iodide in the reaction medium is controlled by at least one setting of the partial pressure of hydrogen in the krill reactor; The concentration of methyl acetate in the cell medium and the concentration of methyl iodide in the reaction medium. Acetic acid production system The processes for the production of acetic acid through acetic acid can appropriately be divided into three basic areas: Reaction Systems and Processes » Light End Recovery Systems and Processes / Separation of Acetic Acid Product; Acetic acid product purification systems and processes. Low-water, low-energy processes for the production of acetic acid by means of acetic acid have been developed comprising a catalyst system with rhodium operating at less than 14 w/7 water and using up to 0 two distillation columns in the primary purification series. The primary purification series is directed towards the removal of loose components; for example, water; cine iodide methyl acetate; hydrogen iodide; of the steam product stream from the reactor/ abel to obtain acetic acid. This first purification series receives most of the steam flow from the reactor and obtains acetic acid as the final product. For example; The columns of the primary purification series include the light ends column and the drying column. The primary purification series may exclude columns 5 whose primary function is to remove secondary components such as acetaldehyde; Alkanes and propionic acid. The process to produce acetic acid may generate a cation that collects in the crude acid product. These residual cations are difficult to remove and in the final metal exchange protection layer may be reversibly substituted by iodides. Subsequently; The end product may have unacceptable levels of iodides despite the use of Layer 0 metal exchange protection. The present invention provides a process for removing cations. The cation source may result from many enhancers; co-catalysts; addition materials; on-site interactions; etc; For example low water and low energy processes involving the use of a promoter eg lithium iodide may be formed in situ followed by the addition of lithium acetate or other suitable lithium salts to the reaction mixture. Subsequently; Process streams may contain some quantity

lithium ions. additionally; Since the process uses a maximum of two distillation columns in the precleaning series and preferably the precleaning does not include a column to remove heavy end materials; The crude acid product may contain larger alkyl iodide components; Sie C10-4 alkyl iodides additionally to cations; For example, lithium. sometimes more than 710 iodides present; or even greater than 250; It has an organic chain length greater than 10 carbon atoms. Subsequently; may be greater than 10 ppb; lis is greater than 20 ppb; greater than 50 ppb; LS of 100 ppb; or greater than 1 ppm alkyl iodides 614©-010. These higher alkyl iodides as well as the usually shorter long-chain iodide impurities may be present in the crude acid product from the ALS process enhanced with iodide; including methyl iodide; HI and 0-hexyl iodide Typical iodide impurities may be removed from the crude acid product using a strong acid Ol exchange resin exchanged with a metal where the metal is silver or mercury; For example. However, it has been found that the silver and/or mercury in a strong acid ion exchange resin exchanged with a metal may be displaced by the residual lithium; This results in lower resin potency and capacity and the potential for silver or mercury contamination of the product. The cation in the crude acid product may result from the use of ligands of an organic alkali salt, eg ligands of an organic lithium salt; For example that described in Canadian Patent No. 1 and Canadian Patent No. 1,349,855 therefore the entire disclosure and contents are incorporated by reference. Canadian Patent No. 101053841 Describes a Bonded Compound Comprising Lithium Acetate or Lithium Oxalate Canadian Patent No. 1349855 describes a bimetallic 0 catalyst having a lithium-metal organometallic ligand with a cis-dicarbonylrhodium 0 structure only 055-01681000. The organic bonding compound lithium metal may be a pyridine derivative, for example lithium pyridine-2-formate dithium pyridine—2-formate lithium pyridine -3-formate clithium pyridine-3-formate lithium pyridine-4-formate lithium (pyridine-4-formate lithium pyridine-3-acetate clithium pyridine-3-acetate lithium 5-pyridine-4-acetate or lithium pyridine-3-propionate

‎lithium pyridine—3-propionate in fact; The lithium salt component of all these ligands is believed to generate lithium iodide in situ within the reaction medium after exposure to methyl iodide at a reaction temperature pressure in the krill reactor. At least some of a small section of the lithium component that goes into the purification system. Subsequently; Purification systems according to the present disclosure may remove lithium formed in situ using these types of organic bonding compounds. Cations may also be present as a result of the use of non-lithium salts; For example, through the use of bimetallic Rh chelate catalysts having a camine function, eg those described in Canadian Patent No. 1,640,543.” Thus the entire disclosure and contents are incorporated for reference. According to Canadian Patent No. 16040543, cation species contain donor atoms NO and © and form 0 aminobenzoic acid. The amine may convert to the tetrameric form with methyl iodide in situ within the reaction medium at reaction pressure and temperature to form a tetranitrogen cation . The aerosol nitrogen cation may conduct; similar with lithium cation; During the crude acid product it may be removed using the present invention prior to the metal exchange protection layers. Embodiments include less water and lower energy processes for the production of acetic acid by means of 5 acetic acid; dimethyl ether and/or methyl acetate in the presence of 0.1 to less than 14 wt 7 cele metal catalyst; Methyl iodide and lithium iodide. In embodiments » low-energy processes using up to two distillation columns in the primary purification series (eg light-ends column and dewatering or dewatering column without the use of a third “ALE”-ends column) and the resulting acidic acid product is purified with a cation exchanger in the acid form AY Lithium ions left over and then treated with a 0 ion exchange resin with a metal having acid cation exchange sites comprising at least one metal selected from the group consisting of silver, mercury, palladium and rhodium A metal ion exchange resin may have at least 71 exchange sites worked strong acid “daily mercury” palladium and/or rhodium; ie at least 71 of silver mercury; palladium and/or rhodium” at least 75 of dad) mercury; palladium and/or rhodium”; at least 710 of silver; (ail) palladium and/or 5 rhodium; or at least 720 silver (Ga) palladium and/or rhodium. using a cation exchanger

To remove lithium prior to using a resin having strong acid cation sites exchanged with a metal the mercury and/or rhodium from the metal exchange sites is reduced or displaced by a lithium process that uses up to two distillation columns in the primary purification series. in embodiments; Other purification systems in addition to the primary purification series may use distillation columns to remove impurities from the reactor components; Examples of the ally system are aldehydes where the acetaldehyde of the other PRCs is removed from the methyl iodide phase before the methyl iodide is returned to the reaction medium. Particularly preferred processes are those that use a cation exchanger to remove the lithium followed by an exchanged cation substrate with silver to remove the iodides. The crude acid product in many cases includes organic iodides with C10 or more aliphatic chain length being at dala 0 for removal. sometimes more than 710 iodides present; such as more than 730 or even more than 250; which has an SST organic chain length of 10 carbon atoms. The decyl iodides and dodecyl iodides are particularly prevalent in the absence of heavy ends and other polishing devices (the lill) of the product. The silver cationic substrates of the present invention are typically removed through 790 of 5 iodides; The crude acid product often has from 10 to 1,000 ppb of total iodide prior to processing that makes the product unusable for iodide-sensitive applications. An iodide level of 20 eda ppb to 1.5 gga ppb in the crude acid product prior to iodide treatment is typical; While the iodide removal treatment should preferably be run 0 to remove at least about 795% of the total iodide present. In a typical embodiment; The lithium/iodide removal treatment includes contacting the acid crude product with a cation exchanger to remove 795 or more lithium ions and then contacting the crude acid product with a large lattice ion exchange resin functionalized as a sulfonic acid exchanged with silver; Where the product has an organic iodide content greater than 100 ppb before curing and an organic iodide content less than 10 ppb after contact with the resin.

It was found that lithium enters into the crude acid product in the presence of heavy ends and other polishing device. Even very small amounts of 10 ppb of lithium in the crude acid mite may cause a problem for iodide removal. There should be up to 10 ppm lithium by weight of the crude acid product; Die up to 5 ppm Old) up to 1 ppm; up to 5 ppb; up to 300 ppb; or even 100 parts per billion; In the acid-containing crude acid product coming out of the drying column of the acetic acid process; Such as the last column in the primary purification series. For domains; may be from 0.01 ppm to 10 a per million lithium in the crude acid product; For example, from 0.05 ppm to 5 ppm or from 0.05 ppm to 1 ppm. using a cation exchanger in the form of 0 acid prior to introducing the crude acid product into an exchanged resin with a metal; Sufficient amounts of lithium can be removed. For example more than 90 wt 7 of lithium can be removed in the stream by means of the cation exchanger; For example, 95 wt7 or 99 wt. Subsequently; The stream from an acid-forming cation exchanger may contain less than 50 ppb lithium; For example, less than 10 ein per billion; or less than 5 ppb. This removal of lithium can significantly extend the life of the catalyst 5 reciprocal resin. Reaction processes and systems as shown in Figure 1; The process for producing mes-stick 100 includes a reaction system which includes a cryel carbonylation reactor 104 of which the reaction medium is continuously removed through line 113 and subjected to low pressure flash or distillation in system 0 separation lie flasher 112; used to separate acetic acid and other volatile components from the reaction medium and recycle the non-volatile components back into the reaction medium through stream 23.110 then direct the volatile components from the reaction medium up through line 2 to the processes and product separation systems Acetic Acid/Light Ends Restoration; starting with light ends column 124.

As shown in Figure 1; A methanol—containing feed stream 101 and a carbon monoxide—containing feed stream 102 are directed to the liquid phase reaction medium of the krill reactor ua 4. The krill reaction takes place In Jolin's medium the catalyst included water; methyl iodide; acetate (fie acetic acid; iodide salt; HI and other reaction medium components. In embodiments the Jolie Krill 104 may be a stir vessel; a bubble column type vessel; or a combination thereof; within which the contents are maintained The slurry or liquid reactants at constant levels with normal operation In embodiments the carbon monoxide is continuously introduced into the reaction medium from the krill reactor including under agitation used to stir the contents Preferably the gaseous feed is completely dispersed through the reactant by the stirring means In these embodiments, the reactor system may additionally include a number of recycling lines where various components are recycled back to the reaction medium from other parts of the process, various steam purge lines which may be subject to further treatment etc. All nozzles and steam purge lines are understood to be Miscellaneous is in contact with the gas scraper system 139 one or “ST” and that all condensable components are finally recycled back to the krill reactor before the steam stream is released into the atmosphere as readily understood by a person with the slightest skill in art.in embodiments;s d A gaseous purge stream 106 is vented from reactor 104 to the scrubber system 139 to prevent build-up of gaseous by-products and to control partial pressure of carbon monoxide and/or total reactor pressure. Additional reactor system may include pump 0 around loop 1000 103 to control reactor temperature. in embodiments; The reaction medium includes a metal catalyst or a group 9 metal catalyst; or a catalyst containing rhodium and/or iridium. in embodiments; The reaction medium includes a rhodium catalyst. in embodiments; The rhodium component of the catalyst system is believed to exist in the form of a rhodium-symmetric complex with a halogen component providing at least one of the ligands of this compound

Harmonic. plus harmonies of rhodium and halogen; It is also believed that cron monoxide will harmonize with rhodium. in embodiments; The rhodium product may be supplied from the catalytic system by introduction into the rhodium reaction zone in the form of metal rhodium; Rhodium salts, for example, oxides, oxides, acetals, 85, iodides, 1,001,065, carbonates, hydroxides, chydroxides, 5 chlorides, etc.; or other compounds that lead to the formation of a rhodium-coordinated complex in the reaction environment. in alternate incarnations; The krill catalyst comprises rhodium dispersed in a liquid reaction medium or supported on an inert solid sale. Rhodium can be introduced into the reaction system in any of several forms; The exact nature of the rhodium moiety within the catalytically active complex may be imprecise. 10 in embodiments; The catalyst concentration can be maintained in the reactor at amounts from about 200 to about 5,000 parts per million by weight; Depending on the total weight of the reaction medium. in embodiments; The reaction medium may additionally include a halogen-containing catalyst promoter. Suitable examples include organic calkyl aryl halides and alkyl halides or substituted aryl halides. in embodiments; dag is a halogen-containing catalytic promoter in the alkyl halide form in which the alkyl moiety corresponds to the alkyl moiety of the feed alcohol for which the ALS process is performed. Thus in the ALS process methanol to [eli-acid] will include a halide promoter; methyl halide; or (Mel) methyl iodide in embodiments; The reaction medium comprises greater than or equal to about 5 wt 7 Mel depending on the total weight of the reaction medium. In embodiments the reaction medium comprises greater than or equal to about 0 5 wt 7 and less than or equal to about 50 wt 7 Mel In embodiments the reaction medium comprises greater than or equal to about 7 wt 7” 10 wt 7 Mel and less than or equal to about 30 wt 7” or 0 wt 7 Mel depending on the total weight of the reaction medium. The liquid reaction medium used is any solvent compatible with the catalyst system and may include pure alcohols;

Liquid reaction on acetic acid (80011). in embodiments; The reaction medium comprises greater than or equal to about 50 by weight of 7 ACOH in embodiments; The reaction medium comprises greater than or equal to about 50 wt 7 and less than or equal to about 90 wt 7 ACOH embodiments; The reaction medium comprises greater than or equal to about 50 wt7 or 60 wt 7 ACOH 5 and less than or equal to about 80 7035 or 70 wt 7 ACOH depending on the total weight of the reaction medium. In embodiments, the reaction medium comprises a concentration At least limited water In embodiments the reaction medium comprises a detectable amount of water In embodiments the reaction medium comprises greater than or equal to about 0.001 wt7 water In embodiments the reaction medium comprises greater than or equal to about 0.001 wt7 and less than or equal to about 14 wt7 water.In embodiments the reaction medium comprises greater than or equal to about 0.05 e039 or 0.1 wt#; or 0.5 wt7 or 1 wt#” or 2 wt#” or 3 wt#” or 4 wt 7 cola and less than or equal to about 10 wt 7 or 5 wt 7 cola depending on the total weight of the reaction medium. The reaction medium contains methyl acetate In embodiments the reaction medium comprises ≥ 0.5 wt. The reaction is greater than or equal to about 1 wt 7 and less than or equal to about 50 wt 7 ©1/06/8. in embodiments; The reaction medium comprises greater than or equal to about 1.5 wt# or 2 wt#; or 3 wt. 7 (MeAc) and less than or equal to about 0 20 wt. # or 10 wt 7 8/8©6/A; depending on the total weight of the reaction medium. In embodiments, the reaction medium additionally comprises an additional iodide ion which is Above or above the iodide ion present as hydrogen iodide.In embodiments; iodide ion concentration provided by iodide salt; or lithium (Lil) iodide in embodiments; medium maintained

The reaction is under reduced water concentrations where methyl acetate and lithium ionide are present in sufficient concentrations to act as rate enhancers (see US Patent #5001259). in embodiments; At least a portion of the iodide ion concentration in the reaction medium results from a salt

Metal iodide or iodide salt of an organic cation or cations based on ely amines phosphinate 0105001065 etc. in embodiments; Iodide is the salt of a metal; iodide salt from

Group 1 or Group 2. In embodiments; The reaction medium includes alkali metal iodide; or iodide

Lithium. in embodiments; The iodide concentration is above els of the iodide ion present as iodide

hydrogen. in embodiments; The reaction medium includes an amount of iodide salt; or lithium iodide; in quantity

sufficient to produce a total iodide ion concentration greater than about 2 wt. in embodiments; Medium included

0 reaction on an amount of iodide salt; or iodide candid in an amount sufficient to produce a total iodide ion concentration greater than or equal to about 2 wt7 and less than or equal to about 40 wt7; Depending on the total weight of the reaction medium. in embodiments; The reaction medium comprises greater than or equal to about 5 wt#, 10 wt#, or 15 wt7 iodide ions; and less than or equal to about 30 wt7 or 720 iodide ions; Depending on the total weight of the reaction medium.

in embodiments; The addition of the Jang reaction includes hydrogen; Determined according to partial hydrogen pressure present in the reactor. in embodiments; The partial hydrogen pressure in the ST reactor is of or equal to about 0.7 kPa (0.1 pressure per square inch) or 3.5 kPa (0.5 pressure per square inch) or 6.9 kPa (1 pressure per square inch); and less than or equal to about 1.03 MPa (150 psi) or 689

0 kPa (100 psi) or 345 kPa (50 psi) or 138 kPa (20 psi).

In embodiments, the reactor temperature is the temperature of the reaction medium; greater than or equal to about 150°C. In embodiments the reactor temperature is greater than or equal to about 0°C and less than or equal to about 250°C. In embodiments » the temperature of reactor 5 is greater than or equal to about 180°C and less than or equal to about 220°C.

in embodiments; The partial pressure of carbon monoxide in the reactor is greater than or equal to ss 200 kPa. in embodiments; The partial pressure of CO is greater than or equal to about 200 kPa and less than or equal to about 3 MPa. in embodiments; The partial pressure of CO in the reactor is greater than or equal to about 300 kPa. or 400 kPa; or 500 kPa and less than or equal to about 2 MPa; or 1 MPa. The reactor pressure, SH, is the combined partial pressure of all the reactants; products; and by-products in it. in embodiments; The total reactor pressure is greater than or equal to about 1 MPa and less than or equal to about 4 MPa. In embodiments the liquid reaction medium is drawn from Jolie krill 104 and directed to the scintillator 0 112 which has a pressure lower than that in the reactor at a rate sufficient to maintain a constant level in it; It is inserted into the scintillator 112 at a midpoint between its top and bottom. in flashing; Less volatile components are withdrawn; specifically the catalyst solution; As a base stream of 110 (predominantly acetic acid containing rhodium and iodide salt along with smaller amounts of methyl acetate; Jive iodide acetic acid and water) slag cycled back into the reaction medium. The upper head of scintillator 122 largely comprises the 5-acetic acid produced alongside methyl iodide; methyl acetate; water; and 0405. In addition to the gaseous byproducts, die cmethane, part of the carbon monoxide, may be released; carbon dioxide; Etc. from dad al wamad. acetic acid product separation processes and systems/recovery of light ends in embodiments; The upper head current from the flasher 112 is directed to the light 0 terminals column 124 and is referred to in the Art as the stripping column; like current 122; Where distillation produces a low-boiling upper head steam stream 126, here referred to as Lad as first overhead stream 126 and a purified acetic acid product stream 128 where it is removed in Embodiments as a side stream. Further producing a light-terminal column 124 is a high-boiling residual stream 116) which may undergo further purification and/or may be recycled back into the reaction medium.

— 5 2 — in embodiments; The first upper head 126 condenses and then faces into an overhead phase separation unit 134 (referred to here as an upper head decanter). In embodiments, the first upper head 126 comprises methyl iodide; methyl acetate; reducing at least one PRC 3 compound; heavy phase 137; at least a portion of the light 0 phase 135 or a combination thereof into the reaction medium through lines 118 and 114, respectively. Reaction as Hes. In embodiments the heavy phase 37 1 is recycled to the reactor through line 118. In embodiments the light phase is directed 135; heavy phase 137 or a combination thereof into 5 or more purification processes 108 (Sie aldehyde removal system; through stream 142. The purified stream is subsequently returned to the process through one or more streams collectively referred to as 155. Although it may The specific compositions of the light liquid phase 5 vary widely. Some representative compositions are given below in Table 1. Table 1 Representative light liquid phase from top to bottom for light ends Concentrate (wt7) | Concentrate (wt7) | Concentrate (wt7)

— 6 2 — in embodiments; The upper head clapper 134 is arranged and constructed to maintain a low interface level to prevent excess build-up of methyl iodide. Although they may vary aly the specific compositions of the heavy liquid phase 137) Some representative compositions are provided below in Table 2. Table 2 Representative heavy liquid phase from top header to light ends concentrate (7 wt) | wt7) 2-0.01 1-0.05 0.9-1 25-0.1 20-0.5 15-0.7 1 | ' 98-40 95-50 85-60 although not showing a light liquid phase section 135 and/or a heavy liquid phase 137 may be separated and directed to an acetaldehyde removal system or PRC to recover methyl iodide and methyl acetate while the acetaldehyde is still removed as shown in Tables 1 and 2 (ging both the liquid phase Casall 135 0 and/or the heavy liquid phase 137 on PRC's and the process may include removal of acetaldehyde "creonyl" impurities, which deteriorate the quality of the acetic acid product and may be removed in suitable de-staining columns and apparatus

absorbency as described in US Patents Nos. 6,143,930; 6,339,171; ¢7223883 ¢7223886 7855306; ¢7884237 8889904” and US Patent Application No. 0011462/2006; which are incorporated here in full for reference. Chronyl impurities may react; For example, acetaldehyde; with iodide catalyst enhancers to form alkyl iodides; e.g. edi iodide propyl iodide; butyl iodide; pentyl iodide; hexyl iodide; etc. Also because many impurities originate with acetaldehyde; It is desirable to remove carbonyl impurities from the liquid light phase. A section of the light liquid phase 135 and/or the heavy liquid phase 137 fed to the acetaldehyde removal system or PRC may vary from 71 to 799 from the mass flow of either the light liquid phase 5 off 133 the heavy liquid phase 134; such as 1 to 750; from 2 to 745; 5 to 0 240 5 to 730 or 5 to 7220. Lad in some embodiments; A portion of each of the light liquid phase 135 and the heavy liquid phase 137 may be fed to the acetaldehyde removal system or PRC A portion of the light liquid phase 135 not fed to the acetaldehyde removal system or 086 may be re-condensed to the first column or recycled to the reactor; as described here. A portion of the heavy liquid phase 137 that is not fed to the acetaldehyde removal system or PRC may be recycled to the reactor. Although 5 the vapor of a portion of the heavy liquid phase 137 may be re-condensed to the first column; It is more desirable (sale) a heavy liquid phase enriched with methyl iodide 137 to the reactor. in one embodiment; A portion of the light liquid phase 135 and/or the heavy liquid phase 7 is fed into the distillation column which fertilizes the floathead from that with acetaldehyde and methyl budide. depending on the body; There may be two distillation columns separating; The upper vertex of the second column may be 0 rich in acetaldehyde and methyl iodide. Dimethyl ether may also be present; formed on site; in the upper head. The upper head may undergo one or more stages of extraction to remove raffinate 46 rich in methyl iodide and extract material. A portion of the raffins may be returned to the distillation column “Jl column” overhead decanter and/or reactor. For example; Lovie treats the heavy liquid phase 7 in the PRC aly) It may be desirable to return a portion of the raffins to either the reactor or 5 distillation column. also for example; When the light liquid phase 135 is treated in the removal system

(PRC) It may be desirable to return a portion of the rafin to either the first column, upper head clapper, or the reactor. In some embodiments, the extract may be further distilled to remove water, which is returned to one or more stages of extraction, containing more methyl acetate and methyl iodide from the light liquid phase 135; it is recycled to the reactor 104 and/or its vapor is re-condensed to the first column 124. Appropriate purification processes include that described in US Patent Nos. «20090036710 20090062525) 20132515) 20130026458 201300116470“ 20130204014 20130261334 ”0 2013 5 at the bottom of the column and the aqueous upper head collects in the upper head decanter 148) the section whose vapor is re-condensed by returning to the drying column 130 prior to returning to the reactor 104. Other embodiments include channeling acetic acid into the heavy ends column (see International Application No. 0216297); and/or contact with an absorbent material; one or more adsorbents » or ion exchange resins in a resin bed or hardening column 200 to remove various impurities (see US Patent No. 6,657,078); and similar in the product purification sector of the process; As described in full here. As shown; The drying column 130 separates the acetic acid side draw 128 into an upper head stream composed primarily of water and a bottom stream composed primarily of acetic acid. The upper head stream cools and condenses in the phase separation Ha clarifier sang 148) to form a light sh and a heavy phase. As riage the vapor from the light phase is re-condensed and the remainder of the light phase is returned to the reactor. Preferably The heavy phase, which is typically an emulsion comprising water and methyl iodide, is completely returned to the reactor Representative compositions of the light phase for the upper head of the drying column are provided below in Table 3.

— 9 2 — Table 3 Representative light phase compositions from top head of drying column Fooly Concentrate | For Fooly Concentrate / Concentrate (wt. 7) in embodiments; small amounts of an alkali component such as KOH Side Draw 128 may be added prior to entry to the desiccant column 130. In other embodiments, the alkali component may also be added to the desiccant column 130 at the same height as the stream 128 fed into the desiccant column 130 or at a higher height than the level of height as the stream 128 fed into the desiccant column 130. These may equal Addition HI in the column In embodiments the drying column bottoms stream may include or consist primarily of acetic acid In embodiments the drying column bottoms stream contains acetic acid in amounts greater than 0 90 wt# ie greater than 95 wt# or greater than 98 wt 7. In embodiments; essentially this stream may be anhydrous; eg "containing less than 0.15 wt 7 cole eg less than 2 wt 7 water or less than 0.1 wt # of water. However; as is Discussion The stream may contain varying levels of impurities.In Figure 1 the crude acid product is drawn off as a residue in the Glad column cial dryin stream g column bottoms stream 15 146. In embodiments; The crude acid product may be taken up from the drying column 30 1 from a side stream at a position slightly above the bottom of the column 30 1 0. The side stream may be drawn in the liquid or vapor phase. When the clouds are in the vapor phase it may be from

Additional condensation and cooling is necessary prior to removal of alkaline contaminants; Mie lithium contaminants. For example; The crude acid product may take as a bypass from the lower gad of the column; While the waste stream is drawn from the base of the drying column 130 and removed or recycled. This side stream contains the crude acetic acid product which is sent to cation exchange resin for lithium removal. This may allow separation of a fraction having a higher boiling point than the crude acid product in the tailings stream. in embodiments; Residual current is subtracted or purged from process 100. In embodiments; The resulting crude acid product is further treated by column drying 130) by passing through a series of OM-functionalized iodide removal ion exchange resins before being stored or transported for commercial use. In embodiments, the further acetic acid production process involves the introduction of a lithium compound in The reactor to maintain a concentration of lithium acetate in an amount of 0.3 to 0.7 wt.7 in the reaction medium. In embodiments; an amount of lithium compound is introduced into the reactor to maintain a concentration of hydrogen iodide in an amount of 0.1 to 1.3 7059 in the reaction medium. In embodiments; a catalyst concentration is maintained rhodium in an amount of 300 to 3000 wt per million in the reaction medium; a concentration of water is maintained in an amount of 0.1 to 4.1 wt7 in the reaction medium; ig 5 a concentration of methyl acetate is maintained from 0.6 to 4.1 wt7 in the reaction medium; at Based on the total weight of the reaction medium contained in the krill reactor. In embodiments the lithium compound introduced into the reactor is selected from the group consisting of “lithium acetate”; lithium cryoxylate; lithium crionate; lithium hydroxide; other organic lithium salts; and mixtures thereof. compound Lithium is soluble in 0 react medium. in one of the embodiments»; Lithium acetate hydrate 6(gh) can be used as a lithium complex source. Jolin lithium acetate with hydrogen iodide according to the following equilibrium reaction (1) to form lithium iodide and acetic acid: (I) LiOAc + HI s Lil + HO

Lithium acetate provides improved control of hydrogen iodide concentration relative to other acetates; Jie methyl acetate; present in the reaction medium. without being bound by theory; Lithium acetate is a base conjugate of acetic acid and therefore reactive towards hydrogen iodide via an acid-base reaction. This property is thought to lead to an equilibrium reaction (1) that favors the reaction products

than those produced by the corresponding equilibrium of methyl acetate and hydrogen iodide. This improved equilibrium is favored at water concentrations of less than 4.1 wt# in the reaction medium. in addition to; The relatively low volatility of lithium acetate compared to methyl acetate allows the lithium acetate to remain in the reaction medium except for volatilization losses and small amounts of gall drawn into the vapour crude product. On the contrary; The relatively high volatility of methyl acetate allows the substance to be distilled in a purification series; Leading

0 to more difficult to control methyl acetate. Lithium acetate is an easy to maintain and control process at relatively low concentrations of hydrogen iodide. Accordingly, a relatively small amount of lithium acetate relative to the amount of methyl acetate needed can be used to control the concentrations of hydrogen iodide in the reaction medium. It was also found that lithium acetate is at least three times more effective than methyl acetate in promoting the oxidative addition of methyl iodide to the rhodium-5 complex[].

in embodiments; The concentration of lithium acetate in the reaction medium remains greater than or equal to 0.3 wt#” or greater than or equal to 0.35 wt#; or greater than or equal to 0.4 wt 7; or greater than or equal to 0.45 wt 7; or greater than or equal to 0.5 wt 7; and/or in embodiments; The concentration of lithium acetate in the reaction medium remains less than or equal to 0.7 20039 or less than or equal to 0.65

0 weight”; or less than or equal to 0.6 7035 or less than or equal to 0.55 wt7; When determined according to the perchloric acid titration to the end point of the gall measurement

It was found that an excess of lithium acetate in the reaction medium may adversely affect the other compounds in the reaction medium, leading to a decrease in productivity. On Sal, it was found that the concentration of lithium acetate in the reaction medium is less than about 0.3 wt 7, which leads to the loss of the ability to control the concentrations

5 Hydrogen iodide is in the reaction medium.

in embodiments; The lithium compound may be introduced continuously or intermittently into the reaction medium. in embodiments; Lithium compound can be introduced during reactor start-up. in embodiments; Lithium compound is introduced intermittently to replace powder material losses.

A series of experiments is being conducted to clarify the effect of enhanced lithium acetate in the krill reactor

and to determine the effect of lithium acetate on the oxidative addition of methyl iodide to the rhodium complex; [012]602>]Na confirms the enhanced effect of lithium acetate on reaction rates. A linear increase of reaction rates associated with increasing lithium acetate concentrations is observed. This association is indicative of first-order reinforcing effects of the interaction between methyl iodide and [12)00(2]a. These experiments show a Lilia (non-heal) intercept, confirming that lithium acetate is not required for the occurrence of

0 reaction (Mel-Rh(l)) but lithium acetate provides a significant enhancing effect even at low concentrations.

in embodiments; The process may additionally include maintaining the concentration of butyl acetate in the acetic acid product at 10 wpm or less without removing the butyl acetate directly from the acetic acid product. in embodiments; The concentration of butyl acetate in the acetic acid product Ale may be kept below 10 ppm by removing acetaldehyde from the reaction medium.

5 acetaldehyde from a stream derived from the reaction medium”; and/or control the reaction temperature” and/or partial hydrogen pressure; and/or the concentration of the metal catalyst in the reaction medium. in embodiments; The concentration of butyl acetate in the final acetic acid product is maintained by temperature control of one or more of the krill reaction temperatures from 150°C to 250°C; partial hydrogen pressure in the krill reactor at 0.3 to 2 atm; catalyst concentration Rhodium metal is in the reaction medium

0 at 100 to 3000 wpm; on the basis of the total weight of the reaction medium; and/or an acetaldehyde concentration in the reaction medium of 1500 ppm or less.

in embodiments; The acetic acid product formed according to the process embodiments disclosed herein has a concentration of butyl acetate of less than or equal to 10 w/ppm; or less than or equal to 9 weight per ppm; or less than or equal to 8 weight per ppm; or less than or

5 is equal to 6 weight per ein per million” or less than or equal to 2 weight per ppm; on

— 3 3 — gross weight basis of the acetic acid product. in embodiments; The acetic acid product is substantially free of butyl acetate; any; The concentration of butyl acetate is less than 0.05 w/ppm or is undetectable by means of detection known in the art. in embodiments; The acetic acid product may also have a propionic acid concentration of less than 250 w/i per million; or less than 225 ppm” or less than 200 weight per gia per million. in embodiments; The concentration of butyl acetate in the acetic acid product can be controlled by Gob

Control the concentration of acetaldehyde in the reaction medium. without being attached to a theory; Butyl acetate is thought to be a by-product produced by aldol concentration of acetaldehyde. The applicant finds that by maintaining the acetaldehyde concentration in the reaction medium at less than 1500 w/ppm;

0, the concentration of butyl acetate in the final acetic acid product can be controlled below 10 w/ppm. in embodiments; The concentration of acetaldehyde in the reaction medium remains at less than or equal to 0 w/ppm; or less than or equal to 900 wpm; or less than or equal to 500 weights per million eda; or less than or equal to 400 ppm” based on the total weight of the reaction medium.

in embodiments; The concentration of butyl acetate in the acetic acid product can be controlled by controlling the reaction temperature of the krill reactor at a temperature greater than or equal to 0 mt; or 180"C; and less than or equal to 250"C; or 225 "C; and/or the partial hydrogen pressure in Jolie krill can be controlled at greater than or equal to 0.3 atm; or Jara 0.35 atm 3 or 4.0 Jara 3 5.0 atm Jara 3 atm and less than or equal to 2 atm '

Or 1.5 atm or 1 atm.

While the relatively high partial pressure of hydrogen leads to improved reaction rates; selective improved catalytic activity; lower temperatures; The applicant finds that the hydrogen partial pressure increases; The production of impurities also foams; Including Led Butyl Acetate.

in embodiments; The hydrogen partial pressure can be controlled by adjusting the amount of hydrogen present in the carbon monoxide source and/or increasing or decreasing the reactor vent flows to obtain the desired hydrogen partial pressure in the krill reactor. A series of experiments is conducted to clarify the effect of partial hydrogen pressure and acetaldehyde concentration in the reaction medium on the concentration of butyl acetate in the final acetic acid product. These experiments confirmed the relationship between lower butyl acetate concentrations in the final acetic acid product; and the relatively low acetaldehyde concentrations in the reaction medium and/or the relatively low hydrogen partial pressures in the krill reactor. Experiments with the acetaldehyde concentration in the reactor kept below 1500 ppm and the partial hydrogen pressure of the reactor kept below 0.6 atm resulted in butyl acetate levels 10 wppm lower in the final acetic acid product. Further experiments showed an acetaldehyde concentration in the reactor below 1500 wppm and a reactor partial hydrogen pressure of 0.46 atm leading to a butyl acetate concentration of less than 8 wppm in the final acetic acid product. Similar conditions where hydrogen partial pressures of 0.30 atm lead to lower butyl acetate levels of 5 6 wppm; and hydrogen partial pressures of 0.60 atm result in lower butyl acetate concentrations of 0.2 wppm in the final acetic acid product. Nevertheless; Perform comparative experiments with hydrogen partial pressures of 0.4 and 0.3 on Jig but in the absence of an aldehyde removal system such that acetaldehyde concentrations in the reactor exceed 0 w/ppm; to a final acetic acid product having 0-butyl acetate levels of 13 wppm and 16 wppm respectively. The applicant also found that the concentration of propionic acid in the final acetic acid product could be affected by the concentration of butyl acetate in the acetic acid product. Accordingly. by judging the concentration of butyl acetate in the final acetic acid product to 10 w/ppm or less; The concentration of propionic acid in the final acetic acid product can be controlled to less than 5 250 w/ppm; or less than 225 ppm; or J of 200 weight per part in

million. in a similar way” by controlling the ethanol content in the reactor feed; which may be present as impurities in the methanol source; The concentrations of propionic acid and butyl acetate in the final acetic acid product can also be controlled. in embodiments; The ethanol concentration in the methanol feed to the krill reactor is controlled to be less than or equal to 150 w/ppm. in

embodiments; if cand the concentration of ethanol in the methanol feed to the reactor is less than or equal to 0 wt ppm; or 50 weight per ein per million; Or 25 weight per ppm.

The applicant further finds that the formation of ethyl iodide can be affected by several variables;

including acetaldehyde concentrate; ethyl acetate; Methyl acetate and methyl iodide are in the reaction medium.

0 additional; It was found that the ethanol content in the methanol source » partial hydrogen pressure and the hydrogen content in the carbon monoxide source affect the concentration of ethyl iodide in the reaction medium and thus; The concentration of propionic acid in the final acetic acid product.

in embodiments; The concentration of ethyl iodide in the reaction medium is maintained/controlled to be less than or equal to 750 w/ppm or less than or equal to 650 w/ppm

5 million; or less than or equal to 550 wpm; or less than or equal to 450 wpm; or less than or equal to 350 ppm. in alternate incarnations; The concentration of ethyl iodide in the reaction medium is maintained/controlled at ≥1 w/ppm; or 5 wt per ppm” or 10 wt per ppm; or 20 weight per ppm” or 25 weight per ppm; and less than or equal to 650 wt

0 ppm” or 550 weight per ppm; or 450 weight per ppm; or 0 ppm.

in embodiments; The concentration of propionic acid may also be kept in the acetic acid product below 0 w/ppm by maintaining the concentration of ethyl iodide in the reaction medium at less than or equal to 750 w/ppm without removing the acid

5 propionic from an acetic acid product.

in embodiments; The ethyl iodide concentrate may be present in the reaction medium and propionic acid in the acetic acid product in a weight ratio of 1:3 to 2:1; or from 5:2 to 1:2; Or from 1:2 to 1:. in embodiments; The acetaldehyde:ethyl iodide concentration remains in the reaction medium at a weight ratio of 2:20 to 1 or 15:1 to 2:1; or from 1:9 to 1:2.

in embodiments; The concentration of ethyl iodide in the reaction medium may be maintained by controlling the partial hydrogen pressure; methyl acetate concentrate; an iodide concentration (edad) and/or at least one acetaldehyde concentration in the reaction medium.

A series of experiments carried out to determine the effect of acetaldehyde and other reaction conditions on ethyl formation indicated the relationship between the concentration of acetaldehyde and the concentration of ethyl iodide in the 0 reaction medium; In addition to the relationships between the concentration of ethyl iodide reactor and the concentration of propionic acid in the final acetic acid product. in general; An ethyl iodide concentration of less than 750 wppm and an acetaldehyde concentration of less than 1500 wp edn per million in the reaction medium result in propionic acid concentrations of less than 250 wppm in the acetic acid product. 5 layer iodide removal/ion exchange resin use: In embodiments acetic acid product streams may be contaminated with lig halides (iodides) and lithium may contact an acid forming cation exchange resin followed by a metal exchange ion exchange resin having acidic cation exchange sites including one metal at the lowest selected from the group consisting of silver; lily Palladium and Rhodium under the range of operating conditions. in embodiments; The 0 ion exchange resin formulations are available in fixed coats. The use of fixed iodide removal layers to purify contaminated carboxylic acid streams is well documented in the art (see eg US Patents Nos. 4615806; 5653853; 5731252; and 6225498; incorporated herein by full reference). in general; The contaminated liquid crioxylic acid stream communicates with the above mentioned ion exchange resin formulations. By flowing through a series of static static layers. JI reported lithium pollutants

through the cation exchanger in acid form. Next JI halide pollutants; Old iodide pollutants; By reacting with a metal ion exchange resin with a metal to form metal iodides. in some embodiments; Hydrocarbon moieties may act; lie methyl groups that may bond with iodide on the esterification of trioxylic acid. For example Jad) in Ala acetic acid contaminated with methyl iodide + methyl acetate will be produced as a by-product of iodide removal. Formation of the esterification product typically has no detrimental effect on the cured trioxylic acid stream. Similar iodide contamination problems may exist in acetic anhydride manufactured via a rhodium-iodide catalytic system. Subsequently; The innovative process can be interchangeably used to purify the acetic anhydride crude product streams. The acid forming cation exchangers suitable for the removal of the metal ion contaminants of the present invention may include strong acid cation exchange resins; For example, strong acidic, large-pore lattice resins; For example 15” Purolite C145 (DOW) Amberlyst® resin or 61145 Purolite Load resin may be a medium pore strong acid cation exchange resin to form an acid. The suitably stable ion exchange resins used with the present invention may also be used to prepare an exchange resin with silver or mercury for iodide removal. Typically they are of type “450311” classified (aes strong acid which is; Sulfonic acid; large lattice type (large pore) cation exchange resins. Particularly suitable ion exchange substrates include Amberlyst® 35 resins (Amberlyst® 15 and 36 (DOW) Amberlyst® suitable for use at 0°C. Can The use of stable substrates (AT) for ion exchange such as zeolites, provided that the material is stable in the organic medium under the conditions under study, meaning that it will not chemically release Aad or release silver or mercury into the organic medium in unacceptable quantities. RSH is done of cation exchange substrates for zepolite” eg; in US Patent No. 5,962,735) the disclosure of which is incorporated herein by reference.

At temperatures greater than about 50 C, the exchangeable cationic substrate with silver or mercury may tend to release small amounts of silver or mercury on the order of 500 ppb or less and thus the exchanged substrate with silver or mercury is chemically stable under the conditions under consideration. Silver losses of less than 100 ppb in organic media are most preferred and Jif is more preferred than 20 ppb in organic media.Silver losses may be slightly higher to begin with.However, if a layer is desired of an acid-forming cationic material that may be placed after the silver or mercury exchange material as well as a layer of acid-forming cationic material before the silver or mercury exchange to capture any released silver or (35) pressures during contact steps with exchange resins are restricted only by 0 physical strength route of resins.In one embodiment the connection is made at pressures from 0.1 MPa to 1 MPa, such as from 0.1 MPa to 0.8 MPa or from 0.1 MPa to 0.5 MPa.For the sake of convenience,however,it is preferable to clamp each of pressure and temperature so that the contaminated carboxylic acid stream is treated as a liquid. Therefore, for example; when operating at atmospheric pressure; 5 which is generally preferred on the basis of economic considerations; The temperature may range from 17°C (the freezing point of acetic acid) to 118°C (the boiling point of acetic acid). It is within the competence of those skilled in the art to specify similar ranges of product streams which include other carboxylic acid compounds. Preferably, the temperature of the contact step should be kept low enough to limit dissolution of the resin. in one embodiment; Contact is made at a temperature of 25°C to 120°C; Sie from 25"C to 100"C or 0 from 50"C to 100"C. fas Some large lattice cationic resins typically decompose significantly (via an acid-catalyzed aromatic desulfonation mechanism) at temperatures of 150°C. Carboxylic acids with up to 5 carbon atoms (Sle) remain unchanged. Up to 3 liquid Creon atoms at these temperatures. Therefore, the contact temperature must be kept below the melting temperature of the resin used. In some cases

Embodiments » Operating temperature remains below resin temperature limit; Consistent with the operation of the liquid phase and the desired kinetics of libthium and/or halide removal. The appearance of the resin layers may vary in the purification series for acetic acid; But the cation exchanger must be before the resin exchanged with the metal. in preferred embodiments; The resin layers are primed after a final column drying. It is preferable to prepare the resin layers in a location where the temperature of the crude acid product is low; Less than 120°C or less than 100°C. The current connecting the cation exchange resin forming the acid and the current connecting the exchange resin to the metal can be set to the same or different temperatures. For example, the current bringing the acid-forming cation exchange resin to a temperature can be set from 25°C to 120°C; 0 eg 25 C to 85 "C; 40 C to 70" C; ie 40"C to 60"C; While the current connecting the resin exchange with the metal can be set to a temperature of 50°C to 0°C; e.g. 50°C to 85°C; 55°C to 75°C; or 60°C to 0°C. Apart from the discussed benefits of coded low temperature operation provides less wear compared to high temperature operation. Low temperature operation provides for the formation of less corrosive 5-Physical contaminants” as discussed above; This can shorten the overall life of the resin. lial so that lower operating temperatures result in less wear; The vessels should not be made of expensive (JST) and low grade metals; lie standard stainless steel can be used. Referring to Fig. 1 the drying column bottoms stream is first passed through a 0 cation exchange resin bed 0800016 for the removal of lithium ions. Although a single layer of Jalal cationic resin 200 is visible, it should be understood that (Sa) the use of a group of layers of cation exchange resin in series or in parallel. The cation exchange layer may also remove other cations present in the current Potassium Jie If added to drying column 130 as potassium salt selected from the group consisting of potassium acetate Potassium carbonate Potassium hydroxide 5 and JSG viz The resulting cross-current Olde intermediate acid product can then be passed through a bed

a metal-exchange ion exchange resin having acid cation exchange sites comprising at least one metal selected from the group formed by silver; lily palladium and rhodium to remove iodides from the streams to produce a purified product 146. Although block 200 purification resins are demonstrated, it should be noted that a combination of alternating ion exchange resin layers can be used with phases in series or in parallel . In addition to the resin layers; Heat exchangers (not shown) can be placed prior to the mill layer to adjust the temperature of the current 146 1825 to the appropriate temperature before the resin layers contact. likewise; The crude acetic acid product can be fed into the cation exchange resin bed from a drying shaft side stream. Heat exchangers or capacitors may be placed prior to the ll layer to set the temperature of the current to the appropriate temperature prior to the contact of the resin layers.

in one embodiment; The flow rate through the resin layers ranges from 0.1 bed volumes per hour (81 // 5+7") to 50 bed volumes/hour; e.g. 1 bed volumes/hour to 20 bed volumes/hour Or from 6 bed volumes/hour to 0 bed volumes/hour The layer volume of the organic medium is the volume of the medium that is equal to the volume occupied by the resin layer A flow rate of 1 bed volumes/hour means that the amount of liquid

5 Organic matter equal to the volume occupied by the resin bed is passed through the resin bed in a period of one hour.

A purified acetic acid composition is obtained as a result of resin bed treatment. The purified acetic acid composition includes; in one embodiment; at less than 100 weights per billion; iodides » e.g. less than 90 wppg » less than 50 wppg; or

0 is less than 25 wpc. in one embodiment; The composition of the purified acetic acid includes less than 100 w/ppb of lithium »e.g. <50 w/ppb» <20 w/ppb; or less than 10 weight per ppb. Regarding domains; The purified acetic acid composition may include from 0 to 100 weight per ga billion iodides; Sle from 0 to 50 weight per billion parts per billion; and/or from zero to

5 100 weight per eda per billion of lithium” is the same as 1 to 50 weight per eda per billion. in

Other Embodiments » The resin layers remove at least 25 wt. # of iodides from the crude acetic acid product; lia at least 50 wt7 or at least 75 wt7. in one embodiment; Mull layers remove at least 25 wt 7 lithium from the acetic acid product (lie ala) at least 0 wt 7 or at least 75 wt 7.

Accordingly; in embodiments; Product may contact acetic acid; or intermediate compound one or more process recycle streams with absorbent ale; adsorbent or one or more ion exchange resins; They are collectively referred to here as purification resins. Acetic acid is contacted in a resin bed or protection column 200 to remove various impurities to produce the final acetic acid product.

Aja impurities from refining resins may include alkyl iodides. specifically; 0-alkyl iodides include from 1 to about 20 kreon atoms. Other impurities include various corrosive metals such as ca SU nickel; Iron; etc. Refining resins suitable for purposes herein include strong acid cation exchange resins; Large reticulum with at least 1 percent of its active sites metamorphosed as silver or lilac. The amount of silver or mercury attached to the resin may be from 1 to 7100 active resin sites; or 5 about 725 to about 275; Or at least about 750 of the active sites may convert to the form of silver or mercury (see » US Patent No. 4,615,806; the full contents herein are incorporated by reference). Other suitable examples include (USP No. 5,139,981) directed at the removal of iodides from a halide-contaminated liquid croxylic acid by contact of the liquid halide-contaminated acid with a large mesh resin exchanged with silver (A). Appropriate examples of 0 purification resins include 15 resin. (Rohm and Haas) Amberlyst(R) Jalal ion cationic substrates for zeolites (ail) ¢ US Patent No.: 596273); etc. Other suitable purification resins and methods include those disclosed in US Patent No.: 5,227,524; US Patent No.: 5801279 US Patent No.: 5220058 « European Patent No.: 0685445» US Patent No.: 6657078; 5 Their contents are fully incorporated here by reference.

in embodiments; The acetic acid contacts with the purification resin at a temperature of at least about 0ºC; or about 60°C to about 100°C; or at temperatures greater than or equal to about 150"C depending on the type of purification resin used. In embodiments the flow rate of acetic acid through the column may be from about 0.5 to about 20 bed sizes/hour (81//08); Cus The bed volume is defined as the volume occupied by the resin in the bed. In embodiments the flow rate may be about 6 to about 10 bed volumes/hour; or about 7 to about 8 bed volumes/hour. In embodiments the column may include Anionic protectant; includes pyrrolidone or pyrrolidone resin The terms mul refer to pyridine resin "ring-containing polymer 10106/a0"; polymer and the like used herein to a polymer containing substituted or unsubstituted pyridine rings or polycondensed rings containing pyridine; Substituted or unsubstituted as quinoline rings 0©6a00100. in embodiments; Resins may have a high degree of crosslinking; any; greater than 10 weight7. Substitutes include those inert to the ALS process conditions in methanol 5 such as the alkyl group and the alkoxy group alKOXY. Suitable examples of insoluble pyridine ring-containing polymers include those resulting from the reaction of vinylpyridine with a monomer (gla Vinyl divinyl or on the reaction of vinyl pyridine blocking the monomer of vinyl contains a divinyl monomer “Jie” copolymers of 4-vinylpyridine and divinylbenzene ddivinylbenzene copolymers of 2-vinylpyridine 2-vinylpyridine 0 and divinylbenzene; copolymers of styrene vinylbenzene and divinylbenzene copolymers of vinylmethylpyridine and divinylbenzene and copolymers of vinylpyridine »methyl acrylate and ethyl diacrylate lil) ethyl diacrylate « US Patent No.: 5,334,755; whose disclosure is merged here by reference).

The appropriate 'pyrrolidone resin'; sels! contains a pyrrolidone ring—containing polymer Pyrrolidone polymer and the like include polymers containing substituted or unsubstituted pyrrolidone rings. Substitutions may include those inert to the ALS medium in methanol such as alkyl groups or alkoxy groups. Examples of an insoluble pyrrolidone ring-containing polymer include those resulting from the reaction of vinylpyrrolidone 06008 with a vinyl monomer containing a divinyl monomer such as a copolymer of vinylpyrrolidone and divinylbenzene. Pyrrolidone those disclosed in US Patent No.: 5,466,874 (USPt: 5,286,826; USPt: 4,786,699, USPt. 0: 4,139,688 whose disclosures are incorporated herein by reference; and those available under the trade name Reillex(R) ) of Reilley Tar and Chemical Corporation of Indianapolis, USA In embodiments; the heterocyclic polymer may bind to at least 0” or at least 715 or at least 720” and less l of 750, 760, or 1775 5 tl to provide mechanical resistance” where “dad” denotes the degree of crosslinking to Lad (sina) for * by weight; Diphenyl monomer or other crosslinking moiety. in embodiments; Suitable pyridine or pyrrolidone insoluble polymers include free base forms; and/or N= oxide forms and/or forms converted to the allotropic form. in embodiments; The ring-containing polymer may be pyridine or pyrrolidone; insoluble in 0 bead or granular form; or spherical shape; has a particle diameter of 0.01- 2 alle or 0.1- 1 millimeter; or 0.25-0.7 mm. Commercially available pyridine-containing polymers include KEX- 316 «(Reilly Tar and Chemical Corporation) Reillex-425 «(products of Koei Chemical Co., Ltd.) KEX-212 3 KeX-501 etc. in embodiments; The acetic acid product is withdrawn from the drying column 130 at or near 5 column bottom by stream 146 and is combined with one or more resins in the column which

Includes purification resin. As used herein, a column that includes the purification resin as a cdl column may be referred to as a collector or a protective layer column; or simply as a column. These terms are used here interchangeably. The complex of the protective or purifying layer is generally represented as 1 with the number 200.

in embodiments; As can be seen in Figure 2; The security layer pool may include 560 guard

assembly 5 200 on one or more dallas tools Mia column 202; and column

column 204" both contain inlet end 206 and 210; respectively; outlet end 208 and 212; respectively. The entrances are separated from the exits by an inner chamber, 214 and 216. A quantity of purification resin 8 and 220 is placed in the inner chamber.

dng) 10 acetic acid from the process; Which contains impurities at first concentration 146 through the inner chamber 214 and 216 in contact with the purification resin 218 and 220 at a sufficient temperature and flow rate to produce a purified acetic acid stream 222 in which impurities are present »on each A state at a second concentration lower than the first concentration of impurities. According to lid the second impurity concentration may be zero or otherwise undetectable.

15 in embodiments; The pane may additionally include heat exchangers 224 5 226 that control the temperature at which the acetic acid reaches the baie resin. in embodiments; Columns 202 and 204 are plug flow columns; It flows steeply with gravity from top to bottom. Nevertheless; Lad envisions an instrument flowing against gravity from the bottom entry end to the top exit end.

20 in embodiments; First column 202 includes exit end 208 in direct fluid contact with entry end 210 second column 204. In embodiments; The tubes can be arranged between the different tools so that any one of the de gana columns may be the first processing tool and any of the remaining columns may then be placed in series. in embodiments; Columns can be arranged in parallel.

in embodiments; The purification resin 218 of the first column 202 may differ from the purification resin 220 of the second column 204 and/or the temperature of the first column 202 may differ from that of the second column 4 and/or the size of the inner chamber 214 of the first column 202 may differ from the size of the inner chamber 6 of the second column 204. As shown in Figure 3; in embodiments; The column 400 may comprise an inner chamber 402 associated with a set of plurality of sides 404 radially regular about a central axis 406. In embodiments; Column 400 has an infinite number of sides; any; It has a circular cross section. Column 400 additionally includes an inlet end 408 in a fluid connection (re and longitudinally separated from the outlet end 410 0 through the inner chamber 402. In embodiments, column 400 Lala) has a set of ports Sampling ports 412 placed through at least one side 404. The sampling ports may be hard duee ports; liquid sampling ports; or a union of them. As can be seen in Figure 4; in embodiments; Each sampling port 412 comprises a first open flow path 414 between the sample inlet 416 thread 5 in the inner chamber 402 and a first flow control element 418 operable between an open position ( As exemplified by flow control element 420;lie ball valve ball); a closed position (LS) illustrated in flow control 418); The flow control is located outside of the inner chamber 402 in an external environment 2. The term “open flow path” refers to a flow path that is dimensionally defined and uniform to allow both liquid and solid matter to pass through. Accordingly, the relative size of the open flow path must be determined relative to the average particle size of the solid or semi-solid through which it will pass. Loveie The flow control is in the open position; A fluid connection exists between the inner chamber 402 and the outer environment 422. In embodiments; The first flow path 414 5 and the second flow path 424 are in fluid contact with the external environment 422 when the control is

— 6 4 — in the corresponding stream 4205418 respectively; in the open position. When the flow control element is in the closed position fluid contact between the inner chamber 402 and the outer environment 422 is prevented in embodiments; The sample port further comprises a second flow path 424 comprising a porous element 426 positioned between the sample inlet 416 and a second flow control element 420 operable between an open position and a closed position positioned outside the inner Al chamber 2. In embodiments the flow path includes the second 424 on the position of the first stream path 414 between the dual input 416 and the first stream control 418. Accordingly; in embodiments; 0 may be the second flow path in the direction of 'A level' or 'Level 7' outside the first flow path so that a sample exiting from the first control 418 is taken from the same location in the inner chamber 402 as a sample exiting the second flow control 420. In embodiments; As shown in Fig. 3 the first flow path 414; the second flow path 242; or both additionally comprise a heat exchanger 428 positioned between the sample inlet 416 and the external environment 422. In embodiments, the heat exchanger 8 may be removablely attached to a section of the path flow behind the flow control element as shown. Accordingly » heat exchanger 428 also referred to as a "sample cooler" i.e. a piece of piping cooled in a vessel of ice water may be used to obtain the lie from the inner chamber 402; when the internal chamber temperature is (dad) yo. In embodiments, the first flow path 414 is placed in a first conduit 430 having a first outlet end 432 equipped with a first valve 434 incorporating an element 1st Flow Control 418. In embodiments, the valve may be a ball valve; valve pyloric and/or the like. in embodiments; The first valve shall be a heavy duty ball valve equipped with a system

Push seat flush system 436 to block particulate matter; lie ion exchange resin placed in the inner chamber 402; Inhibition of valve closure after sample acquisition. in embodiments; The second stream path 424 Wise is at least within a second stream 438 linked at the point of connection 440 with the first stream 430; It has a second exit end 442 fitted with a second valve 444 incorporating the second flow control element 420. In embodiments; The porous element 426 is located at or near the coupling point 440; At or near the end of Exit 442 Second or Union thereof. in embodiments; porous element includes grial; porous cud a candidate element or a union thereof; represented by dale as 446. In embodiments; when using many porous items; The item exclusion size may vary. For example; in embodiments; 0 may be the grail or filter element 446 of the porous element 426 is dpe of 100 eyes in first position; a sieve of 200 wells in a second later position; Depending on the relative size of the particulate matter Olle (refining resin) contained in the inner chamber 402. In embodiments; The first open flow path 414 is dimensioned and arranged to allow both liquid 450 and solids 448 in the inner chamber 402 to flow from sample inlet 5 416 through the first flow control element 418 in the open position; and to an external environment 422; The second flow path 424 is dimensioned and arranged to allow the flow of liquid 450 in the inner chamber 402 from the sample inlet 416 through the porous element 426; Through the second flow control 420 in the open position. and to the external environment 422 Lay at least a portion of the solid or semi-solid 448 contained in the inner chamber 402 0 - is excluded from the flow through the second flow control 420. In embodiments; At least section 456 of the first flow path 414 lies within a first stream 0 extending into the inner chamber 402 away from the inner surface 458 of the side 404 through which the sampling port 412 is placed; So that the entrance to the sample 416 is located inside the inner chamber 402 at a distance from lal 404.

— 8 4 — as shown in Figure 3; in embodiments; The sample inlet 416 is located at the side 404 within which the sampling port 412 is placed. In embodiments; Inner chamber 402 has an average inner diameter of 4352 delimited perpendicular to center axis 406 between opposite sides 404 that is less than 750 of the mean length 454 of inner chamber 402 delimited parallel to center axis 406 between inner end 408 and outer end 406. In embodiments; The first stream includes 430 as many sample entries as 6. In embodiments; Each of the many sample inlets of a single first stream 430 is coplanar with a plane 460 perpendicular to the central axis 406 in embodiments; The sampling ports 412 are arranged longitudinally (along with at least section 0 of one or more sides parallel to the central axis of entry end 408 and exit end 0) at essentially equal intervals 462 along at least section of side 404. In embodiments; It includes provisioning a column 400 according to any one or combination of embodiments declared herein containing at least one of them; Many preferred sampling ports 412 according to any one or combination of the embodiments herein declared wherein the inner chamber 402 comprises an amount of 5 purification resin 448 at least partially filling the inner chamber 402. The stream to be cleaned is then directed 4. eg acetic acid stream and/or Intermediate production stream having one or more impurities at first concentration through the column from the inlet end 408 through the inner chamber 402 connected with the refining resin 448 thereafter through the outlet end 410 at a temperature and flow rate sufficient to produce a clear liquid stream 466; for example; A purified acetic acid stream and/or intermediate production stream has a doping at a second 0 concentration lower than the first concentration. in embodiments; The purification resin includes 448 strong acids; Reticular Cum ion exchange resin At least about 71 of the active sites of the resin convert to the form of silver or mercury; where the temperature is at least about 50°C; and where the ion exchange resin is cross-linked

Silver or mercury is effective for the removal of at least about 790 wt organic iodides 01-620 in acetic acid stream. in embodiments; The purification resin 448 is housed in the inner chamber 402 in many layers

8 5 470’ The first range 468 is between the end of entry 408 and the second range 470; ging domain

the second 470 between the first range 468 and the end of Exodus 410. In embodiments; The purification resin in the first band 468 is the same as the purification resin in the second band 470. In alternative embodiments; The purification resin in the first band 468 is different from the purification resin in the second band 470. In embodiments; The purification resin in the first band 468 is a strong acid; non-functional pS grid; Ion exchange resin and purification resin in the second range includes 470 strong acid; Reticulated “pS” exchange resin

0 ion in which at least about 71 of the active sites of the resin convert to the form of silver or mercury.

in embodiments; Further includes a process in accordance with one or more embodiments herein declared Operating a first flow control 418 from a closed position to an open position for a period of time sufficient to obtain a sample comprising liquid 450 and Mie 448 purification resin Taking a first sample and then returning the flow control the first 418 reverse to the closed position; and/or run a control in

5 A second flow 420 from a closed position to an open position for a period of time sufficient to obtain a sample including liquid 450 from the Jol due taking port and then return the second flow control 420 back to the closed position.

in embodiments; The process additionally includes the analysis of one or more samples to determine one or more concentrations of one or more impurities at the corresponding sampling port. in embodiments;

0 The process additionally involves linking a heat exchanger with the outlet of the sampling port before operating the valve to obtain a sample that has a lower temperature relative to the chamber temperature than the inner chamber. in embodiments; The process additionally includes providing multiple columns where the exit end of a first column is in direct fluid contact with the entry end of a second column. Operation and monitoring of the purification column

— 0 5 — in embodiments; Samples from the sampling ports may include due to the purification resin in the column; die liquid from the acetic acid stream in the column; or both. The arrangement of the sampling ports allows samples to be obtained at discrete points through the resin bed. The sampling port may also be located near the final purified acetic acid stream produced by the column. Determining the levels of impurities present in a sample necessarily depends on the type of sample to be analyzed. Liquid sample control is facilitated with gas chromatographic (GC) and dle high pressure liquid chromatography (01 PLC) 6 which is understood to include a “normal phase”; Inverse phase » ion exclusion ‘ ion pair » exclusion 0 size » ion exchange and ion chromatographic techniques easily understood by one with even the slightest skill in the art. Any form that has a suitable reagent may be used. likewise; Resin samples may be extracted and/or digested to allow for various chromatographic techniques; and/or may be analyzed by wet chemical techniques; atomic absorption analysis; which may include analysis of inductively coupled plasma (ICP) coupled plasma, ICP-MS spectroscopy and/or etc. in embodiment; cle 15 resin may be analyzed using OX ray fluorescence techniques as is readily understood by one with minimal skill in the art. in embodiments; Samples may be analyzed for halogens; Or iodide and/or various transition metals from groups 3 to 12) or typical corrosion metals for the production of acetic acid such as “Cr (Fe) and/or Ala and may also decompose for the presence of the metal or a cleavage with which the active sites of the resin shift 3 which may include silver and/or mercury.In embodiments, a combination of the use of sampling and analysis ports may be used to control column operation, which may include monitoring the ability of the column to remove impurities and divert the flow around the column before the column exhausts retaining or removing properties.

— 1 5 — in embodiments; The impurity concentration of a sample may be compared with a predetermined impurity concentration value that indicates whether or not the refining resin is working or has become depleted. This information can be combined with the location of the sample port such that the impurity concentration of the sample indicates depletion of the refining resin at a point in the column corresponding to the location of the sample port from which the sample is obtained.

in embodiments; A resin depletes when it has been able for a longer period to purify the acetic acid to an acceptable level. in embodiments; A purification resin is considered “run out” when the acetic acid in contact with this resin has an iodide concentration greater than 100 ea bwt; a Cr Fe and/or Ni concentration greater than 500 ea bwt; or a union thereof.

In addition to that; in embodiments; A sample of resin containing more than or equal to 0 about 10 wt 7 of impurities is also deemed to be insufficient for the purposes herein stated. however; It is understood that these levels only reflect current requirements for the acetic acid product; Any of these levels may be used. Furthermore it; The analysed (identified) impurities may be different from the iodide and JST metals on the basis of the current applied to the column. In embodiments; denotes a passive column as determined by means of a final purified acetic acid sample 5 which has a doping pattern above an acceptable level; may result in flow through the specified column which is stopped and/or shifted by an appropriate column. In embodiments "; the swatches' progression through the column may be used to determine the rate at which the column becomes exhausted; therefore gold may be used by life expectancy or otherwise to control the Use of the column in the process.In one embodiment, a depleted resin setting near the end of the column, but 0 and not Lad in the final purified acetic acid, may be used to stop or otherwise divert the flow around the column to allow for resin replacement and/or resin regeneration.In an embodiment Once the flow of acetic acid through the column has ceased, the resin may be regenerated.In embodiments“regeneration of the spent resin” includes removing at least a portion of the waste resin from the column and refilling at least a portion of the column with an active purification resin.In embodiments, a section includes

— 2 5 — Least of the active resin used to refill the column A previously spent resin that has been regenerated into an active purification resin. in embodiments; At least part of the oleophobic resin is regenerated into the active purification resin inside the column; Lad ad) referred to as an on-site renewal. Resin regeneration depends on the type of resin and the impurities to be removed. Regeneration processes involve contact of the resin with solvents; suitable reagents; and/or etc. Charge the column with resin as shown in Figure 5; in embodiments»; Jodi method or process 500 steps providing a column according to any one or combination of embodiments declared herein comprising an inner chamber 2. The process additionally involves a column comprising one or more sample ports arranged between column 0 inlet and column exit; At least one sample port includes a liquid sample port; solid sample port; or both; And open at least one sample port 505. The method or process then involves directing an amount of refining resin into the inner chamber sufficient to fill a section of the inner chamber 504. In embodiments; Column filling involves Mie opening at least one sample. in embodiments; Sample ports may be used to wash the resin to remove steam from the resin; 5 To purge the inner chamber with inert gas while charging the resin; and/or etc. in embodiments; The resin may be placed in the column in a dry or wet form by either manually transferring the resin to the top of the column or pumping a slurry into the column. in embodiments; The resin may be supplied as a slurry in a container; For example, carry a liquid »; tank truck; Or Le Jaa rail fluid 3 Jag to the column by means of compressed air. accordingly; In embodiments, a lower outlet of a container comprising a slurry comprising the refining resin is placed in fluid contact with the inner chamber. Thereafter pressure is applied to the top space of the container in an amount sufficient to pneumatically transfer at least a portion of the slurry from the container to the inner chamber 506. In embodiments; After the resin is pneumatically transferred to the column by pumping or by compressing the container; Alia water) or AT solvent is added to the container and transfers are repeated

— 3 5 — to ensure the transfer of all resin essential. before and/or during transfer of the resin; In Embodiments the column and/or containers are purged with nitrogen or another inert gas to remove oxygen 508. In Embodiments; The resin is then backwashed 510 with a fluid (Jud typically water or solvent Al) to remove particles, foreign matter, and traces of production. Washing continues for at least 60 minutes 518. Backwashing is sent to waste or otherwise recycled as appropriate. May be Wash times are 1 hour or “AST” at relatively high flow rates to ensure even distribution of the resin within the column and to prevent pockets in the resin. The wash may then be removed from the resin by applying pressure to the top of column 512 with nitrogen, etc.; and maintaining pressure until inflation Gas through the outlet of the column, indicating that essentially all washing has been removed. The resin may be back-flushed, this time only with acetic acid 514. In embodiments, the acid back-flushes at a relatively slow rate, with the acid flowing into the base of the column of Less than 0.05 or less than 0.04 layer volumes JS min 516. Reverse thrust may be conducted until all vapor in the column has been displaced by liquid.In embodiments JI at least some of the vapor through one or more ports Open sample 5 in embodiments; Slay initially and only from chamber the interior is resin-lined to allow the resin to swell; which in embodiments may be as much as 740 or more when the resin is exchanged from water to acetic acid. Once the resin is backwashed; The column may be brought into use by directing an acetic acid stream having a first impurity concentration from the inlet end to the exit end at a purification temperature and flow rate sufficient to produce a purified acetic acid stream having a second impurity concentration at the outlet end 0 less than the first impurity concentration 520. As is evident from the figures and context provided above. Visualize a variety of embodiments: embodiment 1. process; These include: (a) providing a curing column with an inner chamber containing an active purification resin located between the column inlet and column outlet; The column additionally includes one or more sample ports arranged between

— 4 5 — shaft inlet and shaft outlet; Mie sampler includes at least one liquid sample port; Mic sample dba or both; and (b) the acetic acid stream having a first concentration of impurities flows through the column at a temperature and flow rate sufficient to produce a purified acetic acid stream at the outlet of the column having a second impurity concentration; If found; which is lower than the first concentration. embodiment 2. Operation according to embodiment 1; Additional include at least one sample port opening. embodiment 3. Operation according to embodiment 1 or 2; Where the impurity includes iodine; chromium; nickel iron; or a union thereof. embodiment 4. The operation according to any one of embodiments 1 through 3; The purification resin includes 0 nS strong netic acid; The ion exchange resin has about at least 71 active sites in the form of silver or mercury. Embodiment 5. The process according to any one of Embodiments 1 to 4 where the temperature is at least about 50°C. Embodiment 6. The process according to any one of Embodiments 1 to 5; includes additionally obtaining 5 samples of the purification resin through a solid sample port at least one liquid sample of the acetic acid stream in the column through at least one liquid die port; or a combination thereof; and determination of the impurity concentration in at least one sample. Gla chromatography Me pressure liquid chromatography atomic absorption inductively coupled 0 plasma spectrometer mass spectrometry X-ray fluorescence spectrometry or a combination thereof Embodiment 8. The process according to Embodiment 6 or Embodiment 7 additionally includes comparison of the impurity concentration of a sample At least one with a pre-defined impurity concentration value and specifying if the impurity concentration of

— 5 5 —

Sample indicates depletion of the purification resin at a point in the column corresponding to the location of the sample port from which the sample is obtained.

Embodiment 9. The process according to any one of Embodiments 1 through 8; Additional include stops the flow of acetic acid through the column.

Embodiment 10. Process according to any one of Embodiments 1 through 9; where acid flow stops

plastic before basically running out of all the purification resin (Jail) in the column.

Embodiment 11. The process according to either of Embodiments 1 to 10) includes additionally the provision of a second column comprising an inner chamber containing active purifying resin located between the inlet of a second column and the outlet of a second column and the flow of an acetic acid stream having a first concentration of impurities through the second column at

0 temperature and flow rate sufficient to produce the purified acetic acid stream at the outlet of the second column having the second concentration of impurities”; If found; which is lower than the first concentration.

Embodiment 12. Process according to any one of Embodiments 1 through 11; Additional include regeneration of at least a portion of the spent resin and completion of the acetic acid stream flow through the column to produce a purified acetic acid stream.

Exemplation 13. Process according to Exemplation 12 where the spent resin regeneration comprises removal of at least a portion of the spent resin from the column and refilling of at least a portion of the column with active refining resin.

Exhibit 14. The process according to Embodiments 12 or 13 where at least a portion of the active resin used to refill the column comprises previously spent resin that has been regenerated into a refining resin

active.

Embodiment 15. The process according to either of Embodiments 2 through 14 whereby at least a portion of the spent resin is regenerated into the in-column active purification resin. Embodiment 16. Process includes:

— 6 5 — (a) provide a process tool shaft comprising an inner chamber enclosed by several radially arranged sides around a central axis and having an entry end in fluid contact with; longitudinally separated from; exit end through the inner chamber; (b) To direct an amount of purification resin into the inner chamber sufficient to fill a section of the inner chamber; (c) the flow of an aqueous wash fluid from the outlet end through the inner chamber to the inlet end at a flow rate and for a period of time sufficient to wash and/or remove particulate matter from the refining resin; and (d) an acetic acid stream having a first concentration of impurities flows through the column at a sufficient temperature and flow rate to produce a purified acetic acid stream at the exit of the column that has a second impurity concentration, 0 if ang, which is lower than the first concentration. embodiment 17. Operation according to embodiment 16; where the column includes one or more sample ports arranged between the column inlet and column outlet; At least one sample port includes Mie liquid sample; solid sample port; or both; The process additionally includes opening at least one die port. embodiment 18. Operation according to embodiment 16 or embodiment 17; Where the aqueous washer fluid 5 flows for at least 60 minutes. Embodiment 19. The process according to any one of Embodiments 16 to 18; It additionally includes directing a quantity of inert gas to the column inlet in a quantity; and at sufficient pressure to obtain an inert gas flow through the exit end after step (c). Embodiment 20. Process according to any one of Embodiments 16 to 19; Jai additionally directs 0 reverse thrust flow from acetic acid to the exit end at flow rate; And for a period of time sufficient to remove essentially all the steam from the inner chamber.

— 7 5 — embodiment 21. Process according to embodiment 20 wherein the backflow flow rate of acetic acid is less than or equal to Mss 0.05 of the bed volumes in dada and the time period Jal is of or equal to about 30 min. Embodiment 22. Process according to any one of Embodiments 16 to 21; Where said routing of the refining resin to the inner chamber includes the provision of a fluid connection between the inner chamber and a bottom outlet of a container containing the slurry containing the refining resin; and applying pressure to the upper space of the container of sufficient quantity to pneumatically transfer at least a portion of the slurry from the container to the inner chamber. Embodiment 23. Process according to any one of Embodiments 16 to 22; Include additional disinfection 0 inner chamber; upper void of the container; or both with an amount of dels gas such that the inner chamber and/or the upper space comprises less than 1 wt 7 oxygen prior to said routing of the purification resin to the inner chamber. Embodiment 24. Process according to any one of Embodiments 16 to 23; Where the impurity includes iodine; chromium; nickel iron; or union thereof; Where the purification resin includes large retinal acid; 5 strong; The ion exchange resin has about (JV) 71 active sites in the form of silver or mercury; where the temperature is at least about 50°C; or a combination thereof. Embodiment 25. Process according to either of Embodiments 16 to 23; where the impurity includes iodine; chromium; nickel; iron; or a combination thereof; where the refining resin includes acid Large lattice; strong; ion exchange resin having at least about 71 active sites in the form of silver or mercury; where 0 temperature is at least about 50"C; or a union thereof. Embodiment 26. Process according to any one of Embodiments 1 through 15; wherein the provision of the column having an inner chamber containing an active purification resin is located between the column inlet and column outlet; According to any one of Embodiments 16 through 25.

— 8 5 — embodiment 27. A process involving at least one daly member selected from the group formed by methanol; dimethyl ether; methyl acetate in the presence of 0.1 to less than 14 wt 7 water; catalyst (cag) methyl iodide and lithium iodide; To form a reaction medium comprising acetic acid in (Jeli 5 medium Separate Je tal) into a liquid recycle stream and a steam product stream ¢ Separate the vapor product stream in up to two distillation columns in a prepurification series to produce a crude acid product comprising acetic acid Includes lithium cations; contact of the crude acetic acid product with a cation exchanger in the acid form within a pretreatment to produce an intermediate acid product; 0 and contact of an acetic acid intermediate product with a metal exchange ion exchange resin having acid cation exchange sites within a second treatment device to produce purified acetic acid; where the connection is within lal the first handler, the second handler tool; or both according to any one of Embodiments 1 through 15. Embodiment 28. A process comprising: cryolization of at least one member selected from the group formed by methanol; gla methyl “off” and methyl acetate in the presence of 0.1 to less than 14 wt 7 water; catalyst (cag) methyl iodide and lithium iodide; to form a reaction medium comprising acetic acid in a reactor; separation of the reaction medium into a liquid recycle stream and a vapor product stream; Separation of the vapor product stream in up to two distillation columns in a pre-cleaning series to produce a crude acid 0 product comprising acetic acid comprising lithium cations; contact of a crude acetic acid product with a first purification resin comprising a cation exchanger in the acid form within a pretreatment to produce an intermediate acid product; And

— 9 5 — Contact of the acetic acid intermediate product with a second purification resin comprising a metal exchange ion exchange resin having acid cation exchange sites within a second process to produce a purified acetic acid stream; lal first treatment; second processing tool; or both individually include Mie at least one sampling subject through the processing tool side; Obtain a sample of the first purification resin, the second purification resin; liquid due to the stream of acetic acid contained in the curing tool; or union thereof through the corresponding sample port; Determination of impurity concentration in at least one sample. embodiment 29. Operation according to embodiment 27 or embodiment 28; Additional include comparison of the impurity concentration of at least one sample with a predetermined impurity concentration value and determination if an impurity concentration of 0 sample indicates depletion of the refining resin at a point in the curing tool corresponding to the location of the sample port from which the sample is obtained. Embodiment 30. Process according to any one of Embodiments 27 to 29; Additional include stopping the flow of acetic acid through the curing tool before substantially all of the active purification resin in the curing tool has been exhausted; Regeneration of at least a portion of the spent resin according to any one of 5 Embodiments 16 to 26; and complete the acetic acid stream flow through the processing device to produce the purified acetic acid stream. Embodiment 31. Process according to any one of Embodiments 27 to 30; Whereas, the metal-exchange ion exchange resin includes at least 71 strong acid exchange sites occupied by silver. Embodiment 32. Process according to any one of Embodiments 27 to 31; The 0 product includes crude acid up to 10 ppm Lithium. Exhibit 33. The process according to either of Embodiments 27 to 32 where separation of the steam product stream includes:

— 0 6 — distill the vapor product stream into a first distillation column and take a side draw to produce a distilled acetic acid product; And on acetic acid and lithium cations.

Embodiment 34. Process according to any one of Embodiments 27 to 33; Additional includes the step of adding a potassium salt selected from the group consisting of potassium acetate» potassium carbonate; potassium hydroxide to the distilled acetic acid product prior to distillation of the distilled acetic acid product in a second distillation column; At least part of the potassium is removed by the cation exchanger in the acid form.

Embodiment 35. Process according to any one of Embodiments 27 to 34; The crude acetic acid product contacts the cation exchanger at a temperature of 50°C to 120°C.

Embodiment 36. Process according to either one of Embodiments 27 to 35) wherein the acetic acid intermediate product contacts with a metal exchange ion exchange resin at a temperature of 50 °C to 5 °C; or a combination thereof.

Embodiment 37. Process according to any one of Embodiments 27 to 36; Where is the product

Central acetic acid Lithium ion concentration is less than 50 parts per billion.

Embodiment 38. Process according to any one of Embodiments 27 to 37; The acid-form cation exchanger comprises a large lattice resin for the exchange of a strong acid cation in the form of a macroporous or medium-porous acid.

Embodiment 39. Process according to any one of Embodiments 27 to 38; Additional include treatment of the purified acetic acid product with a cation exchange resin to recover any silver; (Gi) Palladium or Rhodium.

— 1 6 — embodiment 40. Operation according to any one of embodiments 27 to 39; Where the concentration of water in the reaction medium is controlled from 0.1 to 5 wt#; based on the total amount of reaction medium present. Embodiment 41. Process according to any one of Embodiments 27 to 40; additionally include the inclusion of a lithium compound selected from the group consisting of capil acetate lithium croxylate compounds; lithium carbonate compounds; lithium hydroxide; and mixtures of it into the reactor to maintain a lithium acetate concentration of 3. 0 to 7 0 and zb" in the medium of Je lal). Embodiment 42; the process according to embodiment 4 [includes additionally: maintaining a hydrogen iodide concentration of 0.1 to 0.3 wt. 7 in the reaction medium; 0 maintaining a rhodium catalyst concentration of 300 and 3000 wt. per million oda in the reaction medium; maintain a water concentration of 0.1 to 4.1 wt7 in the reaction medium; maintain a concentration of methyl acetate from 0.6 to 4.1 wt7 of the reaction medium; or a combination thereof. Embodiment 43. Process according to either embodiment 27 to 42; further includes control of the concentration of butyl acetate in the acetic acid product at or below 10 wppm without removing 5 butyl acetate directly from the acetic acid product. By maintaining the concentration of acetaldehyde at or below 1500 ppm in the reaction medium Exhibit 45. Process according to Exhibit 43 or Exit 44 wherein the concentration of butyl acetate is controlled by controlling the temperature in the reactor from 150 to 250°C. Embodiment 46. Process according to any one of Embodiments 43 to 45; Where the concentration of butyl acetate is controlled by controlling the partial pressure of hydrogen in the reactor from 0.3 to 2 atmospheric.

— 2 6 — embodiment 47. Operation according to any one of embodiments 43 to 45; The concentration of the butyl acetate is controlled by controlling the concentration of the rhodium catalyst from 100 to 3000 w/ppm in the reaction medium. Embodiment 48. The process according to either of Embodiments 27 to 47 further includes controlling the concentration of ethyl iodide in the reaction medium at less than or equal to 750 w/Sa per million. embodiment 49. Operation according to embodiment 48; Cua The concentration of propionic acid in the acetic acid product is less than 250 w/ein per million” without removing the propionic acid directly from the acetic acid product. embodiment 50. Operation according to embodiment 48 or embodiment 49; Wherein ethyl iodide is present in the reaction medium and propionic acid in the acetic acid product in a weight ratio of 1:3 to 2:1. Embodiment 51. Process according to any one of Embodiments 48 to 50; Wherein, acetaldehyde and ethyl iodide are present in the reaction medium in a weight ratio of 1:2 to 1:20. Embodiment 52. Process according to any one of Embodiments 48 to 51; where the concentration of 5 ethanol in the methanol feed in the reactor is less than 150 w/gpm; or a union thereof. Embodiment 53. Process according to any one of Embodiments 48 to 52; Where the concentration of ethyl iodide in the reaction medium is controlled by at least one adjustment of the partial pressure of hydrogen in the ASH reactor the concentration of methyl acetate in the reaction medium; And the concentration of methyl iodide in the medium of Je lal). The thing (Dag) is not restrictive in the property. It is understood that only some embodiments are indicated and described and that it requires the protection of all changes and modifications that came within the spirit of embodiments. It should be understood that when the use of words such as I < “lad gad is desirable” indicates ¢ is preferred better ¢ preferred» more preferred or

the representation used in the description above indicates that the feature also described may be better desired or distinctive; However, they may not be necessary and embodiments lacking the same may be construed as being within the scope of the invention; Scope is limited by the following safeguards. when reading the claims; Means that when words such as Can' ca 'at least one'; or 'at least one section' are used there is no intention to limit the claim to only one clause unless specifically stated to the contrary in the claim. When the and method is used at least" and/or the and element can include a section

and/or an entire clause unless specifically stated otherwise.

Claims (1)

Claims 1- A process that includes: carbonylating one or more members selected from the group consisting of methanol, dimethyl ether and methyl acetate in the presence of 1 to less than 14 by weight of 7 cele Rhodium catalyst 10010077 Methyl iodide and lithium iodide dlithium iodide to form a reaction medium including acetic acid in te lee Separating the reaction medium including acetic acid into liquid recycle stream and ¢vapor product stream Separation of the vapor product stream into two distillation columns in a 0 primary purification series to produce an ald acid product including acetic acid including Lithium cations Connection of acetic acid raw product comprising acetic acid 0 comprising lithium cations with first purification dn resin 0 comprising a cation exchanger in the form of acid within a first treatment device 5 to produce an intermediate acid product; And the contact of the acetic acid intermediate product with a second purification resin that includes a metal exchange ion exchange resin with acid cation exchange sites inside a second treatment device to produce an acetic acid stream. filter first treatment device second treatment device or both separately comprising one or more sampling ports placed through the sla (ula) streatment device including open flow passage A first path between a die inlet inside the treatment device, a flow control element that operates between open mode 5 and a closed position outside the treatment device, and an SB flow path that includes an element Pore element 0010005 located between the sample inlet and the flow control SEI element and operates between an open and a closed position located outside the treatment device first purification resin due second purification resin liquid lal acetic acid in the cttreatment device or a combination thereof through the corresponding sample port; Determination of impurity concentration in at least one sample. 2- The operation according to claim 1; It additionally includes comparing the concentration of impurities of at least one sample with a predetermined impurity concentration value and determining if the concentration of impurities from the sample indicates depletion of purification resin 0 at a point in the sla treatment device corresponding to the location of the sample port from which Get the sample. 3- The process according to Claim 2 additionally includes cig flowing acetic acid through the treatment device before basically exhausting all the active purification 7 resin contained in the treatment device. aud of at least spent resin 5 and continue to flow the acetic acid stream through the treatment tool © to produce the purified acetic acid stream. 4. The process according to claim 1; Where the crude acid product includes up to 10 ppm Li-Ina and/or Cus, the crude acetic acid product contacts the cation exchanger at a temperature from 50"C to 120"C. 0 5 - operation according to claim 1; Where the separation of the vapor product stream includes distilling the vapor product stream in the first Jol distillation column and taking a side draw to produce a distilled acetic acid product; Distillation of the distilled acetic acid product in a second distillation column 25 to produce a crude acid product that includes acetic acid and Jithium cations ad 6. The process according to claim 1; Lilia) includes the step of adding Hil potassium From the group consisting of potassium acetate, potassium carbonate (potassium carbonate and potassium hydroxide) to an acid product Acetic acid distilled before distillation of the distilled acetic acid product in a column 5 second distillation distillation column 560000; where at least aud is removed from the potassium 0 by cation exchanger in acid form. 7. Process pursuant to claim 1; where the acetic acid intermediate product bonds with metal exchange ion exchange resin at 50°C to 85°C; or union thereof; and/or where the acetic acid intermediate product has a lithium ion concentration of less than 0 50 ppb. 5- The process according to claim 1 where the cation exchanger in acid form includes a resin of Strong acid cation exchange large lattice resins in the form of large or medium porous (men pores. 9. Process pursuant to claim 1; Whereas, a metal exchange ion exchange resin comprises a strong acid exchange resin having 71 or more exchange sites occupied by silver. 0 - operation according to claim 1; Additional include dallas, an acetic acid product purifier with cation exchange resin to recover any silver; lily palladium or rhodium 07 1- The process according to claim 1, where the concentration of water in the reaction medium 0 is controlled from 0.1 to 5 weight 7” based on the total amount of reaction medium existing. 2- The process according to claim 1 includes (Lilia) the introduction of a lithium compound selected from the group dithium carboxylates aid dithium acetate consisting of lithium acetate lithium carbonates dithium hydroxide and mixtures of 5 that to the reactor to maintain the lithium acetate concentration from 0.3 to 0.7 wt. in the reaction medium 3- The process pursuant to claim 12; Additional include: Maintaining a concentration of hydrogen iodide from 0.1 to 1.3 wt. 7 in the reaction medium Maintaining a rhodium catalyst concentration of 300 and 3000 w/ppm in the reaction medium Preserving Water concentration from 0.1 to 4.1 wt 7 in reaction medium Je ll or a combination thereof. 14 The process according to claim 1 additionally includes controlling the concentration of butyl acetate in the acetic acid product at 10 wpm or less without removing the butyl acetate directly from the acetic acid product. acetic acid 5. Process pursuant to claim 14; where the concentration of butyl acetate is controlled by maintaining the acetaldehyde concentration at 1500 gia ppm or less in the 5 ¢ reaction medium The temperature in the reactor is controlled from 150 to 250ºC; The partial pressure of hydrogen in the reactor is controlled from 0.3 to 2 atm; The concentration of rhodium catalyst 1100010 is controlled from 100 to 3000 wpm 3a per million in the reaction medium or a combination thereof. 0 16 - operation according to claim 1; Additional controls include controlling the concentration of ethyl iodide in the reaction medium at less than or equal to 750 w/ppm. 7- The process according to Claim 16 (Cua) the concentration of propionic acid in the acetic acid product is less than 250 weight per ppm” without removing the propionic acid directly from the cacetic acid product acid Cus ethyl iodide is present in the reaction medium and propionic acid in the acetic acid product with a weight ratio of 1:3 to ¢2:1 Gua there is acetaldehyde 6 and ethyl iodide ethyl iodide in reaction medium 5 in a weight ratio of 1:2 to 1:20; Where the concentration of ethanol in the methanol feed in the reactor is less than 0 w/ppm; or a union thereof. 8. Process pursuant to claim 17; Where the concentration of ethyl iodide in the reaction medium is controlled by adjusting at least one of the 10 partial pressure of hydrogen in the carbonylating reactor, the concentration of methyl acetate in the reaction medium and the concentration of Methyl iodide is present in the reaction medium reaction media 0 6 9 0 x x & - 4 « A x vas dash to LEY vee s RE EM MG ¢ TEN Woz Hmm ,. £8 Sed « 8 $Y . UNG hae 7 te ry ml 00 NP A 2 3 8 0 1 en) 1 um A] ! A lina to any | 2 wa | YY 8 1 A A 1 Ny 1 : Ye} | l 1 n t = MeOH———1 | J 0 3 : Lhasa 1 : ! \ ¢ £ A 00h EE CQ To / m : © File (Cane 4% Pole) 4 3 A) ¥ . a ty Ste id wn 1 fig — 7 0 — ¥ BAH * DLA 4 YER ~ (WN 0 as SLA 4 anti UN Yea] TET ~~ TY Ae for Neyy YAY vy a “le” form ? 0 7 1 0 H 3: a a H & A pf n a hepa < FEI) { & & A 1 3 ih oa $ * 3 a a l i ! - > according a a z + co d am d l la sml et ¥ ¥ i 7 3 tent) A DA D I i) SN ERE SERRE Sh J x ! A. $ $9 oT ay 5 p iy 0 abta al sr = lee lb 3 a a and jo that a 0 cm eee rel for || DA DH LD AGOUT A L LA DA 5131 £3 i 347 en 5 a 1 0" and a anan ana kA eg 3 pass SI TIO God A Asl La Sam um hi ed - sb sidda sd #1 2 0 2 sr £1 SR iru san | ta oe AA Mr : 5 { $2 a YE a 4 da and "? #Haid AA ¥ EY ~~ ja b 4 . v. Ww VF Ped + A M | SE $y $b Pa I a th say a a m i AYA 8 s ! i § { FON Sama Makkah i § i ! 0 cm hE + form ? b 0 rokh lc talhsin “and 3 3 weer sees BS Pa > 1 pa aa a . 0 i HAT ARRAY ah ah ya ya 2 ah : hi 1 TUN hi 1 TUN ee ee I SI oN £ re Tasleel Sirte SS as S (Se) squirt sala A A 1 A A 7 x Boat Nm xc { L A Ps % HAD SYA I CUTE ae TE 3 Alk — oe SE ma fn Me yd AH - > < A 3 L I L ES - 1 {BA A LINES im LOA Bnd 3? Sir a a rani Ea ' - 1 a 1 a ala a a a ras moa mmm mmm 7 H LE ¥ 1 TT HN #4 i : mr profit mma lag 1 da 1 4 ss i H — i — 1 H m — H H 0 1 1 een od H H 0 1 i Gon fee aa + figure : m to < ja group b 0 8 i provide a column that includes an inner chamber surrounded by many sides i 1 0 luxury iG 3 Ula 3 rest oy 21 3 and arranged radially around a central axis and has an entry end in connection 570 ats: with and separate from; The end of the SoM plaster as the inner chamber. 0 arbitrary cents ye petee tsia Qa a OE TE Th Sel 1 end WEEN R EE TE EE = 4 Column includes one or more sample ports arranged between inlet ape poral >2 and column outlet includes one sample port At least one liquid sample. 2A EET g hes oe lat a a a l a dda sample port or both and at least one sample port opening. | Purification of the inner chamber with an amount of gas |._) to 11 pulp “Nl Se Amal” so that the inner chamber includes less than t a jana to the entrance end with a sufficient quantity to fill the . 1 1 Weight of # oxygen before the mentioned directive, La IEA ih Jal 5 for GT at 8 at least section of the inner chamber. Pd resin to the end of the entry. ee mm | ee mm | 5 AH and TAQD 1 Km TEL A 4 Yam 24 1 REE and a mesconic corridor for the internal 1 2 gs to the end of the entry ysl 3 zymlia and at a caffeine flow rate of 1 ara and 3 1 7 4 r and WR os wy ¥ voy { jab . ERY ane & Sa das 1 ort a l a l ad ang and remove chips from fe ee od = 7 on TNA l l l l l resin; And to apply the pressure of the upper vacuum of the container in the amount of TU 1 v “ap Sg oy PPR a REN a German fluid od enough Jail divided on JB t Hilly LEE Uta LY | i 1a 3 2: a wa 1. a 5 for me a at least before ْ | BEY Pa yx is the compressed a from IE ty nosed { | 1 container to the inner end. SUSUR 3 wy 5 a aw ta um and EINE = the amount of Lala Je we to the max of the column by the amount of 3 when pressing Sad i read + Al 1. On the aie high NS es Lad The intent of the sata avi to get the ambient stream through the egress end: | For a thousand i Sa dal Had ean ES on the upper AR Sa bans PEAS THE Le MAT JE container 8 + a quantity of inert gas: so that it includes era 7 a for RYT yasa | The upper thighs are lower to 1 with the direction of the reverse thrust flow from the acid above to the exit end. A + SIE 8 4 1 and B at a flow rate: and for a period of time sufficient to remove essentially all A from the aforementioned production of A and R 3 LN: that is, only that from A to the inner g stone. Go to the end of the entry. Grouting TE EEE aa: SA reverse thrust Jie flow rate less than or 15 d3 equal to 2 sya of layer sizes per minute a 1 RT EE EET for 1]| An atom less than or equal to about MET directs the flow of an atic eid having an impurity concentration first from the entry end to the Ae EAM dad. 5 d oY i a . 0 yo cod a shan to exit c at a sufficient purification temperature and flow rate to produce “loti geet acid” as an EN HSE. The cod and i Las has a second aspect concentration at the end of z that is less than the concentration of at GER - form e Sued Authority for Intellectual Property RE .¥ + \ A 0 § 8 Ss o + < M SNE A J > E K J TE I UN BE Ca a a a ww > Ld Ed H Ed - 2 Ld, provided that the annual financial consideration is paid for the patent and that it is not null and void for violating any of the provisions of the patent system, layout designs of integrated circuits, plant varieties and industrial designs, or its implementing regulations. Ad Issued by + bb 0.b The Saudi Authority for Intellectual Property > > > This is PO Box 1011 .| for ria 1*1 v= ; Kingdom | Arabic | For Saudi Arabia, SAIP@SAIP.GOV.SA