SA517382040B1 - Process to Control HI Concentration in Residuum Stream - 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

Process to Control HI Concentration in Residuum Stream Full Description Background The production of acetic acid by carbonylation involves the continuous reaction of methanol and carbon monoxide in the presence of catalyst in a reactor. The reaction mixture in the reactor includes a transition metal; which may be a group 9 metal; which may be 1801000 and/or rhodium 5 or nickel; It may additionally include one or more cole solvents and various stabilizers; covalent catalysts; reinforcers»; etc. Reaction mixtures known in the art may include acetic acid 0 methyl acetate methyl iodide chydrogen iodide hydrogen iodide promoter etc. There is a complex network of interdependent equilibria involving the 0 liquid acetic acid reaction components within the reaction mixture 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. The impurities present in acetic acid include permanganate reducing compounds (PRCs), for example, acetaldehyde. Or it dissociates in a solvent as chydriodic acid in the reaction mixture according to the various production programs. however; HIE corrodes metals in the form of diag Je Various challenges in the production of acetic acid -acetic acid Attempts in art aim to reduce hydrogen iodide HI hydrogen iodide outside 0 reactor; With the ultimate goal of removing it from the reactor. Examples include processes involving injection of methanol into a distillation column with the purported purpose of reacting methanol with hydrogen iodide

HI hydrogen iodide contained therein to form methyl iodide methyl iodide and water; (See Japanese Patent No. 72712-2000 (Japanese Application No. 244590-10; Filed August 31, 1998; their contents and disclosures are incorporated herein by reference in their entirety.) However, operations relate to reducing HI to reduce or eliminate problems with JST failed to realize the benefits associated with dala HI concentrations 5 outside the reactor There is a dala for controlling HI concentrations within particular ranges in various aspects of the acetic acid production process General description of the invention in embodiments according to the present disclosure; include Methods for producing acetic acid Processes where current densities are controlled to ensure separation of critical phases AY acetaldehyde 0 and other impurities In embodiments hydrogen iodide HI iodide may be produced and control of highest lower concentration and/or within a concentration range selected above the minimum concentration in one or more streams outside the krill reactor.In embodiments, this HI hydrogen iodide allows the formation of dimethyl ether within the disclosed purification processes that facilitate phase separation and reduction Amount of methyl iodide lost as waste. particulary; Various distillation stream densities may be controlled during a stream distillation within the .aldehyde removal process in embodiments; The process includes providing a feed stream of initial density comprising water; acetic acid; at least one PRC “methyl acetate”; and greater than the weight of 7 methyl iodide to a distillation column comprising distillation zone and 0 bottom basin zone; distillation of the feed stream at sufficient pressure and temperature to produce an overhead stream of second density and comprising greater than about 40 wt. 7 of methyl iodide (PRC); at least one methyl iodide; where the percentage decreases between the first density and the second density, which is from 720 to 735. In embodiments; The process includes the steps:

(a) Krill media Jelds comprising a substrate feed stream comprising methanol; imethyl acetate “dimethyl ether” or mixtures thereof; cola catalyst rhodium iodide salt and methyl iodide methyl iodide in an acetic acid formation reactor 80616;

(b) Distillation of a stream derived from the reaction medium in a first column to produce an acetic acid bypass stream, which is further purified to produce a product acetic acid stream; a first upper stream comprising methyl iodide; cele acetic acid methyl acetate and at least one 0806;

(c) Biphasic separation of the first upper stream into a light phase comprising methyl iodide

0 methyl iodide ¢ methyl acetate (acetic acid) at least one methyl acetate ¢ PRC; greater than about 30 wt 7 water; and a heavy phase comprising cole acetic acid PRC “methyl acetate 806006 acid” at least one and greater than about 30 Le of methyl iodide;

(d) direct a second column feed stream containing or derived from the heavy phase to a distillation column

5 second including dripping area and bottom basin area;

(e) Distillation of the second column feed stream at a pressure and temperature sufficient to produce a second overhead stream of second density and comprising greater than 40 wt. 7 methyl iodide of at least one 5 methyl iodide PRC; and a lagging stream flowing from a lower basin area having a third density which is less than the first density and which includes greater than about 0.1 £035 cole where the percentage decreases

between the first density and the second density being 720 to 735;

(f) Extraction of at least a section of the upper stream of the second column comprising at least one methyl iodide iodide PRC 5 Jil with water to produce a water stream comprising one PRC on JN and a purified sale stream (raffinate) having a fourth density which is greater than the first; and which includes greater than about 90 by weight of 7 methyl iodide; and

(g) Direct at least the Jol portion of the refinery stream back to the distillation zone of the second distillation column. 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. Brief Explanation of the Drawings Figure 1: It is a schematic diagram of a process for the production of acetic acid according to the embodiment; Figure 2: is a schematic diagram of the 4085 alternate process according to the embodiment; Figure 3: is a cross-sectional drawing of a second distillation column according to embodiment 3 0 1 Figure 4: is a cross-sectional drawing of N A liquid redistribution of a second distillation column according to embodiment ¢ Figure 5: is a cross-sectional drawing of a liquid redistribution device for a second distillation column according to for another embodiment; and Fig. 6 is a cross-sectional drawing of a liquid redistributer for a second distillation column according to embodiment CAT 5. Detailed description: In the beginning; It should be noted that in the development of any actual incarnation, various implementation decisions must be made to achieve the particular objectives of the developer; For example, compliance with system-related and work-related restrictions; which varies from implementation to implementation. In addition to that; Processes detected herein may also include components other than those specifically mentioned or referred to; As evident 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"(@bout) (unless it is also already explicitly modified); Then read once

other as not modified unless otherwise specified in the context. Also in the abstract 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; including final points; As mentioned. For example; 'Range from 1 to 10' is read as referring to any and all possible numbers along the string between about 1 and about 10. Hence; Even if the private data points are within range; or even data points that are not in range; clearly defined or refer only to a few particular data points” it is understood that the inventors appreciate and understand that any and all data points within range are specified; and that the inventors have knowledge of the total range and all points within the range. by full description; La including protection elements; The following terms shall have the meanings referred to herein unless otherwise specified. As used in the specification and claims; pall' from (0681) 'inclusive' at (81)". The term and/or (and/or) refers to the blanket case 'and (8110)' and the exclusive case 'or (01)'; used here for brevity For example, a mixture comprising acetic acid and/or methyl acetate may contain acetic acid only methyl asd acetate 5 or both acetic acid. and methyl acetate All percentages are expressed as a percentage by weight (7 wt) based on the total weight of the specified formulation or stream present unless otherwise noted Room temperature 259 °C For purposes herein abbreviated as acetic acid acetic acid as ¢ “AcOH” acetaldehyde is abbreviated as ¢ “AcH” methyl acetate is abbreviated as ¢ “MeAc” methanol is abbreviated as “ 16011/(;

Methyl iodide is abbreviated as “Mel” and carbon monoxide is abbreviated as “00”; Dimethyl ether is abbreviated as “DME” HI refers to whether hydrogen iodide is molecular hydrogen iodide or hydroiodic acid dissociated when at least partially ionized in a polar medium; Typically the medium includes at least some water; unless specified otherwise; The two are referred to interchangeably. unless specified otherwise; The concentration of HI is determined by an acid-base titration using precisely the potentiometric end point; The HI concentration is determined by titration with a standard lithium acetate solution with the potential difference endpoint. It should be understood as 0 for purposes here that the concentration of I is not determined by subtracting the assumed iodide concentration of be associated with measured JBI metals or other non-HF cations from the total 100106 ionic present in the sample. It should be understood that the HI concentration does not indicate the concentration of ion 6 . In particular, the concentration HI refers to the concentration of A as determined by a potential difference titration. This subtraction method is an unreliable and inaccurate method for determining comparatively lower HI hydrogen iodide 5 concentrations eg (less than about 5 wt. 7) due to the fact that it assumes that all cations other than H+ (eg cations from iron dron Fe Nickla 108l 1 Ni Cr Chromium Molybdenum binds exclusively with the iodide anion 100106. In fact, a large part of the metal cations in this process may bind additionally with the acetate anion; Many of these metal cations may have multiple ESE states, which increases the non-0 reliability even further assuming the amount of iodide anion that can bind with these metals.Finally these methods give an unreliable determination of the hydrogen iodide concentration actual HI iodide”; particularly in terms of being able to perform a simple titration that directly represents the concentration of HI hydrogen iodide.

For the purposes stated cla “(Overhead) lel distillation column refers to at least one of the lower boiling condensable fractions that exits at or near the apex (ie, nearly from the apex); of the distillation column and/or the condensate form of this stream or composition. Clearly. All fractions are ultimately condensable; also for this purpose used here. A condensable fraction is condensable under conditions present in the process as readily understood to one skilled in the art. Examples of non-condensable fractions may include nitrogen; hydrogen; etc. Likewise, the upper stream may be taken only below the uppermost upper outlet of a distillation column, for example JE where the lowest boiling fraction is a non-condensable stream or represents a trace stream" as is readily understood by one of the slightest skill

in Art.

Distillation column lag refers to one or more higher boiling fractions that exit at or near the bottom of the distillation column; It is also referred to here as the flow from the lower basin to the shaft. It must be understood that the retarder can only be taken up to the very bottom outlet of the distillation column; For example JO where the very bottom fraction is produced by the column being salt; unusable tar; A solid waste product or stream in a small amount as is easily understood by one having the slightest skill in the art.

For objects in use (ba) Distillation columns include a dripping area and a lower pan area. The dripping zone includes everything above the basin area (lin) ie between the bottom pan area (Lady) of the column. For objects in use cla refers to the bottom pan area for the lower section of the distillation column where the liquid reservoir for the higher boiling components (eg bottom of the distillation column) is located from which the lower or back stream flows on exit from the column The lower basin area may include reboilers;

0 control equipment; etc.

It should be understood that the terms 'passages' 'flow paths' 'flow conduits' etc. in relation to the internal components of a distillation column are used interchangeably to refer to openings; tubes; channels » fissures; banks, etc.; which are placed through and/or which provide a path for liquid and/or vapor to move from one side of the internal component to the other side of the component

5 procedure. Examples of tracks placed during construction are such as the liquid spreader of a distillation column

Drainage holes include “drain tubes”; drainage cracks etc.; that allow fluid to flow through the masonry from one side to the other. Mean retention time is determined as the sum total of all volume of liquid retained for a given phase within the distillation zone divided by the average flow rate for that phase through the distillation zone. This may include collection tools; distribution tools; etc.; In addition to the liquid on the trays »; daly downpipes; and/or within randomly or orderly packed layer segments. It is necessary that the mean time f of the total retention of the feed stream in the distillation zone of the column is less than (and does not denote) the total retention time of the feed stream within the distillation column. Retention time 0 Total distillation column stream is the sum of both the total retention time of the feed stream in the distillation zone and the total retention time of the feed stream in the lower basin area of the column. As used herein, the internal components located within the distillation zone of the column include packing sectors”; Distributors (ila) collectors (Jil) redistributors (iba trays; clas de etc. As used here the mass flow rate is indicated in kg/hr unless otherwise specified cell) 5 and may be specified Directly or calculated from volumetric measurements. Depending on the use here, a acrylate reactant is any substance that reacts with carbon monoxide under reaction conditions to produce acetic acid, or the product in question. The acrylate reactant includes methanol, methyl acetate methyl acetate “methyl formate” dimethyl ether etc. As used herein when at least part of an additional gal stream or composition is treated by recycling or forwarding back to the AT section of the Operation; it is understood that '(portion) refers to an entire fraction of the stream or composition. Sg in another way; (Portion) aud refers to a portion of the total mass flow of the stream or the total portion of the composition. It is clearly understood that "aud" of the current or combination does not refer to the selected components contained herein. Accordingly, it does not include

Recycle a section of the stream Any process in which the components in the stream at the original point do not exist at the offset point. when a portion of the stream or composition is directly recycled or otherwise directed to the displacement point; The mass of each component originally present in the stream at the point of displacement exists in the same relative proportions. A portion of the stream or composition which is indirectly recycled or otherwise directed may combine with other streams; also the absolute mass of each component present in the original stream is still present at the point of displacement; And changes in the overall composition are the result of the union of a particular stream with others. As used herein may include a stream or combination 'derived from another stream' that is all current 0 or may include less than all of the individual components initially present in the stream. accordingly; A stream derived from another stream does not necessarily require recycling the mass of each component originally present in the stream at the point of displacement. Thus a stream or composition 'derived' from a specific stream may include a stream that undergoes additional treatment or purification prior to displacement. For example, a stream that distills before being recycled to the final displacement point is derived from the original stream. For purposes used cbs are reducing compounds Permanganates (PRCS) include “butyraldehyde” methyl ethyl ketone “acetone acetaldehyde” “2-ethyl butyraldehyde (2- ethyl crotonaldehyde .crotonaldehyde etc.) and aldol condensation products transient 5 aldol thereof. For used purposes (la) is determined by the density on a stream at an average temperature of a specified stream under 0 process conditions; unless specified otherwise. distillation column at an average temperature of 50"C; for purposes used here La is to determine the relative increases and decreases between the densities of the two streams" The first stream density is set at 60"C (the average process temperature corresponding to the specified stream) and the second stream density is set at 50" (corresponding average process temperature)

— 1 1 — for the specified current). For the purposes used here, the denaturing ratio decreases between the first density and the second density determined according to the equation |: (first density - second density)/ first density x 7100 (1) For the purposes used here, the denaturing ratio increases between the first density and the second density, which is the absolute value of the specified value In equation (a), that is, as soon as the increase in density from the first density to the second density will produce a negative number according to equation (a), the absolute value of the negative result obtained is stated.HI has physical properties that are generally considered harmful For the different process components that are typically found in commercial acetic acid processes due to corrosion problems. Specifically, 0 is considered to be present only in “la” distillation columns, especially for heat exchange surfaces, such as reboilers, etc., while it is necessary for HI to be present within The krill reactor used to produce 0 acetic acid during “Monsanto” and AO® technology processes Many applications in the art concern the reduction and/or elimination of HI in streams outside the krill reactor. However; It is found that when HI is present at T specific substrates within one or more streams 5 output of the krill reactor for acetic acid process acid 80816; One or more previously unknown benefits are achieved. For example; It is suggested that ALA is effective in forming dimethyl ether (DME) under the conditions in an aldehyde removal system (ARS) distillation column according to the balance equation: HI (cat) CH30H = CH30CH3 + H20 20 2 CH30H + CH3COOH = CH3COOCH3 + H20 Hi(aq) = CH3I + 0 + 0113011

— 1 2 —

CH30H + CH3l C 011300113 + HI Methyl iodide This dimethyl ether acts unexpectedly to reduce the concentration of the aldehyde as shown in the patent in the waste stream of the liquid produced by the US No. 7223883 7223886 and 8076507; etc; They are all incorporated here for reference. Accordingly, prior art disclosures relate to HE removal outside the reactor that fails to achieve the benefits that flow from HE concentrations according to the embodiments shown here. The embodiments shown here further provide methods by which the formation of HI within an aldehyde removal system distillation column and the concentration of HI within this distillation column basin may be controlled by controlling the concentration of HI in the distillation column basin. (ARS) The amount of DME produced in the column may be controlled to obtain the benefits flowing from it. In embodiments the process includes providing a feed stream having a first density comprising cele acetic acid 806106; methyl acetate at least one methyl acetate ¢ PRC; and greater than about 30 wt 7 methyl iodide to a distillation column comprising a distillation zone and a lower basin area; and the feed stream distilled at a pressure and temperature sufficient to produce an upper stream of second density and comprising Greater than about 40 wt 7 methyl iodide and one PRC 5 on Gua (BY) The percentage between the first density and the second density decreases at 50"C to be from 720 to 735. Process from Claim 1 where is The sensitized gravity of the second density relative to water is from 5 to 1.6 at 50"C. In embodiments; the residual stream that flows from an area a low basin has a third density of which 0 is lower than the first density; It contains more than about 0.1 70055 water. in embodiments; The residual current has a greater than or equal to about 0.11 wt. in embodiments; The percentage decreases between the first density and the third density, which is from 75 to 710.

in embodiments; Distillation of the feed stream produces a first liquid phase comprising greater than about 50 by weight of water and a second liquid phase comprising greater than about 50 by weight of methyl jas iodide Distillation zone; As the distillation zones include many internal components; Each has a component liquid retention volume; Where the dimensions of each of the internal components are determined and arranged so that

The mean retention time for the first liquid phase and the mean retention time for the second liquid phase in each of the ingredient liquid retention volumes is less than about 30 minutes. in embodiments; At least one internal component is dimensioned and arranged such that the mean retention time of the second liquid phase is greater than or equal to the mean retention time of the first liquid phase in the corresponding component fluid retention volume.

in embodiments; The process additionally involves channeling an apical surge stream comprising

0 -_Water in the dripping zone at an ALS flow rate that is greater than or equal to 70.1 mass flow rate of the feed stream. in embodiments; The apical impulse current includes a section of the lower lagging current.

in embodiments; The process additionally includes downstream surge routing comprising

‎acetic acid‎ acetic acid; cole or both in a lower basin region at a mass flow rate

5 which is greater than or equal to 70.1 for the mass flow rate of the feed stream. in embodiments; includes

The upstream is on dimethyl ether. in embodiments; is a dimeric ether concentration

methyl dimethyl ether in the upper stream from 0.1 wt7 to 50 wt72; Depending on the total amount of overhead current present.

in embodiments; The process comprises creel steps amidst a reaction comprising a feed stream

20 reactant containing methanol Methanol acetate Al-761 Methyl acetate; raised

dimethyl ether or mixtures thereof; cole radium catalyst rhodium salt

iodide nag and methyl iodide to form acetic acid acid 806116; distillation

A stream is derived from the reaction medium in a first column to produce an acetic side stream

which is further purified to produce a product acetic acid stream; And the first upper stream includes

methyl iodide 25 ele acetic acid methyl acetate

cacetate and at least one 0406; biphasic separation of the first upper stream into a light phase comprising methyl iodide ¢ acetic acid 806116; methyl acetate 16 methyl acetate » PRC at least one; and greater than about 30 wt 7 cole and a heavy phase comprising at least one cole acetic acid methyl acetate PRC (methyl acetate); and greater than about 30 wt 7 smethyl iodide shaft feed stream steering a second comprising or derived from the heavy phase to a second distillation column comprising a distillation zone and a lower basin region; the second column feed stream distilled at a pressure and temperature sufficient to produce a second upper stream of a second density and wherein it contains greater than 40 by weight of 7 methyl iodide at least one PRC; and a lag stream flowing from a lower basin area having a third density which is 0 less than the first density; and where it contains greater than about 0.1 by 7 water; where the percentage between the first density and the second density which is 720 decreases to 735; extract at least a portion of the second column top stream comprising at least aly PRC 5 methyl iodide with water to produce an aqueous drain stream comprising at least one PRC; and a purified material stream comprising greater than about 90 wt 7 methyl iodide Methyl iodide has a fourth density that is greater than 5 first condensation; and direct at least a first section of the filter material stream back to the distillation zone of the second distillation column.

in embodiments; The specific gravity of the second density with respect to water is from 1.15 to 1.6 at 50"C. In embodiments, the percentage between density I and IV is increased from 710 to 720. In embodiments, the process further includes steering of a peak impulse stream comprising 0 water to the distillation zone of the second distillation column at a mass flow rate greater than or equal to about 1 of the mass flow rate of the second column feed stream where the apical rush stream comprises a section of the lower residual stream; at a section (BY) of the first section of the filter material stream; Department of

light phase separated from the first upper stream; or unite from it.

— 5 1 — in embodiments; The process further includes directing a bottom surge stream comprising acetic acid acid 80600; water; or both to the lower trough area of the second distillation column at an ABS flow rate greater than or equal to about 70.1 of the mass flow rate of the second column feed stream. in embodiments; The upper stream of the second column comprises dimethyl ether 5 in embodiments; The process (Lila) involves directing a second section of the filter stream comprising 100 106 methyl iodide and dimethyl ether back to the reaction medium. in embodiments; The mass flow rate of the first section of the fillet stream is greater than or equal to the mass flow rate of the second section of the fillet stream. in embodiments; The bottom temperature of the second distillation column is about 70 C to about 100 "C; the top temperature of the second distillation column 10 C is about 0 C to about 60" C; The pressure of the second distillation column is from atmospheric pressure to about 700 kPa higher than atmospheric pressure; or a union thereof. Acetic acid production system The processes for producing acetic acid through acetic acid through acetic acid can be appropriately divided into three main areas: reaction systems, internal purification systems, and product purification systems. Reaction systems include the krill reactor; blinkers etc. Internal filtration systems include acetic acid product separation systems; light ends recovery; Aldehyde hs removal systems Product purification systems include drying columns “resin layers” etc. directed to purify acetic acid 0 800 acetic acid to produce the final product. Examples of processes suitable for producing a distillation column feed stream according to the present disclosure include those described in US Patent No.: 3,769,329; US Patent No.: 6 US Patent No.: 4,039,395; US Patent No.: 4,255,591; US Patent No.: 4,615,806; US Patent No.: 5001259; patent

US No: 5026908; US Patent No.: 5,144,068; US Patent (ad) 7 US Patent No.: 5334755; US Patent No.: 5,625,095; US Patent No.: 5,653,853; US Patent No.: 5,683,492; US Patent No.: 5,831,120; US Patent No.: 5,227,520; US Patent (ad) 5 5416237 US Patent No.: 5731252; 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 No.: 6,339,171; US Patent (ad) 8 US Patent No.: 7,208,624; US Patent No.: 7,223,883; US Patent No.: 7,223,886; US Patent No.: 7,271,293; US Patent 0: 7476761; US Patent No.: 7838701 US Patent (ad) 6 US Patent No.: 86076507; US Patent Application No.: 6 US Patent Application No.: 20090036710; US Patent Application No.: 20090259072; US Patent Application No.: 20090062525; US Patent Application No.: 20110288333; US Patent Application No.: 20120090981; US Patent Application No.: 2010078012; US Patent Application No.: 20130116470; US Patent Application No.: 20130261334; US Patent Application No.: 20130264186; US Patent Application No.: 5 US Patent Application No.: 20130261334; US Patent Application No.: 20130281735; European Patent No.: 0161874; Intl No.: 0 9822420; International Application No.: 0216297; ISBN: 2013137236; etc; merge

For reference, the entire contents are disclosed.

Reaction processes and systems as shown in Figure 1; Processes 100 include directing a methanol —containing feed stream 101 and a feed stream containing 5 carbon monoxide (carbon 01000006- containing feed stream) 102 to a reaction medium

Liquid phase reaction medium (ilu 105 for carbonylation reactor) 104” where agin contact occurs in the presence of the catalyst water; methyl dodide methyl acetate acetic acid iodide salt acetic acid dodide and other reaction medium components for the production of acetic acid HI reaction medium 105 from reactor 104 to flashing 112 through line and is constantly removed 5 this stream may undergo flashing or Low pressure distillation in flash 112 where .113 (line) and other volatile components of the non-volatile components acetic acid aii in the presence of the reaction medium. The volatile components in the reaction medium up through line 122 to the terminals column .0

0 Light 124.

As shown in the figure; The process includes a number of recycling lines in which the various streams are recycled back into the reaction medium from the other parts of the process; The process also includes various steam purge lines; and etc. It is understood that the nozzles and other steam lines are connected to a scrubber with one or more nozzle systems and all condensable components discharged to

The scrubber system is finally recycled back to the krill reactor.

in embodiments; The reaction medium includes a metal catalyst or a group 9 metal catalyst; or the catalyst includes radium000100; nickel and/or iridium in embodiments; The reaction medium includes radium catalyst typically from about 200 to about 5000 parts per million by weight depending on the total weight of the reaction medium.

in embodiments; The reaction medium additionally comprises a halogen-containing catalyst promoter; Typically methyl iodide (Mel) embodiments” The reaction medium comprises greater than or equal to about 5 by weight 7 Mel or from about 5 by weight 7 to about 50 by weight 7 Mel in embodiments; The reaction medium comprises greater than or equal to about 50 by weight 7 ACOH

— 8 1 — in embodiments; The reaction medium includes a final concentration of water 0 in so-called low-water processes; The reaction medium comprises a final concentration of water up to about 14 wt 7. In embodiments; The reaction medium has a final water concentration. in embodiments; the concentration of water in the reaction medium is greater than or equal to 0.1 dais or 0.5 wt#” or 1 Lins or 2 wt#; or 3.5 wt#” or 4 wt#” or 5 wt#” and less than or equal to 10 wt# “7 wt#”; or 6 wt 7. in embodiments; The concentration of the reactor water is from 0.1 to 5 wt#; or 0.2 to 4 wt#; or 1 to 3 wt7” depending on the total amount of reaction medium present. in embodiments; The reaction medium further comprises from about 0.5 7035 to less than 20 by weight 7 of methyl acetate acetate (MeAc) inal. in embodiments»; The reaction medium further comprises hydrogen iodide and one iodide salt or 5ST' typically lithium iodide (I); In an amount sufficient to produce a total ion concentration of 100106 greater than or equal to about 2 wt 7 and less than or equal to about 30 wt 7 from the reaction medium. In the embodiments “the reaction medium additionally comprises hydrogen”; Determined according to the pressure of 5 mole hydrogen present in the reactor. in embodiments; the partial pressure of hydrogen in the reactor is greater than or equal to about 0.7 kPa (0.1 psi) or 3.5 kPa (0.5 pSI) or 6.9 kPa (1 pSI); and less than or equal to about 3 MPa (150 dag) or 689 kPa (100 dag) or 345 kPa (50 dag) or 138 kPa (20 dag) 0 in embodiments”; The temperature of the reactor is any; 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 reactor temperature is greater than or equal to about 0 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 about 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 total reactor pressure is the combined partial pressure of all the reactants; products; and by-products contained 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; Vapor product stream 122 from scintillator 0 112 comprises methyl iodide (acetic acid), methyl iodide, methyl acetate (cL “methyl acetate) and hydrogen iodide in one embodiment Steam product stream 122 comprises acetic acid in an amount of 45 to 5 wt. 7 methyl iodide methyl iodide in an amount of 20 to 50 wt. and water in an amount less than or equal to 15 5 wt?” Depending on the total weight of the steam product stream.In the AT embodiment the steam product stream 2 comprises acetic acid in the amount of from 45 to 75 wt 7 methyl jil iodide iodide of 24 to less than 36 (39) 7 methyl acetate of less than or equal to 9 wt. 7#; and water of less than or equal to 15 wt. #; depending on the total weight of the steam product stream. In embodiments, the stream includes Steam product 122 on acetic acid 0 in an amount of 55 to 75 wt. 7; methyl iodide in an amount of 24 to 35 wt. 7 methyl acet − methyl acetate in an amount of 0.5 to 8 wt.7; slag by 0.5 to 14 wt#. still in other incarnations; Steam product stream 122 comprises acetic acid 0 by 60 to 70 wt 7 methyl iodide 25 to 35 wt 7 methyl iodide 0.5 to 6.5 wt 7 methyl acetate; and water in an amount of 1 5 to 8 wt#. The concentration of acetaldehyde in the vapor product stream may be in the order of 0.005 to 1

wt7» depending on the total weight of the steam product stream, for example from 0.01 to 0.8 wt7; or from 1 to 0.7 wt 7. In some embodiments; Acetaldehyde may exist less than or equal to 1 wt#. Steam product stream 122 may include hydrogen iodide in an amount less than or equal to 1 wt#; Depending on the total weight of the lad product current is less than or equal to 0.5 wt 7 or less than or equal to 0.1 wt 7. Steam product stream 122 may be substantially free of; i.e. containing less than or equal to 0.0001 weight 7; acid 000010016 depending on the total weight of the vapor product stream.

The sale stream 110 liquid recycle stream includes acetic acid as a metal catalyst for corrosion metals; In addition to the various vehicles. in embodiment; Stream 0 Recycling Liquid 110 comprises acetic acid in the amount of 60 to 90 wt. 7 metal catalyst in the amount of 0.01 to 0.5 wt#; corrosion metals (Slag) nickel; Iron 5 (chromium in a total amount of 10 to 2500 wt.eda per million; lithium iodide 100106 lithium by 5 to 20 wt.7; methyl iodide in an amount of 0.5 to 5 wt.7; methyl methyl cali acetate 0.1 to 5 wt#; water 0.1 to 8 wt. 7; acetaldehyde 5 less than or equal to 1 wt” (eg 0.0001 to 1 wt. 7 hydrogen iodide 5 ¢ (acetaldehyde less than or equal to 0.5

7 Die weight) from 0.0001 to 0.5 weight of 7 hydrogen iodide.

Acetic acid product separation processes and systems [acetic acid] recovery of light ends in embodiments; The overhead stream from the flasher 112 is directed as stream 122 to the first distillation column 0 124 (which Load may be referred to as the light ends column or stripper column accordingly; the feed stream directed to the first distillation column is derived from the reaction medium because it undergoes distillation prior to entering the first distillation column Distillation of the feed stream into the light ends column 124 results in a low-boiling first overhead vapor stream 126; hereinafter referred to as the stream first upper 126; acetic stream 800 5 purified acetic acid stream 128. stream 128 is

crude acetic acid stream; which is intrinsically refined. in embodiments; The acetic acid stream 128 is removed as a bypass. Further producing a light-terminal column 124 is a high-boiling residual stream 116 that may undergo further purification and/or may be recycled back into the reaction medium. Each distillation column used in the process may be a conventional distillation column; Ole lamellar column packed column and others. Lamellar columns may include a perforated lamellar column; bubble wrap column; Kittel Tray Column Unidirectional Refining Tray; or a crispy tray column. It is not limited to distillation column material and may include glass; Ceramic metal” or other suitable materials may be used. For the lamellar column; The theoretical platelet count is not particularly limited and depends on the types of component to be separated; It may depend on the component to be separated; may contain up to 500-800 plates; repetitions from 2 to 80; from 5 to 60; from 5 to 50; or more preferably 7 to 5. The distillation column may incorporate the combination of different distillers. For example; A combination of a bubble cap column and a perforated laminate column may be used in addition to a combination of a perforated laminate column and a Las column.

Appropriately the pressure and temperature of the distillation may be selected in the distillation system depending on case 5, for example, the types of target carboxylic acid and types of distillation column, or the target removed from an impurity having a lower boiling point and an impurity having a higher boiling point is selected according to the composition of the feed stream. For example (JU in dlls where acetic acid purification is performed by distillation column; the internal pressure of the distillation column (usually; column top pressure) may be from 0.01 to 1 MPa; say from 0.02 to 0.7 MPa and more preferably 0.05 to 0.5 MPa with respect to the pressure gauge.However, the distillation temperature of the distillation column, namely the internal temperature of the column at the tip-of-the-column temperature, can be controlled by adjusting the internal pressure of the column. Be from 20 to 200 "Celsius; for example, from 50 to 180"Celsius; with more

About 100 to 160"C. The material may be per member or unit associated with the distillation system including columns; 5 valves; condensers; (Juana) seal pumps; reboilers; internals; and lines

different; All of them in contact with the distillation system is a suitable material such as ez asl ceramic metal; or union thereof; It is not particularly limited to one specific one. in embodiments; The material of the pre-distillation system and the various lines is a transition metal or an alloy based on a transition metal, for example an iron alloy; for example steel no daar nickel or a zirconium alloy (Js or an alloy of zirconium thereof” titanium or an alloy of titanium thereof; or an aluminum alloy A suitable iron-based alloy includes any alloy containing iron as a principal constituent lie stainless steel which includes chromium Lad nickel and others includes a suitable nickel-based alloy containing nickel as the principal constituent and one or more cchromium iron cobalt tungsten molybdenum magnesium and others eg HASTELLOY ™ and INCONEL™ Corrosion resistant metals may be suitable

0 in particular as materials for distillation system and various lines. in embodiments; Acetic acid stream 128 undergoes further purification; In the product purification section of the Die process in the drying column 130 to remove water to produce the final product acetic acid stream. in embodiments; acetic acid stream 128 may be further purified in a heavy ends column (cf. IS No. 0216297); and/or in contact with an absorbent material; one or more adsorbents; 5 or purification resins in protection column 200 to remove various impurities (compare US Patent No. 8)) to produce a finished product acetic acid stream; ad) is indicated in Figure 1 as the product

Purified. in embodiments; The first overhead 126 is condensed and then oriented in an overhead phase separation unit 134 (top clapper 134).0 The first overhead 126 comprises methyl iodide; methyl cacetic acid cacetate water; at least one PRC.In embodiments the first upper stream separates condensed 126 into a light aqueous phase 135 comprising more than about 30 wt. 7 water; or 7 wt. cole or 50 wt. 7 at least one acetic acid cele methyl iodide PRC 5 methyl acetate; and a heavy phase 137 comprising greater than about 30 5 wt 7 methyl iodide; or 40 wt 7 methyl iodide methyl iodide; or 50

— 3 2 — the weight of 7 imethyl iodide imethyl acetate and at least one 0846. From Lali Qabilah two methyl iodide in water and vice versa; The heavy phase 137 includes some water and the light phase 135 includes some methyl iodide. The exact combinations of these two streams are a function of methyl acetate; acetaldehyde acetic acid 5 and other constituents of which Lad is found in the upstream of the light terminals 126. Although the specific compositions of the light liquid phase 135 may vary widely some representative compositions are provided below in Table 1. A representative light liquid phase is shown below. Table 1 From top head to lightly concentrated ends (Fooly | for Fooly concentrate / concentrate (by weight 7) Methyl Acetate 1-50 25-1 15-1 Methyl Acetate Acetic Acid 40-1 25-1 15-5 Acetic methyl iodide >10 >5 >3 Methyl lodide In embodiments, the upper decanter 134 is arranged and constructed to maintain a low interface level to prevent excess build-up of methyl iodide.Although formulations may vary widely of the heavy liquid phase 137; some representative compositions are provided below in Table 2.

— 4 2 — Table 2 Representative heavy liquid phase from top head to light ends (Fooly | for (Fooly) / concentrate (wt. 7) 2-0.01 1-0.05 0.9-0.1 Methyl Acetate |25-0.1 20- 5 15-0.7 - ‎Methyl lodide 98-40 95-50 85-60 Methyl iodide In embodiments; All of the light phase 135 is essentially recycled back to the reactor and the heavy phase 137 is sent to the aldehyde removal process 108. For purposes used here the examples relate to sending the heavy phase 137 to the aldehyde aly process 8. It is understood that however the phase may be sent The light phase 135 in combination with the heavy phase 135 leads to aldehyde removal 108. In embodiments; of the light phase 135' typically from about 5 to 40 size A may be routed to the aldehyde ally system 108 and the remainder recycled to the center of (Le lal) 10 in embodiments; A portion of the light phase 3 135 typically from about 5 to 40 volume/ to the aldehyde ally system 1 08 together with 1 00 volume A may be channeled primarily from the heavy phase 137 and the remainder recycled to the reaction medium. in embodiments; At least a section of the upper head of the first condensed column 138 is directed back to the light ends column 124 as a fluid refluxed through the stream 140. In embodiments; The current is derived from the upper header of the first column 126; That is, there is a heavy phase (5 137) and a light phase (135) or a combination of these two streams as a feed-through 142 to a removal system

(ARS) 108 (aldehyde removal system) aldehyde Feed stream 142 comprises methyl iodide; water; Cacetic acid Methyl acetate PRC 5 cmethyl acetate At least one. For purposes used herein direct a second column feed stream comprising or derived from the heavy phase to a second distillation column which indicates that it is greater than 50 by weight 7 of the total proportion of both the light phase 135 and the heavy phase 137 present in the second column feed stream which is; or derived from the heavy phase. in embodiments; The feed stream 142 has at least 10 weight7 light phase 135; or 20 light phase weight 135” or 30 light phase weight 135 (or 40 7035 light phase 135) 0 and/or the feed stream 142 comprises at least 50 weight7 of heavy phase 137; or 60 weight7 of heavy phase 137” or TO wt7 heavy phase 137) or 80 wt7 heavy phase 137 or 0 wt7 heavy phase 137 (or substantially composed of heavy phase 137) depending on the total amount of both heavy phase and light phase present in the second shaft feed stream 2. ACCORDINGLY” the feed stream 142 comprises at least a portion of the upper head of the first shaft 126; the total amount of the upper head of the first shaft 126 contained in the feed stream 142 consists of 6 light phase 135 5 Y% heavy phase 137; where 100 % = X% + Y% For the purposes of this calculation the feed stream 142 is understood to include additional components and/or streams other than relative proportions to stream 126. In embodiments the aldehyde removal system comprises at least one distillation column 150. column Distillation 150 includes distillation zone 312 and bottom sump zone 314 (compare Figure 3).As shown in Figure 1, Jody mounted the aldehyde ally system 108 on a distillation column. de 150. In Figure 1; The ARS embodiment of a single distillation column as dale is denoted as 2. In this embodiment; ARS feed stream 142 is distilled into a second distillation column 150 to remove water;

acid 3061006 methyl iodide and methyl acetate from residue 4 and to form a second upper stream 152 comprising 5:040 (acetaldehyde) concentrated in methyl iodide.

As shown in Figure 2; in alternate incarnations; The aldehyde ally system 108 may include at least two distillation columns 170 and 172. This ARS multiple column is generally referred to as 133. In block 133; The feed stream 142 is directed to a separating column 170 to remove the acetic acid water as a waste stream 174. The overhead 178 includes PRC's 5 "methyl acetate" methyl iodide. Boomerang section of

Upper head 178 with reference to the separating shaft as stream 181.

The upstream 178 is then directed to the second atomizing column 172 as stream 179. Stream 9 is here referred to as the alternate second column feed stream 179. The feed stream 179 is distilled into the second distillation column 172 zy a second upstream 152 comprising methyl iodide iodide At least one PRC methyl. Additional produces a distillation of the alternate second column feed stream 179 a residual stream 154 flowing from the lower basin area of column 172 containing water and being greater than or equal to about 0.11

Hoye 5 Each of these ARS systems is described here using similar descriptions for similar indicators used to describe currents that are essentially identical in each system. The upper head of second column 152 and lagging second column 154 produced using collector 132 are essentially identical to the same streams 152 and 154 using collector 133. Accordingly; For purposes used here 0 indicates different flow rates; channeling different currents; alternately between the complexes described in 132 and 133. in embodiments; The second upstream addition 152 includes dimethyl ether in embodiments; The process may work so that the DME forms in its place; within a second distillation column 150 or 172. In embodiments; where DME is intentionally formed within the process; DME is known to accumulate in the upper head of the second shaft 152 (upper head accumulator tank 160; the remainder of

ARS System 5

in embodiments; The upper head of second column 152 is condensed and sent to an overhead separator 160. The condensing second column upper head section 162 may reflux back to the second distillation column (150 or 172) through lines 167 and 164. at least a section of the upper head of the second stacked column 162 is cooled (through a heat exchanger 173); and communicates with 5. a water stream 166 (typically water) in at least one extractor 169; Typically at an extraction temperature of less than about 25°C, or less than about 20°C; or less than 5 pH; or less than 10" centile; or less than about 5" centile. however; in embodiments; The extraction temperature may be from 50°C to 30°C. The upper head extraction of the second column yields 152 water stream 168 containing PRC and a small amount of 100 106 methyl methyl iodide which GY 0 is removed from the process as a residue. Extraction also produces a purified sole stream (raffinate stream) 158" which includes methyl iodide. when the upper vertex of the second column 152 contains dimethyl ether; Filter stream 158 also includes .dimethyl ether

In order to provide adequate and family removal for other PRC’s 4 acetaldehyde”; The extraction step necessarily requires a phase separation between the liquid phase and the purified methyl iodide. The density of the two liquids as well as the partition coefficient of the two phases is critical to this separation. Water is typically used for extraction; It has a density of about 1 g/mL. The upper head of the second column, which is typically 50 wt 7 or more, can be reduced in density to methyl iodide in the presence of 06 80618106 acetate aldehyde; methanol methyl acetate 0 and other components. Depending on SIN the presence of the other components in the upper head of the second column may result in less effective separation or, in the worst case, lack of phase separation. Accordingly, in embodiments; The densities of the different currents produced in the aldehyde removal system can be controlled to apply a more effective removal for

PRC's 4 acetaldehyde is added during the extraction process. in embodiments; AUS second feed stream 142 to ARS purification system 5 108 is from 1.506 to 2.260. in embodiments; be

The second feed stream density 142 is greater than 1.5, 1.55", 1.6", 1.65", 1.7, 1.75", 1.8", 1.85", 1.9", 1.95" or 2 and less than 2.3 when specified at process temperatures. In embodiments, the mean process temperature for the feed stream 142 arriving at the second distillation column is from 50 to 75 °C; With typical 65 to 70" C. embodiments; the upper current density of the second column 152 is greater than 1.2" or 1.25" or 1.3" or 1.35" or 1.4 or 1.45 or 1.6" or 1.65 and less than 1.75 when specified at process temperatures. In embodiments, the average process temperature for the second column overhead current is 152 at the overhead receiver of 160 from 35 to 55"C with 40 to 45"C 0 being typical. In embodiments, the residual current density for the second column is 154 from 1.3 to 2.1 In embodiments, the residual current density of the second column 154 is greater than 1.35 or 1.4” or 1.45 or −1.5 or 1.55” or 1.6 or <1.65 or 1.7 or 1.75 or 1.8 or 1.85 or 1.9 or 5.+ or 2 and less of 2.1; when specified at process temperatures. In embodiments, the mean process temperature of the second column backstream is 154 from 75 to 90"C with 80 to 85"C typical. In embodiments, the feed density of the second column upstream to a tool is extractor 162 after being cooled in heat exchanger 173 from 1.15 to 1.75.In embodiments the feed current density is top of second column to extractor greater than 1.2; or 1.25; or 0 1.3 or 1.35” or 1.4 or 1.45” or 1.6 or 1.65” and less than 1.75; When specified at process temperatures. in embodiments; The average temperature of the second shaft topstream feed to the extractor is 5 to 15"C with 7 to 12"C being typical. in embodiments; The 4806S purifier stream 158 is from 1.7 to 2.3 at process temperatures. in embodiments; The stream density of purified material 158 is greater than 1.75, 1.8 or 1.85

— 9 2 — or 41.9 1.95 or 2” or 2.05” or 2.1 or 462.15 2.2 or 2.25 Jil from 2.3 when specified at process temperatures. in embodiments; The average process temperature for the purified material is 10 to 25°C with 17 to 20°C being typical. The water stream is typically fed into the extractor at approximately the same temperature as the upper stream of the second column is fed into the extractor. The aqueous stream exits the extractor at a temperature of 20 to 40 °C. Similarly, the increased temperature of the purified material. Ole from 10 °C to 18 °C is due to an exothermic resulting from splitting the stream with water during the extraction process. In embodiments The top current density of the second column is less than the feed current density of the second column. 72 m or 725 or 730. In the embodiments the second shaft retarded current density is less than the second shaft feed current density In the embodiments the percentage drop between the second shaft feed current density 142 and the second shaft retarder density 154 is from 75 to 710. This percentage drop is greater than 7 or 9 In embodiments the density of the second column upstream feed to the extractor 162 is greater than water In the embodiments the specific JBI of the second column upstream feed to the extractor 162 pr pH to water from 1.15 to 1.6; When specified at 10" recess. In embodiments; the specific gravity of the second shaft overflow feed to the extractor 162 with respect to 0 to water is greater than ¢1.2, 1.25", 1.3, 1.35, 1.4", 1.45, 1.5" or 1.55 Ji of 1.6; when set at an extraction temperature of 10"C. in embodiments»; The AUS of the sieved material is greater than the second column feed current density. in embodiments; The percentage increase between the second column feed current density 142 and the material density

purified 158 from 710 to 720. in embodiments; This percentage increase is greater than 712; or 5); or 218 but less than 720. In embodiments; At least one portion of the refined stream 158 is recycled back to the second distillation column by means of line 161 which improves the 0:5 quantity present in the upper head of the second column 152 as substantially as is known to one skilled in the art. in embodiments; The refinery stream 158 is divided into two parts: a first portion 161 aud and a second portion 163. The first portion of the raffinate stream flow 161 is recycled back to the distillation column the second. The second part of the raffinate stream flow 163 is recycled back to the reaction medium from the Gob 0 stream Sle (155 (stream) by means of a combining stream 155 with the stream (stream) 116' 118;and/or the like. Recycling a portion of the purifier stream back into the reaction medium consumes the DME present in the stream. This prevents excessive accumulation of DME in the second distillation column 150 or 172; It thus prevents overpressure of the second distillation column 150 or 172 (see; US Patent No.: 7223883).The build-up of pressure in column 150 or 172 causes the upper separator 5 to be ventilated 160 to the scrubber system 139. This results in Ventilation to non-foaming recycling for acetaldehyde back to the reaction medium In embodiments the mass flow of the first section of the purifier is 161 ST of or equal to the mass flow of the second section of the purifier 163. In embodiments the mass flow of the first section is of filtered matter 161 is greater than or equal to about 21; or 25 or 210 or 220 or 230 or 0 240” or 250 or 260 or 270 or 280 or 290 and less than 7500 of the second part mass flow of purified material 163. In embodiments; The mass flow of the second part of the refined material 3 is greater than or equal to about Ll or 25; or 210 or 220 or 230 or 240 or 50 or 7260 or 270; or £80 or 790 and less than 7500 mass flow for the first part of the purified material 161.

in embodiments; The second distillation column (150 or 172) may optionally include a sidestream 157 from which a stream comprising methyl acetate Optional sidestream 157 allows the second distillation column to be operated under desired conditions to obtain a lel concentration for acetaldehyde in the upstream of the second column 152 with a mechanism provided to remove the methyl acetate and/or methanol that might otherwise accumulate in the center of the second distillation column (eg; methyl acetate esi methyl acetate) is eventually driven into 2nd shaft top stream 152. [sale] preferably rotate optional side stream 157; which includes methyl cli acetate ; if it is used; Back to the process. Embodiments of the instantaneous process may further include a top flush stream 0 164 including water to the second distillation column 150 or 172. The top flush 164 may include fresh material; However, it is preferable that it be generated from a current generated by the process of controlling the water content in the system. in embodiments; Peak Stream 164 comprises acetic cle 0 08118001 methanol or any combination thereof. in embodiments that use Compound 133; A portion of the backstream of column 5 chapter 174 may be directed via the stream 156 and 164 to the alternate second distillation column 172 as the apical surge stream 164. In embodiments where the apparatus (apparatus 132) is used the apical surge stream may include at least a portion of the residual stream 154; directed by current 156 to 164. In embodiments the apical impulse stream 164 may include a portion of the light phase upper current 135; eg by a portion of stream 114 consisting primarily of light phase 135 directed to 0 164. In embodiments; The mass flow rate of the apical rush stream 164 is greater than or equal to about 71 of the total mass flow rate of the feed stream 142) second shaft feed stream 143; or the feed stream 179 where applicable. In embodiments, the mass flow rate of the apical rush stream 164 is greater than or equal to about 75 or 210; or 7220 or 30; or 40; or 250 or 5 260 or 270 or 280 or 790 or 7100 or 7150” and less than 7500 Flow Rate

feed stream mass 142; second column feed stream 143; or feedstream 179 where applicable. in embodiments; The process may additionally include directing a bottom flush stream 165 to the second distillation column distillation zone and/or to the second distillation column bottom sump region. Lower surge stream 165 may include water; “acetic acid” or both. in embodiments; The lower surge stream 165 shall have at least 10 Kays or 20 wt#; or 30 Ais or 40 wt# or 50 wt# or 60 Lis or As TO or 80 wt or 90 Zs or 95 Oj of acid 06a808. in embodiments; The lower impulse stream consists of; or is primarily composed of .acetic acid in embodiments; the mass flow rate of the downstream rush 165 to the second distillation column 150 or 172 is greater than or equal to about 70.1 of the total mass flow rate of the feed stream 142; or second shaft feed stream 143 or 179. In embodiments; The mass flow rate of the lower impulse stream 165 is greater than or equal to about 25; or 210; or £20 or 30; or 250 or 260” or 270 or 280” or 90 or 2100 or 7150 or 2200 or 5 2300; and less than 7500 feed stream mass flow rate 142) second column feed stream 3+ or feed stream 179 where applicable. In embodiments where the second column feed stream is or is derived from the heavy phase 137; the water content of the second distillation column may be Sufficient to produce HI in ionized form dissociated in the aqueous phase.According to SIN the lower basin area of the distillation column may have a minimum water concentration of about 5 0 wt “” or 4 wt #” or less present only as hydrogen iodide vapor Consequently, the hydrogen iodide is distilled down the upper head with the upper stream of the second column rather than being concentrated in the lower basin region.In these embodiments the amount of aqueous apical eruption can be adjusted to ensure that the resulting HI is present in the second distillation column as a loose and ionized aqueous solution.In addition to that or yar that the bottom rush may include enough water to produce a bottom back stream including HI 5 the bottom rush stream can be added over the inlet of the feed stream to the second distillation column so that there is the resulting HIE

in the lower basin area of the distillation column. cially a lower impulse stream can be added directly to the lower pelvic region to keep the Jie HE focused on selected levels in the lower trailing stream. in embodiments; The combined mass flow rates of the apical impulse stream 164 and the lower impulse stream 165 are about 21.1 or 25; or 210 or 220; or 30 or 40 or 50 or 260” or 7270 or 280 or 290 or 2100 or 2150 or 7200 or 7300 and less than 0 of the feed stream mass flow rate 142; second column feed stream 143; or feedstream 179 where applicable. in embodiments; The mass flow rate of the apical impulse stream is 164; The mass flow rate 0 of the bottom rush stream 165) or the combined mass flow rates of the apical rush stream 164 and bottom rush stream 165 from about 71 to about 750 of the mass flow rate of the backing stream 4. In embodiments, the tailing stream of the second distillation column 154 includes acetic “cle 0 and about 0.11 wt 7 at least LHI embodiments; leftover stream 154 includes 5 greater than or equal to about 5 wt 7 cele or 10 wt # or 20 wt #”; or 03930 or 40 Zs or 50wt “or 60wt#” or “Zi TO” or 80wt “” or 90 wt 3s or 95wt 7 water In embodiments the residual current 154 comprises greater than or equal to about 5 wt7 cacetic acid or 10 Zs or 20 wt#” or 30 wt#” or 40 wt “or 50 wt” or 60 wt7; or TO “wt#” or 80 wt#”; or 90 Zs or 95 wt 7 acetic acid in embodiments; 0 the residual stream 154 includes greater than or equal to about 5 wt 7 methyl iodide or 10 wt# or 20 wt# or 30 wt# or 40 wt#” or 50wt#; or 60wt7 or 70wt#” or 80wt#; or 90 703s or 95wt7 .methy iodide l iodide Jill in embodiments; The 154 second shaft lagging current has greater than or equal to about 0.11 wt. 7 HIE embodiments; The lagging current includes 154 greater than or equal to

Approximately 0.21WH7 HE or greater than or equal to Approximately 0.25WT 7HE or greater than or equal to Approximately 0.3WT 7CHIE or greater than or equal to Approx. 0.35WT 7HIE or greater than or equal to Approximately 0.4WT 7 HE or greater than or equal to about 0.5 by weight of 7 a 1 a ; or greater than or equal to about 0.6 7035 a1a; or greater than or equal to approximately 0.65 wt7 (HE) or greater than or equal to approximately 0.7 wt7 HIE

in embodiments; HI is produced in a second distillation column; Typically through hydrolysis for methyl iodide to methanol or else. Therefore more Gay 111 exits the distillation column (150 or 172) via the upstream 152 and/or backstream 154 than enters the column in the column feed stream 142. Corrosion considerations make excessive amounts of HI unfoamed 0 in general. As discussed above; A certain amount of HI is controlled within a specific range; foamed to induce the formation of a controlled amount of DME in the column. This DME has been found to have a beneficial effect on phase separation in a liquid-to-liquid extraction system combined with acetaldehyde removal systems as described in US Patent No.: 7223883 (US Patent No.: 7223886) and US Patent No.: 80765017. In embodiments The 154 residual stream includes less than or equal to about 10 A7wt or less than or equal to about 5a7wt or less than or equal to about 2a7wt# or less than or equal to about 1.5a7wt or Less than or equal to approximately 1.2W7 HE or less than or equal to approximately 1.1W7 HE or less than or equal to approximately 1W7 HE or less than or equal to approximately 0.9W7 HE or 0.75WT 7 HI or Less than or equal to about 0.7 wt 7 HI or less than or equal to about 0.65 wt 7 HI 0 or less than or equal to about 0.6 wt 7 (HI or less than or equal to about 0.55 755 HI is less than or equal to about 0.5 wt 7 HE or less than or equal to about 0.45 wt 7 HI based on the total weight of the waste stream. 154 to an acceptable corrosion level under the conditions presented here. Accordingly; may be allowed

Selection of materials with higher HI concentrations in residues higher than 11 wt7.

in embodiments; Residual stream 154 may additionally include methyl iodide; methanol A01617800; methyl acetate ¢ and/or -acetaldehyde in embodiments; A section of the back stream 154 may be directed to the drying shaft 130; Sle by means of a reflux liquid derived from the drying column decanter 148) to the reactor 104; or both.

As can be seen in Figure 3; in one embodiment; The second distillation column includes (Fig. 3 shows column 150 representing either 150 or 172 for purposes of figures) distillation zone 312 and lower basin area 314. distillation area 312 is everything above lower basin area 314; It may include various internal components including, but not limited to, filler segments; sale tools] liquid dispensing/collection tools; trays; buttresses etc.

in embodiments; The second distillation column contains at least 100 trays and operates at a temperature from about 101°C at the bottom to about 60°C at the top. In an alternative embodiment the second distillation column comprises structural packing instead of trays. In embodiments; structural packing; random packing ; or a combination thereof having an interfacial area of 150 to 400 m"2/ jie 37 and may include a metal-ceramic; polymeric; austenitic-ferbitan (©200510116-180110); or a combination thereof.

5 in embodiments; The bottom temperature of the second distillation column shall be from about 90°C to about 0C; the pressure of the second distillation column shall be from atmospheric pressure or about 150 kPa above atmospheric pressure; to about 700 kPa above atmospheric pressure; or a combination thereof.

in embodiments; The dimensions of the distillation zone are determined and regulated to control the contact time between methyl iodide 100 106 methyl and water to control the concentration of the residual SHI of the second distillation column 154.

in embodiments; The liquid phase in the second distillation column comprises a first liquid phase comprising greater than about 50 wt 7 of water (liquid or water phase) and a second liquid phase comprising greater than about 50 wt 7 of methyl iodide (methyl iodide phase iodide

in embodiments; The dimensions of the distillation area 312, specifically the various internal components in the distillation area, are determined and regulated to control the contact time between the methyl iodide phase

and phase water to the minimum amount required to produce a residual stream for the second column 154 having a concentration of only ≥ 0.11 wt 7. In embodiments; The internal components are designed (dimensionalized and regulated) to reduce the retention time of the liquid phase in the distillation column under process conditions. find that the minimum contact time between the aqueous phase and the phase of 100 106 methyl methyl iodide in the second distillation column is necessary to produce a residual stream flowing from the lower basin area that includes water and is greater than or equal to 0.11 wt 7 HI however; It was also found that the prolonged contact time between the separated sections of the aqueous phase and the methyl iodide phase, Wa, affected the ability to control the amount of HE in the residual current. Prolonged communication times may result from the aggregation and/or reservation of discrete sections of a private phase 0 in the private internal components of the column; Without affecting the total retention time of the liquid phase in the distillation column. As can be seen in Figure 3; in embodiments; A second distillation column 150 or 172 may have a set of internal components which may include liquid collectors 0.300' etc.; which can be dispersed between a set of 5 packing sections 302 and 304 each of which individually includes structural packing; random filling; or a union of them. in alternate incarnations; The internal components may be drip dishes or trays; With various 308 supports and assembly hardware. in embodiments; Distillation Zone 312 includes a vapor phase and a liquid phase; The liquid phase includes a first liquid phase 326 (see Fig. 4) and a second liquid phase 0 328 (see Fig. 4); Where the first liquid phase contains more than about 50 weight 7 of water and the second liquid phase includes more than about 50 weight 7 of 56 methyl iodide. Far from some inner solubility; The two liquid phases are generally immiscible.

As can be seen in Figure 4; Each internal component includes an associated or corresponding liquid phase retention size that depends on the dimensions and organization of the component. In embodiments where both liquid phases are present in the distillation column, the total retention volume of the liquid phase associated with a special component is equal to the sum of the first liquid phase retention volume 326 and the second liquid phase retention volume 328 within the special component. The liquid phase retention volume in the drip zone is therefore equal to the sum of both the liquid phase retention volumes of the components in the drip zone plus the amount on the sides and other non-functional surfaces of the column. Each component retention size has a corresponding retention time for the first liquid phase and a corresponding retention time for the second liquid phase under operational conditions. The retention time of the particular liquid phase in the internal component is 0 equal to the mean time; A discrete amount of this particular liquid phase remains within the component retention volume under operational conditions. Nevertheless; Physical properties of the two liquid phases. The drain position or flow paths of the Jala component and/or other aspects of the internal component may cause a liquid phase to collect or trap within its retention volume. The liquid phase retained within a particular component retention volume may have an average retention time within that particular component that exceeds the average retention time of the entire liquid phase in the column drip zone. Accordingly, the retention times of the special liquid phases within the internal components of a Bale distillation column shall be measured, calculated and/or modeled under operating conditions on the basis of the physical characteristics of the liquid phases and the design and arrangement of the special components. As can be seen in Figure 4 where the two liquid phases 326 and 328 ol distillation » are the 0 internal parts of the column that do not include the lower drains; or which do not include suitably sized and placed bottom drains will serve to accumulate the second liquid phase 328 for the heavier methyl iodide under the lighter aqueous first liquid phase 326; Even though the methyl iodide phase has a lower boiling point than the aqueous phase. The methyl iodide phase will then tend to the heavier methyl iodide phase when carried with the aqueous phase

the lightest. The heavier phase may also accumulate in a retention volume and then engulf the different constructs in the column. Column designs lead to unexpectedly long retention times for the separated sections of the second liquid phase. likewise; As can be seen in Fig. 4 the internal parts of the column that have inferior drains but do not include apical drains; or which do not include appropriately sized or placed apical drains will serve to accumulate the lighter aqueous first liquid phase 326 within the internal component retention volume. The first liquid phase 326 may then be held in relation to the heavier, better drained second liquid phase 328 that drains through the accumulated first liquid phase 326 Play one or more bottom drain holes 340. Thereafter the lighter first liquid phase will tend to advance through the column only when carried with the heavy phase; or by immersing various constructions in the shaft; which leads to prolonged retention times for the separated sections of the first aqueous liquid phase within a retention volume.

Specific internal component constructs.

As can be seen in Figure 4; in one embodiment; The distribution ale] AL tray or other interior of column 300 may include one or more vapor risers 316 that allow the vapor phase to flow through the construction; and one or more drip tubes 318 to allow fluid to pass through the construction from side to side. in one embodiment; One or more drippipes 318 may include at least one of a first set of passages 324; placed therein which are regular vacuoles for the first liquid phase drainage 326; which is less dense (lighter) than the second liquid phase 328; Thus they are placed away from the bottom of the masonry. Each additional dripline 318 may include at least one of a second set of Passages 330 placed in it which are regular recesses close to the bottom of the masonry to drain the second heavier liquid phase 328 through them. Figure 5 shows an embodiment where each driptube 320 comprises at least one of a first set of united passages with a second set of slit passages 332 placed through it along a vertical wall of the driptube 320 that allows drainage of both the light phase

The first 326 and the second heavy phase 328 through celal

Fig. 6 shows an embodiment where each drip-tube 322 has at least one of a first set of passages in the form of a slit 334 placed in it along only one section of a vertical wall of the drip-tube 322; regular to allow first light phase 326 to be fired during construction; Each additional dripline 322 may include at least one of a second set of passages 336 placed in lg regular recesses close to the bottom of the masonry to drain the second heavier liquid phase 8 through them. in embodiments; As can be seen in Figure 4; construction may include a baffle or weir having a side height Dis 338 (side height of the liquid redistributor side 300 or column tray) allowing the lighter first phase 326 to be drained by pouring over the side; In conjunction with the tray is equipped with one or more 0 bottom 340 drain gaps to allow the heavy phase to drain through. in embodiments; Load can select the column padding; if you exist; to reduce fluid retention; Those with reasonable skill in art also understand cle, etc. Experiments are performed by simulation to determine the average aqueous phase retention time for a second distillation column operating with an apical surge current and partial column return fluid in an aldehyde removal system 5 from a commercial acetic acid production process; Which produces a residual current that has a concentration HI that is difficult to control. In comparative examples; The mean retention time of the aqueous phase in the second distillation column distillation zone that includes only the bottom drains in the [sale] liquid dispensers is determined by simulation to be about 6 hours; which was not reflected in the total retention time of the feed stream in the distillation column. Accordingly; The aqueous phase is trapped in sections of the column. The column is then simulated to be equipped 0 with drip tubes configured with a first and second set of fluid passages as shown in Figures 4 5; and 6 in separate modeling experiments. Under the same conditions as the comparative example simulation; The average aqueous phase retention time in the innovative column distillation zone is reduced from about 6 hours to about 11 minutes on average.

The use of a second distillation column according to the embodiments shown here has an average liquid phase retention time within the jail area of about 1 minute to about 60 minutes; Where the distillation area includes a group of internal components; Each of them has a liquid material retention volume of the component; Where each of the internal components is dimensioned and organized so that the average retention time for the first liquid phase and the average retention time for the second liquid phase in each liquid material retention volume of the component is less than approximately 30 minutes; resulting in a second column residual current having a HE concentration between 0.11 7.035 and 0.9 wt 7 in embodiments; The mean feed stream retention time in the second distillation column distillation zone is about 1 dads to about 60 minutes or about 1 minute to about 30 minutes; or 0 for about 1 minute to about 15 minutes. in embodiments; The distillation area includes a range of internal components; They each have a liquid material retention volume from the component. Each of the internal components is dimensioned and arranged so that the average retention time of the first liquid phase within the liquid retention volume of each component is less than approximately 0 minutes; or about 0 minutes; or about 10 minutes; or about 5 minutes. in embodiments; 5 are dimensioned and each of the internal components are arranged so that the average retention time of the second liquid phase within the liquid retention volume of each component is less than about 30 minutes; or about 20 minutes; or about 10 minutes; or about 5 minutes; When determined by modeling or direct measurement. in embodiments; dimensions and organization of at least one internal component are determined; or all internal components present in the distillation zone such that the mean retention time of the first liquid phase is greater than 0 or equal to the mean retention time of the second liquid phase in the liquid substance retention volume of the corresponding component when determined by modeling or direct measurement. in embodiments; It includes at least one internal component; lie drip tray; liquid collection device; distribution tool; or (aig sale] on a first set of 324 (322 and/or 334) dimensioned and regular Sie flow paths such that the average first liquid phase retention time of approx.

— 1 4 — 1 minute to about 20 minutes; or to about 10 minutes; or to about 5 minutes in the LMR of the corresponding component when determined by modeling or direct measurement. in embodiments»; At least one internal component additionally includes a second set of flow paths (eg 330 (332 336; and/or 340) dimensioned and regular such that the average retention time of the second liquid phase is from about 0.1 min to about 20 min; or to about 10 min or to dea 5 min in the EV of the corresponding component when determined by modeling or direct measurement.In embodiments, the concentration of HI in the second column residue can be controlled by selecting different states associated with the second distillation column.In In embodiments, the concentration of second column residue AHI can be controlled between 0.1 A U9 and 0.9 A a9 by selecting the distillation temperature and pressure 'ie' the second distillation column bottom temperature and second distillation column pressure. Controlling the HI concentration in the second column retardant by selecting the apical surge stream composition; the apical surge current mass flow rate; the bottom surge current mass flow rate; and/or the bottom surge stream mass flow rate. For example (Jaa) to reduce the concentration of HI in retarded 5 second column; the amount of lower inrush current can be increased with respect to Column feed rate to dilute and wash the HI in the column basin. in embodiments; The HI concentration in the column retardant SUH can be controlled by selecting the average liquid phase retention time in the distillation zone ¢ and/or by controlling the average retention time of one or more liquid phases within the retention volumes of one or more internal components ; 0 as per discussion here. in addition to; Any combination of the control programs above can be selected to produce a residual current comprising about 0.11 7035 of HI to less than or equal to 0.9 wt 7 of HE in embodiments; Additional acetic acid production may include introducing a lithium a sill compound into the reactor to maintain a concentration of lithium acetate (sill) in an amount of 0.3 to 0.7 wt. 7 in the reaction medium. in embodiments»; A quantity of lithium sill compound is introduced into the reactor to maintain

On the concentration of hydrogen iodide in an amount of 0.1 to 1.3 wt.7 in the reaction medium. in embodiments»; The radium catalyst concentration of rhodium is maintained at an amount of 300 to 0 wt/ppm in the cde lit medium and the water concentration is maintained at an amount of 0.1 to 4.1 wt7 in the reaction medium; The concentration of methyl acetate is maintained from 0.6 to 4.1 7035 in the reaction medium; Based on the total weight of the deli 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 carboxylates; lithium chloride; lithium chloride; lithium hydroxide; dithium carbonates; other organic lithium 10 salts; and mixtures thereof. in embodiments; The lithium component is soluble in the reaction medium. in one embodiment; Lithium acetate dihydrate can be used as a source for a jithium compound. Lithium acetate reacts with hydrogen iodide according to the following equilibrium reaction (a) to form: acetic acid lithium iodide Lil + HO Ac (I) 15 5K LiOAc + HI Lithium acetate provides improved control of hydrogen iodide concentration relative to other acetates such as methyl acetate present in the reaction medium. without being bound by theory; Lithium acetate is a conjugate base of acetic acid and is therefore reactive towards hydrogen iodide via a 0 acid-base reaction. This property is believed to result in an equilibrium reaction (1) that favors the Je lal products over those produced by the counterbalance for methyl acetate and hydrogen iodide 170000©0. This improved equilibrium is favored at concentrations of ele less than 4.1 wt 7 in the reaction medium In addition, the relatively low volatility of lithium acetate compared to methyl acetate allows lithium acetate 5 to remain in the reaction medium Led except for volatilization losses and small amounts of The material drawn into the steam raw product.

— 4 3 —

On the contrary; The relatively high volatility of methyl acetate allows the substance to be distilled in a purification series; Which leads to more difficulty in controlling methyl acetate. Lithium acetate is easy to maintain and control in the process at low concentrations proportionally for hydrogen iodide. Accordingly, a relatively small amount of lithium 8061816 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 methyl iodide dala) oxidative stress.

to the complex rhodium radium [a].

in embodiments; The concentration of lithium acetate in the reaction medium remains greater than or equal to 3 . 0 A) / 3 or greater than or equal to 35 . 0 A) / 3 or greater than or equal to 4 0 and zb / 3 or greater than or equal to 45 . 0 U9 / 3 or greater than or equal to 5 . 0 U9 / 3 and/or in embodiments the concentration of lithium acetate in the reaction medium remains less than or equal to 0.7 wt 2 or less than or equal to 65. 0 U9 / 3 or less than or equal to 6 . 0 A U9 3 or less than or equal to 55 . 0 U9 / 3

5 when determined according to the perchloric acid titration to the end point of the potentiometer.

aaj that an excess of lithium acetate in the reaction medium may adversely affect the other compounds in the reaction medium; Which leads to lower productivity. On Sal, I find that the concentration of lithium acetate in the reaction medium is less than Mea 0.3 wt 7 leading to the loss of the ability to control hydrogen iodide concentrations in the reaction medium.

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

A series of experiments are conducted to clarify the effect of lithium acetate enhanced in the krill reactor and to determine the effect of lithium acetate on the addition of methyl iodide iodide

Oxidative methylation to complex 100000 and [and(00)Ra0”]Na confirm the enhancing effect of lithium acetate 1586 on reaction rates. nd Note linear increases of reaction rates associated with increasing lithium acetate concentrations. This association is indicative of first-order reinforcing effects of the interaction between methyl iodide and [00(2)Ra40]Na. These experiments further demonstrate a non-zero objection confirming that lithium acetate is not required for the Mel-Rh(l) reaction to occur, but that lithium acetate provides a significant enhancing effect even

at low concentrations. in embodiments; The process may additionally include maintaining the concentration of butyl acetate 186 in the acetic acid product at 10 ppm or less without

0 removal of butyl acetate directly from product acetic acid in embodiments; The concentration of butyl 4158 in the final acetic acid product may be kept below 10 ga ppm by removing the acetaldehyde from the reaction medium” Oli. Removing the acetaldehyde from a stream derived from the reaction medium; if the reaction temperature and/or partial hydrogen pressure is controlled; and/or the concentration of the metal catalyst in the reaction medium. In embodiments” the concentration of butyl acetate is maintained at zie

acetic 800 5 final by temperature control of one or more krill reaction temperatures from 150"C to 250"C; partial hydrogen pressure in the krill reactor at 0.3 to 2 atm; the concentration of the radium metal catalyst in the reaction medium at 100 to 0 w/ppm; Based on the total weight of the deli medium and/or the concentration of the acetaldehyde 4 reaction medium at 1500 ea per million or less.

20 in embodiments; The acetic acid product formed according to embodiments of the process disclosed herein has a concentration of butyl acetate less than or equal to 10 w/ppm; or less than or equal to 9 wppm” or less than or equal to 8 wppm; or less than or equal to 6 w/pm” or less than or equal to 2 w/ppm; Based on the total weight of the acetic acid product. in embodiments; The acetic acid product is essentially free of butyl

“acetate 5” i.e.; The concentration of butyl acetate is less than 0.05 w/ppm or is not

Detectable by means of detection known in the art. in embodiments; A lead acid product may have a propionic acid concentration of less than 250 w/ppm; or less than 225 ppm; or less than 200 weights per million ein. In embodiments, the concentration of butyl acetate in the acetic acid product can be controlled by controlling the concentration of acetaldehyde in the reaction medium. without being attached to a theory; It is believed that butyl zie acetate is secondary produced by aldol concentration of acetaldehyde . The concentration of butyl acetate in the finished acetic acid product is less than 10 w/ppm. in embodiments; The concentration of acetaldehyde in the reaction medium remains at less than 0 . than or equal to 1500 w/ppm; or less than or equal to 900 ppm; or less than or equal to 500 weight per ppm; or less than or equal to 400 weight per 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 greater than or equal to 150°C; or 5 180°C; and less than or equal to 250°C; or 225"C; and/or the partial hydrogen pressure in the krill reactor can be controlled at greater than or equal to 0.3 atm; or 0.35 atm or 0.4 atm; or 0.5 atm and less than or equal to 2 atm or 1.5 pressure “Sg” or 1 atm. While the relatively high hydrogen partial pressure leads to improved reaction rates; selectivity; 0 improved catalytic run and lower temperatures; the applicant found that hydrogen partial pressure increases and also increases impurity production, including 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.

Dale gd conducted experiments to clarify the effect of the pressure of hydrogen Al and the concentration of 6 in the reaction medium on the concentration of butyl acetate in the final acetic acid product. These experiments confirmed the relationship between the lower concentrations of 80618160 butyl in the final acetic acid zu. 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 concentration of acetaldehyde in the reactor kept below 1500 gia per million and the hydrogen partial pressure of the reactor kept below 0.6 atm resulted in butyl acetate levels of 10 wt ea per million in the acetic product 0 Final. Further experiments showed an acetaldehyde concentration in the reactor below 1500 wppgpm and a reactor partial hydrogen pressure of 0.46 atm resulting in 0 butyl acetate concentration of less than 8 wgpm in the final acetic acid product. . Similar conditions where hydrogen partial pressures of 0.30 atm lead to butyl acetate levels lower than 6 wpm” and hydrogen partial pressures of 0.60 atm lead to butyl acetate concentrations lower than 0.2 wt ein per million in acetic 0 finished product. Nevertheless; Comparative experiments in which the partial pressure of hydrogen 5 is 0.4 and 0.3, respectively; but in the absence of an aldehyde removal system so that the concentrations of 6 in the reactor exceed 1500 w/ppm; to a final acetic acid product with butyl acetate levels of 13 wt ppm and 16 w ppm

straight. The applicant also found that the concentration of propionic acid in the final acetic acid product 0 can be affected accordingly by the concentration of butyl acetate in the acetic acid product by controlling the concentration of butyl acetate in the acetic acid product. final to 10 ppm or less; The concentration of propionic acid in the final acetic acid product can be controlled to less than 250 w/ppm; or JET of 225 eda per million; or less than 200 ppm. in a similar manner” by controlling the ethanol content in the reactor feed; which may be present as impurities 5 in the methanol source; Lad can control the concentrations of propionic acid and butyl acetate in

The final acetic acid product. in embodiments; The concentration of ethanol in the methanol feed methanol to the cryel reactor is controlled to less than or equal to 150 w/ppm. in embodiments; can 13) the concentration of ethanol in the methanol feed to the reactor is less than or equal to 0 w/ppm” or 50 w/ppm; Or 25 weight per ppm. The applicant further finds that the formation of ethyl iodide can be affected by several variables; Including the concentration of ethyl acetate (acetaldehyde methyl acetate) and methyl iodide in the reaction medium.(Lila) Find the ethanol content in methanol source methanol partial hydrogen pressure and hydrogen content In a carbon monoxide source 0 affects the concentration of 100106 ethyl 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 J of or equal to 750 weight per ppm; or less than or equal to 650 weight per ppm” or less than or equal to 550 weight per ppm; or less than or equal to 450 weight per ppm; or less than or equal to 350 wppm.In alternative embodiments the concentration of ethyl iodide in the reaction medium is maintained/controlled at greater than or equal to 1 wppm or 5 wppm or 10 weight per a per million or 20 weight per ppm; or 25 weight per sia per million; less than or equal to 650 weight per ppm; or 550 weight per ppm or 450 weight per ppm; or 350 0 wt. ppm. in embodiments; The concentration of propionic acid may also be kept in the acetic acid product below 250 wppa by maintaining the concentration of ethyl iodide in the reaction medium at less than or equal to 750 wppa without removing the propionic acid from the acefic .acid product

— 8 4 — in incarnations»; A concentration of ethyl iodide may be present in the medium of propionic acid 5 Je lll in an acetic acid product in a weight ratio of 1:3 to 2:1; or from 2:5 to 2:1; or from 1:2 to 2:1. in embodiments»; The concentration of ethyl iodide :acetaldehyde remains in the reaction medium at a weight ratio of 2 to 1:20 or from 1:15 to 1:2; or from 1:9 to 1:2. in embodiments; The concentration of ethyl iodide in the reaction medium may be maintained by controlling at least one partial hydrogen pressure; methyl acetate concentration; The concentration of methyl vag “methyl iodide” and/or the concentration of acetaldehyde in the reaction medium. A series of experiments carried out to determine the effect of acetaldehyde and other reaction conditions on the formation of ethyl indicated the relationship between the acetaldehyde concentration and the ethyl iodide concentration in 0 reaction medium, in addition to the relationships between the ethyl iodide reactant concentration and the propionic concentration acid in the final acetic acid product. In the ale form, an ethyl iodide concentration of less than 750 wpm oa and an acetaldehyde concentration of less than 1500 wpm oa in the reaction medium lead to propionic acid concentrations of less than 250 wpm oa in Product 80616 .acid 15 as shown in the figures and text above; de gana is envisioned in a variety of incarnations. Personification 1. Process includes: a. provision of a feed stream having a primary density that includes acetic acid cele methyl acetate “at least one PRC”; and larger than about 30 wt. 7 of methyl iodide to a distillation column comprising a distillation area and a lower basin area; and 0_b. distillation of the feed stream at sufficient pressure and temperature to produce an overhead stream of second density and comprising greater than about 40 wt. 7# of at least one PRC g methyl iodide; Gua The percentage drop between the first ASEH and the second density is from 720 to 735.

— 9 4 — embodiment 2. Operation Gig for embodiment 1 where the specific gravity of the second density with respect to water is from 1.15 to 1.6; When specified at 10" recess. Embodiment 3. Process according to Embodiment 1 or Embodiment 2, wherein a backward stream flowing from the lower basin area has a third density less than the first; and includes greater than about 0.1 wt. 7 of water. Embodiment 4. Process according to either Embodiment of Embodiments 1 to 3, wherein the residual stream comprises greater than or equal to about 0.11 by weight of 7 of the HI hydrogen iodide Embodiment 1 - 4. Process according to Embodiment 4, wherein at least a portion of the HI hydrogen iodide is produced In a distillation column, Embodiment 5. Process according to any of Embodiments 1 to 1-4, wherein the percentage reduction between the first and third density is from 75 to 710. Embodiment 6. Process according to any of Embodiments 1 to 5, wherein Distillation of the feed stream A first liquid phase includes greater than about 50 weight 7 of water and a second liquid phase includes greater than about 0 weight A of methyl iodide in the distillation area » Whereas the distillation area 5 1 includes a set of internal components; Each of them has a volume of liquid matter retention from the component;» and where the mean retention time of the first liquid phase and the mean retention time of the second liquid phase in each of the liquid material retention volumes of the component is less than 30 min. First liquid phase in at least one retention volume of liquid 0 of the constituent Embodiment 8. Process according to any of Embodiments 1 to 7; additionally includes directing a peak rush stream comprising water to the distillation zone at a mass flow rate greater than or equal to about 70.1 of The mass flow rate of the feed stream.

— 0 5 — embodiment 9. Operation according to embodiment 8; Where the apical impulse current includes a section of the lower lagging current. Embodiment 10. Process according to any of Embodiments 1 to 9; further comprising the directing of a downstream surge comprising cacetic acid water; or both to the lower trough area at a mass flow rate greater than or equal to about 70.1 of the feed stream's mass flow rate. Embodiment 11. Process according to any of Embodiments 1 to 11; where the upstream contains dimethyl ether Jie embodiment 1-11. process according to any of Embodiments 1 to 11; where the stream lal) comprises from 0.1 wt.7 to 50 wt.7 dimethyl ether embodiment 2-11. process according to any of Embodiments 11 or 1-11; Where at least a portion of dimethyl ether is produced in the distillation column. Embodiment 12. Process comprising: J acrylate reaction medium comprising reactant feed stream comprising methanol; methyl acetate; dimethyl ether or mixtures thereof; cole; radium catalyst; rhodium 5 salt iodide and methyl iodide in a reactor to form acetic tacid B. Distillation of a stream derived from the reaction medium in a first column to produce a side stream acetic acid additionally purified to produce the product stream cacetic acid and an upper stream 1st including methyl iodide “water” acetic acid 8081816 except 008; at least one 5 PRC; 0 C. Two-phase separation of the first upper stream into a light phase comprising “methyl iodide PRC “methyl acetate at least one acetic acid” and greater than about 30 wt. 7 of water; and a heavy phase comprising cacetic acid “at least one wt. PRC methyl acetate” and greater than about 30 wt. 7 of ¢methyl iodide

— 1 5 — d. directing a feed stream of a second column comprising or derived from the heavy phase to a second distillation column comprising a distillation area and a lower basin area; H. distillation of the Sal column feed stream at sufficient pressure and temperature to yield z a second upper stream of second density and comprising greater than about 40 wt. 7 of PRC methyl iodide; One methyl iodide on (BY) 5 and a backward stream flowing from the lower basin region has a third density lower than the first; It includes greater than about 0.1 7039 cele where the percentage decrease between the first density and the second density is from 720 to 735; And the. extract at least one section from the upper stream of the second column comprising at least one methyl iodide PRC; with water to produce a water stream including at least one PRC; 0 A chord of a purified substance has a fourth density greater than the first; which includes greater than Mss 90 wt. 7 ¢tmethyl iodide and g. Directing at least a first part of the purified stream back to the distillation area of the second distillation column. embodiment 13. Operation according to embodiment 12; Cua The specific gravity of the second density with respect to water is from 1.15 to 1.6 when specified at 10" cua. Embodiment 14. Process according to Embodiments 12 or 13; wherein the percentage increase between density first and density four is from 710 to 720. Embodiment 15. Process according to any of Embodiments 12 to 14; further includes directing a top rush stream comprising water to the second distillation column distillation zone at a mass flow rate greater than or equal to about 70.1 of the mass flow rate of the second column feed stream wherein the top rush stream 0 comprises a section of the lower residual stream; at least one portion of the first portion of the purified material stream; a portion of the light phase separated from the first upper stream; or a combination thereof. lew includes cacetic acid water; or both to the lower basin area of the distillation column

— 2 5 — second at a mass flow rate greater than or equal to about 70.1 of the second shaft feed stream's mass flow rate. Embodiment 17. Process according to any of Embodiments 12 to 16; Where the upper stream of the second column includes dimethyl ether and additionally includes directing a second section of the purified stream comprising methyl iodide 5 dimethyl ether Jie St back to the reaction medium. embodiment 18. Process according to embodiment 17; where the mass flow rate of the first part of the softener stream is greater than or equal to the mass flow rate of the second part of the softener stream. Embodiment 19. Process according to any of Embodiments 12 to 18) wherein the degree of Sha 0 bottom of the second distillation column is about 70" to 100"C. Embodiment 20. Process according to any of Embodiments 12 to 19 wherein the degree of Sha top of the second distillation column is about 0° to 45°60; Cua the pressure of the second distillation column is embodiment 21. Process according to any of embodiments 12 through 20; wherein the HI concentration is 15 in the medium Je tal) From 0.1 to 1 3 WEIGHT 7. Embodiment 22. Process according to any of Embodiments 12 to 21; The concentration of the radium catalyst in the reaction medium ranges from 300 to 3000 w/ppm. Embodiment 23. Process according to any of Embodiments 12 to 22; wherein the concentration of water in the medium (Je tal) is from 0.1 to 4.1 wt. 7. Embodiment 24. Process according to any of Embodiments 12 to 23; Where the concentration of methyl acetate in the reaction medium ranges from 0.6 to 4.1 by weight of 7.

— 3 5 — embodiment 25. Process according to any of embodiments 12 to 14; The partial hydrogen pressure in the reactor is 0.3 to 2 atm. Embodiment 26. Process according to any of Embodiments 12 to 25; It additionally includes introducing a lithium compound selected from the group consisting of dlithium acetate lithium carbonates dithium carboxylates lithium chydroxide and steps from that into the reactor to maintain the concentration of lithium acetate from 0.3 to 0.7 Weigh 7 in the reaction medium. Embodiment 27. Process according to any of Embodiments 12 to 26; It additionally includes controlling the concentration of butyl acetate in the acetic acid product stream at 10 w/ppm or

.acetic acid directly from the product of butyl acetate ali} less without 0

Exodus 28. Process according to Exodus 27 Cus The concentration of butyl acetate in the product stream acetic acid is controlled by maintaining the concentration of acetaldehyde in the reaction medium at 0 ppm or less.

Embodiment 29. Process according to Embodiment 27 or 28) where the concentration of butyl acetate is controlled

5 in the acetic acid product stream by controlling the temperature in the krill reactor from 150 to

0 residual.

Embodiment 30. Process according to any of Embodiments 27 to 29; The concentration of butyl acetate in the acetic acid product stream is controlled by controlling the partial hydrogen pressure in the reactor from 0.3 to 2 atm.

Embodiment 31. Process according to any of Embodiments 27 to 30; Where the concentration of butyl acetate in the acetic acid product stream is controlled by controlling the concentration of the radium metal catalyst, rhodium, in the reaction medium from 100 to 3000 weight per ppm.” based on the total weight of the reaction medium.

— 4 5 — Embodiment 32. The process according to any of Embodiments 12 through 31 additionally includes controlling the concentration of ethyl iodide in the reaction medium at less than or equal to 750 w/ppm. Embodiment 33. Process according to any of Embodiments 12 to 32; Additional includes control of propionic acid to less than 250 wp ela per million without propionic acid 4) directly from the product .acetic acid embodiment 34. Process according to embodiment 32 to 33 where ethyl iodide is present in The reaction medium and 8010 propionic in the product acetic acid in a weight ratio of 1:3 to 2:1. Embodiment 35. Process according to any of Embodiments 32 to 34; Cus ethyl iodide 5 acetaldehyde 0 is present in the reaction medium in a weight ratio of 1:2 to 1:20. Embodiment 36. Process according to any of Embodiments 32 to 35; where the methanol source comprises methanol from the krill reactor containing less than 150 wt gia per million of ethanol Embodiment 37. Process according to any of Embodiments 32 to 36; where the concentration of 100 106 ethyl in the reaction medium is controlled by controlling the partial hydrogen pressure in the Krill 5 reactor. Embodiment 38. Process according to any of Embodiments 32 to 37; Where the concentration of ethyl iodide in the reaction medium is controlled by controlling the concentration of methyl acetate in the reaction medium. Embodiment 39. Process according to any of Embodiments 32 to 38; Where the 0 concentration of ethyl iodide in the reaction medium is controlled by controlling the concentration of methyl iodide in the medium (Je tal). Embodiment 40. Process according to any of Embodiments 12 to 39; wherein the second upper stream comprises from 0.1 7035 to 50 wt 7 of .dimethyl ether

— 5 5 — Embodiment 41. Process according to Embodiment 40) wherein at least one portion of dimethyl ether is produced in the distillation column. Embodiment 42. Process according to any of Embodiments 12 to 41, wherein the residual stream which flows from Second distillation column basin on greater than or equal to about 0.11 weight of HE embodiment 43. Process according to embodiment 42 where at least one portion of HI hydrogen iodide is produced in the distillation column. Whereas embodiments are described and explained Detailed in the above drawings and descriptions; the same is taken into account as an illustration rather than a limitation; it is understood that only some embodiments are illustrated and described and that all changes and modifications within the scope of the embodiments must be protected. It must be understood that the use of the words (Lilie Jie) desirable; preferred” in cami form (Jambo more preferred or representative) used in the above description denotes the characteristic described may be more desirable or distinctive ¢ however may be superfluous and embodiments not containing the same as in the scope of the invention may be conceived; The field is subject to the following claims water 5 is meant when dan' da Jie '(at least one) or ad '(at least one portion) is not intended to limit the claims to only one element. The specification dag is not otherwise specified in the claims.

Claims (1)

Claims 1- A process that includes: (a) Provide a feed stream having an initial density comprising water; ‎acetic acid‎ acetic acid; Methyl acetate + permanganate reducing compounds (PRC compound) and greater than 30 wt. 7 methyl iodide to the distillation column including distillation area and bottom basin area; And (b) distillation of the feed stream at a pressure and temperature sufficient to produce an upper stream of a second density and comprising greater than 40 wt. 7 of methyl iodide and the said PRC permanganate reducing compound; Where the ratio between the first density and the second density decreases to be from 720 to 735; wherein the lagging stream which flows from the bottom basin area has a third density which is lower than the first density; It contains more than 0.1 by 7 water; where the residual stream comprises greater than or equal to 0.11 by weight of 7 HI and where a portion of the HI hydrogen iodide is produced in the distillation column. 5 2. The process pursuant to claim 1; where the specific gravity of the secondary density with respect to water is from 5 to 1.6 when it is determined at 10" density. 3- Process according to claim 1; whereby the percentage decreases between the first density and the third density which is from 75 to 710. 4. The process according to claim 1; Where the distillation of the feed stream produces a first liquid phase comprising LSI of 50 wt. 7 water shally, the second liquid comprising more than 50 wt. 7 Jala methyl iodide. Each has a component liquid retention volume; and where is the mean retention time of the liquid phase — 5 7 — The first, average, and retention time of the second liquid phase in each of the component liquid retention volumes is less than 0 min. 5. The process according to claim 4; where the mean retention time of the second liquid phase is greater than or equal to the mean retention time of the first liquid phase in a one-component liquid retention volume. 6- Operation Wy of claim 1; further comprising the directing of an apical surge stream comprising water in the distillation zone at a mass flow rate that is greater than or equal to 70.1 of the trim lal mass flow rate; and/or directing a downstream surge containing acetic acid; or both in the bottom basin area at a mass flow rate that is greater than or equal to 70.1 for the trim stream mass flow rate. 7. The process according to claim 6; The apical impulse current includes a section of the lower lagging current. 5 8 The process pursuant to claim 1; The upper stream contains dimethyl ether .ether 9- A process comprising: (a) cryolization of a reaction medium comprising a reactant feed stream comprising methanol, dimethyl ether, “methyl acetate”; or mixtures of eld cole catalyst rhodium iodide and methyl iodide in a reactor to form acetic acid 80616; (b) Distillation of a derived stream from the reaction medium in a first column to produce a side stream of acetic acid which is further purified to produce a zie acetic acid stream and a first top stream 5 comprising methyl iodide water; acetic acid, methyl acetate tPRC, and permanganate reductase compounds “methyl acetate (c) Two-phase separation of the first upper stream into a light phase comprising methyl iodide iodide Jill ¢ acetic acid 8010 806116; the said PRC methyl acetate and greater than 30 7039 cele and a heavy phase comprising water “” Acetic acid PRC “methyl acetate (Jill) mentioned; and greater than 30 wt# of methyl iodide 5 (d) Directing a second column feed stream comprising or derived from the heavy phase to the distillation column The second includes a distillation area and a bottom basin area; (e) Distillation of the second column feed stream at sufficient pressure and temperature to produce a second upper stream having a dali mass and where it contains greater than 40 weight 7 jodide except 008; 00 “Sal” and a stream of 0 residual flowing from the bottom basin area having a third density which is lower than the first density; where it includes a ST of 0.1 weight of 7 cele where the percentage decreases between the first density and the second density which is from 720 to 735; (f) extraction of a portion of The upper stream of the second column comprising methyl iodide and the aforementioned PRC permanganate reductase compounds with ele to produce a water stream comprising For the aforementioned PRC permanganate reductase compounds; and a purified sale stream (raffinate) has a daly density that is greater than the first density” and where it includes greater than 90 by weight of 7 iodide at 76; and (g) directing a first section of the raffinate stream back to the distillation zone of the second distillation column; Where the residual stream flows from the bottom basin of the second distillation column comprising greater than or equal to 0 0.11 weight of hydrogen iodide, HE, where a portion of hydrogen iodide, AHI, is produced in the second distillation column. 0 The process according to claim 9 where the specific gravity of the second density with respect to water is from 5 to 1.6 Lexie is determined at 10 “Celsius” and/or where the percentage increases between the first density 5 and the fourth density which is from 710 to 720. 1. The process pursuant to claim 9; further comprising the directing of an apical surge stream comprising water to the distillation zone of the second distillation column at a mass flow rate greater than or equal to 70.1 lal mass flow rate of the second column feed where the apical surge stream comprises a portion of the lower tail stream; At a section of the first section of the purified material stream o(raffinate) a section of the light stream separated from the first upper stream; or union thereof; and/or additionally include a downstream surge steer containing acid 90608 acetic acid; cole or both to the bottom pan area of the second distillation column at a mass flow rate greater than or equal to 70.1 of the second column feed stream's mass flow rate. 0 12- The process according to Claim 9 Cum The upper stream of the second column includes dimethyl ether and additionally includes directing a second section of the purified material stream (raffinate) comprising hydrogen iodide methyl iodide and 6163 except 0106 ether Dimethyl by reference to the reaction medium. 5 13- Process according to claim 12) where the mass flow rate of the first part of the refinery stream is greater than or equal to the mass flow rate of the second part of the refined material stream 4- The process according to Clause 9 (raffinate). The pressure of the second distillation column is from atmospheric pressure to 700 kPa higher than atmospheric pressure, where the concentration of AHI in the reaction medium is from 0.1 to 1.3 wt7, where the concentration of the rhodium catalyst in the reaction medium is from 300 to 3000 wt per million; Where the concentration of water in the reaction medium is from 0.1 to 4.1 wt 7; where the concentration of methyl acetate in the reaction medium is from 0.6 to 4.1 wt7; Where the partial hydrogen pressure in the reactor is from 30.4 to 202.7 kPa (0.3 to 2 atmospheres); or a union thereof. 5- The process according to claim 9 where it additionally includes: (1) the introduction of a lithium compound selected from the group consisting of clithium acetate lithium carboxylates lithium carbonates 10 lithium hydroxide clithium hydroxide and mixtures thereof to the reaction medium to maintain a concentration of lithium acetate between 0.3 and 0.7 wt. 7 in the reaction medium; (2) Controlling the concentration of butyl acetate in the acetic acid product stream at 10 w/ppm or less without removing butyl acetate 186 directly from the acetic acid product stream. 3) Controlling the concentration of ethyl iodide in the reaction medium at less than or equal to 0 w/ppm; or a combination thereof. 6-1 — Jah m / rat aa te mah malaga naa sa sara A with aa aa sass Ae more general nn ian ar at aa aha um a oe den l And his nation is more general than what he said about his nation. ITN TY, AE id i. ) ES Sus ww SHA ' X A 3 Mag , - ; : ! 2 Classes R Ra : A yw > CC j : a" A 7 0 Lar Matta Aves Sir 4 Le Pel HR 8 : 1 Les : § Sg? 1 : i 4 1 1 : 1 D 1 Insomnia Nd 207 RAEN EE Nd Count J Return: A y H 1 A L: 1 º: A” A SN A 1 2 § :: .. 1: A 4 SUR FAT I SE cE YT EE : YE 0 bd vay - SN Fa I SE == AYA k x Ye 3 vat ; a.b!1 3 Yo - 1 STS MeOH ;Fas Ba EY : ¥ SRE A 1 'Co ten bs amob oe at eer mt ee a | 0 ja abla ee oi oi product 1 form 0 6 2 0 B 0 & Bo in your absorbent (the 55 AH ((Waa: A ML 1 GA 1 1 1 § 2 2) º A Lll ee Z 1 BE a ) 1 l £7 Pant : H } N AA 7 BAER a ! AY ) wr VEY Ad : EE secret ; ; A 5 and H EY 1 1 5 1 ¢ A B } Noone SN, 141 N N § 3 . X Cw 1 be Z : 3 1 H a 1 01 : 1 ¢ mi ima wm sme wm ber mm Sms mm mms mm. d mn wm ema mm sme wm ves am ad 0" | 2 > 11 Back Ay YORE — 3 6 — YoY cm for a | LFA 3 i = ¥ EI | 3 00000000 sr 00000000 sr 00000099 [ Ny ESE 9% 990000 hag , 00000000 blkhlmm “H'hama. z YAY TEN 00800000 PALE 0_7 , a] 7 a , z ah six current amperage 0 co da sad Fe mene nd a z © © © © © © © MIEN | A « KELLELELMN z hah) 009000000 CLL XX) ِ Lla A La La Pa | + + No A ERE Ye | | 9 . Crime 5 08 Yr / Aja AN HE | | l sna LO and the hills” + hati l d l form ¢ YY. ry. ry, 7 ery } m ) bm } ah BNE “EE PE Emit a to break the shape oe a yyy ry 1 bm y es TT s Tel To = - form + 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