# US 10,308,581 B2 · Method for producing acetic acid > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,308,581 B2 - Document ID: US10308581B2 - Status: Granted - Kind: B2 - Application number: 15/542,855 - Filed: 2017-05-25 - Published: 2018-10-04 - Granted: 2019-06-04 - Earliest claimed: 2017-03-28 - Assignees: Daicel Corporation - Applicants: Daicel Corporation - Inventors: Masahiko Shimizu - Web page: https://patentgrep.com/patent/US10308581B2 ## CPC - C07C 51/12: on an oxygen-containing group in organic compounds, e.g. alcohols - B01D 3/009: {in combination with chemical reactions} - B01D 3/143: {by two or more of a fractionation, separation or rectification step} - C07C 51/44: by distillation - C07C 53/08: Acetic acid (pyroligneous acid C10C; preparation of vinegar C12J) - Y02P 20/10: Process efficiency - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract There is provided a method allowing industrially efficient production of high quality acetic acid having a good potassium permanganate test value and a low impurity content without a large cost. The method for producing acetic acid according to the present invention has a carbonylation reaction step, an evaporation step and a lower boiling point component removal step, and wherein with heating of the evaporator, (i) an acetaldehyde concentration in the aqueous phase of an overhead condensate in a lower boiling point component removal column is controlled to not less than 2340 ppm by mass; and/or (ii) a methyl acetate concentration in the aqueous phase is controlled to less than 19.0% by mass and/or; (iii) a methyl acetate concentration in the organic phase of the overhead condensate in the lower boiling point component removal column is controlled to less than 38.0% by mass, and then at least a portion of the aqueous phase is treated in the acetaldehyde separation and removal step to recycle a residual liquid after the acetaldehyde separation and removal to the reaction vessel and/or the acetaldehyde separation and removal step and/or other processes. ## Claims ### Claim 1 A method for producing acetic acid, comprising: a carbonylation reaction step of reacting methanol with carbon monoxide in a reaction vessel in the presence of a catalyst system containing a metal catalyst and methyl iodide as well as acetic acid, methyl acetate, and water to produce acetic acid; an evaporation step of introducing and heating a reaction mixture obtained in the carbonylation reaction step in an evaporator to separate the reaction mixture into a vapor stream and a residual liquid stream; a residual liquid stream recycle step of recycling the residual liquid stream to the reaction vessel; a lower boiling point component removal step of separating the vapor stream with a first distillation column into a first overhead stream rich in methyl iodide and acetaldehyde and a first acetic acid stream rich in acetic acid and of condensing and separating the first overhead stream to obtain an aqueous phase and an organic phase; a first overhead stream recycle step of recycling at least a portion of the aqueous phase and/or the organic phase to the reaction vessel; and an acetaldehyde separation and removal step of separating and removing acetaldehyde in a process stream, wherein the ratio between the vapor stream and the residual liquid stream to be separated in the evaporation step is 28/72 to 60/40 in terms of a mass ratio wherein evaporation rate is 28 to 60% by mass, wherein with regard to operation conditions of the first distillation column, when only the aqueous phase is refluxed to the first distillation column, a reflux ratio of the aqueous phase is not less than 2; when only the organic phase is refluxed, a reflux ratio of the organic phase is not less than 1; and when both the aqueous and organic phases are refluxed, a total reflux ratio of the aqueous and organic phases is not less than 1.5, and wherein with heating of the evaporator, (i) an acetaldehyde concentration in the aqueous phase is controlled to not less than 2340 ppm by mass; (ii) a methyl acetate concentration in the aqueous phase is controlled to less than 19.0% by mass; and (iii) a methyl acetate concentration in the organic phase is controlled to less than 38.0% by mass, and at least a portion of the aqueous phase is treated in the acetaldehyde separation and removal step to recycle a residual liquid after the acetaldehyde separation and removal to the reaction vessel and/or the acetaldehyde separation and removal step and/or other processes. ### Claim 2 (depends on 1) The method for producing acetic acid according to claim 1, wherein the catalyst system further contains an ionic iodide. ### Claim 3 (depends on 1) The method for producing acetic acid according to claim 1, further comprising a dehydration step of separating the first acetic acid stream with a second distillation column into a second overhead stream rich in water and a second acetic acid stream more enriched with acetic acid than the first acetic acid stream. ### Claim 4 (depends on 3) The method for producing acetic acid according to claim 3, wherein in the second acetic acid stream, a crotonaldehyde concentration is not more than 1.10 ppm by mass; and/or a 2-ethyl crotonaldehyde concentration is not more than 0.80 ppm by mass; and/or a propionic acid concentration is not more than 130 ppm by mass. ### Claim 5 (depends on 1) The method for producing acetic acid according to claim 1, wherein an acetaldehyde concentration in the residual liquid stream in the evaporator is set to not more than 70 ppm by mass. ### Claim 6 (depends on 1) The method for producing acetic acid according to claim 1, wherein in the reaction mixture liquid of the reaction vessel, a crotonaldehyde concentration is not more than 1.7 ppm by mass; and/or a 2-ethyl crotonaldehyde concentration is not more than 1.8 ppm by mass; and/or a propionic acid concentration is not more than 240 ppm by mass. ### Claim 7 (depends on 1) The method for producing acetic acid according to claim 1, wherein in the vapor stream fed to the first distillation column, a crotonaldehyde concentration is not more than 2.4 ppm by mass; and/or a 2-ethyl crotonaldehyde concentration is not more than 0. 45 ppm by mass; and/or a propionic acid concentration is not more than 106 ppm by mass. ### Claim 8 (depends on 1) The method for producing acetic acid according to claim 1, wherein in the first acetic acid stream, a crotonaldehyde concentration is not more than 1.34 ppm by mass; and/or a 2-ethyl crotonaldehyde concentration is not more than 0.60 ppm by mass; and/or a propionic acid concentration is not more than 106 ppm by mass. ### Claim 9 A method for producing acetic acid, comprising: a carbonylation reaction step of reacting methanol with carbon monoxide in a reaction vessel in the presence of a catalyst system containing a metal catalyst and methyl iodide as well as acetic acid, methyl acetate, and water to produce acetic acid; an evaporation step of introducing and heating a reaction mixture obtained in the carbonylation reaction step in an evaporator to separate the reaction mixture into a vapor stream and a residual liquid stream; a residual liquid stream recycle step of recycling the residual liquid stream to the reaction vessel; a lower boiling point component removal step of separating the vapor stream with a first distillation column into a first overhead stream rich in methyl iodide and acetaldehyde and a first acetic acid stream rich in acetic acid and of condensing and separating the first overhead stream to obtain an aqueous phase and an organic phase; a first overhead stream recycle step of recycling at least a portion of the aqueous phase and/or the organic phase to the reaction vessel; and an acetaldehyde separation and removal step of separating and removing acetaldehyde in a process stream, wherein the ratio between the vapor stream and the residual liquid stream to be separated in the evaporation step is 28/72 to 60/40 in terms of a mass ratio wherein evaporation rate is 28 to 60% by mass, and wherein with heating of the evaporator, (i) an acetaldehyde concentration in the aqueous phase is controlled to not less than 2340 ppm by mass; (ii) a methyl acetate concentration in the aqueous phase is controlled to not more than 17.5% by mass; and (iii) a methyl acetate concentration in the organic phase is controlled to not more than 35.0% by mass, and an acetaldehyde concentration in the residual liquid stream is controlled to not more than 70 ppm by mass; at least a portion of the aqueous phase is treated in the acetaldehyde separation and removal step to recycle a residual liquid after the acetaldehyde separation and removal to the reaction vessel and/or the acetaldehyde separation and removal step and/or other processes; and a reflux ratio of the aqueous phase of the first distillation column is not less than 2. ### Claim 10 (depends on 9) The method for producing acetic acid according to claim 9, wherein the catalyst system further contains an ionic iodide.