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<article article-type="research-article" dtd-version="1.3" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xml:lang="en"><front><journal-meta><journal-id journal-id-type="publisher-id">chemicallytech</journal-id><journal-title-group><journal-title xml:lang="en">Fine Chemical Technologies</journal-title><trans-title-group xml:lang="ru"><trans-title>Тонкие химические технологии</trans-title></trans-title-group></journal-title-group><issn pub-type="ppub">2410-6593</issn><issn pub-type="epub">2686-7575</issn><publisher><publisher-name>MIREA – Russian Technological University (RTU MIREA).</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.32362/2410-6593-2019-14-4-24-32</article-id><article-id custom-type="elpub" pub-id-type="custom">chemicallytech-1281</article-id><article-categories><subj-group subj-group-type="heading"><subject>Research Article</subject></subj-group><subj-group subj-group-type="section-heading" xml:lang="en"><subject>THEORETICAL BASIS OF CHEMICAL TECHNOLOGY</subject></subj-group><subj-group subj-group-type="section-heading" xml:lang="ru"><subject>ТЕОРЕТИЧЕСКИЕ ОСНОВЫ ХИМИЧЕСКОЙ ТЕХНОЛОГИИ</subject></subj-group></article-categories><title-group><article-title>Separation of water – formic acid – acetic acid mixtures in the presence of sulfolane</article-title><trans-title-group xml:lang="ru"><trans-title>Разделение смеси вода – муравьиная кислота – уксусная кислота в присутствии сульфолана</trans-title></trans-title-group></title-group><contrib-group><contrib contrib-type="author" corresp="yes"><contrib-id contrib-id-type="orcid">https://orcid.org/0000-0002-5664-4409</contrib-id><name-alternatives><name name-style="eastern" xml:lang="ru"><surname>Раева</surname><given-names>В. М.</given-names></name><name name-style="western" xml:lang="en"><surname>Raeva</surname><given-names>V. M.</given-names></name></name-alternatives><bio xml:lang="ru"><p>кандидат технических наук, доцент кафедры химии и технологии основного органического синтеза </p><p>Scopus Author ID 6602836975,</p><p>ResearcherID C-8812-2014</p><p>119571, Россия, Москва, пр-т Вернадского, д. 86</p></bio><bio xml:lang="en"><p>Cand. of Sci. (Engineering), Associate Professor of the Chair of Chemistry and Technology of Basic Organic Synthesis</p><p>86, Vernadskogo pr., Moscow, 119571, Russia</p><p>Scopus Author ID 6602836975</p><p>ResearcherID C-8812-2014</p></bio><email xlink:type="simple">raevalentina1@gmail.com</email><xref ref-type="aff" rid="aff-1"/></contrib><contrib contrib-type="author" corresp="yes"><name-alternatives><name name-style="eastern" xml:lang="ru"><surname>Громова</surname><given-names>О. В.</given-names></name><name name-style="western" xml:lang="en"><surname>Gromova</surname><given-names>O. V.</given-names></name></name-alternatives><bio xml:lang="ru"><p>магистр, кафедра химии и технологии основного органического синтеза</p><p>119571, Россия, Москва, пр-т Вернадского, д. 86</p></bio><bio xml:lang="en"><p>Master, Chair of Chemistry and Technology of Basic Organic Synthesis</p><p>86, Vernadskogo pr., Moscow, 119571, Russia</p></bio><xref ref-type="aff" rid="aff-1"/></contrib></contrib-group><aff-alternatives id="aff-1"><aff xml:lang="ru"><institution>МИРЭА – Российский технологический университет (Институт тонких химических технологий имени М.В. Ломоносова)</institution><country>Россия</country></aff><aff xml:lang="en"><institution>MIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)</institution><country>Russian Federation</country></aff></aff-alternatives><pub-date pub-type="collection"><year>2019</year></pub-date><pub-date pub-type="epub"><day>31</day><month>08</month><year>2019</year></pub-date><volume>14</volume><issue>4</issue><fpage>24</fpage><lpage>32</lpage><permissions><copyright-statement>Copyright &amp;#x00A9; Raeva V.M., Gromova O.V., 2019</copyright-statement><copyright-year>2019</copyright-year><copyright-holder xml:lang="ru">Раева В.М., Громова О.В.</copyright-holder><copyright-holder xml:lang="en">Raeva V.M., Gromova O.V.</copyright-holder><license xml:lang="ru" license-type="creative-commons-attribution" xlink:href="https://creativecommons.org/licenses/by/4.0/" xlink:type="simple"><license-p>Данная работа распространяется под лицензией Creative Commons Attribution 4.0.</license-p></license><license xml:lang="en" license-type="creative-commons-attribution" xlink:href="https://creativecommons.org/licenses/by/4.0/" xlink:type="simple"><license-p>This work is licensed under a Creative Commons Attribution 4.0 License.</license-p></license></permissions><self-uri xlink:href="https://www.finechem-mirea.ru/jour/article/view/1281">https://www.finechem-mirea.ru/jour/article/view/1281</self-uri><abstract><p>In this paper, extractive distillation flowsheets for water–formic acid–acetic acid mixtures were designed. Flowsheets not involving preliminary dehydration were considered, and the relative volatilities of the components in the presence of sulfolane were analyzed. The result of extractive distillation depends on the amount of sulfolane. The structure of the flowsheet is determined by the results of the basic ternary mixture extractive distillation. In three-column flowsheets (schemes I, II), water is isolated in the distillate of the extractive distillation column. In the second column, distillation of the formic acid–acetic acid–sulfolane mixture is carried out, yielding formic acid (90 wt %) and acetic acid (80 wt %). The recycled flow is returned to the first column. Dilution of the formic acid–acetic acid–sulfolane mixture with sulfolane (second column of flowsheet II) allows for acids of higher quality (main substance content equal to or more than 98.5 wt %) to be obtained. Flowsheet III includes four columns and two recycling stages. First, the water–formic acid mixture is isolated in the distillate of the extractive distillation column. Then, water and formic acid are separated in a two-column complex by extractive distillation, also with sulfolane. We were carrying out calculations for column working pressure 101.32 and 13.33 kPa. To prevent thermal decomposition of sulfolane, working pressure for regeneration columns was always 13.33 kPa. The extractive distillation column of the basic three-component mixture is the main factor contributing to the total energy consumption for separation (in all schemes).</p></abstract><trans-abstract xml:lang="ru"><p>При экстрактивной ректификации (ЭР) водных смесей низших карбоновых кислот (муравьиной и уксусной), в зависимости от выбора селективного агента, возможно выделение в дистиллате воды или смеси вода – муравьиная кислота. Однако обычно задача выделения всех практически чистых компонентов не рассматривается. Здесь предлагаются схемы выделения муравьиной (МК) и уксусной (УК) кислот из водной смеси экстрактивной ректификацией (ЭР) с сульфоланом, не предусматривающие предварительное обезвоживание. Анализ рядов относительных летучестей компонентов в присутствии сульфолана показал, что в зависимости от количества вводимого агента возможны три варианта организации ЭР. В схемах, состоящих из трех колонн, в дистиллате колонны ЭР базовой смеси вода–МК–УК выделяют воду, в последней колонне схемы УК отделяют от агента, возвращаемого в первую колонну схемы. Во второй колонне схемы I проводят ректификацию смеси МК–УК–сульфолан с получением МК (90% масс.) и УК (80% масс.), в схеме II смесь МК–УК разбавляют сульфоланом, что позволяет получать кислоты более высокого качества: МК (УК) с содержанием основного вещества не менее 98.5% масс. Схема III состоит из двух двухколонных комплексов ЭР: сначала выделяют смесь воды и муравьиной кислоты, которую затем разделяют ЭР также с сульфоланом. Расчеты схем проведены для рабочих давлений колонн 101.32 и 13.33 кПа. Для предотвращения термического разложения сульфолана колонны регенерации всегда работают при давлении 13.33 кПа. Максимальный вклад в суммарные энергозатраты на разделение во всех схемах вносит колонна ЭР базовой трехкомпонентной смеси.</p></trans-abstract><kwd-group xml:lang="ru"><kwd>муравьиная кислота</kwd><kwd>уксусная кислота</kwd><kwd>вода</kwd><kwd>сульфолан</kwd><kwd>экстрактивная ректификация</kwd><kwd>схема разделения</kwd></kwd-group><kwd-group xml:lang="en"><kwd>formic acid</kwd><kwd>acetic acid</kwd><kwd>water</kwd><kwd>sulfolane</kwd><kwd>extractive distillation</kwd><kwd>separation flowsheet</kwd></kwd-group><funding-group><funding-statement xml:lang="ru">Работа выполнена при финансовой поддержке гранта РФФИ № 1803-01224-а.</funding-statement></funding-group></article-meta></front><back><ref-list><title>References</title><ref id="cit1"><label>1</label><citation-alternatives><mixed-citation xml:lang="ru">Кушнер Т.М., Тациевская Г.И., Серафимов Л.А., Львов С.В. Выделение низших карбоновых кислот из фракции оксидата прямогонного бензина // Хим. пром. 1969. № 1. C. 20–23</mixed-citation><mixed-citation xml:lang="en">Kushner T.M., Tatsiyevskaya G.I., Serafimov L.A., Lʼvov S.V. Isolation of lower carboxylic acids from the fraction of straight-run gasoline oxide. Khimicheskaya promyshlennostʼ= Chemical Industry. 1969;1:20-23 (in Russ.).</mixed-citation></citation-alternatives></ref><ref id="cit2"><label>2</label><citation-alternatives><mixed-citation xml:lang="ru">Фролов Г.М., Шабуров М.А. Производство уксусной кислоты. М.: Лесная промышленность, 1978. 240 с</mixed-citation><mixed-citation xml:lang="en">Frolov G.M., Shaburov M.A. Acetic acid production. Moscow: Lesnaya promyshlennostʼ Publ., 1978. 240 p. (inRuss.).</mixed-citation></citation-alternatives></ref><ref id="cit3"><label>3</label><citation-alternatives><mixed-citation xml:lang="ru">Muurinen E.I., Solo J.K. Solvent recovery in peroxyacid pulping. In: Proceed. of the First European Congress on Chemical Engineering. Florence, Italy. May 4-7, 1997;1:543-552.</mixed-citation><mixed-citation xml:lang="en">Muurinen E.I., Solo J.K. Solvent recovery in peroxyacid pulping. In: Proceed. of the First European Congress on Chemical Engineering. Florence, Italy. May 4-7, 1997; 1:543-552.</mixed-citation></citation-alternatives></ref><ref id="cit4"><label>4</label><citation-alternatives><mixed-citation xml:lang="ru">Painer D., Lux S., Grafschafter A., Toth A., Siebenhofen M. Isolation of carboxylic acids from biobased feedstock. Chem. Ing. Tech. 2017;89(1-2):161-171. https://doi.org/10.1002/cite.201600090</mixed-citation><mixed-citation xml:lang="en">Painer D., Lux S., Grafschafter A., Toth A., Siebenhofen M. Isolation of carboxylic acids from biobased feedstock. Chem. Ing. Tech. 2017;89(1-2):161-171. https://doi.org/10.1002/cite.201600090</mixed-citation></citation-alternatives></ref><ref id="cit5"><label>5</label><citation-alternatives><mixed-citation xml:lang="ru">Patil K.D., Kulkarni B.D. Review of recovery methods for acetic acid from industrial waste streams by reactive distillation. J. Water Pollut. Purif. Res. 2014;1(2):13-18. https://www.researchgate.net/publication/263327618</mixed-citation><mixed-citation xml:lang="en">Painer D., Lux S., Grafschafter A., Toth A., Siebenhofen M. Isolation of carboxylic acids from biobased feedstock. Chem. Ing. Tech. 2017;89(1-2):161-171. https://doi.org/10.1002/cite.201600090</mixed-citation></citation-alternatives></ref><ref id="cit6"><label>6</label><citation-alternatives><mixed-citation xml:lang="ru">Saha B., Chopade S., Mahajan S. Recovery of dilute acetic acid through esteriﬁcation in a reactive distillation column. Catal. Today. 2000;60(1):147-157. http://dx.doi.org/10.1016/S0920-5861(00)00326-6</mixed-citation><mixed-citation xml:lang="en">Patil K.D., Kulkarni B.D. Review of recovery methods for acetic acid from industrial waste streams by reactive distillation. J. Water Pollut. Purif. Res. 2014;1(2):13-18. https://www.researchgate.net/publication/263327618</mixed-citation></citation-alternatives></ref><ref id="cit7"><label>7</label><citation-alternatives><mixed-citation xml:lang="ru">Painer D., Lux S., Siebenhofen M. Recovery of formic acid and acetic acid from waste water using reactive distillation. Separation Science and Technology. 2015;50(18):2930-2936. https://doi.org/10.1080/01496395.2015.1085407</mixed-citation><mixed-citation xml:lang="en">Patil K.D., Kulkarni B.D. Review of recovery methods for acetic acid from industrial waste streams by reactive distillation. J. Water Pollut. Purif. Res. 2014;1(2):13-18. https://www.researchgate.net/publication/263327618</mixed-citation></citation-alternatives></ref><ref id="cit8"><label>8</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Separation of formic acid from acetic acid by extractive distillation: pat. 4,692,219 US; ﬁled 12/03/1986; publ. 09/08/1987.</mixed-citation><mixed-citation xml:lang="en">Saha B., Chopade S., Mahajan S. Recovery of dilute acetic acid through esterification in a reactive distillation column. Catal. Today. 2000;60(1):147-157. http://dx.doi.org/10.1016/S0920-5861(00)00326-6</mixed-citation></citation-alternatives></ref><ref id="cit9"><label>9</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Separation of formic acid from acetic acid by extractive distillation with acetyl salicylic acid: pat. 4,909,907 US; ﬁled 01/17/1989; publ. 03/20/1990.</mixed-citation><mixed-citation xml:lang="en">Saha B., Chopade S., Mahajan S. Recovery of dilute acetic acid through esterification in a reactive distillation column. Catal. Today. 2000;60(1):147-157. http://dx.doi.org/10.1016/S0920-5861(00)00326-6</mixed-citation></citation-alternatives></ref><ref id="cit10"><label>10</label><citation-alternatives><mixed-citation xml:lang="ru">Cohen L.R. Method for separating carboxylic acids from mixtures with non-acids: pat. 4,576,683 US; ﬁled 06/06/1984; publ. 03/18/1986.</mixed-citation><mixed-citation xml:lang="en">Painer D., Lux S., Siebenhofen M. Recovery of formic acid and acetic acid from waste water using reactive distillation. Separation Science and Technology. 2015;50(18):2930-2936. https://doi.org/10.1080/01496395.2015.1085407</mixed-citation></citation-alternatives></ref><ref id="cit11"><label>11</label><citation-alternatives><mixed-citation xml:lang="ru">Muuriner E. A review and distillation study related to peroxyacid pulping. Organosolv pulping. Oulu, Finland: Publ. House Oulu Yliopisto, 2000. 314 p. http://herkules.oulu.ﬁ/isbn9514256611/isbn9514256611.pdf)</mixed-citation><mixed-citation xml:lang="en">Painer D., Lux S., Siebenhofen M. Recovery of formic acid and acetic acid from waste water using reactive distillation. Separation Science and Technology. 2015;50(18):2930-2936. https://doi.org/10.1080/01496395.2015.1085407</mixed-citation></citation-alternatives></ref><ref id="cit12"><label>12</label><citation-alternatives><mixed-citation xml:lang="ru">Sprakel L.M.J., Schuur B. Solvent developments for liquid-liquid extraction of carboxylic acids in perspective. Separation and Puriﬁcation Technology. 2019;211:935-957. https://doi.org/10.1016/j.seppur.2018.10.023</mixed-citation><mixed-citation xml:lang="en">Berg L. Separation of formic acid from acetic acid by extractive distillation: pat. 4,692,219 US; filed 12/03/1986; publ. 09/08/1987.</mixed-citation></citation-alternatives></ref><ref id="cit13"><label>13</label><citation-alternatives><mixed-citation xml:lang="ru">Behroozi M., Vahedpour M., Shardi Manaheji M. Separation of formic acid from aqueous solutions by liquid extraction technique at diﬀerent temperatures. Phys. Chem. Res. 2019;7(1):201-215. https://dx.doi.org/10.22036/pcr.2019.154646.1557</mixed-citation><mixed-citation xml:lang="en">Berg L. Separation of formic acid from acetic acid by extractive distillation: pat. 4,692,219 US; filed 12/03/1986; publ. 09/08/1987.</mixed-citation></citation-alternatives></ref><ref id="cit14"><label>14</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L., Yeh An-I. Dehydration of formic acid by extractive distillation: pat. 4,642,166 US; ﬁled 02/10/1986; publ. 02/10/1987.</mixed-citation><mixed-citation xml:lang="en">Berg L. Separation of formic acid from acetic acid by extractive distillation with acetyl salicylic acid: pat. 4,909,907 US; filed 01/17/1989; publ. 03/20/1990.</mixed-citation></citation-alternatives></ref><ref id="cit15"><label>15</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L., Kraig M., Szabados R.J. Dehydration of formic acid by extractive distillation: pat. 5,173,156 US; ﬁled 12/09/1991; publ. 12/22/1992.</mixed-citation><mixed-citation xml:lang="en">Berg L. Separation of formic acid from acetic acid by extractive distillation with acetyl salicylic acid: pat. 4,909,907 US; filed 01/17/1989; publ. 03/20/1990.</mixed-citation></citation-alternatives></ref><ref id="cit16"><label>16</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Dehydration of formic acid by extractive distillation: pat. 4,786,370 US; ﬁled 01/04/1988; publ. 11/22/1988.</mixed-citation><mixed-citation xml:lang="en">Cohen L.R. Method for separating carboxylic acids from mixtures with non-acids: pat. 4,576,683 US; filed 06/06/1984; publ. 03/18/1986.</mixed-citation></citation-alternatives></ref><ref id="cit17"><label>17</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Dehydration of formic acid by extractive distillation with dicarboxylic acids; pat. 4,877,490 US; ﬁled 01/23/1989; publ. 10/31/1989.</mixed-citation><mixed-citation xml:lang="en">Cohen L.R. Method for separating carboxylic acids from mixtures with non-acids: pat. 4,576,683 US; filed 06/06/1984; publ. 03/18/1986.</mixed-citation></citation-alternatives></ref><ref id="cit18"><label>18</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L., Yeh An-I. Dehydratation of impure formic acid by extractive distillation; pat. 4,735,690 US; ﬁled 04/28/1986; publ. 04/05/1988.</mixed-citation><mixed-citation xml:lang="en">Muuriner E. A review and distillation study related to peroxyacid pulping. Organosolv pulping. Oulu, Finland: Publ. House Oulu Yliopisto, 2000. 314 p. http://herkules.oulu.fi/isbn9514256611/isbn9514256611.pdf)</mixed-citation></citation-alternatives></ref><ref id="cit19"><label>19</label><citation-alternatives><mixed-citation xml:lang="ru">Buelow H., Hohenschutz H., Schmidt J.E., Sachsze W. Puriﬁcation of formic acid by extractive distillation; pat. 4,076,594 US; ﬁled 10/04/1976; publ. 02/28/1978.</mixed-citation><mixed-citation xml:lang="en">Muuriner E. A review and distillation study related to peroxyacid pulping. Organosolv pulping. Oulu, Finland: Publ. House Oulu Yliopisto, 2000. 314 p. http://herkules.oulu.fi/isbn9514256611/isbn9514256611.pdf)</mixed-citation></citation-alternatives></ref><ref id="cit20"><label>20</label><citation-alternatives><mixed-citation xml:lang="ru">Prajapati Chintan, Bhatt R.P. Separation of azeotropic mixture of formic acid − water by using Li-Br as a salt by extractive distillation. IJARIIE. 2016;2(3):607-612 (available from http://www.ijariie.com).</mixed-citation><mixed-citation xml:lang="en">Sprakel L.M.J., Schuur B. Solvent developments for liquid-liquid extraction of carboxylic acids in perspective. Separation and Purification Technology. 2019; 211:935-957. https://doi.org/10.1016/j.seppur.2018.10.023</mixed-citation></citation-alternatives></ref><ref id="cit21"><label>21</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Separation of formic acid from acetic acid by extractive distillation: pat. 54,692,219. US; ﬁled 03/12/1986; publ. 08/09/1987.</mixed-citation><mixed-citation xml:lang="en">Sprakel L.M.J., Schuur B. Solvent developments for liquid-liquid extraction of carboxylic acids in perspective. Separation and Purification Technology. 2019; 211:935-957. https://doi.org/10.1016/j.seppur.2018.10.023</mixed-citation></citation-alternatives></ref><ref id="cit22"><label>22</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Separation of formic acid from acetic acid by extractive distillation; pat. 5,227,029 US; ﬁled 01/29/1993; publ. 07/13/1993.</mixed-citation><mixed-citation xml:lang="en">Behroozi M., Vahedpour M., Shardi Manaheji M. Separation of formic acid from aqueous solutions by liquid extraction technique at different temperatures. Phys. Chem. Res. 2019;7(1):201-215. https://dx.doi.org/10.22036/pcr.2019.154646.1557</mixed-citation></citation-alternatives></ref><ref id="cit23"><label>23</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Separation of formic acid from acetic acid by extract separation of formic acid from acetic acid by extractive distillation; pat. 4,909,907 US; ﬁled 01/17/1989; publ. 03/20/1990.</mixed-citation><mixed-citation xml:lang="en">Behroozi M., Vahedpour M., Shardi Manaheji M. Separation of formic acid from aqueous solutions by liquid extraction technique at different temperatures. Phys. Chem. Res. 2019;7(1):201-215. https://dx.doi.org/10.22036/pcr.2019.154646.1557</mixed-citation></citation-alternatives></ref><ref id="cit24"><label>24</label><citation-alternatives><mixed-citation xml:lang="ru">Kirk-Othmer Encyclopedia of Chemical Technology. V. 8. Online ISBN: 9780471238966 Copyright © 1999-2014 by John Wiley and Sons, Inc.</mixed-citation><mixed-citation xml:lang="en">Berg L., Yeh An-I. Dehydration of formic acid by extractive distillation: pat. 4,642,166 US; filed 02/10/1986; publ. 02/10/1987.</mixed-citation></citation-alternatives></ref><ref id="cit25"><label>25</label><citation-alternatives><mixed-citation xml:lang="ru">Гайле А.А., Сомов В.Е., Варшавский О.М., Семенов Л.В. Сульфолан: Свойства и применение в качестве селективного растворителя. СПб.: Химиздат, 1998. 144 с.</mixed-citation><mixed-citation xml:lang="en">Berg L., Yeh An-I. Dehydration of formic acid by extractive distillation: pat. 4,642,166 US; filed 02/10/1986; publ. 02/10/1987.</mixed-citation></citation-alternatives></ref><ref id="cit26"><label>26</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Dehydration of acetic acid by extractive distillation; pat. 5,167,774 US; ﬁled 02/06/1992; publ. 12/01/1992.</mixed-citation><mixed-citation xml:lang="en">Berg L., Kraig M., Szabados R. J. Dehydration of formic acid by extractive distillation: pat. 5,173,156 US; filed 12/09/1991; publ. 12/22/1992.</mixed-citation></citation-alternatives></ref><ref id="cit27"><label>27</label><citation-alternatives><mixed-citation xml:lang="ru">Раева В.М. Особенности поведения азеотропных смесей и их разделение при варьировании давления. Дис. … канд. техн. наук. Москва,1998. 168 с.</mixed-citation><mixed-citation xml:lang="en">Berg L., Kraig M., Szabados R. J. Dehydration of formic acid by extractive distillation: pat. 5,173,156 US; filed 12/09/1991; publ. 12/22/1992.</mixed-citation></citation-alternatives></ref><ref id="cit28"><label>28</label><citation-alternatives><mixed-citation xml:lang="ru">Раева В.М., Фролкова А.К. Разделение азеотропных смесей с использованием комплексов, основанных на варьировании давления // Росс. хим. журн. 1998. Т. XLII. № 6. С. 76–88</mixed-citation><mixed-citation xml:lang="en">Berg L. Dehydration of formic acid by extractive distillation: pat. 4,786,370 US; filed 01/04/1988; publ. 11/22/1988.</mixed-citation></citation-alternatives></ref><ref id="cit29"><label>29</label><citation-alternatives><mixed-citation xml:lang="ru">Bates R.G., Pawlak Z. Solvent eﬀects on acid-base behavior: Five uncharged acids in water-sulfolane solvents. J. Solution Chem. 1976;5(3):213-222. https://doi.org/10.1007/BF00654338</mixed-citation><mixed-citation xml:lang="en">Berg L. Dehydration of formic acid by extractive distillation: pat. 4,786,370 US; filed 01/04/1988; publ. 11/22/1988.</mixed-citation></citation-alternatives></ref><ref id="cit30"><label>30</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Dehydration of formic acid by extractive distillation with dicarboxylic acids; pat. 4,877,490 US; filed 01/23/1989; publ. 10/31/1989.</mixed-citation><mixed-citation xml:lang="en">Berg L. Dehydration of formic acid by extractive distillation with dicarboxylic acids; pat. 4,877,490 US; filed 01/23/1989; publ. 10/31/1989.</mixed-citation></citation-alternatives></ref><ref id="cit31"><label>31</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Dehydration of formic acid by extractive distillation with dicarboxylic acids; pat. 4,877,490 US; filed 01/23/1989; publ. 10/31/1989.</mixed-citation><mixed-citation xml:lang="en">Berg L. Dehydration of formic acid by extractive distillation with dicarboxylic acids; pat. 4,877,490 US; filed 01/23/1989; publ. 10/31/1989.</mixed-citation></citation-alternatives></ref><ref id="cit32"><label>32</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L., Yeh An-I. Dehydratation of impure formic acid by extractive distillation; pat. 4,735,690 US; filed 04/28/1986; publ. 04/05/1988.</mixed-citation><mixed-citation xml:lang="en">Berg L., Yeh An-I. Dehydratation of impure formic acid by extractive distillation; pat. 4,735,690 US; filed 04/28/1986; publ. 04/05/1988.</mixed-citation></citation-alternatives></ref><ref id="cit33"><label>33</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L., Yeh An-I. Dehydratation of impure formic acid by extractive distillation; pat. 4,735,690 US; filed 04/28/1986; publ. 04/05/1988.</mixed-citation><mixed-citation xml:lang="en">Berg L., Yeh An-I. Dehydratation of impure formic acid by extractive distillation; pat. 4,735,690 US; filed 04/28/1986; publ. 04/05/1988.</mixed-citation></citation-alternatives></ref><ref id="cit34"><label>34</label><citation-alternatives><mixed-citation xml:lang="ru">Buelow H., Hohenschutz H., Schmidt J.E., Sachsze W. Purification of formic acid by extractive distillation; pat. 4,076,594 US; filed 10/04/1976; publ. 02/28/1978.</mixed-citation><mixed-citation xml:lang="en">Buelow H., Hohenschutz H., Schmidt J.E., Sachsze W. Purification of formic acid by extractive distillation; pat. 4,076,594 US; filed 10/04/1976; publ. 02/28/1978.</mixed-citation></citation-alternatives></ref><ref id="cit35"><label>35</label><citation-alternatives><mixed-citation xml:lang="ru">Buelow H., Hohenschutz H., Schmidt J.E., Sachsze W. Purification of formic acid by extractive distillation; pat. 4,076,594 US; filed 10/04/1976; publ. 02/28/1978.</mixed-citation><mixed-citation xml:lang="en">Buelow H., Hohenschutz H., Schmidt J.E., Sachsze W. Purification of formic acid by extractive distillation; pat. 4,076,594 US; filed 10/04/1976; publ. 02/28/1978.</mixed-citation></citation-alternatives></ref><ref id="cit36"><label>36</label><citation-alternatives><mixed-citation xml:lang="ru">Prajapati Chintan, Bhatt R.P. Separation of azeotropic mixture of formic acid − water by using Li-Br as a salt by extractive distillation. IJARIIE. 2016;2(3):607-612 (available from http://www.ijariie.com).</mixed-citation><mixed-citation xml:lang="en">Prajapati Chintan, Bhatt R.P. Separation of azeotropic mixture of formic acid − water by using Li-Br as a salt by extractive distillation. IJARIIE. 2016;2(3):607-612 (available from http://www.ijariie.com).</mixed-citation></citation-alternatives></ref><ref id="cit37"><label>37</label><citation-alternatives><mixed-citation xml:lang="ru">Prajapati Chintan, Bhatt R.P. Separation of azeotropic mixture of formic acid − water by using Li-Br as a salt by extractive distillation. IJARIIE. 2016;2(3):607-612 (available from http://www.ijariie.com).</mixed-citation><mixed-citation xml:lang="en">Prajapati Chintan, Bhatt R.P. Separation of azeotropic mixture of formic acid − water by using Li-Br as a salt by extractive distillation. IJARIIE. 2016;2(3):607-612 (available from http://www.ijariie.com).</mixed-citation></citation-alternatives></ref><ref id="cit38"><label>38</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Separation of formic acid from acetic acid by extractive distillation: pat. 54,692,219. US; filed 03/12/1986; publ. 08/09/1987.</mixed-citation><mixed-citation xml:lang="en">Berg L. Separation of formic acid from acetic acid by extractive distillation: pat. 54,692,219. US; filed 03/12/1986; publ. 08/09/1987.</mixed-citation></citation-alternatives></ref><ref id="cit39"><label>39</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Separation of formic acid from acetic acid by extractive distillation: pat. 54,692,219. US; filed 03/12/1986; publ. 08/09/1987.</mixed-citation><mixed-citation xml:lang="en">Berg L. Separation of formic acid from acetic acid by extractive distillation: pat. 54,692,219. US; filed 03/12/1986; publ. 08/09/1987.</mixed-citation></citation-alternatives></ref><ref id="cit40"><label>40</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Separation of formic acid from acetic acid by extractive distillation; pat. 5,227,029 US; filed 01/29/1993; publ. 07/13/1993.</mixed-citation><mixed-citation xml:lang="en">Berg L. Separation of formic acid from acetic acid by extractive distillation; pat. 5,227,029 US; filed 01/29/1993; publ. 07/13/1993.</mixed-citation></citation-alternatives></ref><ref id="cit41"><label>41</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Separation of formic acid from acetic acid by extractive distillation; pat. 5,227,029 US; filed 01/29/1993; publ. 07/13/1993.</mixed-citation><mixed-citation xml:lang="en">Berg L. Separation of formic acid from acetic acid by extractive distillation; pat. 5,227,029 US; filed 01/29/1993; publ. 07/13/1993.</mixed-citation></citation-alternatives></ref><ref id="cit42"><label>42</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Separation of formic acid from acetic acid by extract separation of formic acid from acetic acid by extractive distillation; pat. 4,909,907 US; filed 01/17/1989; publ. 03/20/1990.</mixed-citation><mixed-citation xml:lang="en">Berg L. Separation of formic acid from acetic acid by extract separation of formic acid from acetic acid by extractive distillation; pat. 4,909,907 US; filed 01/17/1989; publ. 03/20/1990.</mixed-citation></citation-alternatives></ref><ref id="cit43"><label>43</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Separation of formic acid from acetic acid by extract separation of formic acid from acetic acid by extractive distillation; pat. 4,909,907 US; filed 01/17/1989; publ. 03/20/1990.</mixed-citation><mixed-citation xml:lang="en">Berg L. Separation of formic acid from acetic acid by extract separation of formic acid from acetic acid by extractive distillation; pat. 4,909,907 US; filed 01/17/1989; publ. 03/20/1990.</mixed-citation></citation-alternatives></ref><ref id="cit44"><label>44</label><citation-alternatives><mixed-citation xml:lang="ru">Kirk-Othmer Encyclopedia of Chemical Technology. V. 8. Online ISBN: 9780471238966 Copyright © 1999-2014 by John Wiley and Sons, Inc.</mixed-citation><mixed-citation xml:lang="en">Kirk-Othmer Encyclopedia of Chemical Technology. V. 8. Online ISBN: 9780471238966 Copyright © 1999-2014 by John Wiley and Sons, Inc.</mixed-citation></citation-alternatives></ref><ref id="cit45"><label>45</label><citation-alternatives><mixed-citation xml:lang="ru">Kirk-Othmer Encyclopedia of Chemical Technology. V. 8. Online ISBN: 9780471238966 Copyright © 1999-2014 by John Wiley and Sons, Inc.</mixed-citation><mixed-citation xml:lang="en">Kirk-Othmer Encyclopedia of Chemical Technology. V. 8. Online ISBN: 9780471238966 Copyright © 1999-2014 by John Wiley and Sons, Inc.</mixed-citation></citation-alternatives></ref><ref id="cit46"><label>46</label><citation-alternatives><mixed-citation xml:lang="ru">Gayle A.A., Somov V.Ye., Varshavskiy O.M., Semenov L.V. Sulfolan: Properties and use as a selective solvent. Saint-Petersburg: Khimizdat Publ., 1998. 144 p. (in Russ.).</mixed-citation><mixed-citation xml:lang="en">Gayle A.A., Somov V.Ye., Varshavskiy O.M., Semenov L.V. Sulfolan: Properties and use as a selective solvent. Saint-Petersburg: Khimizdat Publ., 1998. 144 p. (in Russ.).</mixed-citation></citation-alternatives></ref><ref id="cit47"><label>47</label><citation-alternatives><mixed-citation xml:lang="ru">Gayle A.A., Somov V.Ye., Varshavskiy O.M., Semenov L.V. Sulfolan: Properties and use as a selective solvent. Saint-Petersburg: Khimizdat Publ., 1998. 144 p. (in Russ.).</mixed-citation><mixed-citation xml:lang="en">Gayle A.A., Somov V.Ye., Varshavskiy O.M., Semenov L.V. Sulfolan: Properties and use as a selective solvent. Saint-Petersburg: Khimizdat Publ., 1998. 144 p. (in Russ.).</mixed-citation></citation-alternatives></ref><ref id="cit48"><label>48</label><citation-alternatives><mixed-citation xml:lang="ru">Gayle A.A., Somov V.Ye., Varshavskiy O.M., Semenov L.V. Sulfolan: Properties and use as a selective solvent. Saint-Petersburg: Khimizdat Publ., 1998. 144 p. (in Russ.).</mixed-citation><mixed-citation xml:lang="en">Gayle A.A., Somov V.Ye., Varshavskiy O.M., Semenov L.V. Sulfolan: Properties and use as a selective solvent. Saint-Petersburg: Khimizdat Publ., 1998. 144 p. (in Russ.).</mixed-citation></citation-alternatives></ref><ref id="cit49"><label>49</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Dehydration of acetic acid by extractive distillation; pat. 5,167,774 US; filed 02/06/1992; publ. 12/01/1992.</mixed-citation><mixed-citation xml:lang="en">Berg L. Dehydration of acetic acid by extractive distillation; pat. 5,167,774 US; filed 02/06/1992; publ. 12/01/1992.</mixed-citation></citation-alternatives></ref><ref id="cit50"><label>50</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Dehydration of acetic acid by extractive distillation; pat. 5,167,774 US; filed 02/06/1992; publ. 12/01/1992.</mixed-citation><mixed-citation xml:lang="en">Berg L. Dehydration of acetic acid by extractive distillation; pat. 5,167,774 US; filed 02/06/1992; publ. 12/01/1992.</mixed-citation></citation-alternatives></ref><ref id="cit51"><label>51</label><citation-alternatives><mixed-citation xml:lang="ru">Berg L. Dehydration of acetic acid by extractive distillation; pat. 5,167,774 US; filed 02/06/1992; publ. 12/01/1992.</mixed-citation><mixed-citation xml:lang="en">Berg L. Dehydration of acetic acid by extractive distillation; pat. 5,167,774 US; filed 02/06/1992; publ. 12/01/1992.</mixed-citation></citation-alternatives></ref><ref id="cit52"><label>52</label><citation-alternatives><mixed-citation xml:lang="ru">Raeva V.M. Features of the behavior of azeotropic mixtures and their separation with varying pressure: thesis ... Cand. of Sci. (Engineering). Moscow, 1998. 168 p. (in Russ.).</mixed-citation><mixed-citation xml:lang="en">Raeva V.M. Features of the behavior of azeotropic mixtures and their separation with varying pressure: thesis ... Cand. of Sci. (Engineering). Moscow, 1998. 168 p. (in Russ.).</mixed-citation></citation-alternatives></ref><ref id="cit53"><label>53</label><citation-alternatives><mixed-citation xml:lang="ru">Raeva V.M. Features of the behavior of azeotropic mixtures and their separation with varying pressure: thesis ... Cand. of Sci. (Engineering). Moscow, 1998. 168 p. (in Russ.).</mixed-citation><mixed-citation xml:lang="en">Raeva V.M. Features of the behavior of azeotropic mixtures and their separation with varying pressure: thesis ... Cand. of Sci. (Engineering). Moscow, 1998. 168 p. (in Russ.).</mixed-citation></citation-alternatives></ref><ref id="cit54"><label>54</label><citation-alternatives><mixed-citation xml:lang="ru">Raeva V.M. Features of the behavior of azeotropic mixtures and their separation with varying pressure: thesis ... Cand. of Sci. (Engineering). Moscow, 1998. 168 p. (in Russ.).</mixed-citation><mixed-citation xml:lang="en">Raeva V.M. Features of the behavior of azeotropic mixtures and their separation with varying pressure: thesis ... Cand. of Sci. (Engineering). Moscow, 1998. 168 p. (in Russ.).</mixed-citation></citation-alternatives></ref><ref id="cit55"><label>55</label><citation-alternatives><mixed-citation xml:lang="ru">Raeva V.M., Frolkova A.K. Separation of azeotropic mixtures using pressure-based complexes. Russian Journal of General Chemistry. 1998;XLII(6):76- 88 (in Russ.).</mixed-citation><mixed-citation xml:lang="en">Raeva V.M., Frolkova A.K. Separation of azeotropic mixtures using pressure-based complexes. Russian Journal of General Chemistry. 1998;XLII(6):76- 88 (in Russ.).</mixed-citation></citation-alternatives></ref><ref id="cit56"><label>56</label><citation-alternatives><mixed-citation xml:lang="ru">Raeva V.M., Frolkova A.K. Separation of azeotropic mixtures using pressure-based complexes. Russian Journal of General Chemistry. 1998;XLII(6):76- 88 (in Russ.).</mixed-citation><mixed-citation xml:lang="en">Raeva V.M., Frolkova A.K. Separation of azeotropic mixtures using pressure-based complexes. Russian Journal of General Chemistry. 1998;XLII(6):76- 88 (in Russ.).</mixed-citation></citation-alternatives></ref><ref id="cit57"><label>57</label><citation-alternatives><mixed-citation xml:lang="ru">Raeva V.M., Frolkova A.K. Separation of azeotropic mixtures using pressure-based complexes. Russian Journal of General Chemistry. 1998;XLII(6):76- 88 (in Russ.).</mixed-citation><mixed-citation xml:lang="en">Raeva V.M., Frolkova A.K. Separation of azeotropic mixtures using pressure-based complexes. Russian Journal of General Chemistry. 1998;XLII(6):76- 88 (in Russ.).</mixed-citation></citation-alternatives></ref><ref id="cit58"><label>58</label><citation-alternatives><mixed-citation xml:lang="ru">Bates R.G., Pawlak Z. Solvent effects on acid-base behavior: Five uncharged acids in water-sulfolane solvents. J. Solution Chem. 1976;5(3):213-222. https://doi.org/10.1007/BF00654338</mixed-citation><mixed-citation xml:lang="en">Bates R.G., Pawlak Z. Solvent effects on acid-base behavior: Five uncharged acids in water-sulfolane solvents. J. Solution Chem. 1976;5(3):213-222. https://doi.org/10.1007/BF00654338</mixed-citation></citation-alternatives></ref><ref id="cit59"><label>59</label><citation-alternatives><mixed-citation xml:lang="ru">Bates R.G., Pawlak Z. Solvent effects on acid-base behavior: Five uncharged acids in water-sulfolane solvents. J. Solution Chem. 1976;5(3):213-222. https://doi.org/10.1007/BF00654338</mixed-citation><mixed-citation xml:lang="en">Bates R.G., Pawlak Z. Solvent effects on acid-base behavior: Five uncharged acids in water-sulfolane solvents. J. Solution Chem. 1976;5(3):213-222. https://doi.org/10.1007/BF00654338</mixed-citation></citation-alternatives></ref><ref id="cit60"><label>60</label><citation-alternatives><mixed-citation xml:lang="ru">Bates R.G., Pawlak Z. Solvent effects on acid-base behavior: Five uncharged acids in water-sulfolane solvents. J. Solution Chem. 1976;5(3):213-222. https://doi.org/10.1007/BF00654338</mixed-citation><mixed-citation xml:lang="en">Bates R.G., Pawlak Z. Solvent effects on acid-base behavior: Five uncharged acids in water-sulfolane solvents. J. Solution Chem. 1976;5(3):213-222. https://doi.org/10.1007/BF00654338</mixed-citation></citation-alternatives></ref></ref-list><fn-group><fn fn-type="conflict"><p>The authors declare that there are no conflicts of interest present.</p></fn></fn-group></back></article>
