CS256584B1 - Method of cyclohexane's selective oxidation into cyclohexanone and cyclohexanol - Google Patents
Method of cyclohexane's selective oxidation into cyclohexanone and cyclohexanol Download PDFInfo
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- CS256584B1 CS256584B1 CS867206A CS720686A CS256584B1 CS 256584 B1 CS256584 B1 CS 256584B1 CS 867206 A CS867206 A CS 867206A CS 720686 A CS720686 A CS 720686A CS 256584 B1 CS256584 B1 CS 256584B1
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- Prior art keywords
- cyclohexane
- cyclohexanone
- cyclohexanol
- reaction
- oxygen
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title abstract description 22
- 238000000034 method Methods 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- WRJBSKQYDASILN-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1.O=C1CCCCC1 WRJBSKQYDASILN-UHFFFAOYSA-N 0.000 claims 1
- 150000002642 lithium compounds Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 4
- 150000001869 cobalt compounds Chemical class 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Predmetom riešenia je sposob selektívnej oxidácie cyklohexánu na zmes cyklohexanónu a cyklohexanolu v přítomnosti katalyzátorov, s výhodou zlúčenín kobaltu a/alebo chrómu v jedno alebo viacstupňovom reakčnom systéme, ktorý sa vyznačuje tým, že cyklohexán je do reakčného systému dávkovaný v objemovom pomere cyklohexánu k reakčnému objemu reaktor v rozsahu 0,667 až 1,8 hod.-1. Postupom sa dosiahne zvýšenie selektivity oxidácie cyklohexánu na cyklohexanón a cyklohexanol o 2,5 až 4,5 »/o.The subject of the solution is a selective method oxidizing cyclohexane to a mixture of cyclohexanone and cyclohexanol in the presence of catalysts, preferably cobalt compounds and / or chromium in one or more stages reaction system which is characterized in that the cyclohexane is in the reaction system dosed in a cyclohexane volume ratio to the reaction volume of the reactor in the range 0.667 to 1.8 hr-1. Here's how achieves an increase in the selectivity of cyclohexane oxidation to cyclohexanone and cyclohexanol by 2.5 to 4.5? / o.
Description
Vynález rieši spósob selektívnej oxidácie cyklohexánu na cyklohexanón a cyklohexanol v kvapalnej fáze kyslíkom alebo plynom obsahujúcim kyslík.The invention provides a process for the selective oxidation of cyclohexane to cyclohexanone and cyclohexanol in the liquid phase by oxygen or oxygen-containing gas.
Rozhodujúcim článkom výroby cyklohexanónu alebo zmesi cyklohexanónu a cyklohexanolu je oxidácia cyklohexánu. Selektivita tejto reakcie je ovplyvňovaná viacerými reakčnými parametrami, z ktorých významné sú reakčná teplota, koncentrácia katalyzátora, poměr dávkovaných množstiev cyklohexánu a kyslíka, konštrukcia reakčného zariadenia a reakčný čas.The decisive element in the production of cyclohexanone or a mixture of cyclohexanone and cyclohexanol is the oxidation of cyclohexane. The selectivity of this reaction is influenced by several reaction parameters, of which the reaction temperature, the catalyst concentration, the ratio of the quantities of cyclohexane to oxygen dosed, the design of the reaction apparatus and the reaction time are significant.
Oxidáciou cyklohexánu v kvapalnej fáze vzniká okrem žiadaných produktov značné množstvo vedfajších oxidačných produktov, Aj keď je známy celý rad postupov zameraných na ich hospodárné využitie ako druhotných petrochemických surovní, v súčasnosti značné zhoršujú ekonomiku výroby v závislosti od ich vznikajúceho množstva.Liquid phase oxidation of cyclohexane produces a significant amount of oxidation by-products in addition to the desired products. Although a number of processes for their economic use as secondary petrochemical raw materials are known, they currently greatly deteriorate the economics of production depending on the amount produced.
Publikovaný je viacstupňový proces oxidácie cyklohexánu, pri ktorom sa zvýšenie selektivity dosiahne dávkováním určitého množstva cyklohexánu do každého- reakčného stupňa. Cyklohexán a plyn s obsahom kyslíka sa pridávajú do každého stupňa v konštantnom objemovom pomere, pričom přidávané příslušné množstvo cyklohexánu je úměrné uvolněnému teplu a znižuje množstvo tepla odvádzané vypařováním cyklohexánu (ZSSR pat. 503 846). Podobný postup, v ktorom sa zmes cyklohexanónu a cyklohexanolu získává tak, že časť cyklohexánu sa dávkuje len do 2. a 3. stupňa v množstve 5—20 % z množstva cyklohexánu dávkovaného do 1. stupňa, pričom teplota v každom stupni je konštantná alebo má klesajúcu tendenciu v smere prúdenia reakčnej zmesi. Využitím postupu sa dosiahne zníženie tvorby organických kyselin a vedfajších produktov (ZSSR pat. 675 759). Postup oxidácie cyklohexánu v troch alebo viacerých stupňoch využívá dávkovanie kyslíka alebo plynu obsahujúceho kyslík do každého stupňa v takom množstve, aby všetok kyslík zreagoval alebo bol dávkovaný v nrebvtku odpovedajúcom koncentrácii kyslíka v odplynocn i—2 % obj. (BE patent 827 835).A multi-stage cyclohexane oxidation process is disclosed in which an increase in selectivity is achieved by feeding a certain amount of cyclohexane to each reaction stage. Cyclohexane and oxygen-containing gas are added to each stage in a constant volume ratio, the respective amount of cyclohexane being added being proportional to the heat released and reducing the amount of heat dissipated by cyclohexane evaporation (USSR Pat. 503,846). A similar process in which a mixture of cyclohexanone and cyclohexanol is obtained such that a portion of cyclohexane is dosed only to stages 2 and 3 in an amount of 5-20% of the amount of cyclohexane fed to stage 1, the temperature in each stage being constant or a downward trend in the flow direction of the reaction mixture. By using the process, the formation of organic acids and by-products is reduced (USSR Pat. 675,759). The cyclohexane oxidation process in three or more stages utilizes the addition of oxygen or oxygen-containing gas to each stage in an amount such that all of the oxygen has reacted or is dosed at a corresponding oxygen concentration of at least about 2% by volume. (BE patent 827,835).
Aj keď vyššie uvedené vynálezy sú charakterizované zvyšováním selektivity, známe údaje z literatúry, ako aj z výrobného procesu velkofcapacitných jednotiek indikujú ďalšie možnosti zvyšovania selektivity oxidácie cyklohexánu, a tým aj ekonomickejšie využitie surovin a energií.Although the above inventions are characterized by an increase in selectivity, the known literature data as well as the production process of large capacity units indicate further possibilities for increasing the selectivity of cyclohexane oxidation and hence more economical use of raw materials and energies.
Pri štúdiu oxidácie cyklohexánu bolo zistené, že na selektivitu reakcie výrazné vplýva objemový prietok cyklohexánu k reakčnémn objektu,In a study of cyclohexane oxidation, it was found that the volumetric flow rate of cyclohexane to the reaction object significantly influenced the selectivity of the reaction,
Predmetom tohoto vynálezu je spósob selektívnej oxidácie cyklohexánu na cyklohexanón a cyklohexanol v kvapalnej fáze kyslíkom alebo plynom obsahujúcim kyslík v jednom alebo viacerných reakčných stupňoch pri teplotách 130—220 °C a tlakoch 0,5-1,5 MPa za přítomnosti katalyzátora, najčastejšie zlúčenín kobaltu a/alebo chrómu, a/alebo lítia, ktorý sa vyznačuje tým, že cyklohexán do reakčného systému pozostávajúceho z reaktora a skrubérov je dávkovaný v takom množstve, aby poměr objemového prietoku cyklohexánu k účinnému reakčnému objemu reaktora bol 0,667 ažThe object of the present invention is a process for the selective oxidation of cyclohexane to cyclohexanone and cyclohexanol in liquid phase by oxygen or oxygen-containing gas in one or more reaction stages at temperatures of 130-220 ° C and pressures of 0.5-1.5 MPa in the presence of a catalyst, most commonly cobalt compounds. and / or chromium and / or lithium, characterized in that the cyclohexane to the reaction system consisting of the reactor and the scrubbers is metered in such an amount that the ratio of the cyclohexane volume flow rate to the effective reaction volume of the reactor is 0.667 to
1,8 hod.-1. Ostatně reakčné parametre sa udržuj ú na hodnotách, ktoré zaručujú efektivně využitie kyslíka a bezpečnú prevádzku reaktora. Zo vzniknutej reakčnej zmesi sa oddělí nezreagovaný cyklohexán, ktorý sa vracia ro oxidačného procesu spolu s čerstvým cyklohexánom a získaná zmes sa dalej spracuje známými postupmi.1.8 h -1 . Moreover, the reaction parameters are maintained at values that guarantee efficient oxygen utilization and safe reactor operation. Unreacted cyclohexane is separated from the resulting reaction mixture, which is returned to the oxidation process together with fresh cyclohexane, and the resulting mixture is further worked up according to known methods.
Postupom podfa tohto vynálezu sa dosiahne výrazné zvýšenie selektivity oxidácie cyklohexánu na cyklohexanón a cyklohexanol, zvýši sa kvalita finálného výrobku v důsledku nižšej tvorby vedfajších produktov. Postup pozitivně ovplyvní další proces separácie cyklohexanónu a cyklohexanolu z reakčnej zmesi. Jeho využitím sa dosiahne výrazné zníženie mernej spotřeby surovin a energií. Výhodou je tiež jednoduchosť realizácie a riadenla procesu oxidácie s možnosťou aplikácie u róznych typov reaktorov. Na výhody podfa tohoto postupu poukazujú následovně příklady:The process of the present invention achieves a significant increase in the selectivity of cyclohexane oxidation to cyclohexanone and cyclohexanol, improving the quality of the final product due to lower byproduct formation. The process positively affects the further process of separating cyclohexanone and cyclohexanol from the reaction mixture. Its use will significantly reduce specific consumption of raw materials and energy. The advantage is also the simplicity of implementation and control of the oxidation process with the possibility of application in different types of reactors. The advantages of this procedure are illustrated by the following examples:
Příklad 1 (porovnávací)Example 1 (comparative)
Do reakčného systému pozostávajúceho z reaktora a skrubérov sa pri teplote 160 až 164 °C a tlaku 0,9 MPa dávkuje vzduch a cyklohexán s obsahom katalyzátora ccaAir and cyclohexane with a catalyst content of approx. 160 to 164 ° C and a pressure of 0.9 MPa are charged to the reaction system consisting of the reactor and the scrubbers.
2.5 ppm kobaltu v takom množstve, aby poměr objemového prietoku cyklohexánu k účinnému reakčnému objemu reaktora bol 2,58 hod.1. Za týchto podmienok sa dosiahne selektivita 82 až 84 %.2.5 ppm of cobalt in an amount such that the ratio of the volume flow rate of cyclohexane to the effective reaction volume of the reactor was 2.58 hours. 1 . Under these conditions, a selectivity of 82 to 84% is achieved.
Příklad 2Example 2
Do reakčného systému a za pracovných podmienok ako v příklade 1 sa dávkuje vzduch a cyklohexán v takom množstve, aby poměr objemového prietoku cyklohexánu k účinnému reakčnému objemu reaktora bolAir and cyclohexane are metered into the reaction system and under the operating conditions of Example 1 in such an amount that the ratio of the cyclohexane volume flow to the effective reaction volume of the reactor is
1.6 hod.-1. Za týchto podmienok sa dosiahne selektivita 86 až 87,5 °/o.1.6 h -1 . Under these conditions, a selectivity of 86-87.5% is achieved.
Příklad 3Example 3
Do reakčného systému a za podmienok ako v příklade 1 sa dávkuje vzduch a cyklohexán v takom množstve, aby poměr objemového prietoku cyklohexánu k účinnému objemu reaktora bol 1,75 hod.-1. Za týchto podmienok prebieha proces oxidácie cyklohexánu na cyklohe xanón a cyklohexanol so selektivitou 87 až 88 %.Air and cyclohexane are metered in to the reaction system and under the conditions as in Example 1 in such an amount that the ratio of the cyclohexane volume flow to the effective reactor volume is 1.75 hours. -1 . Under these conditions, the cyclohexane oxidation process on the cyclohexanone and cyclohexanol takes place with a selectivity of 87-88%.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS867206A CS256584B1 (en) | 1986-10-06 | 1986-10-06 | Method of cyclohexane's selective oxidation into cyclohexanone and cyclohexanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS867206A CS256584B1 (en) | 1986-10-06 | 1986-10-06 | Method of cyclohexane's selective oxidation into cyclohexanone and cyclohexanol |
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| Publication Number | Publication Date |
|---|---|
| CS720686A1 CS720686A1 (en) | 1987-08-13 |
| CS256584B1 true CS256584B1 (en) | 1988-04-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS867206A CS256584B1 (en) | 1986-10-06 | 1986-10-06 | Method of cyclohexane's selective oxidation into cyclohexanone and cyclohexanol |
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1986
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| CS720686A1 (en) | 1987-08-13 |
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