TW200410924A - Process for oxidation of cyclohexane - Google Patents
Process for oxidation of cyclohexane Download PDFInfo
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- TW200410924A TW200410924A TW092118221A TW92118221A TW200410924A TW 200410924 A TW200410924 A TW 200410924A TW 092118221 A TW092118221 A TW 092118221A TW 92118221 A TW92118221 A TW 92118221A TW 200410924 A TW200410924 A TW 200410924A
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- C07C409/14—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom belonging to a ring other than a six-membered aromatic ring
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Description
200410924 玖、發明說明: 【發明所屬之技術領域】 本發明係關於一種由環己烷之氧化方法製備環己醇、環 己酮及環己基過氧化氫之方法。 【先前技術】 環己烷藉由空氣進行氧化係產生一種包括環己醇(A)、環 己酮⑷、環己基過氧化氫(CHHp)及少量副產物之反應產物 後緊接著分離有機相和水相。進一步處理包含a、K及 CHHP之有機相,致使CHHp分解為κ及a。因此,κ和a係 整個過程之主產物,其混合物通常為 熟知之ΠΚΑ油·’。 上述方法形成之幾種副產物與未反應之環己烷同時混合 於ΚΑ油(粗製)而成為雜質。藉由蒸餾由粗製〖A油製得精製 ΚΑ油。所有副產物、催化劑、添加劑及因腐蝕所衍生之金 屬化合物形成蒸餾塔之尾料(美國專利4,72〇,592)。在最後 步驟中蒸館該ΚΑ油,以消除製程中產生之副產物。κα油經 蒸餾後剩餘 < 物質為一種粘稠物質,通常為黑色,其包括 製私中形成之雜質、非揮發性催化劑及在製程中使用之任 何添加劑。所有此等物質被稱為’,非揮發性殘渣”或,,NVR,,。 尾料泥通常採用蒸發以濃縮。此濃縮流通常為吾人所熟知 <非揮發性殘渣(N VR),常處理用作鍋爐燃料。 不傭鋼所製得之處理容器的腐蝕將鉻添加於NVR中。此 外’採用絡催化劑(美國專利4,465,861)之Chhp分解方法使 絡殘留於NVR中。一般在NVR中可觀察到2至100 ppm之鉻 /辰度。經過鍋爐燃燒後,鉻形成鍋爐煙道氣排放物之一部 86385 200410924 分。該煙道氣需經昂貴之處理來減少鉻,以遵守環境法規。 處理NVR之可替代路徑也很昂貴。 因此,希望採用環己烷氧化方法製備KA油,該方法包括 一個或多個步驟以減少NVR之鉻含量,因此燃燒所產生之 煙道氣會含有可接受之低濃度鉻。
該NVR為水性分散液。典型地,該組合物包括蟻酸、乙 酸、丁酸、戊酸、己酸、6-羥基己酸、琥珀酸、戊二酸、 己二酸、磷酸有機酯、鉻鹽及其它物質。 製備KA過程中形成之NVR之量係顯著的,其可達到所製 得KA油量之20%,且通常採用燃燒並達到燃料值對其進行 處理。因為更嚴格之環境法規,經鍋爐燃燒處理高鉻含量 之NVR將不被允許。
一些消除重金屬礦泥或廢液中之六價鉻之方法為吾人所 熟知,其包括在酸性溶液中將六價鉻還原至三價(日本專利 2001058192 A20010306)。由於處理時全部NVR將溶於水 中,因此該方法不適於除去NVR中之鉻。 也有一些處理系統用於消除電鍍操作中之鉻(美國專利 5,932,109),其使用肼或鋁和銅碎屑(俄羅斯專利2,023,674) ,通過加入氫氧化鈣至特定PH值,然後加入氫氧化鋇以進 一步提高PH值(前蘇聯專利1323537)使鉻沉澱。 本發明之目標為提供一種生產KA油之方法,其具有含低 鉻濃度之NVR副產物。 【發明内容】 本發明揭示一種由環己烷製備環己酮和環己醇混合物同 86385 v/-r x yjy 時回收副產、、 、 办〒" < 万法’該方法包括:(i)氧化環己烷以獲得 m尾料;⑻使該空氣氧化尾料與水接觸;㈣將步 一上勹括于孓此合物分離為第一相和第二相,該第一相實質 έ八;欠、、且刀,忒第二相係包括環己基過氧化氫和有機 、、四(ν)將來自步驟(1ί{)之有機相中之環己基過氧化氫分 γ哀己酮和j衣己醇;(ν)精製步驟(b)所得之環己醇和環 己酮此口物,及(V1)從非揮發性殘餘物中分離出鉻。 【實施方式】 本發明揭7F -種將環己垸氧化之方法,其最終將生成低% 絡口量之NVR副產物。在本發明方法中,環己燒於約⑽它 至約175。(:下,在空氣氧化器中與空氣接觸(1)。該空氣氧化 器可為一塔式氧化器,攪拌式或非攪拌式槽式反應器,攪 拌式或非攪拌式壓熱器。空氣氧化器之尾料與水接觸。空 氣氧化器尾料與水之比例為約忉㈧丨。分離出水相之後(2), 環己基過氧化氫被分解為K和八(3)。 CHHP之分解可採用熱分解、催化分解、催化氫化或其他 催化方法,例如採用金催化劑。熱分解於較高溫度(12〇-175 °C)及較長滯留時間下進行。 CHHP氫化在100-160。(:之溫度下,採用不均相催化劑進 行。氫化催化劑包括,但不僅限於以秒石或氧化銘為載體 之I巴。 CHHP分解還可在l〇(M60°c之溫度下,無須氫參與下, 採用不同不均相催化劑,諸如沉積於矽石或氧化鋁上之金 來完成。 86385 -8 - 200410924 CHHP分解還可在鹼性水溶液中藉由金屬催化分解完 成。該分解藉由CHHP與鈷、鉻或其混合物於鹼性溶液(較 佳地為氫氧化鈉)中接觸完成。當採用此等催化劑之一種或 兩種來分解CHHP時,鈷和/或鉻濃度為0.1至20 ppm之間。
CHHP轉化為K及A之後,蒸餾出過量之環己烷(4)並在KA 精煉塔中於約90至約170 °C下,蒸餾出所得之KA油(5)。該 方法中之一些步驟,諸如水洗AOR尾料,有益於減少催化 劑之失活,但其不係必要之步驟。環己烷蒸餾和KA油精煉 還可採用不同之單元操作,諸如真空蒸餾、水蒸氣蒸餾等 來完成。
將KA精煉塔(5)底部之NVR殘留物送入酸處理反應器 (6)。NVR於約60至約120°C下在(6)中與稀酸溶液(0.2-10%) 接觸。第一步水解階段之後,NVR與電解質水溶液(7)接觸 以萃取鉻進入水層。在電解質水溶液中鉻之萃取步驟可於 約20至約120°C下完成。在傾析器(8)中,將含有減少之鉻量 之NVR與電解質水溶液分離。依據實際製程參數,可能需 要重復萃取和水解步驟以減少鉻至極低含量。水解和萃取 步騾之順序可顛倒。 所得之K和A為一種混合物。氧化該產物(K和A)製得己二 酸。氧化劑可採用硝酸。反之,所得之己二酸可用於製造 尼龍產品、藥物添加劑、食品添加劑、聚胺酯及其它許多 應用。 【圖式簡單說明】 圖1為本發明方法之流程圖,用以輔助理解本方法。空氣 86385 200410924 氧化器(1)用於環己烷之氧化。水分離器(2)用於收集本方法 步驟1所產生之水相。在第二相中存在之環己基過氧化氫在 CHHP分解反應器(3)中分解生成環己酮和環己醇。此等產 物在蒸餾塔(4)中蒸餾,之後在精煉塔(5)中精製KA油。殘 留於精煉塔(5)中之NVR首先和稀酸(6)或者和電解質水溶 液(7)接觸以萃取路。最後,採用相分離器(8)將絡分離至水 相。 環己烷於塔式氧化器(1)中被空氣氧化,該氧化劑尾料與 水接觸。該水經傾析器分離為第一相及第二相。第一相包 括含水(水溶性)組分,且該第二相包括環己醇及有機組分。 清洗有機相之水引入CHHP分解反應器(3),在那將其用辛 酸鉻處理並分解為K和A。採用蒸餾(4)回收並循環使用環己 烷。所得粗製KA油在KA精煉塔(5)中精製,且於塔頂部蒸 餾得K A。於精餾塔底部收集N VR。所得N VR於酸處理反應 器(6)中與酸性溶液接觸。非揮發性殘渣進一步與電解液(7) 接觸,緊接著從有機相中分離出水相(8)。分離所得之有機 相為低鉻濃度(〜2 ppm)之NVR。 【圖式代表符號說明】 1 空氣氧化器 2 水分離器 3 CHHP分解反應器 4 蒸餾塔 5 精煉塔 6 稀酸 7 電解質水溶液 8 有機相 86385 -10-
Claims (1)
- 200410924 拾、申请專利範園: L -種由環己垸製備環己酮和環己醇混合物及副產物回收 之方法,該方法包括: (0將環己烷氧化以得到空氣氧化尾料; (i〇使該空氣氧化尾料與水接觸; ㈣將步驟(π)所得之混合物㈣為第—相和第二相, 該相實質上包括含水組分,而該第二相係包 括裱己基過氧化氫和有機組分; ㈣將來自步驟㈣之有機相中的環己基過氧化氯分 解為己嗣和環己醇; (V)精製步驟(iv)所得之環己醇和環己綱混合物;及 (Vi)從非揮發性殘留物中分離出鉻。 2.如申請專利範圍第α之方法,其中該方法尚包括: ⑴使非揮發性殘留物或該非揮發性殘留物之至少一 部分有機成分與酸性化合物接觸,· (Π)使該非揮發性殘留物或該非揮發性殘留物之至少 崢刀有機成分與電解質水溶液接觸,緊接著從 有機相中分離出水相; (111)以任一順序重復步驟⑴和(fi) 3·如申清專利範圍第丨或2項之方法,其中分解採用熱 分解、催化分解或催化氫化完成。 4. 如申請專利範圍第3項之方法,其中該分解係於鹼 性溶液中藉由金屬催化分解完成。 5. 如申請專利範圍第3項之方法,其中催化劑係包含鈷 86385 200410924 (Co)、路(Cr)或兩者。 6. 如申請專利範圍第4項之方法,其中催化劑係包含金(Au) 和把(Pd)。 7. 如申請專利範圍第1或2項之方法,其中該CHHP分解係於 100°c至175°c下進行。 8. 如申請專利範圍第1項之方法,其中該環己醇與環己酮混 合物之精製係藉由蒸餾達成。 9. 如申請專利範圍第丨項之方法,其中該空氣氧化尾料係經 水洗條。 ι〇_如申請專利範圍第丨項之方法,其中所得之環己醇和環己 酮產物係用於生產己二酸。 86385
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EP (1) | EP1539665B1 (zh) |
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EP2931907A2 (en) | 2012-12-14 | 2015-10-21 | Invista Technologies S.A R.L. | METHODS OF PRODUCING 7-CARBON CHEMICALS VIA CoA-DEPENDENT CARBON CHAIN ELONGATION ASSOCIATED WITH CARBON STORAGE |
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CN105189764A (zh) | 2012-12-31 | 2015-12-23 | 英威达技术有限责任公司 | 通过与辅酶b合成相关的c1碳链延伸生产7-碳化学物的方法 |
CN105008543A (zh) | 2012-12-31 | 2015-10-28 | 英威达技术有限责任公司 | 通过芳香族化合物生产7-碳化学物的方法 |
EP2938731A2 (en) | 2012-12-31 | 2015-11-04 | Invista Technologies S.A R.L. | Methods of producing 7-carbon chemicals via carbon chain elongation associated with cyclohexane carboxylate synthesis |
WO2014105794A2 (en) | 2012-12-31 | 2014-07-03 | Invista North America S.A.R.L. | Methods of producing 7-carbon chemicals via methyl-ester shielded carbon chain elongation |
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US9896702B2 (en) | 2014-06-16 | 2018-02-20 | Invista North America S.A.R.L. | Methods, reagents and cells for biosynthesizing compounds |
WO2015195707A1 (en) | 2014-06-16 | 2015-12-23 | Invista Technologies S.A.R.L. | Methods, reagents and cells for biosynthesizing compounds |
CN104945213B (zh) * | 2014-07-07 | 2017-01-11 | 山东勇智化工有限公司 | 干燥塔负压干燥工艺 |
BR112018006502B1 (pt) | 2015-10-01 | 2022-01-11 | Advansix Resins & Chemicals Llc | Método de conversão de um álcool a uma cetona, catalisador, e método de produzir um catalisador |
CN105315128B (zh) * | 2015-10-28 | 2017-04-12 | 江西科苑生物药业有限公司 | 一种环己烷氧化制备ka油的方法 |
CN106995463B (zh) * | 2017-03-31 | 2019-11-08 | 中国石油化工股份有限公司 | 一种油溶性铬酸异辛酯催化体系 |
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GB1590958A (en) * | 1976-12-31 | 1981-06-10 | Ici Ltd | Oxidation of cyclohexane |
SU1323537A1 (ru) | 1982-01-22 | 1987-07-15 | Рубежанский филиал Ворошиловградского машиностроительного института | Способ очистки сточных вод от шестивалентного хрома |
US4465861A (en) | 1983-04-11 | 1984-08-14 | E. I. Du Pont De Nemours And Company | Process for producing a mixture containing cyclohexanol and cyclohexanone |
US4720592A (en) | 1986-09-05 | 1988-01-19 | E. I. Du Pont De Nemours And Company | Preparation of cyclohexanone and cyclohexanol |
RU2023674C1 (ru) | 1991-07-15 | 1994-11-30 | Ляпкин Александр Александрович | Способ очистки сточных вод от соединений хрома |
US5932109A (en) | 1994-06-02 | 1999-08-03 | Griffin Chemical Company | Plating rinse water treatment |
JP3632233B2 (ja) * | 1995-03-10 | 2005-03-23 | 三菱化学株式会社 | α−オレフイン低重合体の製造方法 |
JP3572811B2 (ja) * | 1996-06-17 | 2004-10-06 | 東ソー株式会社 | クロムを含有する廃触媒の処理方法 |
US5780683A (en) * | 1996-09-11 | 1998-07-14 | Abb Lummus Global Inc. | Cyclohexane oxidation |
JP2001058192A (ja) | 1999-08-23 | 2001-03-06 | Matsushita Sangyo Kk | 六価クロムの除去方法 |
US6814867B2 (en) * | 2002-09-12 | 2004-11-09 | Inuista North America S.à.r.l. | Process for reducing chromium in nonvolatile residue resulting from air oxidation of cyclohexane |
-
2002
- 2002-09-12 US US10/242,544 patent/US6703529B1/en not_active Expired - Lifetime
-
2003
- 2003-07-03 TW TW092118221A patent/TW200410924A/zh unknown
- 2003-09-09 CN CNB038215535A patent/CN1319924C/zh not_active Expired - Fee Related
- 2003-09-09 AU AU2003267072A patent/AU2003267072A1/en not_active Abandoned
- 2003-09-09 KR KR1020057004213A patent/KR20050044918A/ko not_active Application Discontinuation
- 2003-09-09 EP EP03749547A patent/EP1539665B1/en not_active Expired - Fee Related
- 2003-09-09 WO PCT/US2003/028261 patent/WO2004024657A2/en active Application Filing
- 2003-09-09 JP JP2004536396A patent/JP2005539066A/ja active Pending
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CN1681759A (zh) | 2005-10-12 |
US20040054235A1 (en) | 2004-03-18 |
EP1539665B1 (en) | 2011-11-09 |
WO2004024657A2 (en) | 2004-03-25 |
KR20050044918A (ko) | 2005-05-13 |
AU2003267072A1 (en) | 2004-04-30 |
EP1539665A2 (en) | 2005-06-15 |
AU2003267072A8 (en) | 2004-04-30 |
JP2005539066A (ja) | 2005-12-22 |
CN1319924C (zh) | 2007-06-06 |
EP1539665A4 (en) | 2006-07-26 |
WO2004024657A3 (en) | 2004-08-05 |
US6703529B1 (en) | 2004-03-09 |
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