TW200920732A - Integrated process for the production of hydroxylated aromatic hydrocarbons - Google Patents
Integrated process for the production of hydroxylated aromatic hydrocarbons Download PDFInfo
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- TW200920732A TW200920732A TW097132885A TW97132885A TW200920732A TW 200920732 A TW200920732 A TW 200920732A TW 097132885 A TW097132885 A TW 097132885A TW 97132885 A TW97132885 A TW 97132885A TW 200920732 A TW200920732 A TW 200920732A
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- Prior art keywords
- hydrogen peroxide
- catalyst
- aromatic hydrocarbon
- benzene
- acetonitrile
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 138
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 109
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- -1 alkyl cyanide Chemical compound 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000006227 byproduct Chemical class 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000005805 hydroxylation reaction Methods 0.000 claims description 17
- 230000033444 hydroxylation Effects 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000000779 smoke Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011877 solvent mixture Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims 1
- 239000004472 Lysine Substances 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 239000010433 feldspar Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000010354 integration Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910001347 Stellite Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052917 strontium silicate Inorganic materials 0.000 description 1
- QSQXISIULMTHLV-UHFFFAOYSA-N strontium;dioxido(oxo)silane Chemical compound [Sr+2].[O-][Si]([O-])=O QSQXISIULMTHLV-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
200920732 九、發明說明： 【發明所屬之技術領战】 發明領域 本發明係相關於一種製造羥基化芳煙敕人 ^ 正&方法，如 5自苯與過氧化氫製造酚。 L 先前 ;j 發明背景 紛為-種已知之市售產品。製造齡之—方法係涉及使 用過氧化氫而使苯羥基化。目前需要一種增進之方=來製 ίο造酚類’其更有效且成本更低。 a 【^^明内 發明概要 本發明係提供上述問職缺狀—或 在-廣義觀點中，本發明為一種製造經基化芳煙之整 合方法，包含：⑷將過氧化氫與芳烴與燒基氛之混合物接 觸’在催化劑存在下，形成經基化芳烴與水，其中至少一 部分之芳烴、院基氰與過氧化氫來自於步驟(c);⑻將該經 基化芳烴、水及任-副產物，與未反應之芳煙與院基氮分 離；以及(c)使用該來自步驟⑼之未反應芳烴與烧基氰，作 2〇為步驟(A)製造過氧化氫之溶劑。 在某些實施例中’該催化劑為沸石；該催化劑為zsm_5 彿石，s亥催化劑為ZSM-5沸石，其包含鐵與铭；該經基化 芳烴為酚類，該芳烴為笨；該接觸步驟之溫度範圍為約 50至約150C ;該接觸步驟汨)之溫度範圍為約8〇至約13〇 5 200920732 °C ;該烷基氰為乙腈；該笨轉換率範圍為約5至約25% ;該 酚轉換率至少約97% ;以及其組合。 在另一廣義觀點中，本發明為一種製造酚類之整合方 法，包含：（A)將過氧化氫與笨與乙腈之混合物接觸，在催 5 化劑存在下，以形成酚與水，其中至少一部分之苯、乙睛 與過氧化虱來自步驟(C) ’（B)將該盼、水及任一副產物，與 未反應之苯與乙腈分離，以及(C)使用來自步驟(B)之苯與乙 腈，作為步驟(A)製造過氧化氫之溶劑。 在另一廣義觀點中，本發明係相關於一種製造紛類之 10整合方法，包含：（A)將過氧化氫與苯與乙腈之混合物接 觸，在沸石催化劑存在下’以形成酚與水，其中至少一部 分之苯、乙腈與過氧化氫來自步驟(C) ; (B)將該酚、水及任 一副產物，與未反應之苯與乙腈分離，以及(C)使用來自步 驟(B)之苯與乙腈，作為步驟(A)製造過氧化氫之溶劑。 15 在另一廣義觀點中，本發明係相關於一種製造經基化 芳經之整合系統，包含：（A)—經基化反應器，其中過氧化 氫係與芳烴與烷基氰混合物接觸，在催化劑存在下，形成 羥基化芳烴與水，其中至少一部分之芳烴、烷基氰與過氧 化氫來自於過氧化氫反應器（C);(B) —分離器，其中該經基 20 化芳烴、水與任何副產物，係與未反應之芳煙與烧基氰分 離；以及(C)一過氧化氫反應器，其中來自分離器（b)之未反 應芳烴與烷基氰，係作為製造過氧化氫之溶劑混合物。 在另一廣義觀點中，本發明係相關於一種用於製造羥 基化芳烴之整合系統之製造方法’包含：（A)提供經基化 200920732 反應器中過氧化氫係與芳烴與貌基氮混合物接觸，在 催化劑存在下，形成羥基化芳烴與水，其中至少一部分之 芳烴、烷基氰與過氧化氫來自於過氧化氫反應器 提供一分離器，其中該羥基化芳烴、水與任何副產物，係 5與未反應之芳煙與烧基氰分離；以及(c)提供一過氧化氫反 應益，其中來自分離器（B)之未反應芳烴與烷基氰，係作為 製造過氧化氫之溶劑混合物。 本發明提供了多種優點。使用芳烴如苯，與烷基氰如 乙腈之混合物於羥基化反應中，可幫助提供高產率之酚。 10同樣地，使用添補有鐵與鋁之ZSM-5催化劑，可幫助提供 高產率之酚。使用芳烴與烷基氰作為溶劑，用於直接製造 過氧化氫，提供較低成本之製造與純化過氧化氫之方法， 其可於芳烴/烷基氰流中，直接自氧與氫產生，該處氫轉換 為過氧化氫之反應選擇性一般大於6〇%。主要不希望之產 15物為水，其產生量相當低；因此芳烴/烷基氰流中之過氧化 氫出口流可直接使用作為羥基化反應器之進料。 圖式簡單說明 第1圖為本發明整合流程之代表性方塊圖。 【實施方式】 20較佳實施例之詳細說明 將芳烴與過氧化氫接觸，在催化劑存在下，會使芳烴 羥基化（氧化形成羥基），可發生於各種反應器中。一般而 Q，反應器為固定床。在一實施例中，該方法係栓狀流方 式引入。過氧化氫直接合成單元之流出物，係送至羥基化 200920732 反應器中。反應物流過催化劑之流量一般範圍為約01至約 10 WHSV，更常見為約0.5至約5WHSV，且在一實施例中， 為約1至約3WHSV。應瞭解到，WHSV為液時空速（liquid hourly space velocity)，定義為每小時每單位重量催化劑上 5 之液體重量。 在一實施例中，過量之過氧化氫係使用於羥基化反應 器中，某些在羥基化過程中分解為氧與水。一般而言，在 羥基化反應器出口流中並無殘餘之過氧化氫，但會有氧存 在，之後會作為氣流移出並清洗。經基化發生之溫度一般200920732 IX. INSTRUCTIONS: [Technical Highlights of the Invention] Field of the Invention The present invention relates to a method for producing a hydroxylated aryl fluorene, such as 5 from benzene and hydrogen peroxide to produce phenol. L Previous; j Background of the invention - a known commercial product. The age of manufacture - the method involves the use of hydrogen peroxide to hydroxylate the benzene. There is a need for an improved side = to make phenols 'which is more efficient and less costly. A Summary of the Invention The present invention provides the above-mentioned problem of vacancy-or, or in a broad sense, the present invention is an integrated method for producing a ketone-containing aromatic tobacco, comprising: (4) burning hydrogen peroxide with aromatic hydrocarbons The base mixture is contacted to form a grouped aromatic hydrocarbon and water in the presence of a catalyst, wherein at least a portion of the aromatic hydrocarbon, the building cyanide and hydrogen peroxide are derived from step (c); (8) the alkylated aromatic hydrocarbon, water and any a by-product, which is separated from the unreacted aromatic smoke and the hospital base nitrogen; and (c) using the unreacted aromatic hydrocarbon from the step (9) and the alkyl cyanide as a solvent for producing hydrogen peroxide in the step (A). In certain embodiments, the catalyst is a zeolite; the catalyst is zsm_5 stellite, the s-hai catalyst is a ZSM-5 zeolite, which comprises iron and inscription; the alkylated aromatic hydrocarbon is a phenol, the aromatic hydrocarbon is stupid; the contact The temperature of the step ranges from about 50 to about 150 C; the temperature of the contacting step 汨) ranges from about 8 Torr to about 13 〇 5 200920732 ° C; the alkyl cyanide is acetonitrile; the stupid conversion rate ranges from about 5 to about 25 %; the phenol conversion rate is at least about 97%; and combinations thereof. In another broad aspect, the invention is an integrated process for the manufacture of phenols comprising: (A) contacting hydrogen peroxide with a mixture of stupid and acetonitrile in the presence of a nitriding agent to form phenol and water, wherein At least a portion of benzene, acetonitrile and ruthenium peroxide are from step (C) '(B) separating the desired, water and any by-products from unreacted benzene with acetonitrile, and (C) from step (B) Benzene and acetonitrile are used as a solvent for producing hydrogen peroxide in the step (A). In another broad aspect, the present invention relates to a method of manufacturing 10 integrated processes comprising: (A) contacting hydrogen peroxide with a mixture of benzene and acetonitrile to form phenol and water in the presence of a zeolite catalyst, At least a portion of the benzene, acetonitrile and hydrogen peroxide are from step (C); (B) the phenol, water and any by-products are separated from the unreacted benzene and acetonitrile, and (C) is used from step (B) Benzene and acetonitrile are used as a solvent for producing hydrogen peroxide in the step (A). In another broad aspect, the invention relates to an integrated system for the manufacture of a radicalized aromatic, comprising: (A) a radicalized reactor wherein the hydrogen peroxide is contacted with an aromatic hydrocarbon and an alkyl cyanide mixture, Forming a hydroxylated aromatic hydrocarbon with water in the presence of a catalyst, wherein at least a portion of the aromatic hydrocarbon, the alkyl cyanide and the hydrogen peroxide are derived from the hydrogen peroxide reactor (C); (B) the separator, wherein the alkyl group is an aromatic hydrocarbon , water and any by-products, separated from unreacted aromatic smoke and burnt cyanide; and (C) a hydrogen peroxide reactor in which unreacted aromatic hydrocarbons from the separator (b) and alkyl cyanide are produced A solvent mixture of hydrogen peroxide. In another broad aspect, the invention relates to a process for the manufacture of an integrated system for the manufacture of hydroxylated aromatics' comprising: (A) providing a mixture of hydrogen peroxide and aromatics with a base nitrogen in a reformed 200920732 reactor Contacting, in the presence of a catalyst, forming a hydroxylated aromatic hydrocarbon with water, wherein at least a portion of the aromatic hydrocarbon, alkyl cyanide and hydrogen peroxide are supplied from a hydrogen peroxide reactor to provide a separator wherein the hydroxylated aromatic hydrocarbon, water and any by-products , system 5 is separated from unreacted aromatic smoke and alkyl cyanide; and (c) provides a hydrogen peroxide reaction benefit, wherein unreacted aromatic hydrocarbons from the separator (B) and alkyl cyanide are used as hydrogen peroxide production. Solvent mixture. The present invention provides a number of advantages. The use of a mixture of an aromatic hydrocarbon such as benzene and an alkyl cyanide such as acetonitrile in a hydroxylation reaction can help provide a high yield of phenol. 10 Similarly, the use of a ZSM-5 catalyst supplemented with iron and aluminum can help provide a high yield of phenol. The use of aromatic hydrocarbons and alkyl cyanides as solvents for the direct manufacture of hydrogen peroxide provides a relatively low cost process for the manufacture and purification of hydrogen peroxide which can be produced directly from oxygen and hydrogen in an aromatic/alkyl cyanide stream. The reaction selectivity at which hydrogen is converted to hydrogen peroxide is generally greater than 6%. The main undesired product is water, which is produced in relatively low amounts; therefore, the hydrogen peroxide outlet stream in the aromatic/alkyl cyanide stream can be used directly as a feed to the hydroxylation reactor. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a representative block diagram of the integration process of the present invention. [Embodiment] Detailed Description of the Preferred Embodiments 20 The aromatic hydrocarbons are contacted with hydrogen peroxide to hydroxylate the aromatic hydrocarbons (oxidation to form hydroxyl groups) in the presence of a catalyst, which may occur in various reactors. In general, Q, the reactor is a fixed bed. In one embodiment, the method is introduced as a plug flow. The effluent from the direct synthesis unit of hydrogen peroxide is sent to the hydroxylated 200920732 reactor. The flow rate of the reactant stream through the catalyst generally ranges from about 01 to about 10 WHSV, more typically from about 0.5 to about 5 WHSV, and in one embodiment from about 1 to about 3 WHSV. It should be understood that WHSV is the liquid hourly space velocity, defined as the weight of liquid per unit weight of catalyst per hour. In one embodiment, excess hydrogen peroxide is used in the hydroxylation reactor and some are decomposed into oxygen and water during the hydroxylation process. In general, there is no residual hydrogen peroxide in the outlet stream of the hydroxylation reactor, but oxygen is present and will then be removed and purged as a gas stream. The temperature at which the radicalization occurs is generally
至約130oC，用於羥基化笨。To about 130oC, used for hydroxylation stupid.
具有6至約纖碳。料”包括非料性基團，如烧基 15 此芳烴之代表性範例包括， 但不侷限於苯 '甲苯、乙苯、It has 6 to about fibrid. "include", including non-reactive groups, such as alkyl groups. Representative examples of such aromatic hydrocarbons include, but are not limited to, benzene 'toluene, ethylbenzene,
物。在一實施例中’該芳煙為笨。Things. In one embodiment, the aromatic smoke is stupid.
氰為乙腈（曱基氰化物）。Cyanide is acetonitrile (mercapto cyanide).
氰比芳烴之比例範圍為約0.5 : U : 1。在一實施例中，烷基 1至約2 : 1。在一實施例中， 200920732 烷基氰比芳烴之比例範圍為約1·5 : 1。應瞭解到，芳烴已 經羥基化，會降低芳烴與烷基氰混合物中之芳烴量。因此， 組成用之芳烴需要再加至整合流程中，以維持希望之芳煙 比燒》基鼠比例。 5 以過氧化氫使芳烴羥基化過程中所使用之催化劑可廣 泛變化。已知之催化劑如各種沸石（如ZSM-5、絲光沸石， 及其他），以及矽酸鹽催化劑如矽酸鈦皆可使用。該催化劑 可添補各種其他化合物，使用已知技術。此類其他化合物 之代表性範例包括Be、Ti、V、Mn、Fe、Co、Zn、Zr、Rh、 10 Ag、Sn、Sb、A1、B，及其組合物。此類化合物與任一其 他促進劑或材料皆可使用，為此技術領域者顯然可知。 在备基化反應器中之务fe比過氧化氫之比例可廣泛地 變化。一般而言，芳烴比過氧化氫之比例範圍為約〇1 : i 至約1 . 1。在一貫施例中，過氧化氫比芳煙之比例範圍為 15 約 0.5 : 1至約〇.7 : 1。 在本發明方法中，苯轉換為酚之轉換率範圍一般為約 5(%)至約25%。更常見為，該轉換率範圍為約7%至約2〇%。 在本發明之-實施例中，轉換率為至少1〇%。苯轉換率係 定義為（以％表示）職(反應器中轉換之笨/進料於反應器中 20 之苯總量）。 在本發明之方法中，祕選擇率—般為至少約9〇%。 更常見的是，該紛之選擇率為至少約94%。在本發明之〆 實施例中，該酚選擇率為至少約97%。 來自羥基化反應器之流出物係谁、 沒订分離。.因此，水、 200920732 = 之任何副產物，係與 成與烧基氣分離。此分離可使用標準技術完 5 10 15 =:、結晶或固化’搭配傾倒或過渡'萃取， 或”他傳統方法。_基化芳烴可進—步在下游純化。 來自分離步驟之芳烴與燒基氰流出物，之後使用作為 溶劑系統，在過氧化氫反應”。過氧化氫之製造可使用 -般技術引人。—般而言，、氧與催化劑及共催化劑， 係注入過氧化氫反應器中，其中過氧化氫形成。氫盘氧之 使用量為不會造成爆炸混合物之量。苯與絲氰溶劑系統 可溶解在縣化氫合錢程巾形叙軌化氫與水。該催 化劑亦可存在於固定床1流床，或類似物上。揭示過氧 化氫合成之參考文獻代表包括已公開之美國專利申請案號 2003/0083510，在此併入本案以作為參考資料。 已知催化劑可用於製造過氧化氫之反應中。這些催化 劑為週期表上第VIII及/或lb族之一元素，尤其是來自RuThe ratio of cyanide to aromatic hydrocarbons ranges from about 0.5: U:1. In one embodiment, the alkyl group is from 1 to about 2:1. In one embodiment, the ratio of alkyl cyano cyanide to aromatic hydrocarbons of 200920732 ranges from about 1.25:1. It will be appreciated that the aromatic hydrocarbons have been hydroxylated to reduce the amount of aromatics in the mixture of aromatics and alkyl cyanides. Therefore, the aromatics used in the composition need to be added to the integration process to maintain the desired proportion of aromatic smoke compared to the base. 5 The catalyst used in the hydroxylation of aromatic hydrocarbons with hydrogen peroxide can vary widely. Known catalysts such as various zeolites (e.g., ZSM-5, mordenite, and others), and citrate catalysts such as titanium ruthenate can be used. The catalyst can be supplemented with various other compounds using known techniques. Representative examples of such other compounds include Be, Ti, V, Mn, Fe, Co, Zn, Zr, Rh, 10 Ag, Sn, Sb, A1, B, and combinations thereof. Such compounds can be used with any of the other promoters or materials, as will be apparent to those skilled in the art. The ratio of the ratio of hydrogen to hydrogen peroxide in the feed-through reactor can vary widely. In general, the ratio of aromatic hydrocarbon to hydrogen peroxide ranges from about 〇1 : i to about 1.1. In a consistent application, the ratio of hydrogen peroxide to aromatic smoke ranges from about 15:1 to about 7.7:1. In the process of the present invention, the conversion of benzene to phenol is generally in the range of from about 5 (%) to about 25%. More commonly, the conversion rate ranges from about 7% to about 2%. In an embodiment of the invention, the conversion rate is at least 1%. The benzene conversion rate is defined as (in %) (the stupidity of the conversion in the reactor / the total amount of benzene fed to the reactor 20). In the method of the invention, the secret selection rate is generally at least about 9%. More commonly, the selection rate is at least about 94%. In an embodiment of the invention, the phenol selectivity is at least about 97%. The effluent from the hydroxylation reactor is not separated. Therefore, any by-product of water, 200920732 = is separated from the base gas. This separation can be accomplished using standard techniques: 5 10 15 =:, crystallization or solidification 'collapsed or transitioned' extraction, or "his conventional method. - The alkylated aromatics can be further purified downstream. Aromatic hydrocarbons and alkyl groups from the separation step The cyanide effluent is then used as a solvent system to react in hydrogen peroxide. The manufacture of hydrogen peroxide can be introduced using the same techniques. In general, oxygen and a catalyst and a cocatalyst are injected into a hydrogen peroxide reactor in which hydrogen peroxide is formed. Hydrogen disk oxygen is used in an amount that does not cause an explosive mixture. The benzene and silk cyanide solvent system can be dissolved in the chemical vapor of the county. The catalyst may also be present on a fixed bed 1 fluid bed, or the like. References to the disclosure of hydrogen peroxide synthesis include the published U.S. Patent Application Serial No. 2003/0083510, which is incorporated herein by reference. Catalysts are known to be useful in the reaction to produce hydrogen peroxide. These catalysts are one of the elements of Groups VIII and/or lb of the Periodic Table, especially from Ru.
Rh、Pd、Ir、Pt與Au系列之元素，其中P(^pt尤佳。該催 化活性7L素或兀素群知·係結合至顆粒載體上，但也可塗 覆於具有足夠大之活性表面之單片（monolithic)載體上，其 具有通道，或於其他平面載體上。載體結合之貴重金屬催 化劑特佳為適用於涓流床反應器中，作為固定床者，具有 預定之粒徑。一般載體適用之粒徑範圍為約0.01至約5 mm ’尤其是範圍約〇.〇5至約2 mm。載體/催化劑組合物中 之貴重金屬含量一般為約〇.〇1至約10%重。 適當之載體材料’除了活性碳之外，為水-不溶性氧化 20 200920732 物、混合氧化物、硫酸鹽、磷酸鹽，以及驗土金屬、A!、 Si、Sn之矽酸鹽’以及三至六族（IIIa至VIa)金屬。活性礙一 般為較佳載體’但篩選時應注意其分解過氧化氳之作用應 最小化。在氧化物中 ’ Si02、A1203、Sn02、Ti02、Ζ1Ό2、 5 Nt>2〇5，以及Ta2〇5為較佳，以及在硫酸鹽中，硫酸鋇為較 佳。 因此’適當催化劑之代表性範例包括由|巴、翻、|巴與 始合金或非合金組合物，組成之催化劑，具有或不具有促 進劑如銀或金，及類似物，其可存在於支撐物材料上，如 10二氧化石夕、氧化鋁、二氧化鈦、二氧化錯，與沸石，其中 該催化劑可為粉末、擠出物、顆粒，以及類似形式。 請參照第1圖，為本發明整合方法之方塊圖。就第1圖 之目的而$，該务煙為苯，該烧基氰為乙腈，而製造出齡。 在第1圖中，顯示一整合方法，編號為10，其包括一直接合 15成過氧化氫之反應器20 , —羥基化反應器30 ,用於使苯氧 化為酚，以及一分離單元40。 就過氧化氫反應器20而言，來自分離裝置4〇之苯與乙 腈(再循環流），係經由管線44供應至反應器20中。氫與氧係 提供至過氧化氫反應器20中，分別經由管線21與22。經由 20管線23施加適當之催化劑至反應器20中。此外，該催化劑 為預先注入之固定床。因此，過氧化氫可直接於反應器2〇 中製造。過氧化氫，以及笨與乙腈之混合物之後經由管線 24引入反應器30中。 在氧化反應器30(其亦稱之為羥基化反應器）中，組成用 200920732 本係供應至反應器30 ,經由管線31。適當之經基化催化齊ij 係供應至反應器30，經由管線32。此外，氧化催化劑為· 固疋床，其已預先注入。在反應器3〇中，苯係與過氧化氣 接觸，在羥基化催化劑存在下，形成酚與水。反應器玎速 續式或批次式操作。在此二情況下來自反應器3〇之流出 物，其包含苯、乙腈、酚、水，與任一其他不希望之副產 物，係經由管線33送至分離單元40。過氧化氫可使用於羥 基化反應器中，由於在羥基化反應過程中會平行分解成氧 氣(〇2)與水。氧氣被移除並清洗，經由出口清洗管線34。 在分離裝置40中’水、任一副產物以及盼係經分離， 並分別經由管線41、42與43移出。應瞭解到分離單元4〇可 包括-或多個單獨裝置，以完成希望之分離，而該分離單 元40係代表方塊流程步驟。來自分離單元4〇之苯與乙腈係 經由管線44送至過氧化氫反應器2〇中。 下列範例係用於詳細說明本發明，並非用於侷限本發 明範疇或後附之專利申請範圍。除非另有指出，所有百八 比皆為重量百分比。 77 M1J1-5 20 下表顯示經基化反應器所得之結果，其中流出物_ 理以移出酚，而所得之流含有未反應之苯與乙浐 处 ^ 你送至 過氧化氫製造單元中，而來自過氧化氫製造 平70之流出物 則送至羥基化反應器中。存在於羥基化反庫哭6 中之催化劑 為栓狀流配置。表中所提供之資料係基於2週之 * γ 5 Ja^ ψ 未觀察到催化劑失活或鐵漏出。在所有運作過 。柱中，共溶 12 200920732 劑為乙腈’且乙腈比苯之比例紅5 : i。在所有運作過程 中，催化劑之量為4克。Elements of Rh, Pd, Ir, Pt and Au series, of which P(^pt is preferred. The catalytic activity of 7L or alizarin is known to bind to the particle carrier, but can also be applied to a sufficiently large activity. The monolithic support of the surface has channels or other planar supports. The carrier-bound precious metal catalyst is particularly suitable for use in a turbulent bed reactor as a fixed bed having a predetermined particle size. Typical carriers are suitable for particle sizes ranging from about 0.01 to about 5 mm', especially in the range of from about 〇5 to about 2 mm. The precious metal content of the carrier/catalyst composition is generally from about 〇1 to about 10% by weight. A suitable carrier material 'in addition to activated carbon, is water-insoluble oxidation 20 200920732, mixed oxides, sulfates, phosphates, and soil-checking metals, A!, Si, Sn's niobate' and three to Group VI (IIIa to VIa) metals. Activity is generally a preferred carrier', but it should be noted that the role of decomposition of ruthenium peroxide should be minimized. In the oxides 'Si02, A1203, Sn02, Ti02, Ζ1Ό2, 5 Nt> ; 2〇5, and Ta2〇5 are preferred, and Among the sulfates, barium sulfate is preferred. Thus, representative examples of suitable catalysts include catalysts consisting of |bar, turn, and the initial alloy or non-alloy composition, with or without accelerators such as silver or gold. And analogs, which may be present on the support material, such as 10 cerium dioxide, alumina, titania, dioxins, and zeolites, wherein the catalyst may be in the form of powders, extrudates, granules, and the like. Please refer to Fig. 1, which is a block diagram of the integration method of the present invention. For the purpose of Fig. 1, the smoky benzene is benzene, and the alkyl cyanide is acetonitrile to produce age. In Fig. 1, a An integrated process, numbered 10, comprising a reactor 20 that has been coupled to 15 hydrogen peroxide, a hydroxylation reactor 30 for oxidizing benzene to phenol, and a separation unit 40. In the hydrogen peroxide reactor 20 Benzene and acetonitrile (recycle stream) from the separation unit 4 are supplied to the reactor 20 via line 44. Hydrogen and oxygen are supplied to the hydrogen peroxide reactor 20 via lines 21 and 22, respectively. 20 pipeline 23 applies appropriate reminders The catalyst is in the reactor 20. Further, the catalyst is a pre-injected fixed bed. Therefore, hydrogen peroxide can be produced directly in the reactor 2. Hydrogen peroxide, and a mixture of stupid and acetonitrile is introduced into the reactor via line 24. In the oxidation reactor 30 (also referred to as the hydroxylation reactor), the composition is supplied to the reactor 30 using 200920732, via line 31. The appropriate base catalyst is supplied to the reactor 30. Further, via the line 32. Further, the oxidation catalyst is a solid enthalpy bed which has been previously injected. In the reactor 3, the benzene is brought into contact with the peroxidation gas, and phenol and water are formed in the presence of the hydroxylation catalyst. Reactor continuation or batch operation. In either case, the effluent from reactor 3 contains benzene, acetonitrile, phenol, water, and any other undesirable by-products, which are sent via line 33 to separation unit 40. Hydrogen peroxide can be used in the hydroxylation reactor because it will decompose into oxygen (〇2) and water in parallel during the hydroxylation reaction. Oxygen is removed and cleaned, and line 34 is purged via an outlet. In the separation device 40, water, any by-products, and the desired system are separated and removed via lines 41, 42 and 43, respectively. It will be appreciated that the separation unit 4 can include - or a plurality of separate devices to accomplish the desired separation, and the separation unit 40 is representative of the block flow steps. The benzene and acetonitrile from the separation unit 4 are sent to the hydrogen peroxide reactor 2 via line 44. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention or the scope of the appended claims. All hundred and eight ratios are by weight unless otherwise indicated. 77 M1J1-5 20 The table below shows the results obtained from the basic reactor, in which the effluent is taken to remove the phenol, and the resulting stream contains unreacted benzene and acetonitrile. You are sent to the hydrogen peroxide production unit. The effluent from the hydrogen peroxide producing flat 70 is sent to the hydroxylation reactor. The catalyst present in the hydroxylation anti-Crypt 6 is a plug flow configuration. The information provided in the table is based on 2 weeks * γ 5 Ja^ ψ No catalyst deactivation or iron leakage was observed. Worked at all. In the column, co-dissolved 12 200920732 agent is acetonitrile' and the ratio of acetonitrile to benzene is 5: i. The amount of catalyst was 4 grams in all operations.
範例 — 溫度 (°C) 苯： H202 °/。笨轉 換率 催化劑 WHSV %酚選 擇率 產率(g Ph/Kg cat/hr) Fe矽酸鹽 (1.25% Fe) 1 130 0.65 2.25 7.0 97 120 Fe/Al ZSM-5 -- 2 (1.25% Fe, 1.25% Al) 100 0.56 1.1 8.2 94 50 3 Fe/Al ZSM-5 (0.0625% Fe, 1.25% Al) 80 0.56 1.1 12 99 89 Fe/Al ZSM-5 ^ 4 (0.0625% Fe, 1.25% Al) 100 0.56 1.1 14 98 91 Fe/Al ZSM-5 5 (0.0625% Fe, 1.25% Al) 80 0.56 1.1 15 98 N/A 树明之其他修飾與替代實施例，為此技術領域者明 顯可知，經由本份說明。因此，本敘述可理解為僅用於說 明’且用於揭示此技術領域者可進行之方式。應瞭解到本 發明於此顯示之形式與描述，應採用為說明用實施例。等 效之元素或材料可用於替代上面描述者，而本發明之某些 1〇特徵可獨立於其他特徵，為此技術領域者明顯可知，經由 本份說明書之幫助。 【闽式簡單說明】 第1圖為本發明整合流程之代表性方塊圖。 【主要元件符號說明】 10·· •整合方法 21.·.管線 20·..過氧化氫合成反應器 22...管線 13 200920732 23…管線 34…出口清洗管線 24…管線 40…分離單元 30···羥基化反應器 41…管線 31…管線 42…管線 32…管線 43…管線 33…管線 44…管線 14Example - Temperature (°C) Benzene: H202 °/. Stupid conversion rate catalyst WHSV % phenol selectivity yield (g Ph/Kg cat/hr) Fe strontium silicate (1.25% Fe) 1 130 0.65 2.25 7.0 97 120 Fe/Al ZSM-5 -- 2 (1.25% Fe, 1.25% Al) 100 0.56 1.1 8.2 94 50 3 Fe/Al ZSM-5 (0.0625% Fe, 1.25% Al) 80 0.56 1.1 12 99 89 Fe/Al ZSM-5 ^ 4 (0.0625% Fe, 1.25% Al) 100 0.56 1.1 14 98 91 Fe/Al ZSM-5 5 (0.0625% Fe, 1.25% Al) 80 0.56 1.1 15 98 N/A Other modifications and alternative embodiments of the tree, as will be apparent to those skilled in the art, through this description . Accordingly, the description is to be construed as illustrative only and is intended to be illustrative. It is to be understood that the form and description of the present invention is intended to be illustrative. Equivalent elements or materials may be used in place of the above description, and some of the features of the present invention may be independent of other features, as will be apparent to those skilled in the art, with the help of this specification. [Simple Description] Figure 1 is a representative block diagram of the integration process of the present invention. [Explanation of main component symbols] 10·· Integration method 21.·. Pipeline 20·.. Hydrogen peroxide synthesis reactor 22...Line 13 200920732 23...Line 34...Exit cleaning line 24...Line 40...Separation unit 30 ··· hydroxylation reactor 41...line 31...line 42...line 32...line 43...line 33...line 44...line 14
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| US5569791A (en) * | 1995-04-25 | 1996-10-29 | Uop | Production of phenol from a hydrocarbon feedstock |
| US6576214B2 (en) * | 2000-12-08 | 2003-06-10 | Hydrocarbon Technologies, Inc. | Catalytic direct production of hydrogen peroxide from hydrogen and oxygen feeds |
| DE19853491A1 (en) * | 1998-11-19 | 2000-05-25 | Bayer Ag | Single stage production of phenol by catalytic hydroxylation of benzene using an amorphous, microporous mixed oxide obtained by hydrolysis and then co-condensation of metal salts or alkoxides |
| US6180836B1 (en) * | 1999-08-17 | 2001-01-30 | National Science Council Of Republic Of China | Preparation of phenol via one-step hydroxylation of benzene catalyzed by copper-containing molecular sieve |
| DE10153546A1 (en) * | 2001-10-30 | 2003-05-22 | Degussa | Direct synthesis of hydrogen peroxide and its integration in oxidation processes |
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