CN104402675B - A kind of method that bionic catalysis oxidation of isobutane prepares the tert-butyl alcohol - Google Patents
A kind of method that bionic catalysis oxidation of isobutane prepares the tert-butyl alcohol Download PDFInfo
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 92
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000001282 iso-butane Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 239000011664 nicotinic acid Substances 0.000 title claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000003254 radicals Chemical class 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 150000004032 porphyrins Chemical class 0.000 abstract description 3
- 235000013847 iso-butane Nutrition 0.000 abstract 2
- 238000004817 gas chromatography Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- 230000003592 biomimetic effect Effects 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- -1 nitro, methyl Chemical group 0.000 description 4
- INZUQGFQRYAKQQ-UHFFFAOYSA-N 2-acetylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C(=O)C)C(=O)C2=C1 INZUQGFQRYAKQQ-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- IIVWHGMLFGNMOW-UHFFFAOYSA-N 2-methylpropane Chemical group C[C](C)C IIVWHGMLFGNMOW-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CNAVAHHLABPUAL-UHFFFAOYSA-N [O].CC(C)C Chemical compound [O].CC(C)C CNAVAHHLABPUAL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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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
技术领域technical field
本发明涉及一种叔丁醇的制备方法，具体地说，是涉及一种仿生催化异丁烷氧化制备叔丁醇的方法。The invention relates to a method for preparing tert-butanol, in particular to a method for preparing tert-butanol by biomimetic catalysis of isobutane oxidation.
背景技术Background technique
叔丁醇常用来代替正丁醇作为涂料和医药的溶剂，同时也可用作内燃机燃料添加剂(防止化油器结冰)及抗爆剂、有机合成的中间体及生产叔丁基化合物的烷基化原料，在生产甲基丙烯酸甲酯、叔丁基苯酚、叔丁胺重要化工原料方面具有广泛的用途。Tert-butanol is often used to replace n-butanol as a solvent for coatings and medicines. It can also be used as an internal combustion engine fuel additive (to prevent carburetor from freezing) and an antiknock agent, an intermediate in organic synthesis, and an alkane for the production of tert-butyl compounds. It is widely used in the production of important chemical raw materials such as methyl methacrylate, tert-butylphenol and tert-butylamine.
丙烯/异丁烷共氧化是工业生产叔丁醇的一种主要方法，美国Halcon开发并与Arco公司合资组成的Oxriane公司将此方法工业化，此方法一方面可以有丙烯与异丁烷所生成的叔丁基过氧化氢共氧化生成环氧丙烷，另一方面联产叔丁醇，原料利用率高，污染少，但是投资大且工艺复杂。Propylene/isobutane co-oxidation is a main method for industrial production of tert-butanol. Oxriane, a joint venture company developed by Halcon in the United States and formed with Arco, has industrialized this method. On the one hand, this method can produce propylene and isobutane The co-oxidation of tert-butyl hydroperoxide produces propylene oxide, and on the other hand co-produces tert-butanol. The raw material utilization rate is high and the pollution is less, but the investment is large and the process is complicated.
异丁烯水合也常用以制备叔丁醇，其中以离子交换树脂、离子液体或固体酸等为催化剂的直接水合法占据主导(CN 101139251，CN 1714062，CN 1603290)，但直接水合法的缺点是异丁烯与水的互溶性较差，因此转化率较低。硫酸水合法可获得高收率的叔丁醇，但由于存在污染大、设备腐蚀严重等问题，该技术目前已逐渐淘汰。The hydration of isobutene is also commonly used to prepare tert-butanol, wherein the direct hydration method with ion exchange resin, ionic liquid or solid acid etc. as a catalyst is dominant (CN 101139251, CN 1714062, CN 1603290), but the shortcoming of the direct hydration method is that isobutene and Water is less miscible, so conversion is lower. Sulfuric acid hydration method can obtain high yield of tert-butanol, but due to problems such as heavy pollution and serious equipment corrosion, this technology has been gradually eliminated.
异丁烷是由石油裂化过程中产生的碳四馏分经分离即可获得，来源丰富，因此异丁烷直接氧化制备叔丁醇倍受人们关注。美国专利US 2845461公开了异丁烷液相非催化氧化制备叔丁醇的方法，在反应温度100～150℃、反应压力3.4～4.8MPa的条件下,异丁烷的转化率约为20～35％,叔丁醇的选择性为15～20％。中国专利CN 102807469公开了以金属酞菁为催化剂液相催化氧化异丁烷制备叔丁醇的方法，该方法中异丁烷的转化率可达到约30％，产物叔丁醇选择性也可达到～80％，但是所需的反应温度和压力都很高，催化剂用量大。Isobutane can be obtained by separating the C4 fraction produced in the process of petroleum cracking, and has abundant sources. Therefore, the direct oxidation of isobutane to prepare tert-butanol has attracted much attention. U.S. Patent US 2845461 discloses a method for preparing tert-butanol by liquid-phase non-catalytic oxidation of isobutane. Under the conditions of reaction temperature 100-150°C and reaction pressure 3.4-4.8 MPa, the conversion rate of isobutane is about 20-35 %, the selectivity of tert-butanol is 15-20%. Chinese patent CN 102807469 discloses a method for preparing tert-butanol by liquid-phase catalytic oxidation of isobutane using metal phthalocyanine as a catalyst. In this method, the conversion rate of isobutane can reach about 30%, and the selectivity of product tert-butanol can also reach ~80%, but the required reaction temperature and pressure are very high, and the amount of catalyst used is large.
因此，开发反应条件温和、绿色、高效的仿生催化异丁烷氧气氧化制备叔丁醇工艺具有重要的现实意义和应用前景。Therefore, it is of great practical significance and application prospect to develop a biomimetic catalytic isobutane oxygen oxidation process to prepare tert-butanol with mild reaction conditions, green and high efficiency.
发明内容Contents of the invention
为了克服上述现有技术存在的缺陷，本发明的目的在于提供一种仿生催化异丁烷氧化制备叔丁醇的方法。In order to overcome the defects in the above-mentioned prior art, the object of the present invention is to provide a method for preparing tert-butanol by biomimetic catalysis of isobutane oxidation.
为实现本发明的目的，所采用的技术方案是：以异丁烷为原料，以氧气为氧源，加入溶剂、助剂和自由基引发剂，以通式(I)或(II)结构的单核金属卟啉或通式(III)结构的μ-氧-双核金属卟啉为催化剂，控制在反应温度为50～120℃，反应压力为0.5～2MPa的条件下进行催化反应得到叔丁醇，催化剂用量为1～100ppm，助剂用量为原料的0.5～2mol％，自由基引发剂的用量为原料的0.05～1mol％，For realizing the purpose of the present invention, the technical scheme adopted is: take isobutane as raw material, take oxygen as oxygen source, add solvent, auxiliary agent and free radical initiator, with general formula (I) or (II) structure Mononuclear metalloporphyrin or μ-oxygen-binuclear metalloporphyrin of the general formula (III) structure is used as a catalyst, and the catalytic reaction is carried out under the conditions of a reaction temperature of 50-120°C and a reaction pressure of 0.5-2 MPa to obtain tert-butanol , the consumption of catalyst is 1～100ppm, the consumption of auxiliary agent is 0.5～2mol% of raw material, the consumption of free radical initiator is 0.05～1mol% of raw material,
通式(I)中的M1是金属原子Mg、Al、Fe、Co、Mn、Ni、Cu或Zn，X是卤素或氢，R1、R2、R3、R4和R5均选自氢、卤素、硝基、甲基、羟基、烷氧基或磺酸基；通式(II)中的M2是金属原子Cr、Mn、Fe、Co、Ni、Cu、Zn或Sn，X是卤素或氢，R1、R2、R3、R4和R5均选自氢、卤素、硝基、烷基、烷氧基、羟基、羧基或磺酸基，配位基X1是氯或咪唑或吡啶；通式(III)中的M3是金属原子Fe、Co、Mn、Ru或Rh，R1、R2、R3、R4和R5均选自氢、卤素、硝基、烷基、烷氧基、羟基、羧基或磺酸基。M in the general formula ( I ) is metal atom Mg, Al, Fe, Co, Mn, Ni, Cu or Zn, X is halogen or hydrogen, R 1 , R 2 , R 3 , R 4 and R 5 are all selected from From hydrogen, halogen, nitro, methyl, hydroxyl, alkoxy group or sulfonic acid group; M in general formula (II) 2 is metal atom Cr, Mn, Fe, Co, Ni, Cu, Zn or Sn, X is halogen or hydrogen, R 1 , R 2 , R 3 , R 4 and R 5 are all selected from hydrogen, halogen, nitro, alkyl, alkoxy, hydroxyl, carboxyl or sulfonic acid, and the ligand X 1 is Chlorine or imidazole or pyridine; M in general formula (III) 3 is metal atom Fe, Co, Mn, Ru or Rh, R 1 , R 2 , R 3 , R 4 and R 5 are all selected from hydrogen, halogen, nitric acid group, alkyl group, alkoxy group, hydroxyl group, carboxyl group or sulfonic acid group.
在上述仿生催化异丁烷氧化制备叔丁醇的方法中，所述的自由基引发剂选自N-羟基邻苯二甲酰亚胺(NHPI)或其衍生物中的一种。In the method for preparing tert-butanol by biomimetic catalyzed oxidation of isobutane, the free radical initiator is selected from one of N-hydroxyphthalimide (NHPI) or its derivatives.
在上述仿生催化异丁烷氧化制备叔丁醇的方法中，所述的助剂为选自含Cr、Fe、Mn、Co、V、Ni、Cu、Zn、Pd或Ru的无机盐中的一种，优选的助剂为含Fe、Mn、Co或Pd的醋酸盐或氯化物。In the method for preparing tert-butanol by biomimetic catalyzed oxidation of isobutane, the auxiliary agent is selected from inorganic salts containing Cr, Fe, Mn, Co, V, Ni, Cu, Zn, Pd or Ru. A preferred additive is acetate or chloride containing Fe, Mn, Co or Pd.
在上述仿生催化异丁烷氧化制备叔丁醇的方法中，所述的溶剂为选自乙腈、苯腈、乙酸乙酯、二氯甲烷、乙酸或1,2-二氯乙烷中的一种。In the method for preparing tert-butanol by biomimetic catalytic oxidation of isobutane, the solvent is selected from acetonitrile, benzonitrile, ethyl acetate, dichloromethane, acetic acid or 1,2-dichloroethane .
在上述仿生催化异丁烷氧化制备叔丁醇的方法中，所述的催化剂的用量为10～50ppm，自由基引发剂用量为原料的0.1～0.8mol％，助剂用量为原料的0.8～1.5mol％，反应温度为60～100℃，反应压力为0.8～1.5MPa。In the above-mentioned method for preparing tert-butanol by biomimetic catalyzed oxidation of isobutane, the amount of the catalyst used is 10-50 ppm, the amount of the free radical initiator is 0.1-0.8 mol% of the raw material, and the amount of the auxiliary agent is 0.8-1.5 mol% of the raw material. mol%, the reaction temperature is 60-100° C., and the reaction pressure is 0.8-1.5 MPa.
本发明将催化剂均匀溶解在溶剂中，加入自由基引发剂和助剂，使异丁烷和氧气在催化剂的作用下进行催化反应生成叔丁醇。加入的自由基引发剂的目的在于使体系更容易生成自由基，夺取异丁烷的叔氢生成叔丁基自由基，低温下金属卟啉对分子氧有很好的活化作用从而加快低温下异丁烷的转化。加入助剂的目的在于促进叔丁基自由基分解生成产物叔丁醇，从而提高反应速率、异丁烷的转化率以及产物的选择性。本发明各种反应体系下叔丁醇的选择性高，产物易分离，催化剂使用量少，自由基引发剂和助剂通过离心或过滤即可实现重复使用。In the invention, the catalyst is uniformly dissolved in the solvent, and a free radical initiator and an auxiliary agent are added, so that the isobutane and oxygen undergo a catalytic reaction under the action of the catalyst to generate tert-butanol. The purpose of the added free radical initiator is to make the system more likely to generate free radicals, take away the tertiary hydrogen of isobutane to generate tert-butyl free radicals, and metalloporphyrins have a good activation effect on molecular oxygen at low temperatures, thus accelerating the isotropic reaction at low temperatures. Butane conversion. The purpose of adding the auxiliary agent is to promote the decomposition of the tert-butyl radical to generate the product tert-butanol, thereby increasing the reaction rate, the conversion rate of isobutane and the selectivity of the product. The selectivity of the tert-butanol in various reaction systems of the invention is high, the product is easy to separate, the catalyst usage is small, and the free radical initiator and auxiliary agent can be reused through centrifugation or filtration.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1.本发明的效率高、产物选择性高，条件温和，能耗降低。1. The present invention has high efficiency, high product selectivity, mild conditions and reduced energy consumption.
2.本发明采用金属卟啉为催化剂，避免了异丁烯水合法中由于酸性催化剂带来的设备严重腐蚀、环境污染及安全等问题。2. The present invention uses metalloporphyrin as a catalyst, which avoids the problems of severe equipment corrosion, environmental pollution and safety caused by acidic catalysts in the isobutene hydration method.
3.本发明使用的催化剂用量少、工艺简单、经济成本低、绿色安全，具有良好的工业应用前景。3. The catalyst used in the present invention has less consumption, simple process, low economic cost, green and safe, and has good industrial application prospect.
具体实施方式detailed description
下面结合实施例对本发明做进一步的说明，但本发明的保护范围并不局限于实施例表示的范围。The present invention will be further described below in conjunction with the examples, but the protection scope of the present invention is not limited to the scope indicated by the examples.
实施例1Example 1
在高压反应釜中，加入20mL含有100ppm具有通式(I)结构金属卟啉(M1＝Co,X＝H,R1＝NO2,R2＝R3＝R4＝R5＝H)的乙腈溶液，加入0.005mmol的自由基引发剂NHPI和0.02mmolCo(OAc)2，充入10mmol异丁烷和2MPa O2，在温度为120℃的条件下搅拌，经气相色谱检测，异丁烷转化率为41％，叔丁醇的选择性为96％。In the autoclave, add 20mL containing 100ppm metalloporphyrin with general formula (I) structure (M 1 =Co, X = H, R 1 =NO 2 , R 2 =R 3 =R 4 =R 5 =H) Add 0.005mmol of free radical initiator NHPI and 0.02mmol of Co(OAc) 2 , fill with 10mmol of isobutane and 2MPa O 2 , stir at a temperature of 120°C, detect by gas chromatography, isobutane The conversion was 41%, and the selectivity to t-butanol was 96%.
实施例2Example 2
在高压反应釜中，加入20mL含有50ppm具有通式(I)结构金属卟啉(M1＝Mn,X＝F,R3＝Cl,R1＝R2＝R4＝R5＝H)的乙酸乙酯溶液，加入0.1mmol的自由基引发剂NHPI和0.05mmolMn(OAc)2，充入10mmol异丁烷和0.5MPa O2，在温度为50℃的条件下搅拌，经气相色谱检测，异丁烷转化率为38％，叔丁醇的选择性为95％。In the autoclave, add 20mL containing 50ppm metalloporphyrin with general formula (I) structure (M 1 = Mn, X = F, R 3 = Cl, R 1 = R 2 = R 4 = R 5 = H) Ethyl acetate solution, add 0.1mmol free radical initiator NHPI and 0.05mmol Mn(OAc) 2 , fill with 10mmol isobutane and 0.5MPa O 2 , stir at a temperature of 50°C, detect by gas chromatography, iso The conversion of butane was 38%, and the selectivity to t-butanol was 95%.
实施例3Example 3
在高压反应釜中，加入20mL含有1ppm具有通式(I)结构金属卟啉(M1＝Cu,X＝H,R1＝Cl,R2＝R3＝R4＝R5＝H)的1,2-二氯乙烷溶液，加入0.05mmol的自由基引发剂NHPI和0.08mmolPdCl2，充入10mmol异丁烷和0.8MPa O2，在温度为60℃的条件下搅拌，经气相色谱检测，异丁烷转化率为43％，叔丁醇的选择性为97％。In the autoclave, add 20mL containing 1ppm metal porphyrin with general formula (I) structure (M 1 =Cu, X = H, R 1 = Cl, R 2 = R 3 = R 4 = R 5 = H) 1,2-dichloroethane solution, add 0.05mmol free radical initiator NHPI and 0.08mmol PdCl 2 , fill with 10mmol isobutane and 0.8MPa O 2 , stir at 60°C, detect by gas chromatography , the conversion of isobutane was 43%, and the selectivity of tert-butanol was 97%.
实施例4Example 4
在高压反应釜中，加入20mL含有10ppm具有通式(I)结构金属卟啉(M1＝Ni,X＝H,R2＝℃H3,R1＝R3＝R4＝R5＝H)的二氯甲烷溶液，加入0.08mmol的自由基引发剂(N-乙酰基邻苯二甲酰亚胺,NAPI)和0.1mmolMnCl2，充入10mmol异丁烷和1MPa O2，在温度为80℃的条件下搅拌，经气相色谱检测，异丁烷转化率为42％，叔丁醇的选择性为96％。In the autoclave, add 20mL containing 10ppm metal porphyrin with the general formula (I) structure (M 1 =Ni, X = H, R 2 =°C CH 3 , R 1 =R 3 =R 4 =R 5 =H ) in dichloromethane solution, add 0.08mmol free radical initiator (N-acetyl phthalimide, NAPI) and 0.1mmol MnCl 2 , fill with 10mmol isobutane and 1MPa O 2 , at a temperature of 80 Stirring under the condition of ℃, the conversion rate of isobutane is 42% and the selectivity of tert-butanol is 96% through gas chromatography detection.
实施例5Example 5
在高压反应釜中，加入20mL含有10ppm具有通式(II)结构金属卟啉(M2＝Mn,X1＝咪唑,X＝H,R1＝NO2,R2＝R3＝R4＝R5＝H)的苯腈溶液，加入0.04mmol的自由基引发剂(N-乙酰基邻苯二甲酰亚胺,NAPI)和0.12mmolFe(OAc)2，充入10mmol异丁烷和1.2MPa O2，在温度为100℃的条件下搅拌，经气相色谱检测，异丁烷转化率为45％，叔丁醇的选择性为98％。In the autoclave, add 20mL containing 10ppm metalloporphyrin with general formula (II) structure (M 2 =Mn, X 1 =imidazole, X=H, R 1 =NO 2 , R 2 =R 3 =R 4 = R 5 =H) in benzonitrile solution, add 0.04mmol free radical initiator (N-acetylphthalimide, NAPI) and 0.12mmol Fe(OAc) 2 , fill with 10mmol isobutane and 1.2MPa O 2 , stirred at a temperature of 100°C, detected by gas chromatography, the conversion rate of isobutane was 45%, and the selectivity of tert-butanol was 98%.
实施例6Example 6
在高压反应釜中，加入20mL含有30ppm具有通式(II)结构金属卟啉(M2＝Cr,X1＝Cl,X＝H,R3＝CH3，R1＝R2＝R4＝R5＝H)的乙腈溶液，加入0.03mmol的自由基引发剂(N-乙酰基邻苯二甲酰亚胺，NAPI)和0.15mmolFe(OAc)2，充入10mmol异丁烷和1.2MPa O2，在温度为90℃的条件下搅拌，经气相色谱检测，异丁烷转化率为42％，叔丁醇的选择性为96％。In the autoclave, add 20mL containing 30ppm metalloporphyrin with general formula (II) structure (M 2 =Cr, X 1 =Cl, X =H, R 3 =CH 3 , R 1 =R 2 =R 4 = R 5 =H) in acetonitrile solution, add 0.03mmol free radical initiator (N-acetyl phthalimide, NAPI) and 0.15mmol Fe(OAc) 2 , fill with 10mmol isobutane and 1.2MPa O 2. Stir at a temperature of 90° C., as detected by gas chromatography, the conversion rate of isobutane is 42%, and the selectivity of tert-butanol is 96%.
实施例7Example 7
在高压反应釜中，加入20mL含有80ppm具有通式(II)结构金属卟啉(M2＝Co,X1＝Cl,X＝H,R1＝NO2,R2＝R3＝R4＝R5＝H)的乙酸乙酯溶液，加入0.06mmol的自由基引发剂NHPI和0.09mmolZnCl2，充入10mmol异丁烷和1.2MPa O2，在温度为100℃的条件下搅拌，经气相色谱检测，异丁烷转化率为45％，叔丁醇的选择性为97％。In the autoclave, add 20mL containing 80ppm metalloporphyrin with the general formula (II) structure (M 2 =Co, X 1 =Cl, X = H, R 1 =NO 2 , R 2 =R 3 =R 4 = R 5 =H) in ethyl acetate solution, add 0.06mmol of free radical initiator NHPI and 0.09mmol of ZnCl 2 , fill with 10mmol of isobutane and 1.2MPa O 2 , stir at 100°C, and perform gas chromatography Detection shows that the conversion rate of isobutane is 45%, and the selectivity of tert-butanol is 97%.
实施例8Example 8
在高压反应釜中，加入20mL含有50ppm具有通式(II)结构金属卟啉(M2＝Fe,X1＝吡啶,X＝H,R1＝R2＝R3＝R4＝R5＝H)的乙酸溶液，加入0.02mmol的自由基引发剂NHPI和0.18mmolCuCl2，充入10mmol异丁烷和1.5MPa O2，在温度为80℃的条件下搅拌，经气相色谱检测，异丁烷转化率为46％，叔丁醇的选择性为96％。In the autoclave, add 20mL containing 50ppm metalloporphyrin with general formula (II) structure (M 2 =Fe, X 1 =pyridine, X=H, R 1 =R 2 =R 3 =R 4 =R 5 = H) Acetic acid solution, add 0.02mmol free radical initiator NHPI and 0.18mmol CuCl 2 , fill with 10mmol isobutane and 1.5MPa O 2 , stir at a temperature of 80°C, detect by gas chromatography, isobutane The conversion was 46% and the selectivity to t-butanol was 96%.
实施例9Example 9
在高压反应釜中，加入20mL含有40ppm具有通式(III)结构金属卟啉(M3＝Fe,R1＝R2＝R3＝R4＝R5＝H)的乙腈溶液，加入0.07mmol的自由基引发剂NHPI和0.12mmolPd(OAc)2，充入10mmol异丁烷和1.3MPa O2，在温度为90℃的条件下搅拌，经气相色谱检测，异丁烷转化率为56％，叔丁醇的选择性为97％。In the autoclave, add 20 mL of acetonitrile solution containing 40 ppm metalloporphyrin (M 3 =Fe, R 1 =R 2 =R 3 =R 4 =R 5 =H) with the structure of general formula (III), and add 0.07 mmol The free radical initiator NHPI and 0.12mmol Pd(OAc) 2 were filled with 10mmol isobutane and 1.3MPa O 2 , stirred at a temperature of 90°C, and detected by gas chromatography, the conversion rate of isobutane was 56%. The selectivity to tert-butanol is 97%.
实施例10Example 10
在高压反应釜中，加入20mL含有50ppm具有通式(III)结构金属卟啉(M3＝Mn,R1＝Cl,R2＝R3＝R4＝R5＝H)的二氯甲烷溶液，加入0.1mmol的自由基引发剂(3-吡啶甲基-N-羟基邻苯二甲酰亚胺，Py-NHPI)和0.14mmolCo(OAc)2，充入10mmol异丁烷和1.2MPa O2，在温度为90℃的条件下搅拌，经气相色谱检测，异丁烷转化率为40％，叔丁醇的选择性为97％。In the autoclave, add 20 mL of dichloromethane solution containing 50 ppm metalloporphyrin (M 3 =Mn, R 1 =Cl, R 2 =R 3 =R 4 =R 5 =H) with the structure of general formula (III) , add 0.1mmol of free radical initiator (3-pyridyl-N-hydroxyphthalimide, Py-NHPI) and 0.14mmol Co(OAc) 2 , fill with 10mmol isobutane and 1.2MPa O 2 , stirred at a temperature of 90° C., detected by gas chromatography, the conversion rate of isobutane was 40%, and the selectivity of tert-butanol was 97%.
实施例11Example 11
在高压反应釜中，加入20mL含有20ppm具有通式(III)结构金属卟啉(M3＝Ru,R1＝R2＝R3＝R4＝R5＝H)的乙酸乙酯溶液，加入0.01mmol的自由基引发剂(3-吡啶甲基-N-羟基邻苯二甲酰亚胺，Py-NHPI)和0.18mmolMnCl2，充入10mmol异丁烷和1MPa O2，在温度为120℃的条件下搅拌，经气相色谱检测，异丁烷转化率为48％，叔丁醇的选择性为96％。In the autoclave, add 20 mL of ethyl acetate solution containing 20 ppm metalloporphyrin (M 3 =Ru, R 1 =R 2 =R 3 =R 4 =R 5 =H) with the structure of general formula (III), and add 0.01mmol of free radical initiator (3-pyridyl-N-hydroxyphthalimide, Py-NHPI) and 0.18mmol of MnCl 2 , filled with 10mmol of isobutane and 1MPa O 2 , at a temperature of 120°C Stirring under certain conditions, detected by gas chromatography, the conversion rate of isobutane was 48%, and the selectivity of tert-butanol was 96%.
实施例12Example 12
在高压反应釜中，加入20mL含有50ppm具有通式(III)结构金属卟啉(M3＝Rh,R1＝R2＝R3＝R4＝R5＝H)的1,2-二氯乙烷溶液，加入0.08mmol的自由基引发剂NHPI和0.12mmolC℃l2，充入10mmol异丁烷和1.2MPa O2，在温度为80℃的条件下搅拌，经气相色谱检测，异丁烷转化率为46％，叔丁醇的选择性为95％。In the autoclave, add 20 mL of 1,2-dichloroporphyrin containing 50 ppm structure metalloporphyrin (M 3 =Rh, R 1 =R 2 =R 3 =R 4 =R 5 =H) with general formula (III) Ethane solution, add 0.08mmol free radical initiator NHPI and 0.12mmol C°Cl 2 , fill with 10mmol isobutane and 1.2MPa O 2 , stir at 80°C, detect by gas chromatography, isobutane The conversion was 46% and the selectivity to t-butanol was 95%.
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| EP0471561A2 (en) * | 1990-08-16 | 1992-02-19 | Sun Refining and Marketing Company | Metal coordination complex catalysts containing a halogenated ligand for hydrocarbon oxidation |
| CN1546457A (en) * | 2003-12-18 | 2004-11-17 | 北京工业大学 | Method for preparing o-nitrobenzaldehyde by biomimetic catalytic oxygen oxidation of o-nitrotoluene |
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Effective date of registration: 20250214 Address after: Zuohukou District, Zhenjiang City, Jiangsu Province, 2016 Patentee after: JIANGSU ZHONGJIANG MATERIALS TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. Country or region after: China Address before: 516081 room 205, building a, R & D building, No.5, Keji Road, science and Technology Innovation Park, Dayawan West District, Huizhou City, Guangdong Province Patentee before: HUIZHOU RESEARCH INSTITUTE, SUN YAT-SEN University Country or region before: China |