CN1697698A - 用于丙烯和异丁烯的部分氧化的催化剂的制备方法 - Google Patents
用于丙烯和异丁烯的部分氧化的催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 230000003647 oxidation Effects 0.000 title claims abstract description 46
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 46
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 49
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000010937 tungsten Chemical group 0.000 claims abstract description 11
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052759 nickel Chemical group 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 239000011591 potassium Substances 0.000 claims abstract description 9
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 9
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical group [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 7
- 150000001621 bismuth Chemical class 0.000 claims abstract description 4
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 abstract description 31
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052684 Cerium Chemical group 0.000 abstract 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 2
- 238000010304 firing Methods 0.000 abstract 1
- 150000002505 iron Chemical class 0.000 abstract 1
- 238000003801 milling Methods 0.000 abstract 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 8
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- 239000002905 metal composite material Substances 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
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- 239000011733 molybdenum Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- -1 nitrile compound Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C07C45/27—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
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- C07C45/34—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 in unsaturated compounds
- C07C45/35—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 in unsaturated compounds in propene or isobutene
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Abstract
本发明涉及一种用于丙烯和异丁烯的部分氧化的催化剂的制备方法，尤其是涉及能够通过在硝酸水溶液或有机酸溶液中溶解用作催化剂的金属盐以制备催化剂悬浮液，在微波炉中干燥催化剂溶液，然后粉碎和模压干燥的催化剂，并煅烧该催化剂，因而稳定地制备对于丙烯和异丁烯的转化具有高活性从而以高产率获得丙烯醛和甲基丙烯醛的催化剂的制备用于丙烯和异丁烯部分氧化的催化剂的方法。
Description
技术领域
本发明涉及一种用于丙烯和异丁烯的部分氧化的催化剂的制备方法，尤其是涉及能够稳定地制备对于丙烯和异丁烯的转化具有高活性从而以高产率获得丙烯醛和甲基丙烯醛的催化剂的用于丙烯和异丁烯部分氧化的催化剂的制备方法。
背景技术
应用过渡金属复合氧化物作为催化剂的部分氧化在工业上非常重要，因为部分氧化可以生产对化学工程很有用的中间产物，如醛、有机酸、环氧化合物、腈化物等。
在部分氧化中，产生二氧化碳和水的完全氧化是被抑制的，且重要的是如何有选择地生产所需的部分氧化的产物。因而，在部分氧化中使用的催化剂应该能够抑制一氧化碳或二氧化碳的产生，并且同时该催化剂还应具有高活性从而使其具有经济价值。一般的，部分氧化采用金属、单一金属氧化物、复合金属氧化物等作为催化剂，并且尤其是复合金属氧化物被最广泛地应用。
由于部分氧化通常为放热反应，且部分氧化的选择性对反应温度敏感，就需要甚至在低温下也具有活性的复合氧化物催化剂。部分氧化用的催化剂被广泛地应用于多种领域。
一般而言，在复合氧化物催化剂中，丙烯酸和甲基丙烯酸可以通过由丙烯和异丁烯部分氧化制备的丙烯醛和甲基丙烯醛的气相接触氧化而制备出来。这种制备方法在尽可能低的氧浓度和反应温度下进行，所以由于反应物的氧浓度的增加而导致的燃烧就可以被避免，过度反应被制止，且丙烯醛和甲基丙烯醛的选择性不会被减弱。另外，在低反应温度下具有高活性的催化剂比具有相对低活性的催化剂具有更高的失活抗性。因此已进行了许多涉及用于丙烯和异丁烯的部分氧化的催化剂的研究。
迄今为止，为了通过丙烯醛和甲基丙烯醛的气相接触氧化来有效地制备丙烯酸和甲基丙烯酸，已提出了多种方法。
例如日本专利公开出版物Sho 44-12129公开了包含钼、钒和钨的催化剂；日本专利公开出版物Sho 49-11371公开了包含钼、钒、铜、钨和铬的催化剂；日本专利公开出版物Sho 50-25914公开了包含钼和钒的催化剂；日本专利公开出版物Sho 52-85091公开了包含一种或多种选自包含钼、钒、铜、锑和锗的组的成分的催化剂。
另外，欧洲专利No.023,859公开了当催化剂的成分和组成比例相同时，丙烯醛转化率和丙烯酸产率会根据催化剂铸型的方法而变化，并且还公开了制备具有高丙烯酸产率的催化剂的方法。此外，韩国专利申请No.1998-073605描述了通过基于金属盐的总重量控制水的重量以制备催化剂悬浮液的方法，以及韩国专利申请No.1998-073604描述了催化剂活性随颗粒大小而变化。
然而，这些方法具有由于在制备催化剂时使用大量的水而使干燥需要大量的时间和成本的问题，且对催化剂性能的控制也比较困难。
为了改进干燥方法，日本专利No.2002-316047公开了在制备用于丙烷氧化的催化剂时使用微波的方法。然而，由于该方法在制备用于丙烯和异丁烯氧化的催化剂中使用水，所以在制备催化剂浆时由于金属组分的沉淀而产生相分离。如果应用微波的干燥方法被用于层分离的浆液，催化剂活性就会被降低。本发明应用例如硝酸和柠檬酸的有机酸取代层分离浆液以制备完全溶解的浆液，并且通过使用微波干燥如此制备的浆液而改善催化剂活性。
发明内容
[技术问题]
为了解决现有技术的问题，本发明的目的在于提供一种能够减少干燥所需时间和成本并改善催化剂物理性能的，制备用于丙烯和异丁烯部分氧化的催化剂的方法。
本发明的另一个目的是提供对丙烯和异丁烯转化具有高活性，对部分氧化具有高选择性，并能够以高产率获得丙烯醛和甲基丙烯醛的用于丙烯和异丁烯部分氧化的催化剂。
[技术方案]
为了达到这些目的，本发明提供了一种由下面化学式1表示的用于丙烯和异丁烯部分氧化的催化剂的制备方法，该方法包括以下步骤：
a)在硝酸水溶液或有机酸溶液中溶解金属盐，包括
i)钼盐，
ii)铋盐，
iii)铁盐，
iv)一种或多种选自包含钴、钨、钒、锑和镍的组的金属的盐，和
v)一种或多种选自包含钾、铷和铯的组的金属的盐，
以制备催化剂悬浮液；
b)在微波炉中干燥步骤a)的催化剂悬浮液；
c)粉碎和铸型步骤b)的干燥催化剂；和
d)煅烧步骤c)中得到的催化剂粉末
[化学式1]
MoaBibFecXdYeOf
(其中X为钴、钨、钒、锑或镍，
Y为钾、铷或铯，
各a、b、c、d和e代表各金属的原子摩尔比，且当a为12时，b为0.5～2，c为0.5～2，d为3-8和e为0.005～0.2，
并且f决定于每个金属的氧化态。)
本发明还提供了一种由上面化学式1表示的用于丙烯和异丁烯部分氧化的催化剂，该催化剂是通过在硝酸水溶液或有机酸溶液中溶解包括钼盐；铋盐；铁盐；一种或多种选自包括钴、钨、钒、锑和镍的组的金属的盐；一种或多种选自包括钾、铷和铯的组的金属的盐以制备催化剂悬浮液，在微波炉中干燥该催化剂悬浮液，粉碎干燥的催化剂，以及煅烧粉碎的催化剂颗粒制备出来的。
[有益效果]
根据本发明，在制备催化剂中干燥所需时间和成本可被降低，催化剂的物理性能可以被改善，并且可以稳定地制备出具有更高的对丙烯和异丁烯的转化率和对部分氧化的高选择性，并且可高产率地获得丙烯醛和甲基丙烯醛的用于丙烯和异丁烯的部分氧化的催化剂。
具体实施方式
本发明现将被详细地加以描述。
在对能够降低干燥所需时间和成本并改善催化剂物理性能的用于丙烯和异丁烯部分氧化的催化剂的制备方法的研究中，发明人通过在微波炉中干燥通过在硝酸水溶液或有机酸溶液中溶解作为催化剂的金属盐制备的催化剂悬浮液，粉碎干燥的催化剂悬浮液，及铸型和煅烧粉碎的催化剂粉末从而制备催化剂。结果发现制备催化剂时干燥所需时间和成本得以被降低，催化剂的物理性能得以被改善，催化剂具有对丙烯和异丁烯更高的转化率和对部分氧化的高选择性，并且可以高产率制备丙烯醛和甲基丙烯醛。
本发明的用于丙烯和异丁烯的部分氧化的催化剂是通过在微波炉中干燥经过在硝酸水溶液或有机酸溶液中溶解作为催化剂的金属盐制备的催化剂悬浮液，粉碎干燥的催化剂，以及煅烧粉碎的催化剂粉末制备的。
本发明的用于丙烯和异丁烯部分氧化的催化剂的制备方法将加以更加详细地描述。
a)催化剂悬浮液的制备
在本步骤中，作为用于将丙烯和异丁烯部分氧化为丙烯醛的催化剂的金属盐被溶解在硝酸水溶液或有机酸溶液中以制备催化剂悬浮液。
钼、铋、铁、钴、钨、钒、锑、镍、钾、铷或铯是可以被使用的金属。
当金属盐被溶于硝酸水溶液或有机酸溶液中，它们发生相互作用获得完全溶解的悬浮液。
b)干燥
上述制备的催化剂悬浮液在微波炉中被干燥。
对微波炉并无特别的限制。
干燥优选地在频率为600MHz～2.5GHz的微波炉中进行，更优选的为600MHz～1GHz。如果微波炉的频率小于600MHz，干燥时间增加，而如果频率大于2.5GHz，颗粒大小增加。
对10ml催化剂悬浮液的干燥优选地进行30秒到5分钟，更优选的为30秒到2分钟。
在微波炉中干燥相比于常规催化剂的制备干燥所需时间可以降低到大约1/20，因而降低了成本。
c)粉碎
本步骤中，在微波炉中干燥的催化剂被粉碎。
粉碎优选能使颗粒大小为100目或更小。粉碎大小并无特别限制。
d)煅烧
在本步骤中，粉碎的催化剂被铸型和煅烧。铸型可以通过例如挤压成形、惰性载体涂布(inert support coating)等常规方法进行。
煅烧优选地在350℃～450℃进行4～6个小时，且更优选的为在400℃进行5小时。另外，煅烧优选地在空气气氛中进行。
所制备的催化剂具有通过常规方法制备的催化剂两到三倍的表面积，其表面积优选为10～20m2/g。这种催化剂表面积的增加会增加催化剂活性并降低了催化剂的用量。
另外，当催化剂被商业应用时，该催化剂可以被铸型为特殊的尺寸并通过一般方法成型。
本发明中采用的反应条件并无特别限制，并且通过在固定床多管反应器中丙烯和异丁烯的气相催化氧化制备丙烯醛和甲基丙烯醛的通常所知的可用的反应条件均可被应用。
本发明还提供了根据上面方法制备的用于丙烯和异丁烯的部分氧化的催化剂。本发明的催化剂具有更高的丙烯和异丁烯的转化率且具有对丙烯和异丁烯部分氧化的高选择性，并且能够以高产率获得丙烯醛和甲基丙烯醛。
本发明将以下面的实施例为参考进行描述。然而，这些实施例仅用于说明本发明而对本发明并无任何限制。
[实施例]
实施例1
将400mL蒸馏水加入到500cc的玻璃反应器中，并在搅拌下加热到75℃。然后加入300g柠檬酸并溶解，并且随后顺序加入100g钼酸铵、39.4g硝酸亚铁和54.95g硝酸钴并完全溶解。向该溶液中，加入0.286g硝酸钾和34.35g硝酸铋的硝酸溶液，且混合物被完全溶解以制备催化剂悬浮液。
10ml所制备的催化剂悬浮液在频率为600MHz的微波炉中被干燥大约2分钟。干燥的催化剂块被收集并粉碎为40目以制备催化剂粉末。催化剂粉末被收集，挤压成圆柱状小球，并在空气气氛中450℃煅烧5小时以制备组成为Mo12Bi1.5Co4Fe2K0.06的金属复合氧化物催化剂。挤压成型和煅烧处理在下面的实施例中以相同的方式进行。
实施例2
将400ml蒸馏水加入到500cc的玻璃反应器中，并在搅拌下加热到75℃。然后加入200g柠檬酸并溶解，并且随后顺序加入100g钼酸铵、39.4g硝酸亚铁和60.44g硝酸钴并完全溶解。向该溶液中，加入34.35g硝酸铋和0.286g硝酸钾的硝酸溶液，并且被完全溶解以制备催化剂悬浮液。
上述制备的催化剂悬浮液被收集，并且10ml该悬浮液在频率为800MHz的微波炉中被干燥30秒。干燥的催化剂块被收集并粉碎为40目以制备催化剂粉末。催化剂粉末被收集并在空气气氛中450℃煅烧5小时以制备组成为Mo12Bi1.5Co4.4Fe2K0.06的金属复合氧化物催化剂。
实施例3
除了悬浮液在频率为1GHz的微波炉中被干燥30秒以外，以实施例2相同的方法制备了组成为Mo12Bi1.5Co4.4Fe2K0.06的金属复合氧化物催化剂。
实施例4
除了使用400ml硝酸制备悬浮液以外，以实施例2相同的方法制备了组成为Mo12Bi1.5Co4.4Fe2K0.06的金属复合氧化物催化剂。
实施例5
除了使用400ml水制备悬浮液以外，以实施例2相同的方法制备了组成为Mo12Bi1.5Co4.4Fe2K0.06的金属复合氧化物催化剂。
对比实施例1
将400ml蒸馏水加入到500cc的玻璃反应器中，并在搅拌下加热到75℃。加入100g钼酸铵、39.4g硝酸亚铁、66.44g硝酸钴、34.35g硝酸铋及0.286g硝酸钾的硝酸溶液以制备催化剂悬浮液。
100ml制备的催化剂悬浮液在真空中干燥。干燥的块被收集并粉碎为40目以制备催化剂粉末。催化剂粉末被铸型并在炉子中450℃煅烧5小时以制备组成为Mo12Bi1.5Co4.4Fe2K0.06的金属复合氧化物催化剂。
试验1：催化活性的测试
实施例1～5和对比例1中制备的催化剂被分别装入250～350℃及1～3个大气压下的反应器中。然后，1～10vol％的丙烯、1～15vol％的氧气、5～60vol％水蒸气和20～80vol％的惰性气体以500～2000小时的空速(space velocity)(STP)被引入催化剂中。丙烯转化率、丙烯醛和丙烯酸的产率、以及催化剂的表面积如下测定，且结果列于表1中。
a)丙烯转化率-根据下面等式1测定。
[等式1]
丙烯转化率(％)＝(反应的丙烯摩尔数/加入的丙烯摩尔数)×100
b)丙烯醛和丙烯酸产率-根据下面的等式2测定。
[等式2]
产率(％)＝(产生的丙烯醛和丙烯酸的摩尔数/加入的丙烯的摩尔数)×100
c)表面积-通过氮气吸收法测定。
[表1]
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 对比实施例1 | |
| 干燥方法 | 微波(600MHz) | 微波(800MHz) | 微波(1GHz) | 微波(800MHz) | 微波(800MHz) | 真空干燥 |
| 催化剂组成 | Mo12Bi1.5Co4.4Fe2K0.06 | Mo12Bi1.5Co4.4Fe2K0.06 | Mo12Bi1.5Co4.4Fe2K0.06 | Mo12Bi1.5Co4.4Fe2K0.06 | Mo12Bi1.5Co4.4Fe2K0.06 | Mo12Bi1.5Co4.4Fe2K0.06 |
| 反应温度 | 320℃ | 320℃ | 320℃ | 320℃ | 320℃ | 320℃ |
| 丙烯转化率(％) | 97.8 | 97.5 | 97.2 | 97.0 | 96.2 | 95.2 |
| 丙烯醛和丙烯酸产率(％) | 89.1 | 88.8 | 88.4 | 88.1 | 87.3 | 86.2 |
| 表面积(m2/g) | 17.5 | 16.8 | 14.3 | 12.4 | 9.4 | 5.7 |
从表1可以看出，根据本发明通过在微波炉中干燥制备的实施例1～5的催化剂相对于对比实施例1的催化剂具有极佳的丙烯转化率、丙烯醛和丙烯酸产率、以及表面积。
Claims (5)
1、一种由下面化学式1表示的用于丙烯和异丁烯的部分氧化的催化剂的制备方法，该方法包括以下步骤：
a)在硝酸水溶液或有机酸溶液中溶解金属盐，包括
i)钼盐，
ii)铋盐，
iii)铁盐，
iv)一种或多种选自包含钴、钨、钒、锑和镍的组的金属的盐，和
v)一种或多种选自包含钾、铷和铯的组的金属的盐，以制备催化剂悬浮液；
b)在微波炉中干燥步骤a)的催化剂悬浮液；
c)粉碎和模压步骤b)的干燥催化剂；和
d)煅烧步骤c)中得到的催化剂粉末，
[化学式1]
MoaBibFecXdYeOf
其中X为钴、钨、钒、锑或镍，
Y为钾、铷或铯，
各a、b、c、d和e代表各金属的原子摩尔比，且当a为12时，b为0.5～2，c为0.5～2，d为3～8以及e为0.005～0.2，
并且f决定于每种金属的氧化状态。
2、根据权利要求1的用于丙烯和异丁烯部分氧化的催化剂的制备方法，其特征在于：步骤b)包括在微波炉中以600MHz～2.5GHz的频率干燥溶液。
3、根据权利要求1的用于丙烯和异丁烯部分氧化的催化剂的制备方法，其特征在于：对10ml催化剂悬浮液，步骤b)的干燥进行30秒～5分钟。
4、根据权利要求1的用于丙烯和异丁烯部分氧化的催化剂的制备方法，其特征在于：催化剂具有10～20m2/g的表面积。
5、一种由下面化学式1表示的用于丙烯和异丁烯的部分氧化的催化剂，该催化剂是根据权利要求1的方法制备的：
[化学式1]
MoaBibFecXdYeOf
其中X为钴、钨、钒、锑或镍，
Y为钾、铷或铯，
各a、b、c、d和e代表各金属的原子摩尔比，且当a为12时，b为0.5～2，c为0.5～2，d为3～8以及e为0.005～0.2；并且f决定于各金属的氧化状态。
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| US20060183626A1 (en) * | 2005-02-11 | 2006-08-17 | Cavalcanti Fernando Antonio Pe | Process for preparing catalysts and catalysts produced therefrom |
| EP1693107A1 (en) * | 2005-02-11 | 2006-08-23 | Rohm And Haas Company | Method for preparing mixed-metal oxide catalysts and the catalysts produced thereby |
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-
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- 2004-03-19 EP EP04722104.9A patent/EP1613432B1/en not_active Expired - Lifetime
- 2004-03-19 JP JP2005518166A patent/JP4364870B2/ja not_active Expired - Lifetime
- 2004-03-19 CN CNB2004800001070A patent/CN100423837C/zh not_active Expired - Lifetime
- 2004-03-19 US US10/509,645 patent/US7329628B2/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102371157A (zh) * | 2010-08-04 | 2012-03-14 | 日本化药株式会社 | 甲基丙烯醛和甲基丙烯酸制造用催化剂及其制造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20050165252A1 (en) | 2005-07-28 |
| JP2006511348A (ja) | 2006-04-06 |
| WO2004085060A1 (en) | 2004-10-07 |
| EP1613432A1 (en) | 2006-01-11 |
| US7329628B2 (en) | 2008-02-12 |
| KR100497175B1 (ko) | 2005-06-23 |
| CN100423837C (zh) | 2008-10-08 |
| KR20040084092A (ko) | 2004-10-06 |
| EP1613432B1 (en) | 2013-08-28 |
| EP1613432A4 (en) | 2010-10-06 |
| JP4364870B2 (ja) | 2009-11-18 |
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