CN1429217A - 使烃环氧化的方法 - Google Patents
使烃环氧化的方法 Download PDFInfo
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- CN1429217A CN1429217A CN01809556A CN01809556A CN1429217A CN 1429217 A CN1429217 A CN 1429217A CN 01809556 A CN01809556 A CN 01809556A CN 01809556 A CN01809556 A CN 01809556A CN 1429217 A CN1429217 A CN 1429217A
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- 229910052762 osmium Inorganic materials 0.000 claims abstract description 8
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- 150000001299 aldehydes Chemical class 0.000 description 2
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- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910015371 AuCu Inorganic materials 0.000 description 1
- NDROPWHEGJVBDX-UHFFFAOYSA-N CC(C)=O.CC(=O)C=C Chemical compound CC(C)=O.CC(=O)C=C NDROPWHEGJVBDX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- CQVDKGFMVXRRAI-UHFFFAOYSA-J Cl[Au](Cl)(Cl)Cl Chemical compound Cl[Au](Cl)(Cl)Cl CQVDKGFMVXRRAI-UHFFFAOYSA-J 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 241001562081 Ikeda Species 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 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
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
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- 229910052593 corundum Inorganic materials 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- -1 polyene hydrocarbon Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
本发明涉及一种用氧使烃环氧化的方法,该方法是在BET表面积小于200米2/克的载体上含有选自Cu、Ru、Rh、Pd、Os、Ir、Pt、Au、In、Tl、Mn、Ce的至少两种金属的混合物的存在下进行的。本发明方法也涉及在BET表面积小于200米2/克的载体上含有选自Cu、Ru、Rh、Pd、Os、Ir、Pt、Au、In、Tl、Mn、Ce的至少两种金属的混合物在烃环氧化方面的应用。
Description
本发明涉及一种用氧使烃环氧化的方法,该方法是在BET表面积小于200米2/克的载体上含有选自Cu、Ru、Rh、Pd、Os、Ir、Pt、Au、In、Tl、Mn、Ce的至少两种金属的混合物的存在下进行的。本发明也涉及在BET表面积小于200米2/克的载体上含有选自Cu、Ru、Rh、Pd、Os、Ir、Pt、Au、In、Tl、Mn、Ce的至少两种金属的混合物在使烃环氧化时的应用。
环氧化物是聚氨酯工业上一种重要的原料。现有许多它的制造方法。其中一些制造方法已在工业上得到了应用。目前工业上制造环氧乙烷的方法是在含银催化剂的存在下用空气或含分子氧的气体直接氧化乙烯,参见EP-A-2933130。工业上一般在液相中用过氧化氢或次氯酸盐作为氧化剂生产长链环氧化物。EP-A1-0930308例如描述了离子交换的硅酸钛催化剂与这两种氧化剂的应用。
最近,美国专利5623090披露了另一类可以在气相中把丙烯氧化成相应环氧化物的的氧化催化剂。在该专利中,负载在锐钛矿上的金用作催化剂,而在氢气存在下使用的氧气作用氧化剂。该体系的特点是对丙烯氧化有极高的选择性(S>95%)。该方法的缺点是转化率低和催化剂容易失活。
目前文献中关于用于气相选择性直接氧化丙烯和高级烯烃产生环氧化物的银和金以外的其它活性成分报道得不多。
美国专利3644510在Al2O3负载的Ir多相催化剂上进行反应,得到乙酸。视双键的位置不同,高级烯烃产生酮或脂肪酸(美国专利3644511)。在Rh负载催化剂(参见美国专利3632833)或Au负载催化剂(参见美国专利3725482)的存在下,主要的产物是丙烯醛。
由于目前公开的催化剂中还不能在丙烯直接氧化成环氧丙烷的反应中显示令人满意的活性和选择性,所以本发明旨在研究其它的活性成分,以作为已知含银和金催化剂的替代物。一个重要的条件是氧化不能进行完全,以致产生相应的酸、醛、酮或产生二氧化碳。
文献中已知IUPAC1986年元素周期表中第8-11族金属的混合物。不同载体上的Cu/Ru混合物已用于烷烃的氢解或芳烃的氢化(Allan J.Hong et al.;J.Phys.Chem.,1987,91,2665~2671)。
R.S.Drago等人[JACS,1985,107,2898~2901]描述了在液相中未负载Rh(III)/Cu(II)催化剂上用氧气将末端烯烃氧化成相应酮的方法。没有披露形成环氧化物。
T.Inui等人(J.Chem.Soc.,Faraday Trans.1,1978,74,2490~500)用Au、Rh、Ag或它们的混合物改性的Cu催化剂将丙烯氧化成丙烯醛。没有披露形成环氧化物。
Au和Ru的二元负载体系在文献中也是已知的(负载在碳上(美国专利5447896和5629462)、MgO上(J.M.Cowley等人,J.Catal.;1987,108,199~207)、SiO2上(Datye等人,Int.Congress Catal.Proc.8th,1985(会议日期1984),第4卷,IV587~IV598)或Al2O3上(M.Viniegra等人,React.Kinet.Catal.Lett.,1985,28,389~94)。
对于这些金属组合物,也未提及形成环氧丙烷或这些催化剂在直接氧化烯烃方面的应用。早在1976年,Sinfelt等人(美国专利3989764)将负载在SiO2上的AuCu体系用于部分氧化丙烯、异丁烯、1-丁烯和甲苯,分别形成丙烯醛、甲基丙烯醛、亚甲基丙酮(methylene acetone)和苯。没有记载形成环氧丙烷。Ikeda等人(Sekiyu Gakkaishi;1967,10,119~23,来源于HCA 68:113989,摘要)作了类似报道,即在气相中由丙烯形成丙烯醛。CuAu催化剂涂覆在瓷上。
现在令人惊奇地发现,可以用各种金属的混合物和氧气或空气直接氧化丙烯制备环氧丙烷。这是非常不寻常的,因为根据文献,氧化反应不会停留在环氧化物阶段,而是形成相应的酸、酮或醛。
本发明提供一种用氧使烃环氧化的方法。该方法在BET表面积小于200米2/克的惰性载体上含有选自Cu、Ru、Rh、Pd、Os、Ir、Pt、Au、In、Tl、Mn、Ce的至少两种金属的混合物的存在下进行。
术语“烃”是指不饱和或饱和烃,如烯烃或烷烃,它们也可含有杂原子,如N、O、P、S或卤素。要被氧化的有机组分可以是无环的,单环的、双环或多环的,也可是单烯烃、二烯烃或多烯烃。在含有两个或多个双键的有机组分中,这些双键可以是共轭的或非共轭的。被氧化的烃优选是那些能形成反应温度下分压低得足以从催化剂上连续除去的氧化产物的烃。
优选的是含2~20个,更好3~10个碳原子的不饱和烃和饱和烃,具体为丙烯、丙烷、异丁烷、异丁烯、1-丁烯、2-丁烯、顺-2-丁烯、反-2-丁烯、1,3-丁二烯、戊烯、戊烷、1-己烯、1-己烷、己二烯、环己烯和苯。
可以使用大多数形式的氧,如分子氧、空气、氧化氮。优选的是分子氧。
合适的混合物优选是金属Cu、Ru、Rh、Pd、Os、Ir、Pt、Au、In、Tl、Mn、Ce的二元或三元混合物,各种金属的含量分别为1~100%相对重量,一般总和高达100%。
优选的是如下的混合物:CuRu、TlMn、CuRh、IrRu、AuRu、MnCu、RuIr、CuRuPd、CuRuIn、CuRuTl、CuRuMn、CuRuAu、CuRuIr、CuRuCe、MnCuIn、MnCuAu、MnCuCe、MnTlCu、MnTlAu、MnTlIn、MnTlPd、MnTlRh、MnTlPt。
载体包含选自Al2O3、SiO2、CeO2、TiO2的化合物,它的BET表面积小于200米2/克,优选小于100米2/克,更好小于10米2/克,最好小于1米2/克。
孔隙率宜为20~60%,更好为30~50%。
载体的粒度取决于气相氧化的工艺条件,一般为反应器直径的1/10~1/20。
比表面积按Brunauer,Emmett和Teller,J.Am.Chem.Soc.1938,60,309中所述的常规方法测量,孔隙率用水银孔率测定计测定,载体表面上金属粒子的粒度用电子显微镜测定。
载体上金属的浓度一般宜为0.001~50重量%,更好为0.001~20重量%,最好为0.01~5%重量。
在载体上制备金属粒子没有限制到一种方法。在制备金属粒子方面可以列举几种方法实例,如EP-B-0709360第3页第38行等中描述的淀积-沉淀法、溶液浸渍法、初期润湿法、胶体法、溅射法、CVD、PVD。
初期润湿法是指将含可溶金属化合物的溶液加入载体材料中,载体上溶液的体积小于或等于载体的孔隙体积。因此,载体仍是宏观干燥的。可用于初期润湿法的溶剂包括任何可溶解金属前体的溶剂,如水、醇、(冠)醚、酯、酮、卤化烃等。
载体优选用含有金属离子的溶液浸渍,然后干燥、煅烧和还原。上述溶液还可含有本领域中普通技术人员已知的用于提高金属盐在溶剂中的溶解度和/或用于改变金属氧化还原电势和/或改变pH值的组分。具体提到的组分是氨、胺、二胺、羟胺和酸,如HCl、HNO3、H2SO4、H3PO4。
1.浸渍例如可用初期浸渍法进行,但不限于这种方法。初期浸渍法可包括如下步骤:
·用一种金属的单表面改性和/或用另一种金属的重复表面改性,
·在单个步骤中使用一部分金属或使用全部金属的单表面改性,
·在一个或多个连续步骤中使用两种或多种金属的重复表面改性,
·在一个或多个连续步骤中交替使用两种或多种金属的重复表面改性。
2.第1步中制得的带有活性成分的载体在约为40~200℃的温度和常压或减压下进行干燥。常压干燥可在空气氛或惰性气氛(如Ar、N2或He等)中进行。干燥时间为2~24小时,优选为4~8小时。
3.先在惰性气氛中,随后在含氧气氛中或者只在含氧气氛中煅烧第2步中制得的催化剂前体。气流中的含氧量宜为0~21%,优选为5~15%。煅烧温度取决于金属混合物,且一般为400~600℃,较好在450~550℃,最好在500℃。
4.在高温和含有氢气的氮气氛下还原第2和/或3步中制得的催化剂前体。含氢量可以为0~100%体积,但优选为0~25%体积,最好为5%体积。还原温度取决于具体的金属混合物,且为100~600℃。
宜在金属混合物中掺入常规的促进剂或减速剂,如碱土金属和/或碱金属离子,如一种或多种碱土金属和/或碱金属的氢氧化物、碳酸盐、硝酸盐、氯化物。这些物质记载在EP-A1-0933130第4页第39行等中。按照美国的实践,该专利申请的内容也包括在本申请中。
环氧化方法通常在如下条件下进行,优选在气相中进行:
相对于烃、氧和非必要的稀释气体的总摩尔数,烃的摩尔用量以及各组分的相对摩尔比可在宽的范围内变化,且一般取决于烃/氧混合物的爆炸极限。本发明方法一般在上述爆炸极限之上或之下进行。
相对于烃和氧的总摩尔数,含烃量一般≤2%摩尔或≥78%摩尔。在低于爆炸极限的操作模式的情况下,优选的含烃量为0.5~2%摩尔,而在高于爆炸极限的操作模式的情况下,优选的含烃量为78~99%摩。在每种情况下,特别优选的范围为1~2%摩尔和78~90%摩尔。相对于所用的氧(按摩尔计),优选使用过量的烃。
相对于烃、氧和稀释气体的总摩尔数,氧的摩尔用含量可在宽的范围内变化。相对于烃,优选使用摩尔不足量的氧。相对于烃和氧的总摩尔数,氧的用量优选为1~21%摩尔,更优选为5~21%摩尔。
除烃和氧以外,还可以使用稀释气体,如氮气、氦气、氩气、甲烷、二氧化碳、一氧化碳或者类似基本上惰性的气体。也可使用上述惰性组分的混合物。加入惰性组分有利于散发该放热氧化反应过程中释放出的热量,而且从安全角度来看也是有利的。在本发明中,上述原料混合物的组成也可以在爆炸极限范围内,即烃和氧的相对百分摩尔比率可以在0.5∶99.5~99.5∶0.5之间。
烃和催化剂的接触时间一般为5~60秒。
本发明方法一般在120~300℃,优选为180~250℃的温度下进行。
实施例1
用于制备环氧丙烷的活性催化剂的一种可能选择的制备方法例如包括将77.6毫克硝酸铜和3.59克约14%亚硝酰硝酸钌(ruthenium nitrosyl nitrate)溶液溶解在2毫升水中,将此溶液加入约10克Al2O3上,然后让此溶液吸收。将形成的固体放在真空度约为15mmHg的真空干燥箱中于100℃干燥过夜。
最后在500℃用含10%体积H2的氮气以60升/小时的速度将所得的前体还原12小时。
还原后,在一个连续操作的固定床反应器中用含79%体积丙烯和21%体积氧气的喷射(educt)气体组合物在停留时间约为20秒的条件下对10克所得催化剂进行研究。在内温为217℃时,在排出气流中测得的环氧丙烷含量为680ppm。
实施例2
用于制备环氧丙烷的活性催化剂的一种可能选择的制备方法例如包括将77.6毫克硝酸铜溶解在5~6毫升水中,将此溶液加入约10克Al2O3上,然后让此溶液吸收。将形成的固体放在真空度约为15mmHg的真空干燥箱中于60℃干燥12小时。然后根据载体的吸收能力,用约含1.5%重量Ru的亚硝酰硝酸钌溶液,按相同的方式对上述固体进行表面改性。每次表面改性之间按上述方法干燥4小时。
最后在500℃用含10%体积H2的氮气以60升/小时的速度将所得的前体还原12小时。
还原后,在一个连续操作的固定床中用含79%体积丙烯和21%体积氧气的喷射气体组合物在停留时间约为20秒的条件下对10克所得催化剂进行研究。在内温为200℃时,在排出气流中测得的环氧丙烷含量为300ppm。
实施例3
用于制备环氧丙烷的活性催化剂的另一种可能选择的制备方法例如包括将77.6毫克硝酸铜溶解在5~6毫升水中,将此溶液加入约10克Al2O3上,然后让此溶液吸收。将形成的固体放在真空度约为15mmHg的真空干燥箱中于60℃干燥12小时。然后用2.5克约含20%重量Ru的亚硝酰硝酸钌溶液,按相同的方式对上述固体进行表面改性,然后按实施例1所述的方法进行干燥。最后在500℃用含10%体积H2的氮气以60升/小时的速度将所得的前体还原12小时。
还原后,在一个连续操作的固定床中用含79%体积丙烯和21%体积氧气的喷射气体组合物在停留时间约为20秒的条件下对10克所得催化剂进行研究。在内温为200℃时,在排出气流中测得的环氧丙烷含量为280ppm。
实施例4
用于制备环氧丙烷的活性催化剂的一种可能选择的制备方法例如包括将7.4克10%硝酸铑溶液加入约10克Al2O3上,然后让此溶液吸收。将形成的固体放在真空度约为15mmHg的真空干燥箱中于100℃干燥4小时。然后用1.3克约含20%重量Ru的亚硝酰硝酸钌溶液,按相同的方式对上述固体进行表面改性,然后按上述的方法在真空干燥箱中干燥12小时。最后在500℃用含10%体积H2的氮气以60升/小时的速度将所得的前体还原12小时。
还原后,在一个连续操作的固定床中用含79%体积丙烯和21%体积氧气的喷射气体组合物在停留时间约为20秒的条件下对1克所得催化剂进行研究。在内温为199℃时,在排出气流中测得的环氧丙烷含量为360ppm。
实施例5
用于制备环氧丙烷的活性催化剂的另一种可能选择的制备方法例如包括将343毫克硝酸铊溶解在5克水中,然后用所得的溶液浸渍约10克Al2O3。在保持不停运动的条件下,使上述固体吸收上述溶液,然后将形成的固体放在真空度约为15mmHg的真空干燥箱中于100℃干燥4小时。然后用由776毫克硝酸铜(II)和5克水形成的溶液按相同的方式对上述固体进行表面改性,再在真空度约为15mmHg的真空干燥箱中于100℃干燥过夜。
用含10%体积H2的氮气以60升/小时的速度将所得的前体还原12小时。
还原后,在一个连续操作的固定床中用含79%体积丙烯和21%体积氧气的喷射气体组合物在停留时间约为20秒的条件下对1克所得催化剂进行研究。在内温为228℃时,在排出气流中测得的环氧丙烷含量为380ppm。
实施例6
将2.5克亚硝酰硝酸钌溶液溶解在3克水中,然后用所得的溶液浸渍约10克Al2O3。在保持不停运动的条件下,使上述固体吸收上述溶液,然后将形成的固体放在真空度约为15mmHg的真空干燥箱中于100℃干燥4小时。然后用由109毫克24%六氯铱酸溶液和4.5克水形成的溶液按相同的方式对上述固体进行表面改性,再在真空度约为15mmHg的真空干燥箱中于100℃干燥过夜。
用含10%体积H2的氮气以60升/小时的速度将所得的前体还原12小时。
还原后,在一个连续操作的固定床中用含79%体积丙烯和21%体积氧气的喷射气体组合物在停留时间约为20秒的条件下对1克所得催化剂进行研究。在内温为208℃时,在排出气流中测得的环氧丙烷含量为540ppm。
实施例7
将343毫克硝酸铊溶解在5克水中,然后用所得的溶液浸渍10克Al2O3。在保持不停运动的条件下,使上述固体吸收上述溶液,然后将形成的固体放在真空度约为15mmHg的真空干燥箱中于100℃干燥4小时。然后用由1.3克20%亚硝酰硝酸钌溶液形成的溶液按相同的方式对上述固体进行表面改性,再在真空度约为15mmHg的真空干燥箱中于100℃干燥过夜。
用含10%体积H2的氮气以60升/小时的速度将所得的前体还原12小时。
还原后,在一个连续操作的固定床中用含79%体积丙烯和21%体积氧气的喷射气体组合物在停留时间约为20秒的条件下对1克所得催化剂进行研究。在内温为211℃时,在排出气流中测得的环氧丙烷含量为390ppm。
实施例8
将17.86克硝酸铜溶解在103克水中,然后用所得的溶液浸渍230克Al2O3。在保持不停运动的条件下,使上述固体吸收上述溶液,然后将形成的固体放在真空度约为15mmHg的真空干燥箱中于100℃干燥4小时。然后用由43.52克14%亚硝酰硝酸钌溶液和71克水形成的溶液按相同的方式对上述固体进行表面改性,再在真空度约为15mmHg的真空干燥箱中于100℃干燥过夜。
用含10%体积H2的氮气以60升/小时的速度将所得的前体还原4小时。
然后用由6毫克硝酸钯和2.25克水制成的溶液对5克所得的固体进行表面改性,然后在100℃的真空干燥箱中干燥过夜。
用含10%体积H2的氮气以60升/小时的速度将所得的前体还原8小时。
还原后,在一个连续操作的固定床中用含79%体积丙烯和21%体积氧气的喷射气体组合物在停留时间约为20秒的条件下对1克所得催化剂进行研究。在内温为220℃时,在排出气流中测得的环氧丙烷含量为745ppm。
实施例9
将27.6克硝酸锰溶解在103.5克水中,然后用所得的溶液浸渍230克Al2O3。在保持不停运动的条件下,使上述固体吸收上述溶液,然后将形成的固体放在真空度约为15mmHg的真空干燥箱中于100℃干燥4小时。然后用由7.9克硝酸铊和103.5克水形成的溶液按相同的方式对上述固体进行表面改性,再在真空度约为15mmHg的真空干燥箱中于100℃干燥过夜。
用含10%体积H2的氮气以60升/小时的速度将所得的前体还原4小时。
然后用由259毫克硝酸铜和2.25克水制成的溶液对5克所得的固体进行表面改性,然后在100℃的真空干燥箱中干燥过夜。
用含10%体积H2的氮气以60升/小时的速度将所得的前体还原8小时。
还原后,在一个连续操作的固定床中用含79%体积丙烯和21%体积氧气的喷射气体组合物在停留时间约为20秒的条件下对1克所得催化剂进行研究。在内温为240℃时,在排出气流中测得的环氧丙烷含量为1984ppm。
实施例10
将2.76克硝酸锰溶解在103.5克水中,然后用所得的溶液浸渍230克Al2O3。在保持不停运动的条件下,使上述固体吸收上述溶液,然后将形成的固体放在真空度约为15mmHg的真空干燥箱中于100℃干燥4小时。然后用由33.92克硝酸铜和95克水形成的溶液按相同的方式对上述固体进行表面改性,再在真空度约为15mmHg的真空干燥箱中于100℃干燥过夜。
用含10%体积H2的氮气以60升/小时的速度将所得的前体还原8小时。
然后用由6毫克43.5%四氯化金溶液和2.25克水制成的溶液对5克所得的固体进行表面改性,然后在100℃的真空干燥箱中干燥过夜。
用含10%体积H2的氮气以60升/小时的速度将所得的前体还原8小时。
还原后,在一个连续操作的固定床中用含79%体积丙烯和21%体积氧气的喷射气体组合物在停留时间约为20秒的条件下对1克所得催化剂进行研究。在内温为230℃时,在排出气流中测得的环氧丙烷含量为982ppm。
Claims (7)
1.用氧使烃环氧化的方法,其特征在于所述的方法在BET表面积小于200米2/克的载体上含有选自Cu、Ru、Rh、Pd、Os、Ir、Pt、Au、In、Tl、Mn、Ce的至少两种金属的混合物的存在下进行。
2.如权利要求1所述的方法,其特征在于所述的BET表面积小于100米2/克。
3.如权利要求1或2所述的方法,其特征在于所述的载体是Al2O3。
4.如权利要求1~3中任一项所述的方法,其特征在于所述的烃选自丙烯和丁烯。
5.如权利要求1~4中任一项所述的方法,其特征在于使用下列金属混合物中的一种或多种:CuRu、TlMn、CuRh、IrRu、AuRu、MnCu、RuIr、CuRuPd、CuRuIn、CuRuTl、CuRuMn、CuRuAu、CuRuIr、CuRuCe、MnCuIn、MnCuAu、MnCuCe、MnTlCu、MnTlAu、MnTlIn、MnTlPd、MnTlRh、MnTlPt。
6.BET表面积小于200米2/克的载体上含有选自Cu、Ru、Rh、Pd、Os、Ir、Pt、Au、In、Tl、Mn、Ce的至少两种金属的混合物作为烃环氧化催化剂的应用。
7.如权利要求6所述的应用,其特征在于所述的金属混合物选自CuRu、TlMn、CuRh、IrRu、AuRu、MnCu、RuIr、CuRuPd、CuRuIn、CuRuTl、CuRuMn、CuRuAu、CuRuIr、CuRuCe、MnCuIn、MnCuAu、MnCuCe、MnTlCu、MnTlAu、MnTlIn、MnTlPd、MnTlRh、MnTlPt。
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DE10024096A DE10024096A1 (de) | 2000-05-18 | 2000-05-18 | Verfahren zur Epoxidierung von Kohlenwasserstoffen |
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EP (1) | EP1286979A1 (zh) |
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CN (1) | CN1429217A (zh) |
AU (1) | AU2001265930A1 (zh) |
BR (1) | BR0110850A (zh) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102958604A (zh) * | 2010-07-09 | 2013-03-06 | 住友化学株式会社 | 生产烯烃氧化物的方法 |
CN102015095B (zh) * | 2008-04-30 | 2013-05-08 | 陶氏技术投资有限公司 | 多孔体前体,成形多孔体,它们的制备方法和基于它们的终端产品 |
CN102015101B (zh) * | 2008-04-30 | 2013-11-06 | 陶氏技术投资有限公司 | 多孔体前体,成形多孔体,它们的制备方法和基于它们的终端产品 |
Families Citing this family (10)
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DE10139531A1 (de) * | 2001-08-10 | 2003-02-20 | Bayer Ag | Verfahren zur Epoxidierung von Kohlenwasserstoffen |
DE10251325A1 (de) * | 2002-11-05 | 2004-05-13 | Bayer Ag | Katalysator und Verfahren zur Oxidation von Kohlenwasserstoffen zu Epoxiden |
JP2005306803A (ja) * | 2004-04-23 | 2005-11-04 | Hamamatsu Kagaku Gijutsu Kenkyu Shinkokai | 不飽和化合物の酸化方法 |
EP1974808A4 (en) * | 2005-12-15 | 2009-07-22 | Mitsui Mining & Smelting Co | OXYGEN DEACTIVATOR AND PROCESS FOR THE PRODUCTION OF AN OXYGEN DEACTIVATOR |
CA2723160A1 (en) * | 2008-04-30 | 2009-11-05 | Dow Technology Investments Llc | Porous body precursors, shaped porous bodies, processes for making them, and end-use products based upon the same |
US20110152546A1 (en) * | 2009-12-17 | 2011-06-23 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
EP2661323A4 (en) | 2011-01-05 | 2017-02-08 | Sumitomo Chemical Company Limited | Process for producing olefin oxide |
EP2668170B1 (en) * | 2011-01-24 | 2016-10-19 | Sumitomo Chemical Company Limited | Direct conversion of olefin to olefin oxide by molecular oxygen |
WO2013100173A1 (en) | 2011-12-27 | 2013-07-04 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide using a catalyst comprising a ruthenium oxide and a tellurium component |
WO2014003209A1 (en) | 2012-06-29 | 2014-01-03 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3989674A (en) * | 1969-03-26 | 1976-11-02 | Exxon Research And Engineering Company | Novel gold-copper catalysts for the partial oxidation of olefins |
GB1373489A (en) * | 1970-11-09 | 1974-11-13 | Ici Ltd | Oxidation of olefinic compounds |
GB1423339A (en) * | 1972-03-13 | 1976-02-04 | Ici Ltd | Oxidation of olefins |
GB1409421A (en) * | 1972-07-17 | 1975-10-08 | Bryce Smith Derek | Gold compounds |
US5112795A (en) * | 1990-10-12 | 1992-05-12 | Union Carbide Chemicals & Plastics Technology Corporation | Supported silver catalyst, and processes for making and using same |
DE4425672A1 (de) * | 1994-07-20 | 1996-01-25 | Basf Ag | Oxidationskatalysator, Verfahren zu seiner Herstellung und Oxidationsverfahren unter Verwendung des Oxidationskatalysators |
DE19519004A1 (de) * | 1995-05-24 | 1996-11-28 | Hoechst Ag | Neue selen- und rutheniumhaltige Metalloxidkatalysatoren sowie ein Verfahren zu ihrer Herstellung und ihre Verwendung |
WO1997034692A1 (fr) * | 1996-03-21 | 1997-09-25 | Japan As Represented By Director General Of Agency Of Industrial Science And Technology | Catalyseurs et procede pour l'oxydation partielle des hydrocarbures |
DE69708880T2 (de) * | 1996-07-01 | 2002-04-11 | Dow Chemical Co | Verfahren zur direkten oxidation von olefinen zu olefinoxiden |
DE19845975A1 (de) * | 1998-08-27 | 2000-03-02 | Wolfgang Hoelderich | Verfahren zur Herstellung von Epoxiden aus Olefinen und Sauerstoff in Gegenwart von Wasserstoff |
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- 2001-05-07 BR BR0110850-6A patent/BR0110850A/pt not_active Application Discontinuation
- 2001-05-07 US US10/276,341 patent/US20030191328A1/en not_active Abandoned
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- 2001-05-07 WO PCT/EP2001/005136 patent/WO2001087867A1/de not_active Application Discontinuation
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Cited By (4)
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CN102015095B (zh) * | 2008-04-30 | 2013-05-08 | 陶氏技术投资有限公司 | 多孔体前体,成形多孔体,它们的制备方法和基于它们的终端产品 |
CN102015101B (zh) * | 2008-04-30 | 2013-11-06 | 陶氏技术投资有限公司 | 多孔体前体,成形多孔体,它们的制备方法和基于它们的终端产品 |
CN102958604A (zh) * | 2010-07-09 | 2013-03-06 | 住友化学株式会社 | 生产烯烃氧化物的方法 |
US8889892B2 (en) | 2010-07-09 | 2014-11-18 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
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BR0110850A (pt) | 2003-02-11 |
HUP0302061A2 (hu) | 2003-09-29 |
MXPA02011308A (es) | 2003-06-06 |
JP2003533520A (ja) | 2003-11-11 |
AU2001265930A1 (en) | 2001-11-26 |
WO2001087867A1 (de) | 2001-11-22 |
CA2409018A1 (en) | 2002-11-15 |
KR20030009490A (ko) | 2003-01-29 |
US20030191328A1 (en) | 2003-10-09 |
PL358336A1 (en) | 2004-08-09 |
DE10024096A1 (de) | 2001-11-22 |
EP1286979A1 (de) | 2003-03-05 |
CZ20023733A3 (cs) | 2003-02-12 |
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