CN1832923A - 氰基吡啶的制造方法和适合用于它的催化剂 - Google Patents
氰基吡啶的制造方法和适合用于它的催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical class N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 title abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 16
- 239000012018 catalyst precursor Substances 0.000 claims description 13
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 206010013786 Dry skin Diseases 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Natural products C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 3
- -1 pyrazine compound Chemical class 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000006424 Flood reaction Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 13
- 230000009466 transformation Effects 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229940110728 nitrogen / oxygen Drugs 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 229960004217 benzyl alcohol Drugs 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- FNLJLQUTIUDEHI-UHFFFAOYSA-N phosphoric acid vanadium Chemical compound [V].OP(O)(O)=O FNLJLQUTIUDEHI-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 125000005340 bisphosphate group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005111 flow chemistry technique Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- KMZJZEMCGCWSJO-UHFFFAOYSA-N pyridine-2-carbonitrile;pyridine-3-carbonitrile Chemical compound N#CC1=CC=CN=C1.N#CC1=CC=CC=N1 KMZJZEMCGCWSJO-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- VDEWPCJTKKYMOD-UHFFFAOYSA-N 2-methylpyridine;3-methylpyridine Chemical compound CC1=CC=CN=C1.CC1=CC=CC=N1 VDEWPCJTKKYMOD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- KTGLTEKRMQBJFM-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5].OP(O)(O)=O Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5].OP(O)(O)=O KTGLTEKRMQBJFM-UHFFFAOYSA-N 0.000 description 1
- WLMFLUVFGFTJCE-UHFFFAOYSA-J [O-]P([O-])(=O)OP(=O)([O-])[O-].O=[V+4] Chemical compound [O-]P([O-])(=O)OP(=O)([O-])[O-].O=[V+4] WLMFLUVFGFTJCE-UHFFFAOYSA-J 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001394 sodium malate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001429 stepping effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明涉及通过用氨、氧气和适合的催化剂转化甲基吡啶来制造氰基吡啶的方法，所述催化剂除了含有钒和磷外，还含有过渡金属。
Description
描述
本发明涉及氰基吡啶的制造方法和适合用于它的含钒和磷的催化剂。
已知有几种方法用于从甲基吡啶通过与氨和氧气的反应来制造氰基吡啶。它们由反应条件，尤其是催化剂来区分。在这些方法中，仅仅那些具有良好的空间-时间-产率同时还具有高的选择性的方法在大量生产规模中很有意义。
从欧洲专利0726092 B1中可知，通过以下通式所示的催化剂体系满足了所述需求
SbaVbTicX1dX2eOf
尽管这些催化剂很复杂，制造也很昂贵。
从德国专利198 04 839 Al和DD 241 903 Al中可知，通式为(NH4)2(VO)3(P2O7)或(VO)2P2O7的催化剂属于VPO类催化剂，它可用于芳香化合物的氨氧化。这些催化剂需要大于440℃的较高的反应温度，以达到大于90％的转化率。
本发明的目的是开发一种通过甲基吡啶与氨和氧气在高温和同时使用VPO催化剂的条件下的催化反应来制造氰基吡啶的方法，所述催化剂在高达440℃的反应器温度下有很好的空间-时间-产率(高的转化率)和高选择性，所述催化剂制造简单，且可再生。
该目的由以下通式的VPO催化剂来满足
[V1PaXb(Y)cOd]e[Z]f，其中
a＝0.1-2.5
b＝0-3.0，尤其是0.001-3.0
c＝0.1-10
d＝取决于其它元素的化合价
e＝5-100(重量％)
f＝95-0(重量％)，尤其是95-5，条件是b和f不同时为0
X＝Cr，Mo，W，Fe，Ru，Co，Rh，Ir，Ni，Pd，Pt，Zn或Nb
Y＝环状氮化合物
Z＝SiO2，Al2O3，ZrO2或TiO2或其混合物
该催化剂可按如下步骤制造：使五氧化二钒(V2O5)和80-85％的磷酸在回流条件下在有机介质中反应，过滤出形成的催化剂前体，在80℃-140℃干燥，然后优选在300℃-600℃，更优选在350℃-480℃下煅烧1.5-4小时，在100-300℃，尤其是160-250℃下将含有在0-80℃，尤其在15-45℃下用环状氮化合物蒸汽饱和的惰性气体(例如氩气、氦气或氮气)的气体通入到如上得到的磷酸钒上0.1-10小时，尤其是0.5-3小时，接着进行冷却。
流速优选为5-20升/小时。
冷到室温之后，所述催化剂含有0.1-5重量％，尤其是0.5-3重量％的有机环状氮化合物，主要结合(bound)为阳离子。
所述有机环状氮化合物优选6-元环，例如吡啶、喹啉、哒嗪、嘧啶、吡嗪，尤其是皮考啉(3-甲基吡啶)。
所述有机介质一般由体积比为2∶1到1∶3，优选1∶1到1∶2的芳族醇和脂族醇的混合物构成。苄醇适合用作环状醇，这种苄醇说明性地含有1-3个烷基取代基，各个烷基取代基含有1-3个碳原子，所述烷基取代基优选是甲基。C2-C8醇，尤其是正丁醇，用作脂族醇。脂族醇也可具有支链。
在该混合物中，V2O5和磷酸的起始反应摩尔比V∶P为1∶0.1到1∶2.5，尤其是1∶0.7到1∶1.5。
为了给该催化剂提供具有其它用作助催化剂(promoter)的过渡金属氧化物或混合氧化物，制造这些过渡金属X的水溶液或醇溶液。这些过渡金属优选带有阴离子，例如是可通过热处理从固体主体中除去的碳酸根、硝酸根、草酸根或乙酸根。用这些溶液浸渍任选干燥的催化剂前体，并分离掉过量的溶液。
然后在80-140℃下干燥所述浸渍的催化剂前体6-24小时，在煅烧前任选成形(form)。
载体材料优选与浸渍或未浸渍的粉末混合，所述粉末一般是SiO2、TiO2、Al2O3或ZrO2或其混合物。
将所述粉末以所希望的量，通常为20∶1到1∶20的质量比与载体组分密切混合，并在常规磨中碾碎。
接着，所得到的混合物在300℃-600℃，优选350-480℃的温度下煅烧长达48小时。为了这一目的，在混合物中优选使用1∶0.1到1∶10的氮气/氧气混合物。
在任何情况下，向催化剂中引入环状氮化合物在煅烧之后，并在开始实际催化转化之前进行。用于制造催化剂的方法同样是本发明的主题。
所述催化剂可用在所有适合的反应中进行非均相催化的气相反应。因此，可以使用例如连续的固体床反应器、搅拌的容器、固定床反应器或移动床反应器或浆液相反应器。
所述催化剂优选用于在高达440℃，尤其是高达400℃的温度下通过甲基吡啶(例如3-甲基吡啶)、氨和氧气的催化转化来制造氰基吡啶(例如3-氰基吡啶)的方法中。
例如，在欧洲专利0 059 414 B1、欧洲专利0 070 395 B1和欧洲专利0 726092 A1中所描述的方法属于3-氰基吡啶的制造方法。
按照欧洲专利0 059 414 B1，3-甲基吡啶与氨和氧气的转化在气相中以正常的方式发生。对于反应条件的选择，存在很宽的范围。不使用压力或在高达约3巴的低过压(low over-pressure)下和320-460℃，优选340-440℃之间的温度下，可基本实现所述转化。所需的氧气可以有利地以空气来提供，水蒸气可混入到气体中。可在很宽的限制中选择3-甲基吡啶与氨、氧气或空气和任选的水蒸气的量的比。一般来说，每摩尔3-甲基吡啶，使用约2-10摩尔，优选3-8摩尔氨，约10-40摩尔，优选25-35摩尔空气，约0-10摩尔，优选0-8摩尔水蒸气是有利的。对于每升催化剂总体积(bulk volume)，每小时宜向反应器中加入约1-3摩尔的3-甲基吡啶。
在实施例中，若无其它说明，％表示重量百分比。
以下术语用于下面的实施例中：
转化率＝(转化烃的摩尔数/使用的烃的摩尔数)×100％
产率＝(产生的产物的摩尔数/使用的烃的摩尔数)×100％
GHSV＝气体小时空间速度＝(进料气的体积/时间×催化剂的总体积)[1/小时升＝1/小时]
选择性＝(产率/转化率)×100％
实施例
催化剂制造
实施例1(催化剂A，比较例)
按照《无机化学》(Inorg.Chem.)23(1984)1308中的描述，在水介质中制造磷酸氢氧化钒(IV)的半水合物VOHPO4-0.5H2O。该催化剂前体在120℃干燥24小时，在氮气/氧气混合物中于450℃下煅烧3小时，转化为二磷酸氧化钒(oxovanadium diphosphate)(VO)2P2O7。
实施例2(催化剂A)
可按如下步骤在有机溶剂中制造二磷酸氧钒：在回流下将0.1摩尔(18.2g)V2O5悬浮在110毫升正丁醇和73毫升苄醇中的混合物搅拌3小时。接着，在室温下搅拌过夜，然后加入化学计算足量的85磷酸，在回流下再搅拌2小时，在室温下过滤所形成的催化剂前体，并用乙醇洗涤几次，最后在120℃下干燥24小时。在氮气/氧气混合物中于450℃下煅烧3小时，得到二磷酸氧化钒如实施例1的(VO)2P2O7。
实施例3(催化剂C)
按照该实施例，制造负载型催化剂：
为了这一目的，在分离催化剂前体时(即最后的煅烧之前)结束实施例1和2中所描述的合成。将二氧化钛(锐钛矿)粉末(B.E.T表面积计算值为100平方米/克)与实施例1或2制得的催化剂前体粉末(VOHPO4-0.5H2O)以3∶1的重量比混合，并在玛瑙石磨中碾碎，接着在电磨(electric mill)中碾碎(5-10分钟)。然后挤压所述的催化剂组合物并打碎，回收直径约为1-1.25毫米的筛选组分。将该组分在氮气/氧气混合物中于450℃下煅烧3小时，该组分含有磷酸钒，主要是(VO)2P2O7。
实施例4(催化剂D)
将实施例3制得的催化剂与过渡金属助催化剂混合。为了这一目的，在与载体组分进行混合之前，助催化(promote)实施例1或2的催化剂前体。下面以铁助催化为例描述助催化催化剂前体的制造方法：
将实施例1或2得到的0.1摩尔催化剂前体(VOHPO4-0.5H2O)分别用0.05摩尔醋酸铁(III)(溶在乙醇或水中)浸渍。然后蒸发掉溶剂，残留物在120℃下干燥16小时，接着煅烧。
实施例5(催化剂E)
将实施例4中制造的催化剂前体按照实施例3所描述的与二氧化钛(锐钛矿)以1∶3混合，如上述碾碎。干燥和煅烧(如实施例3)后得到含有磷酸钒，主要是(VO)2P2O7的助催化的负载型催化剂。
实施例6(催化剂F)
将实施例2中得到的颗粒尺寸为1-1.25毫米的磷酸氧化钒放在反应管中并于10升/小时的氩气气流(在室温下用3-皮考啉饱和)中以10°K/分钟的步进(step)加热到200℃，历时2小时。然后在氩气流中，冷到室温。IR-光谱和元素分析证实该处理过的催化剂含有3-皮考啉(主要作为阳离子)附加组分。该样品含有约为1.5％皮考啉，主要是皮考啉鎓阳离子。
实施例7(催化剂G)
按照实施例6，用氩气/3-皮考啉气流处理实施例3中的催化剂载体。处理后，所述催化剂含有约为2％3-皮考啉，主要是皮考啉鎓阳离子。
实施例8(催化剂H)
按照实施例6，用氩气/3-皮考啉气流处理实施例4中的铁助催化的载体催化剂。处理后，所述催化剂含有约为2％3-皮考啉，主要是皮考啉鎓阳离子。
3-氰基吡啶的制造
实施例9-15
向石英固定床反应器中加入5克与刚玉1∶1混合的催化剂碎块(chip)。将3-皮考啉和任选的水泵压到空气和氨的反应气流中并汽化。反应条件和所用气体的气相组成示于表1。反应开始10分钟后进行取样。用气相色谱分析和量化反应产物。结果同样示于表1。在使用非预处理的催化剂的试验9-13中反应开始10分钟后得到约50％的皮考啉转化率，而预处理后催化剂主要含有皮考啉鎓阳离子的试验14-15表明反应一开始后已达到≥95％的转化率。在各个试验中，生成3-氰基吡啶的反应的选择性都很高，≥85％。
与催化剂A的比较例
向石英固定床反应器中加入5克与刚玉1∶1混合的催化剂碎块。将3-皮考啉和任选的水泵压到空气和氨的反应气流中并汽化。按以下的摩尔比进行操作：3-皮考啉∶氨∶空气∶水＝1∶4.4∶28.4∶8.5。在催化剂温度为355℃和接触时间为1.5秒时，测得的3-皮考啉的转化率为35％，氰基吡啶(nicotinonitrile)的产率为29％，对应于84％的选择性。
在使用前用含有皮考啉的气流处理所述催化剂，且所述试验按上述的方式进行。
在第二试验中，按以下摩尔比进行操作：3-皮考啉∶氨∶空气∶水＝1∶4.6∶29.4∶8.9。在催化剂温度为362℃和接触时间为1.5秒时，测得的3-皮考啉的转化率为43％，氰基吡啶(nicotinonitrile)的产率为35％，对应于82％的选择性。
表1
| 实施例 | 催化剂 | 反应温度[℃] | GHSV[小时-1] | 空气[MV] | NH3[MV] | H2O[MV] | 转化率[摩尔％] | 产率[摩尔％] | 选择性[摩尔％] | CO[摩尔％] | CO2[摩尔％] |
| 9 | B | 360 | 2300 | 28.4 | 5.6 | 8.2 | 52 | 43.7 | 84 | 0.7 | 4.9 |
| 10 | C | 360 | 2250 | 28.3 | 5.3 | 8.1 | 52 | 46.2 | 89 | 0.3 | 4.7 |
| 11 | D | 350 | 2200 | 29.1 | 5.0 | 8.4 | 53 | 48.9 | 89 | 0.2 | 4.4 |
| 12 | E | 350 | 2200 | 28.9 | 4.4 | 8.5 | 54 | 48.6 | 90 | 0.3 | 4.6 |
| 13 | F | 400 | 2000 | 29.0 | 5.0 | 8.5 | 95 | 80.0 | 84 | 0.6 | 4.9 |
| 14 | G | 350 | 2500 | 29.1 | 4.5 | 8.7 | 97 | 81.3 | 84 | 0.6 | 4.5 |
| 15 | H | 340 | 2000 | 28.6 | 5.7 | - | 99 | 99.0 | 100 | - | - |
Mv＝摩尔比
实施例16-22
继续实施例9-15中所描述的方法，除了在6小时后测定反应产物。在相同的反应条件下得到以下结果。
| 实施例 | 催化剂 | 转化率[摩尔％] | 产率[摩尔％] | 选择性[摩尔％] | CO[摩尔％] | CO2[摩尔％] |
| 16 | B | 62 | 55 | 88 | 6 | 4.8 |
| 17 | C | 63 | 57 | 90 | 3 | 4.6 |
| 18 | D | 62 | 56 | 90 | 2 | 4.3 |
| 19 | E | 65 | 60 | 92 | 3 | 4.4 |
| 20 | F | 95 | 80 | 84 | 5 | 5.0 |
| 21 | G | 98 | 84 | 86 | 5 | 4.3 |
| 22 | H | 99 | 99 | 100 | - | - |
对于未预处理的催化剂，皮考啉的转化率已经提高至10％。在开始时，预处理的催化剂也显示出同样的高性能。实施例16-19所使用的催化剂现在显示出进入到晶格中的3-皮考啉的可论证的比例，例如可从红外光谱中测定3-皮考啉的比例。
上面的讨论仅仅揭示和描述了本发明的示范性的实施方式。从这样的讨论中，本领域技术人员很容易理解，并且从附图和权利要求，可以不偏离权利要求所限定的本发明的本质和范围进行各种变化和修改和变动。
本文所引用的所有参考文献都全文引入本文作为参考。
Claims (6)
1.一种具有以下通式的VPO催化剂，
[V1PaXb(Y)cOd]e[Z]f，其中
a＝0.1-2.5
b＝0-3.0，尤其是0.001-3.0
c＝0.1-10
d＝取决于其它元素的化合价
e＝5-100(重量％)
f＝95-0(重量％)，尤其是95-5，条件是b和f不同时为0
X＝Cr，Mo，W，Fe，Ru，Co，Rh，Ir，Ni，Pd，Pt，Zn或Nb
Y＝环状氮化合物
Z＝SiO2，Al2O3，ZrO2或TiO2或其混合物
按照以下方法制造所述催化剂，其中进行以下几步：
a)使V2O5和浓磷酸在回流条件下在有机介质中转化，
b)分离出形成的催化剂前体，并任选地
c)在80℃-140℃干燥，
d)用金属X的水溶液或醇溶液来浸渍所述的任选干燥的催化剂前体，X与上面具有相同的意义，
e)分离掉过量的溶液，
f)干燥并煅烧所述的浸渍的材料，和
g)任选地成形所获得的催化剂。
2.如权利要求1所述的VPO催化剂，其特征在于，所述催化剂含有SiO2，Al2O3，ZrO2或TiO2或其混合物作为载体。
3.如权利要求1所述的VPO催化剂，其特征在于，所述催化剂含有0.01-5重量％的有机环状氮化合物。
4.如权利要求3所述的VPO催化剂，其特征在于，所述催化剂含有选自于吡啶、喹啉、哒嗪、嘧啶或吡嗪的化合物作为氮化合物。
5.如权利要求3所述的VPO催化剂，其特征在于，所述催化剂含有3-甲基吡啶作为氮化合物。
6.一种制造3-氰基吡啶的方法，所述方法使用权利要求1-5所述的催化剂，通过用氨和氧气在高达440℃的温度下转化3-甲基吡啶进行。
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2003
- 2003-08-02 DE DE10335454A patent/DE10335454A1/de not_active Ceased
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2004
- 2004-07-30 EP EP04779870A patent/EP1654233A4/en not_active Withdrawn
- 2004-07-30 JP JP2006522661A patent/JP5080081B2/ja not_active Expired - Fee Related
- 2004-07-30 WO PCT/US2004/024939 patent/WO2005016505A2/en active Application Filing
- 2004-07-30 CN CNB2004800224897A patent/CN100545149C/zh not_active Expired - Fee Related
- 2004-07-30 US US10/566,868 patent/US7795169B2/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486676B (zh) * | 2008-12-23 | 2010-12-08 | 南京航空航天大学 | 氰甲基吡啶化合物的制备方法 |
| CN105233849A (zh) * | 2015-09-20 | 2016-01-13 | 潜江市富阳化工有限公司 | 一种用于合成3-氰基吡啶的复合催化剂及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100545149C (zh) | 2009-09-30 |
| WO2005016505A3 (en) | 2005-06-09 |
| JP2007501119A (ja) | 2007-01-25 |
| US7795169B2 (en) | 2010-09-14 |
| JP5080081B2 (ja) | 2012-11-21 |
| EP1654233A4 (en) | 2008-10-08 |
| DE10335454A1 (de) | 2005-02-24 |
| US20070117984A1 (en) | 2007-05-24 |
| EP1654233A2 (en) | 2006-05-10 |
| WO2005016505A2 (en) | 2005-02-24 |
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