JP2008037693A - Oxide containing vanadium, oxide having vanadium and phosphorus, catalyst, and manufacturing method of maleic anhydride - Google Patents
Oxide containing vanadium, oxide having vanadium and phosphorus, catalyst, and manufacturing method of maleic anhydride Download PDFInfo
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 71
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 28
- 239000011574 phosphorus Substances 0.000 title claims description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 26
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 20
- 238000001228 spectrum Methods 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 239000012808 vapor phase Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- 235000011007 phosphoric acid Nutrition 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 230000004913 activation Effects 0.000 description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003682 vanadium compounds Chemical class 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- -1 oxyacids Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004820 halides Chemical class 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
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 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
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本発明は、バナジウム含有酸化物、バナジウムとリンとを有する酸化物、触媒、及び、無水マレイン酸の製造方法に関する。より詳しくは、無水マレイン酸の製造において触媒として好適に用いられるバナジウムとリンとを有する酸化物、これからなる触媒、バナジウムとリンとを有する酸化物の原料となるバナジウム含有酸化物、及び、バナジウムとリンとを有する酸化物を触媒として用いた無水マレイン酸の製造方法に関する。 The present invention relates to a vanadium-containing oxide, an oxide having vanadium and phosphorus, a catalyst, and a method for producing maleic anhydride. More specifically, an oxide having vanadium and phosphorus that is preferably used as a catalyst in the production of maleic anhydride, a catalyst comprising the same, a vanadium-containing oxide serving as a raw material for the oxide having vanadium and phosphorus, and vanadium The present invention relates to a method for producing maleic anhydride using an oxide having phosphorus as a catalyst.
バナジウム含有酸化物は、一般に、ブタン、ブテン、ブタジエン等の炭素原子数が４以上の直鎖炭化水素の接触気相酸化によって、無水マレイン酸を製造するための触媒として有効であることが知られている（例えば、特許文献１〜３参照。）。この接触気相酸化反応は、３００℃を超える高温下の反応であり、また無水マレイン酸への選択性が充分に高くないため反応時の発熱量が大きいことから、触媒の熱劣化が大きいという問題を有している。そのため触媒活性を向上させることで反応温度を下げ、かつ無水マレイン酸への選択性を向上させることで反応時における発熱量を低減させ触媒の熱劣化を抑制し、無水マレイン酸の収率を向上させることが求められており、触媒としての種々のバナジウム含有酸化物や触媒を形成するための前駆体が検討されている。
Vanadium-containing oxides are generally known to be effective as catalysts for producing maleic anhydride by catalytic gas phase oxidation of linear hydrocarbons having 4 or more carbon atoms such as butane, butene, and butadiene. (For example, refer to
従来の無水マレイン酸の製造に用いられる触媒としてのバナジウム含有酸化物の前駆体としては、例えば、バナジウム−リン系結晶性酸化物であり、バナジウムの一部が鉄、クロム、アルミニウムのいずれか１種により置換されたものが挙げられる（例えば、特許文献１参照。）。また、一般式［（Ｖ１−ｘ−ｙ−ｚＦｅｘＣｒｙＡｌｚ）Ｏ］２Ｐ２Ｏ７］で表され、（ＶＯ）２Ｐ２Ｏ７と同型の結晶構造を有し、０＜ｘ≦０．４、０≦ｙ≦０．４、０≦ｚ≦０．４、０≦ｘ＋ｙ＋ｚ≦０．４である結晶性酸化物からなる無水マレイン酸製造のための触媒調製用組成物が挙げられる（例えば、特許文献２参照。）。 Examples of the precursor of vanadium-containing oxide as a catalyst used in the production of conventional maleic anhydride include, for example, vanadium-phosphorus crystalline oxide, and a part of vanadium is any one of iron, chromium, and aluminum. The thing substituted by the seed | species is mentioned (for example, refer patent document 1). Also, is represented by the general formula [(V 1-x-y -z Fe x Cr y Al z) O] 2 P 2 O 7], having a (VO) 2 P 2 O 7 and the crystal structure of the same type, Composition for preparing a catalyst for maleic anhydride production comprising a crystalline oxide with 0 <x ≦ 0.4, 0 ≦ y ≦ 0.4, 0 ≦ z ≦ 0.4, 0 ≦ x + y + z ≦ 0.4 (For example, refer to Patent Document 2).
従来の無水マレイン酸の製造に用いられる触媒としてのバナジウム含有酸化物としては、触媒活性成分が主としてバナジウム、リン及び酸素からなる複合酸化物であって、鉄、コバルト、ニッケル及び銅からなる群より選ばれた少なくも２種の活性促進成分を特定量含有した触媒が挙げられる（例えば、特許文献３参照。）。 As a vanadium-containing oxide as a catalyst used in the production of conventional maleic anhydride, the catalytically active component is a composite oxide mainly composed of vanadium, phosphorus and oxygen, from the group consisting of iron, cobalt, nickel and copper Examples include a catalyst containing a specific amount of at least two selected activity promoting components (for example, see Patent Document 3).
しかしながら、無水マレイン酸の製造において、従来のバナジウム含有酸化物からなる触媒を用いて、接触気相酸化反応により無水マレイン酸を製造しても、充分な転化率及び選択率を得て、無水マレイン酸の収率を向上するためには未だ改善の余地があった。
本発明は、上記現状に鑑みてなされたものであり、無水マレイン酸の製造方法において、無水マレイン酸の収率を向上するために好適な触媒の前駆体であるバナジウム含有酸化物を提供することを目的とするものである。 The present invention has been made in view of the above situation, and provides a vanadium-containing oxide which is a precursor of a catalyst suitable for improving the yield of maleic anhydride in a method for producing maleic anhydride. It is intended.
本発明者等は、無水マレイン酸の製造において用いられる触媒の前駆体であるバナジウム含有酸化物について種々検討したところ、Ｘ線回折スペクトルにおいて２θ＝１５．４°、２０．４°、３１．０°、３４．３°、４７．３°及び５１．２°（何れも±０．２°）にピークを示し、かつ、２θ＝２６．２°（±０．２°）にメインピークを示すバナジウム含有酸化物とすると、このバナジウム含有酸化物とリン酸とを反応させて形成したバナジウムとリンとを有する酸化物を触媒として用いて、無水マレイン酸を製造すると、著しく高い収率が得られることを見いだし、上記課題をみごとに解決することができることに想到し、本発明に到達したものである。 The present inventors have conducted various studies on vanadium-containing oxides that are precursors of catalysts used in the production of maleic anhydride. As a result, in the X-ray diffraction spectrum, 2θ = 15.4 °, 20.4 °, 31.0 Shows peaks at °, 34.3 °, 47.3 ° and 51.2 ° (all ± 0.2 °), and shows a main peak at 2θ = 26.2 ° (± 0.2 °) When a vanadium-containing oxide is used, maleic anhydride is produced using an oxide having vanadium and phosphorus formed by reacting the vanadium-containing oxide and phosphoric acid as a catalyst, and a remarkably high yield is obtained. As a result, the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.
すなわち本発明は、バナジウム含有酸化物は、Ｘ線回折スペクトルにおいて２θ＝２６．２°（±０．２°）にメインピークを示すバナジウム含有酸化物である。
以下に本発明を詳述する。
That is, in the present invention, the vanadium-containing oxide is a vanadium-containing oxide that exhibits a main peak at 2θ = 26.2 ° (± 0.2 °) in the X-ray diffraction spectrum.
The present invention is described in detail below.
本発明におけるバナジウム含有酸化物は、Ｘ線回折スペクトルにおいて２θ＝２６．２°（±０．２°）にメインピークを示すものである。
上記バナジウム含有酸化物は、Ｘ線回折スペクトルにおいて２θ＝１５．４°、２０．４°、３１．０°、３４．３°、４７．３°及び５１．２°（何れも±０．２°）にピークを示すことが好ましい。これらのピークは、２６．２°以外の他のピークに比べて強度が大きく、特徴的なものである。上記バナジウム含有酸化物のＸ線回折スペクトルは、これら以外のピークも有していてもよい。
The vanadium-containing oxide in the present invention exhibits a main peak at 2θ = 26.2 ° (± 0.2 °) in the X-ray diffraction spectrum.
In the X-ray diffraction spectrum, the vanadium-containing oxide has 2θ = 15.4 °, 20.4 °, 31.0 °, 34.3 °, 47.3 °, and 51.2 ° (both ± 0.2 It is preferable to show a peak at °). These peaks are characteristic in that they have a higher intensity than other peaks other than 26.2 °. The X-ray diffraction spectrum of the vanadium-containing oxide may have other peaks.
上記Ｘ線回折スペクトルの測定は、測定機器としてスペクトリス（株）製 Ｘ’ｐｅｒｔＰＲＯを用い、以下の条件下で行うことが好ましい。
スタートｐｏｓｏｉｔｏｎ（２θ°）：５
終了ｐｏｓｉｔｏｎ（２θ°）：７５
ステップサイズ（２θ°）：０．０１７
スキャンステップ時間：ｓｅｃ．５．０８
ターゲット：Ｃｕ−Ｋα
Ｘ線出力設定：４５ｋＶ、４０ｍＶ
The measurement of the X-ray diffraction spectrum is preferably performed under the following conditions, using X'pert PROPROTRIS Co., Ltd. as a measuring instrument.
Start poison (2θ °): 5
End position (2θ °): 75
Step size (2θ °): 0.017
Scan step time: sec. 5.08
Target: Cu-Kα
X-ray output setting: 45 kV, 40 mV
本発明におけるバナジウム含有酸化物は、その結晶構造中のバナジウム（Ｖ）の一部が鉄（Ｆｅ）、コバルト（Ｃｏ）及びニッケル（Ｎｉ）からなる群より選択される少なくとも一種の元素によって置換されたものであることが好ましい。このようなバナジウム含有酸化物とリン酸とを反応させて形成したバナジウムとリンとを有する酸化物を触媒として、接触気相酸化により無水マレイン酸を製造すると、極めて高い収率を得ることが可能となる。 In the vanadium-containing oxide in the present invention, a part of vanadium (V) in the crystal structure is substituted with at least one element selected from the group consisting of iron (Fe), cobalt (Co), and nickel (Ni). It is preferable that When maleic anhydride is produced by catalytic gas phase oxidation using an oxide containing vanadium and phosphorus formed by reacting vanadium-containing oxide and phosphoric acid as a catalyst, extremely high yields can be obtained. It becomes.
上記バナジウム含有酸化物は、バナジウム化合物とＦｅ、Ｃｏ及びＮｉからなる群より選択される少なくとも一種の元素を含有する化合物とを酸性又はアルカリ性溶液中で溶解した（溶解工程）後、蒸発乾固し、更に蒸発乾固物を焼成（焼成工程）したものであることが好ましい。 The vanadium-containing oxide is obtained by dissolving a vanadium compound and a compound containing at least one element selected from the group consisting of Fe, Co, and Ni in an acidic or alkaline solution (dissolution step), and then evaporating to dryness. Furthermore, it is preferable that the evaporated and dried product be fired (baking step).
上記バナジウム化合物としては、例えば、五酸化バナジウム、及び、ピロバナジン酸、オキシ三塩化バナジウム等が挙げられる。好ましくは、五酸化バナジウムである。 Examples of the vanadium compound include vanadium pentoxide, pyrovanadic acid, vanadium oxytrichloride, and the like. Vanadium pentoxide is preferable.
上記Ｆｅ、Ｃｏ及びＮｉからなる群より選択される少なくとも一種の元素を含有する化合物としては、これらの硝酸塩、ハロゲン化物、オキシ酸、酢酸塩、リン酸塩等が挙げられる。鉄を含有する化合物としては、Ｆｅ（III）（ＮＯ３）３・９Ｈ２Ｏが好ましい。 Examples of the compound containing at least one element selected from the group consisting of Fe, Co, and Ni include nitrates, halides, oxyacids, acetates, and phosphates. The compound containing iron, Fe (III) (NO 3 ) 3 · 9H 2 O are preferred.
上記溶解工程におけるＦｅ、Ｃｏ及びＮｉの少なくとも一種の元素の割合は、バナジウム原子１モルに対して０．０００５〜０．１モル（０．０５〜１０モル％）であることが好ましい。０．０５％未満では添加効果が認められず、１０％を超えると逆に燃焼活性となりＭＡ（無水マレイン酸）の収率が低下する。より好ましくは０．００１〜０．０５モル（０．１〜５モル％）である。 The ratio of at least one element of Fe, Co, and Ni in the melting step is preferably 0.0005 to 0.1 mol (0.05 to 10 mol%) with respect to 1 mol of vanadium atoms. If it is less than 0.05%, the effect of addition is not recognized, and if it exceeds 10%, the combustion activity is reversed and the yield of MA (maleic anhydride) decreases. More preferably, it is 0.001-0.05 mol (0.1-5 mol%).
上記溶解工程に用いられる溶媒としては、バナジウム化合物を完全に溶解することが可能であり、かつ他の金属カチオンを含まないものであれば特に限定されず、酸性溶媒としては、例えば、塩酸、硝酸、硫酸、フッ化水素酸、蓚酸、酒石酸等が、アルカリ性溶媒としては、例えば、アンモニア水等が挙げられる。中でも硝酸、アンモニアは取扱いやすく好ましい。
上記焼成工程は酸素含有ガス流下で行われるが、蒸発乾固物に残存する硝酸根やアンモニウム根、その他の可燃成分を完全に除去できる条件であればよく、その焼成温度や時間、酸素濃度、ガス流量等を特に限定されない。
The solvent used in the dissolution step is not particularly limited as long as it can completely dissolve the vanadium compound and does not contain other metal cations. Examples of the acidic solvent include hydrochloric acid and nitric acid. Sulfuric acid, hydrofluoric acid, succinic acid, tartaric acid and the like, and examples of the alkaline solvent include aqueous ammonia. Among these, nitric acid and ammonia are preferable because they are easy to handle.
The above firing step is performed under an oxygen-containing gas flow, but it is sufficient that the nitrate radical and ammonium root remaining in the evaporated dry matter and other combustible components can be completely removed, and the firing temperature and time, oxygen concentration, The gas flow rate and the like are not particularly limited.
本発明はまた、上記バナジウム含有酸化物とリン酸とを反応させて形成したバナジウムとリンとを有する酸化物である。
上記バナジウムとリンとを有する酸化物であって、Ｘ線回折スペクトルにおいて２θ＝２３．０°、２８．４°、２９．９°、３３．７°、３６．８°及び４３．２°（何れも±０．２°）にピークを示すものであることが好ましい。
The present invention is also an oxide having vanadium and phosphorus formed by reacting the vanadium-containing oxide with phosphoric acid.
The oxide having vanadium and phosphorus, wherein 2θ = 23.0 °, 28.4 °, 29.9 °, 33.7 °, 36.8 ° and 43.2 ° in the X-ray diffraction spectrum ( It is preferable that both have a peak at ± 0.2 °.
上記バナジウム含有化合物を用いたバナジウムとリンとを有する酸化物の調製法は、特に限定されず、好ましくは水に上記バナジウム含有化合物とリン酸を加え加熱攪拌し（加熱攪拌工程）、焼成した沈殿物を濾過洗浄（洗浄工程）する。得られた化合物１を還元（還元工程）して得られる化合物２を乾燥後（乾燥工程）、必要に応じて成形、焼成（焼成工程）する。その後活性化処理して（活性化処理工程）Ｘ線回折スペクトルにおいて２θ＝２３．０°、２８．４°、２９．９°、３３．７°、３６．８°及び４３．２°（何れも±０．２°）にピークを示すバナジウムとリンとを有する酸化物を形成する工程を含むものであるのがよい。このようなバナジウムとリンとを有する酸化物の調製法（製造方法）もまた、本発明の好ましい形態のひとつである。
The preparation method of the oxide having vanadium and phosphorus using the vanadium-containing compound is not particularly limited. Preferably, the vanadium-containing compound and phosphoric acid are added to water, and the mixture is heated and stirred (heating and stirring step), followed by firing. The product is filtered and washed (washing process). The compound 2 obtained by reducing (reducing process) the obtained
上記リン酸としては、例えば、オルトリン酸、五酸化リン、ピロリン酸、トリポリリン酸、オキシ三塩化リン等の五価のリン化合物等が挙げられる。好ましくは、オルトリン酸である。 Examples of the phosphoric acid include pentavalent phosphorus compounds such as orthophosphoric acid, phosphorus pentoxide, pyrophosphoric acid, tripolyphosphoric acid, and phosphorus oxytrichloride. Orthophosphoric acid is preferable.
上記加熱還流工程におけるバナジウム含有化合物とリン化合物の使用割合は、バナジウム／リン（原子比）として１／１．０〜１／２０が好ましい。より好ましくは１／１．０〜１／１０である。バナジウムに対するリンの比が１／１．０未満であると未反応のバナジウム含有化合物が混入する可能性があり、１／２０より多いと多量の未反応リン化合物が発生することとなり経済的でない。 The use ratio of the vanadium-containing compound and the phosphorus compound in the heating and refluxing step is preferably 1 / 1.0 to 1/20 as vanadium / phosphorus (atomic ratio). More preferably, it is 1 / 1.0 to 1/10. If the ratio of phosphorus to vanadium is less than 1 / 1.0, an unreacted vanadium-containing compound may be mixed, and if it is more than 1/20, a large amount of unreacted phosphorus compound is generated, which is not economical.
また、上記加熱還流工程における還流時間は、１２〜４８時間が好ましい。１２時間より短い場合は未反応バナジウム含有化合物が混入する可能性があり好ましくない。より好ましくは１２〜２４時間である。 The reflux time in the heating reflux step is preferably 12 to 48 hours. When it is shorter than 12 hours, an unreacted vanadium-containing compound may be mixed, which is not preferable. More preferably, it is 12 to 24 hours.
上記洗浄工程では、充分に水洗し未反応リン酸を除去すればよく、操作等は特に限定されない。濾過物の乾燥を早める目的から、アセトン等で洗浄してもよい。濾過洗浄によって得られる化合物１は、（Ｖ（Ｆｅ））ＯＰＯ４ ・２Ｈ２Ｏ型の黄色化合物である。
In the washing step, it is only necessary to sufficiently wash with water to remove unreacted phosphoric acid, and the operation and the like are not particularly limited. You may wash | clean with acetone etc. in order to accelerate | stimulate drying of a filtrate.
上記還元工程は、化合物１を還元溶媒と混合させ、６０〜１５０℃で６〜４８時間かけて行うことが好ましい。より好ましくは８０〜１３０℃で１２〜２４時間である。
還元溶媒としては、１−ブタノール、イソブタノール、ベンジルアルコール、アニスアルコール等５価のバナジウム化合物を還元しうる還元剤としての機能と反応溶媒としての機能を共有するものであればいずれも使用することができるが、１ブタノール、ベンジルアルコールが好ましい。この還元工程の結果得られる化合物２は（Ｖ（Ｆｅ））ＯＨＰＯ４ ・０．５Ｈ２Ｏ型の水色化合物である。
The reduction step is preferably performed by mixing
Any reducing solvent may be used as long as it shares the function as a reducing agent capable of reducing pentavalent vanadium compounds such as 1-butanol, isobutanol, benzyl alcohol, anis alcohol and the function as a reaction solvent. However, 1-butanol and benzyl alcohol are preferable. Compound 2 obtained as a result of this reduction step is a (V (Fe)) OHPO 4 .0.5H 2 O type light blue compound.
上記乾燥工程では、得られた化合物２を濾過した後、通常１００〜１５０℃、好ましくは１２０〜１５０℃で３〜４８時間、好ましくは６〜２４時間、不活性ガス中又は酸素含有ガス中で処理する。
上記焼成工程では、乾燥工程によって得られた乾燥物を粉末状又は成型体とした後、空気等の酸素含有ガス雰囲気、又は、不活性ガスと空気との混合ガス雰囲気下で３５０〜６００℃、好ましくは４００〜５５０℃の温度で１〜２４時間、好ましくは２〜１２時間処理される。
In the drying step, after the obtained compound 2 is filtered, it is usually 100 to 150 ° C., preferably 120 to 150 ° C. for 3 to 48 hours, preferably 6 to 24 hours, in an inert gas or an oxygen-containing gas. To process.
In the firing step, after the dried product obtained by the drying step is made into a powder or molded body, it is 350 to 600 ° C. in an oxygen-containing gas atmosphere such as air or a mixed gas atmosphere of inert gas and air, The treatment is preferably performed at a temperature of 400 to 550 ° C. for 1 to 24 hours, preferably 2 to 12 hours.
上記活性化処理工程ではこの種の酸化触媒において用いられている活性化方法をそのまま採用することができる。例えば、Ｃ４濃度＝２．０体積％、Ａｉｒ ｂａｌａｎｃｅ、ＳＶ＝３０００Ｈｒ−１の条件下で、３００〜５５０℃で５〜２４時間処理する。より好ましくは４００〜５３０℃で１０〜２４時間である。この工程で化合物２がＸ線回折スペクトルにおいて２θ＝２３．０°、２８．４°、２９．９°、３３．７°、３６．８°及び４３．２°（何れも±０．２°）にピークを示すバナジウムとリンとを有する酸化物となる。 In the activation treatment step, the activation method used in this type of oxidation catalyst can be employed as it is. For example, the treatment is performed at 300 to 550 ° C. for 5 to 24 hours under the conditions of C4 concentration = 2.0% by volume, Air balance, SV = 3000Hr −1 . More preferably, it is 10 to 24 hours at 400 to 530 ° C. In this step, Compound 2 was found to have 2θ = 23.0 °, 28.4 °, 29.9 °, 33.7 °, 36.8 ° and 43.2 ° (all ± 0.2 ° in the X-ray diffraction spectrum) ) Is an oxide having vanadium and phosphorus having a peak.
上記バナジウムとリンとを有する酸化物は、結晶構造中のＶの一部が鉄（Ｆｅ）、コバルト（Ｃｏ）及びニッケル（Ｎｉ）からなる群より選択される少なくとも一種の元素によって置換されたものであることが好ましい。これを触媒として分子状酸素含有ガスにより接触気相酸化して無水マレイン酸を製造すると、極めて高い収率を得ることができる。 In the oxide having vanadium and phosphorus, part of V in the crystal structure is substituted with at least one element selected from the group consisting of iron (Fe), cobalt (Co), and nickel (Ni) It is preferable that When maleic anhydride is produced by catalytic vapor phase oxidation with a molecular oxygen-containing gas using this as a catalyst, an extremely high yield can be obtained.
本発明は更に、上記バナジウムとリンとを有する酸化物を含有する触媒でもある。
本発明の触媒は、上記バナジウムとリンとを有する酸化物を含有するものであるため、無水マレイン酸の製造において、活性を高めつつ、無水マレイン酸の選択率を向上させ、著しく高い収率を得ることが可能となる。本発明の触媒は、上述したバナジウムとリンとを有する酸化物と同様の方法で製造することができるが、この触媒の製造方法もまた、本発明の好ましい形態のひとつである。
The present invention is also a catalyst containing an oxide having vanadium and phosphorus.
Since the catalyst of the present invention contains the oxide having vanadium and phosphorus, in the production of maleic anhydride, the selectivity of maleic anhydride is improved while increasing the activity, and the yield is remarkably high. Can be obtained. The catalyst of the present invention can be produced by the same method as the above-described oxide having vanadium and phosphorus, and this method for producing the catalyst is also one of the preferred embodiments of the present invention.
本発明はそして、炭素原子数４以上の脂肪族炭化水素を触媒の存在下で分子状酸素含有ガスにより接触気相酸化して無水マレイン酸を製造する方法であって、上記製造方法は、上記触媒を用いる工程を含む無水マレイン酸の製造方法でもある。 The present invention is also a method for producing maleic anhydride by catalytic gas phase oxidation of an aliphatic hydrocarbon having 4 or more carbon atoms with a molecular oxygen-containing gas in the presence of a catalyst, It is also a method for producing maleic anhydride including a step of using a catalyst.
上記炭素原子数４以上の脂肪族炭化水素としては、炭素原子数４以上の直鎖状炭化水素や側鎖を有する脂肪族炭化水素等が挙げられる。収率を向上させる観点から、好ましくは、炭素原子数４以上の直鎖状炭化水素である。
上記炭素原子数４以上の直鎖状炭化水素としては、例えば、ｎ−ブタン、１−ブテン、２−ブテン、ブタジエン、これらの混合物等が挙げられる。好ましくは、ｎ−ブタン、ブテン類である。
上記炭素原子数４以上の側鎖を有する脂肪族炭化水素としては、例えば、イソブタン、イソブチレン等が挙げられる。
Examples of the aliphatic hydrocarbon having 4 or more carbon atoms include linear hydrocarbons having 4 or more carbon atoms and aliphatic hydrocarbons having side chains. From the viewpoint of improving the yield, linear hydrocarbons having 4 or more carbon atoms are preferable.
Examples of the linear hydrocarbon having 4 or more carbon atoms include n-butane, 1-butene, 2-butene, butadiene, and mixtures thereof. Of these, n-butane and butenes are preferable.
Examples of the aliphatic hydrocarbon having a side chain having 4 or more carbon atoms include isobutane and isobutylene.
本発明の製造方法において、炭素原子数４以上の脂肪族炭化水素を上記触媒の存在下で分子状酸素含有ガスにより接触気相酸化すると、無水マレイン酸が生成する。
上記分子状酸素含有ガスとしては、例えば、空気、又は、窒素、炭酸ガス、ヘリウム等の不活性ガスで希釈された混合気体等が挙げられる。混合気体中の不活性ガスの合計濃度は、通常６０〜９４．５容量％であることが好ましい。より好ましくは、７５〜９０容量％である。
In the production method of the present invention, when an aliphatic hydrocarbon having 4 or more carbon atoms is subjected to catalytic gas phase oxidation with a molecular oxygen-containing gas in the presence of the catalyst, maleic anhydride is produced.
Examples of the molecular oxygen-containing gas include air or a mixed gas diluted with an inert gas such as nitrogen, carbon dioxide, or helium. The total concentration of the inert gas in the mixed gas is usually preferably 60 to 94.5% by volume. More preferably, it is 75 to 90% by volume.
上記製造方法における反応様式については固定床方式及び流動床方式のいずれでもよく、例えば固定床方式では、脂肪族炭化水素の濃度は０．５〜１０．０容量％であることが好ましく、より好ましくは１．０〜５．０容量％である。
上記製造方法における接触気相酸化工程における反応温度は、３００〜５５０℃であることが好ましい。より好ましくは、３５０〜５００℃である。また、反応圧力は、常圧及び加圧のいずれでもよいが、通常常圧で行うのがよい。
The reaction method in the above production method may be either a fixed bed method or a fluidized bed method. For example, in the fixed bed method, the concentration of the aliphatic hydrocarbon is preferably 0.5 to 10.0% by volume, more preferably. Is 1.0-5.0% by volume.
The reaction temperature in the contact gas phase oxidation step in the production method is preferably 300 to 550 ° C. More preferably, it is 350-500 degreeC. In addition, the reaction pressure may be normal pressure or increased pressure, but it is usually preferable to carry out the reaction at normal pressure.
本発明のバナジウム含有酸化物は、上述の構成よりなり、無水マレイン酸の接触気相酸化により酸化して製造する際の触媒の好適な原料を提供することができ、これを用いて形成した触媒により無水マレイン酸を著しく高い収率で製造することが可能となる。 The vanadium-containing oxide of the present invention has the above-described configuration, and can provide a suitable raw material for a catalyst when it is produced by oxidation by catalytic gas phase oxidation of maleic anhydride, and a catalyst formed using this catalyst. Makes it possible to produce maleic anhydride in a remarkably high yield.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「重量部」を、「％」は「質量％」を意味するものとする。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by mass”.
実施例１
水１．８Ｌに濃硝酸４５ｍｌを加えてからＶ２Ｏ５１０ｇとＦｅ（III）（ＮＯ３）３・９Ｈ２Ｏ０．４５ｇを溶かした後、蒸発乾固した。この蒸発乾固残渣を酸素気流（２０ｍｌ／ｍｉｎ）中５００℃で３０時間焼成して、（Ｖ（Ｆｅ））２Ｏ５（バナジウム含有酸化物）を得た。このバナジウム含有酸化物のＸ線回折スペクトルを図１に示す。図１の上段が本実施例で製造したバナジウム含有化合物のＸ線回折スペクトルである。バナジウム含有酸化物は、Ｘ線回折スペクトルにおいて２θ＝２６．２°（±０．２°）にメインピークを示すことがわかった。また、２θ＝１５．４°、２０．４°、３１．０°、３４．３°、４７．３°及び５１．２°（何れも±０．２°）にもピークを示すこともわかった。なお、図１の中段は、Ｖ２Ｏ５のＸ線回折スペクトルであり、図１の下段は、Ｆｅ：Ｖ：Ｏ＝０．１１：２：５．１６である酸化バナジウムのＸ線回折スペクトルである。これら化合物のＸ線回折スペクトルにおいては、２θ＝２６．２°（±０．２°）においてメインピークを有していない。
Example 1
It was dissolved V 2 O 5 10 g and Fe (III) (NO 3) 3 · 9H 2 O0.45g from concentrated nitric acid 45ml added to water 1.8L, and evaporated to dryness. This evaporated and dried residue was calcined at 500 ° C. for 30 hours in an oxygen stream (20 ml / min) to obtain (V (Fe)) 2 O 5 (vanadium-containing oxide). The X-ray diffraction spectrum of this vanadium-containing oxide is shown in FIG. The upper part of FIG. 1 is an X-ray diffraction spectrum of the vanadium-containing compound produced in this example. It was found that the vanadium-containing oxide showed a main peak at 2θ = 26.2 ° (± 0.2 °) in the X-ray diffraction spectrum. It is also found that 2θ = 15.4 °, 20.4 °, 31.0 °, 34.3 °, 47.3 ° and 51.2 ° (all ± 0.2 °) have peaks. It was. The middle part of FIG. 1 is an X-ray diffraction spectrum of V 2 O 5 , and the lower part of FIG. 1 is an X-ray diffraction spectrum of vanadium oxide with Fe: V: O = 0.11: 2: 5.16. It is. The X-ray diffraction spectra of these compounds do not have a main peak at 2θ = 26.2 ° (± 0.2 °).
次に水２５０ｍｌに８５％オルトリン酸５６ｍｌを加えて８０℃とした溶液に、（Ｖ（Ｆｅ））２Ｏ５を全量加え１６時間加熱還流した。沈殿物を濾過後、少量の水とアセトンで洗浄し、（Ｖ（Ｆｅ））ＯＰＯ４・２Ｈ２Ｏ型の黄色化合物を得た。これを１−ブタノール中８０℃で２４時間還元して、（Ｖ（Ｆｅ））ＯＨＰＯ４・０．５Ｈ２Ｏ型の化合物を得た。この化合物１ｇを流通型反応装置に充填し、Ｃ４ｃｏｎｃ＝２．０ｖｏｌ％、Ａｉｒ ｂａｌａｎｃｅ、ＳＶ（空間速度）＝３０００ｈｒ−１の条件下５２０℃で２０時間活性化処理することで、目的の触媒〔（（Ｖ０．９９Ｆｅ０．０１）Ｏ）２Ｐ２Ｏ７〕を得た。得られた触媒を用いて接触気相酸化（炭素原子数４以上の脂肪族炭化水素の酸化反応）により、無水マレイン酸を製造した。このとき、反応温度２８０℃〜５２０℃とした以外は、反応温度以外は活性化条件と全て同条件とした。得られた結果を表１に示す。 Next, the whole amount of (V (Fe)) 2 O 5 was added to a solution obtained by adding 56 ml of 85% orthophosphoric acid to 250 ml of water to 80 ° C., and heated to reflux for 16 hours. The precipitate was filtered and then washed with a small amount of water and acetone to obtain a yellow compound of the (V (Fe)) OPO 4 · 2H 2 O type. This was reduced in 1-butanol at 80 ° C. for 24 hours to obtain a compound of the (V (Fe)) OHPO 4 .0.5H 2 O type. 1 g of this compound was charged into a flow-type reaction apparatus and subjected to activation treatment at 520 ° C. for 20 hours under the conditions of C4conc = 2.0 vol%, Air balance, SV (space velocity) = 3000 hr −1 , ((V 0.99 Fe 0.01 ) O) 2 P 2 O 7 ] was obtained. Maleic anhydride was produced by catalytic gas phase oxidation (oxidation reaction of aliphatic hydrocarbon having 4 or more carbon atoms) using the obtained catalyst. At this time, except for the reaction temperature of 280 ° C. to 520 ° C., all the conditions were the same as the activation conditions except for the reaction temperature. The obtained results are shown in Table 1.
表１中、転化率、選択率及び収率は、以下のように求められる。表２及び３についても同様とする。
転化率（モル％）＝（反応したｎ−ブタンのモル数／供給したｎ−ブタンのモル数）×１００
選択率（モル％）＝（生成した無水マレイン酸のモル数／反応したｎ−ブタンのモル数）×１００
収率（モル％）＝（生成した無水マレイン酸のモル数／供給したｎ−ブタンのモル数）×１００
In Table 1, the conversion rate, selectivity, and yield are determined as follows. The same applies to Tables 2 and 3.
Conversion (mol%) = (number of moles of reacted n-butane / number of moles of supplied n-butane) × 100
Selectivity (mol%) = (number of moles of maleic anhydride produced / number of moles of reacted n-butane) × 100
Yield (mol%) = (number of moles of maleic anhydride produced / number of moles of supplied n-butane) × 100
比較例１（Ｆｅ無添加触媒）
水２５０ｍｌに８５％オルトリン酸５６ｍｌを加え８０℃とした溶液に、市販のＶ２Ｏ５１０ｇを加え１６時間加熱還流し、ＶＯＰＯ４・２Ｈ２Ｏを得た以外は、全て実施例１に記載の方法に従い（ＶＯ）２Ｐ２Ｏ７触媒を得た。得られた触媒は実施例１に記載の反応条件で評価した。得られた結果を表２に示す。
Comparative Example 1 (Fe-free catalyst)
The solution was 80 ° C. was added 85% orthophosphoric acid 56ml water 250 ml, commercially available V 2 O 5 10 g was 16 hours of heating under reflux, except that to obtain a VOPO 4 · 2H 2 O, according to in Example 1 According to the method of (VO) 2 P 2 O 7 catalyst was obtained. The obtained catalyst was evaluated under the reaction conditions described in Example 1. The obtained results are shown in Table 2.
比較例２（Ｆｅ添加触媒−従来の調製法）
水７０ｍｌに８５％オルトリン酸１１．５３ｇを加え、これに水３０ｍｌに塩酸ヒドロキシルアミン２．６０ｇを溶解させた水溶液を添加し、８０℃で還流しながら五酸化バナジウム９．００ｇを少量ずつ添加した。バナジウムの還元に伴う発砲が収まった後、更に３０分間加熱還流し還元を完結させた。
Comparative Example 2 (Fe-added catalyst-conventional preparation method)
11.53 g of 85% orthophosphoric acid was added to 70 ml of water, an aqueous solution in which 2.60 g of hydroxylamine hydrochloride was dissolved in 30 ml of water was added thereto, and 9.00 g of vanadium pentoxide was added little by little while refluxing at 80 ° C. . After the firing associated with the reduction of vanadium was settled, heating was further refluxed for 30 minutes to complete the reduction.
放冷後、三塩化鉄０．１６ｇを添加溶解させ、再度８０℃にて一時間加熱還流を行った。その後溶液を蒸発乾固させ、１３０℃で約１０時間乾燥させた。得られた粉末に水５０ｍｌを加え煮沸しながら攪拌した後に、濾過水洗及び乾燥を行い青色結晶を得た。これを実施例１と同様の条件にて更に反応ガス中５２０℃で２０時間活性化処理する事で目的の （（Ｖ０．９９Ｆｅ０．０１）Ｏ）２Ｐ２Ｏ７型触媒とした。得られた触媒は実施例１に記載の反応条件で評価した。得られた結果を表３に示す。 After allowing to cool, 0.16 g of iron trichloride was added and dissolved, and the mixture was again heated to reflux at 80 ° C. for 1 hour. The solution was then evaporated to dryness and dried at 130 ° C. for about 10 hours. 50 ml of water was added to the obtained powder and stirred while boiling, and then washed with filtered water and dried to obtain blue crystals. This was further subjected to activation treatment at 520 ° C. for 20 hours in the reaction gas under the same conditions as in Example 1 to obtain the desired ((V 0.99 Fe 0.01 ) O) 2 P 2 O 7 type catalyst. . The obtained catalyst was evaluated under the reaction conditions described in Example 1. The obtained results are shown in Table 3.
Claims (8)
該製造方法は、請求項７記載の触媒を用いる工程を含むことを特徴とする無水マレイン酸の製造方法。 A process for producing maleic anhydride by catalytic vapor phase oxidation of an aliphatic hydrocarbon having 4 or more carbon atoms with a molecular oxygen-containing gas in the presence of a catalyst,
The method for producing maleic anhydride, comprising a step of using the catalyst according to claim 7.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014214072A (en) * | 2013-04-30 | 2014-11-17 | 国立大学法人広島大学 | PRODUCTION METHOD OF α-DAWSON TYPE POLY ACID, AND α-DAWSON TYPE POLY ACID PRODUCED BY THE METHOD, α-DAWSON TYPE POLY ACID COMPOUND |
| KR101493619B1 (en) | 2013-12-03 | 2015-02-13 | 경북대학교 산학협력단 | Catalyst system for the producing Maleic acid anhydride |
| JP2015069866A (en) * | 2013-09-30 | 2015-04-13 | Tdk株式会社 | Positive electrode material for lithium ion secondary batteries, positive electrode for lithium ion secondary batteries, and lithium ion secondary battery |
| JP2016518246A (en) * | 2013-03-22 | 2016-06-23 | クラリアント・インターナシヨナル・リミテツド | Removable protective coating to obtain dust-free catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016518246A (en) * | 2013-03-22 | 2016-06-23 | クラリアント・インターナシヨナル・リミテツド | Removable protective coating to obtain dust-free catalyst |
| US10252254B2 (en) | 2013-03-22 | 2019-04-09 | Clariant International Ltd. | Removable protective coating for the receipt of a dust free catalyst |
| JP2014214072A (en) * | 2013-04-30 | 2014-11-17 | 国立大学法人広島大学 | PRODUCTION METHOD OF α-DAWSON TYPE POLY ACID, AND α-DAWSON TYPE POLY ACID PRODUCED BY THE METHOD, α-DAWSON TYPE POLY ACID COMPOUND |
| JP2015069866A (en) * | 2013-09-30 | 2015-04-13 | Tdk株式会社 | Positive electrode material for lithium ion secondary batteries, positive electrode for lithium ion secondary batteries, and lithium ion secondary battery |
| KR101493619B1 (en) | 2013-12-03 | 2015-02-13 | 경북대학교 산학협력단 | Catalyst system for the producing Maleic acid anhydride |
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