JP6366407B2 - Oxidative dehydrogenation catalyst, method for producing oxidative dehydrogenation catalyst, and oxidative dehydrogenation method - Google Patents
Oxidative dehydrogenation catalyst, method for producing oxidative dehydrogenation catalyst, and oxidative dehydrogenation methodInfo
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- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims description 121
- 239000003054 catalyst Substances 0.000 title claims description 116
- 238000000034 method Methods 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000002994 raw material Substances 0.000 claims description 108
- 125000004432 carbon atom Chemical group C* 0.000 claims description 81
- 150000002430 hydrocarbons Chemical class 0.000 claims description 77
- 229930195733 hydrocarbon Natural products 0.000 claims description 76
- 239000004215 Carbon black (E152) Substances 0.000 claims description 70
- 239000011777 magnesium Substances 0.000 claims description 59
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 57
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 56
- 229910052721 tungsten Inorganic materials 0.000 claims description 53
- 229910052749 magnesium Inorganic materials 0.000 claims description 52
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 49
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 46
- 239000010937 tungsten Substances 0.000 claims description 46
- 229910052720 vanadium Inorganic materials 0.000 claims description 45
- 150000005673 monoalkenes Chemical class 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 43
- 125000004429 atom Chemical group 0.000 claims description 40
- 239000012188 paraffin wax Substances 0.000 claims description 38
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 29
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 16
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- 238000006297 dehydration reaction Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 description 25
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- 238000006243 chemical reaction Methods 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- QWTDNUCVQCZILF-UHFFFAOYSA-N iso-pentane Natural products CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- WSXMFMCRLSKYBP-UHFFFAOYSA-N [C].CCCC Chemical compound [C].CCCC WSXMFMCRLSKYBP-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 2
- NLHNESWDZWZZBH-UHFFFAOYSA-N [O-2].[Mg+2].[Mo+4].[O-2].[O-2] Chemical compound [O-2].[Mg+2].[Mo+4].[O-2].[O-2] NLHNESWDZWZZBH-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- -1 carbon monoolefins Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UINUVOICOPGDCZ-UHFFFAOYSA-N [O-2].[V+5].[Mg+2] Chemical compound [O-2].[V+5].[Mg+2] UINUVOICOPGDCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 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
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000000227 grinding 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
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- OPDAZMQZDHDLKT-UHFFFAOYSA-N nickel(2+) niobium(5+) oxygen(2-) Chemical compound [O-2].[Nb+5].[Ni+2] OPDAZMQZDHDLKT-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical class Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、酸化脱水素用の触媒及びその触媒の製造方法、並びにその触媒を用いた炭化水素の酸化脱水素方法に関する。詳しくは、炭素数が３〜５のｎ−パラフィン又は炭素数３〜５のｎ−モノオレフィンを含む炭化水素を酸素の存在下に酸化脱水素して、対応するモノオレフィン又は共役ジエンを製造するための酸化脱水素触媒及びその触媒の製造方法、並びにその触媒を用いた炭化水素の酸化脱水素方法に関する。 The present invention relates to a catalyst for oxidative dehydrogenation, a method for producing the catalyst, and a method for oxidative dehydrogenation of hydrocarbons using the catalyst. Specifically, a hydrocarbon containing n-paraffin having 3 to 5 carbon atoms or n-monoolefin having 3 to 5 carbon atoms is oxidatively dehydrogenated in the presence of oxygen to produce the corresponding monoolefin or conjugated diene. The present invention relates to an oxidative dehydrogenation catalyst, a method for producing the catalyst, and a hydrocarbon oxidative dehydrogenation method using the catalyst.
低級炭化水素の脱水素方法としては単純脱水素プロセスが工業化されているが、このプロセスは平衡の制約から、高収率で目的生成物を得ることは困難であり、且つ高温が必要である。さらにコーク析出による失活が大きく、触媒再生を頻繁に行う必要があるという問題があった。 As a method for dehydrogenating lower hydrocarbons, a simple dehydrogenation process has been industrialized. However, this process is difficult to obtain a target product in a high yield due to equilibrium limitations, and requires a high temperature. Furthermore, there is a problem that deactivation due to coke deposition is large and catalyst regeneration needs to be performed frequently.
一方、平衡上制約がない酸化脱水素方法により、低級パラフィンや低級オレフィンから、低級オレフィン又は共役ジエンを製造する試みが以前から行われており、酸化脱水素により低級アルカンからの低級オレフィンまたは共役ジエンを製造する触媒は種々提案されている。例えば、エタンからのエチレン製造触媒としてニッケル−ニオブ酸化物系触媒（例えば、特許文献１）、プロパンからのプロピレン製造触媒としてバナジウム−マグネシウム酸化物系触媒（例えば、特許文献２）、ｎ−ブタンからのブテン、ブタジエン製造触媒としてモリブデンマグネシウム酸化物系触媒（例えば、特許文献３）などが知られている。これら公知の触媒を用いても特に低級アルカンの反応性は低く工業化に用いることはできないような低性能のものであった。また、反応を進行させようとすると低級アルカンの完全酸化あるいは分解が進行するため、これらの副反応を抑制し、低級オレフィンまたは共役ジエンが効率的に得られる触媒が求められている。 On the other hand, attempts have been made to produce lower olefins or conjugated dienes from lower paraffins and lower olefins by an oxidative dehydrogenation method that has no constraints on equilibrium, and lower olefins or conjugated dienes from lower alkanes by oxidative dehydrogenation. Various catalysts have been proposed for producing the. For example, a nickel-niobium oxide catalyst (for example, Patent Document 1) as an ethylene production catalyst from ethane, a vanadium-magnesium oxide catalyst (for example, Patent Document 2) as a propylene production catalyst from propane, and n-butane As a butene and butadiene production catalyst, a molybdenum magnesium oxide catalyst (for example, Patent Document 3) is known. Even when these known catalysts were used, the reactivity of the lower alkanes was particularly low and the performance was so low that it could not be used for industrialization. Further, since the complete oxidation or decomposition of the lower alkane proceeds when the reaction is allowed to proceed, a catalyst capable of suppressing these side reactions and efficiently obtaining the lower olefin or conjugated diene is desired.
また、脱水素反応により低級アルカンや低級オレフィンから共役ジエンを製造する方法も種々検討されている。例えば、１，３−ブタジエンの製造方法として、モリブデンマグネシウム酸化物触媒等を用いたｎ−ブタンからの酸化脱水素により１，３−ブタジエンを製造する方法（例えば、特許文献３）や、クロミア−アルミナ触媒を用いたブタン・ブテンの単純脱水素によって１，３−ブタジエンを製造する方法（例えば、非特許文献１）、Ｆｅ２Ｏ３−Ｃｒ２Ｏ３−Ｋ２ＣＯ３触媒を用いたブテンの単純脱水素によって１，３−ブタジエンを製造する方法（例えば、特許文献４）が検討されてきた。このうち、ブタン・ブテンの単純脱水素による方法が商業化されたが、コーク失活が大きく、触媒再生を頻繁に行う必要があるという問題があった。 Various methods for producing conjugated dienes from lower alkanes and lower olefins by dehydrogenation have also been studied. For example, as a method for producing 1,3-butadiene, a method for producing 1,3-butadiene by oxidative dehydrogenation from n-butane using a molybdenum magnesium oxide catalyst or the like (for example, Patent Document 3), chromia- A method for producing 1,3-butadiene by simple dehydrogenation of butane / butene using an alumina catalyst (for example, Non-Patent Document 1), butene using an Fe 2 O 3 —Cr 2 O 3 —K 2 CO 3 catalyst A method for producing 1,3-butadiene by simple dehydrogenation (for example, Patent Document 4) has been studied. Among them, the method by simple dehydrogenation of butane / butene has been commercialized, but there is a problem that coke deactivation is large and catalyst regeneration needs to be frequently performed.
また、近年、ビスマス−モリブデン触媒を用いたｎ−ブテンを酸化脱水素することによりブタジエンを製造する方法（例えば、特許文献５）が検討されている。しかしながら、ビスマス−モリブデン触媒は、反応活性と１，３−ブタジエン収率は高いが、触媒系が複雑なことから商業規模での調整が困難であるという問題があった。 In recent years, a method for producing butadiene by oxidative dehydrogenation of n-butene using a bismuth-molybdenum catalyst (for example, Patent Document 5) has been studied. However, although the bismuth-molybdenum catalyst has high reaction activity and 1,3-butadiene yield, there is a problem that adjustment on a commercial scale is difficult due to the complicated catalyst system.
従って、本発明の目的は、ブタン等のｎ−パラフィン又はｉ−パラフィンを含む炭化水素原料の酸化脱水素反応により、ブテン等のｎ−モノオレフィン又はｉ−モノオレフィンや、１，３−ブタジエン等の共役ジエンを得る酸化脱水素反応、又はブテン等のｎ−モノオレフィン又はｉ−モノオレフィンを含む炭化水素原料の酸化脱水素反応により、１，３−ブタジエン等の共役ジエンを得る酸化脱水素反応において、優れた触媒活性を示す酸化脱水素触媒を提供することにある。 Accordingly, an object of the present invention is to oxidize and dehydrogenate a hydrocarbon raw material containing n-paraffin or i-paraffin such as butane, so that n-monoolefin or i-monoolefin such as butene, 1,3-butadiene, etc. Oxidative dehydrogenation reaction to obtain a conjugated diene of 1,3-butadiene or the like by an oxidative dehydrogenation reaction to obtain a conjugated diene of the hydrocarbon raw material containing n-monoolefin or i-monoolefin such as butene It is an object of the present invention to provide an oxidative dehydrogenation catalyst exhibiting excellent catalytic activity.
本発明者らは、上記従来技術における課題を解決すべく、鋭意研究を重ねた結果、バナジウム、マグネシウム及びタングステンを必須成分として含み、且つ、これらの金属成分の比率が特定の比率である酸化脱水素触媒が、パラフィン及びモノオレフィンを酸化脱水素して、対応するモノオレフィン又は共役ジエンを得る酸化脱水素反応において、優れた触媒活性を示すことを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above-described problems in the prior art, the inventors of the present invention include vanadium, magnesium and tungsten as essential components, and the ratio of these metal components is a specific ratio. The inventors have found that the raw catalyst exhibits excellent catalytic activity in the oxidative dehydrogenation reaction in which paraffin and monoolefin are oxidatively dehydrogenated to obtain the corresponding monoolefin or conjugated diene, and the present invention has been completed.
すなわち、本発明（１）は、炭化水素原料中に含まれる炭素数３〜５のパラフィン又は炭素数３〜５のモノオレフィンの酸化脱水素を行うための酸化脱水素触媒であり、
該炭化水素原料が、炭素数３〜５のパラフィンを含む炭化水素原料、炭素数３〜５のモノオレフィンを含む炭化水素原料又は炭素数３〜５のパラフィンと炭素数３〜５のモノオレフィンとを含む炭化水素原料であり、
該酸化脱水素触媒が、バナジウム原子と、マグネシウム原子と、タングステン原子と、を含有し、且つ、バナジウム、マグネシウム及びタングステンの原子換算の合計モル数に対するタングステンの原子換算のモル数の割合（（Ｗ／（Ｖ＋Ｍｇ＋Ｗ））×１００）が０．３〜２．０モル％であること、
を特徴とする酸化脱水素触媒を提供するものである。
That is, the present invention (1) is an oxidative dehydrogenation catalyst for performing oxidative dehydrogenation of paraffins having 3 to 5 carbon atoms or monoolefins having 3 to 5 carbon atoms contained in a hydrocarbon raw material,
The hydrocarbon raw material is a hydrocarbon raw material containing a paraffin having 3 to 5 carbon atoms, a hydrocarbon raw material containing a monoolefin having 3 to 5 carbon atoms, or a paraffin having 3 to 5 carbon atoms and a monoolefin having 3 to 5 carbon atoms, A hydrocarbon feedstock containing
The oxidative dehydrogenation catalyst contains a vanadium atom, a magnesium atom, and a tungsten atom, and the ratio of the number of moles of tungsten in terms of atoms to the total number of moles of atoms in vanadium, magnesium, and tungsten ((W / (V + Mg + W)) × 100) is 0.3 to 2.0 mol%,
An oxidative dehydrogenation catalyst characterized by the above is provided.
また、本発明（２）は、炭化水素原料中に含まれるｎ−ブタンから酸化脱水素反応によってｎ−ブテン及び１，３−ブタジエンを製造するための酸化脱水素触媒であり、
該酸化脱水素触媒が、バナジウム原子と、マグネシウム原子と、タングステン原子と、を含有し、且つ、バナジウム、マグネシウム及びタングステンの原子換算の合計モル数に対するタングステンの原子換算のモル数の割合（（Ｗ／（Ｖ＋Ｍｇ＋Ｗ））×１００）が０．３〜２．０モル％であること、
を特徴とする酸化脱水素触媒を提供するものである。
The present invention (2) is an oxidative dehydrogenation catalyst for producing n-butene and 1,3-butadiene from n-butane contained in a hydrocarbon raw material by an oxidative dehydrogenation reaction,
The oxidative dehydrogenation catalyst contains a vanadium atom, a magnesium atom, and a tungsten atom, and the ratio of the number of moles of tungsten in terms of atoms to the total number of moles of atoms in vanadium, magnesium, and tungsten ((W / (V + Mg + W)) × 100) is 0.3 to 2.0 mol%,
An oxidative dehydrogenation catalyst characterized by the above is provided.
すなわち、本発明（３）は、バナジウム源、マグネシウム源及びタングステン源が水に溶解又は分散されている原料混合液を調製し、次いで、該原料混合液中の水を蒸発させて除去して、原料混合物粉体を得、次いで、該原料混合物粉体を焼成することにより、バナジウム原子と、マグネシウム原子と、タングステン原子と、を含有し、且つ、バナジウム、マグネシウム及びタングステンの原子換算の合計モル数に対するタングステンの原子換算のモル数の割合（（Ｗ／（Ｖ＋Ｍｇ＋Ｗ））×１００）が０．３〜２．０モル％である酸化脱水素触媒を得ることを特徴とする酸化脱水素触媒の製造方法を提供するものである。 That is , the present invention (3) prepares a raw material mixed solution in which a vanadium source, a magnesium source and a tungsten source are dissolved or dispersed in water, and then evaporates and removes the water in the raw material mixture. A raw material mixture powder is obtained, and then the raw material mixture powder is fired to contain vanadium atoms, magnesium atoms, and tungsten atoms, and the total number of moles in terms of atoms of vanadium, magnesium, and tungsten. Production of an oxidative dehydrogenation catalyst characterized by obtaining an oxidative dehydrogenation catalyst having a ratio of the number of moles of tungsten converted to atoms ((W / (V + Mg + W)) × 100) of 0.3 to 2.0 mol% A method is provided.
また、本発明（４）は、本発明（１）の酸化脱水素触媒の存在下、４００〜７００℃で、炭化水素原料中に含まれる炭素数３〜５のパラフィン又は炭素数３〜５のモノオレフィンの酸化脱水素を行う酸化脱水素反応であり、該炭化水素原料が、炭素数３〜５のパラフィンを含む炭化水素原料、炭素数３〜５のモノオレフィンを含む炭化水素原料又は炭素数３〜５のパラフィンと炭素数３〜５のモノオレフィンとを含む炭化水素原料であることを特徴とする酸化脱水素方法を提供するものである。 Moreover, this invention (4) is C3-C5 paraffin or C3-C5 contained in a hydrocarbon raw material at 400-700 degreeC in presence of the oxidative dehydrogenation catalyst of this invention (1). It is an oxidative dehydrogenation reaction for oxidative dehydrogenation of monoolefin, and the hydrocarbon raw material is a hydrocarbon raw material containing paraffins having 3 to 5 carbon atoms, a hydrocarbon raw material containing monoolefins having 3 to 5 carbon atoms, or the number of carbon atoms The present invention provides a oxidative dehydrogenation method characterized by being a hydrocarbon raw material containing 3 to 5 paraffins and 3 to 5 carbon monoolefins.
本発明によれば、ブタン等のｎ−パラフィン又はｉ−パラフィンを含む炭化水素原料の酸化脱水素反応により、ブテン等のｎ−モノオレフィン又はｉ−モノオレフィンや、１，３−ブタジエン等の共役ジエンを得る酸化脱水素反応、又はブテン等のｎ−モノオレフィン又はｉ−モノオレフィンを含む炭化水素原料の酸化脱水素反応により、１，３−ブタジエン等の共役ジエンを得る酸化脱水素反応において、優れた触媒活性を示す酸化脱水素触媒を提供することができる。 According to the present invention, by oxidative dehydrogenation of a hydrocarbon raw material containing n-paraffin or i-paraffin such as butane, an n-monoolefin or i-monoolefin such as butene, or a conjugate such as 1,3-butadiene. In an oxidative dehydrogenation reaction for obtaining a conjugated diene such as 1,3-butadiene by an oxidative dehydrogenation reaction for obtaining a diene or an oxidative dehydrogenation reaction of a hydrocarbon raw material containing an n-monoolefin or i-monoolefin such as butene. An oxidative dehydrogenation catalyst exhibiting excellent catalytic activity can be provided.
本発明の酸化脱水素触媒は、炭化水素原料中に含まれる炭素数３〜５のパラフィン又は炭素数３〜５のモノオレフィンの酸化脱水素を行うための酸化脱水素触媒であり、
該炭化水素原料が、炭素数３〜５のパラフィンを含む炭化水素原料、炭素数３〜５のモノオレフィンを含む炭化水素原料又は炭素数３〜５のパラフィンと炭素数３〜５のモノオレフィンとを含む炭化水素原料であり、
該酸化脱水素触媒が、バナジウム原子と、マグネシウム原子と、タングステン原子と、を含有し、且つ、バナジウム、マグネシウム及びタングステンの原子換算の合計モル数に対するタングステンの原子換算のモル数の割合（（Ｗ／（Ｖ＋Ｍｇ＋Ｗ））×１００）が０．３〜２．０モル％であること、
を特徴とする酸化脱水素触媒である。
The oxidative dehydrogenation catalyst of the present invention is an oxidative dehydrogenation catalyst for performing oxidative dehydrogenation of paraffins having 3 to 5 carbon atoms or monoolefins having 3 to 5 carbon atoms contained in a hydrocarbon raw material,
The hydrocarbon raw material is a hydrocarbon raw material containing a paraffin having 3 to 5 carbon atoms, a hydrocarbon raw material containing a monoolefin having 3 to 5 carbon atoms, or a paraffin having 3 to 5 carbon atoms and a monoolefin having 3 to 5 carbon atoms, A hydrocarbon feedstock containing
The oxidative dehydrogenation catalyst contains a vanadium atom, a magnesium atom, and a tungsten atom, and the ratio of the number of moles of tungsten in terms of atoms to the total number of moles of atoms in vanadium, magnesium, and tungsten ((W / (V + Mg + W)) × 100) is 0.3 to 2.0 mol%,
Is an oxidative dehydrogenation catalyst.
本発明の酸化脱水素触媒は、炭素数３〜５のパラフィン又は炭素数３〜５のモノオレフィンを酸化的に脱水素する酸化脱水素反応用の触媒である。炭化水素原料には、炭素数３〜５のパラフィンを含み炭素数３〜５のモノオレフィンを含まないもの、炭素数３〜５のモノオレフィンを含み炭素数３〜５のパラフィンを含まないもの、炭素数３〜５のパラフィンと炭素数３〜５のモノオレフィンの両方を含むものがある。炭化水素原料に含まれる炭素数３〜５のｎ−パラフィンとしては、プロパン、ｎ−ブタン、ｎ−ペンタンが挙げられ、炭素数３〜５のｉ−パラフィンとしては、ｉ−ブタン、ｉ−ペンタンが挙げられ、炭素数３〜５のｎ−モノオレフィンとしては、ｎ−ブテン、ｎ−ペンテンが挙げられ、炭素数３〜５のｉ−モノオレフィンとしては、ｉ−ペンテンが挙げられる。パラフィンとしてはｎ−ブタンが好ましく、モノオレフィンとしてはｎ−ブテンが好ましい。特に、本発明の酸化脱水素触媒は、ｎ−ブタンを酸化脱水素してｎ−ブテン及び１，３−ブタジエンを得る酸化脱水素反応において、有利に用いられる。 The oxidative dehydrogenation catalyst of the present invention is a catalyst for oxidative dehydrogenation that oxidatively dehydrogenates paraffins having 3 to 5 carbon atoms or monoolefins having 3 to 5 carbon atoms. The hydrocarbon raw material contains paraffins having 3 to 5 carbon atoms and does not contain monoolefins having 3 to 5 carbon atoms, those containing monoolefins having 3 to 5 carbon atoms and no paraffins having 3 to 5 carbon atoms, Some contain both paraffins having 3 to 5 carbon atoms and monoolefins having 3 to 5 carbon atoms. Examples of the n-paraffin having 3 to 5 carbon atoms contained in the hydrocarbon raw material include propane, n-butane and n-pentane. Examples of the i-paraffin having 3 to 5 carbon atoms include i-butane and i-pentane. Examples of the n-monoolefin having 3 to 5 carbon atoms include n-butene and n-pentene, and examples of the i-monoolefin having 3 to 5 carbon atoms include i-pentene. As paraffin, n-butane is preferable, and as monoolefin, n-butene is preferable. In particular, the oxidative dehydrogenation catalyst of the present invention is advantageously used in an oxidative dehydrogenation reaction in which n-butane is oxidatively dehydrogenated to obtain n-butene and 1,3-butadiene.
炭化水素原料は、炭素数３〜５のパラフィン及び炭素数３〜５のモノオレフィン以外の炭化水素を含んでいてもよい。炭化水素原料中の炭素数３〜５のパラフィン及び炭素数３〜５のモノオレフィンの含有量は、特に制限されないが、８５質量％以上、好ましくは９０質量％以上、特に好ましくは９５質量％以上である。なお、炭化水素原料中の炭素数３〜５のパラフィン及び炭素数３〜５のモノオレフィンの含有量とは、炭化水素原料が炭素数３〜５のパラフィンを含み炭素数３〜５のモノオレフィンを含まない場合は、炭素数３〜５のパラフィンの合計含有量を指し、炭化水素原料が炭素数３〜５のモノオレフィンを含み炭素数３〜５のパラフィンを含まない場合は、炭素数３〜５のモノオレフィンの合計含有量を指し、炭化水素原料が炭素数３〜５のパラフィン及び炭素数３〜５のモノオレフィンの両方を含む場合は、炭素数３〜５のパラフィン及び炭素数３〜５のモノオレフィンの合計含有量を指す。 The hydrocarbon raw material may contain hydrocarbons other than paraffins having 3 to 5 carbon atoms and monoolefins having 3 to 5 carbon atoms. The content of the paraffin having 3 to 5 carbon atoms and the monoolefin having 3 to 5 carbon atoms in the hydrocarbon raw material is not particularly limited, but is 85% by mass or more, preferably 90% by mass or more, particularly preferably 95% by mass or more. It is. The content of paraffin having 3 to 5 carbon atoms and monoolefin having 3 to 5 carbon atoms in the hydrocarbon raw material means that the hydrocarbon raw material contains paraffin having 3 to 5 carbon atoms and monoolefin having 3 to 5 carbon atoms. Is included, it indicates the total content of paraffins having 3 to 5 carbon atoms, and when the hydrocarbon raw material contains monoolefins having 3 to 5 carbon atoms and no paraffins having 3 to 5 carbon atoms, 3 carbon atoms are contained. Refers to the total content of ˜5 monoolefins, and when the hydrocarbon raw material contains both paraffins having 3 to 5 carbon atoms and monoolefins having 3 to 5 carbon atoms, paraffins having 3 to 5 carbon atoms and 3 carbon atoms Refers to the total content of ˜5 monoolefins.
本発明の酸化脱水素触媒を用いて、炭素数３〜５のｎ−パラフィン又は炭素数３〜５のｎ−モノオレフィンの酸化脱水素を行い、対応するｎ−モノオレフィン又は共役ジエンを生成させる場合、炭化水素原料中の炭素数３〜５のｎ−パラフィン及び炭素数３〜５のｎ−モノオレフィンの含有量は、３０質量％以上、好ましくは４０質量％以上、特に好ましくは５０質量％以上である。この場合、炭化水素原料中には、炭素数３〜５のｎ−パラフィン及び炭素数３〜５のｎ−モノオレフィン以外の炭化水素が含まれていてもよい。なお、炭化水素原料中の炭素数３〜５のｎ−パラフィン及び炭素数３〜５のｎ−モノオレフィンの含有量とは、炭化水素原料が炭素数３〜５のｎ−パラフィンを含み炭素数３〜５のｎ−モノオレフィンを含まない場合は、炭素数３〜５のｎ−パラフィンの合計含有量を指し、炭化水素原料が炭素数３〜５のｎ−モノオレフィンを含み炭素数３〜５のｎ−パラフィンを含まない場合は、炭素数３〜５のｎ−モノオレフィンの合計含有量を指し、炭化水素原料が炭素数３〜５のｎ−パラフィン及び炭素数３〜５のｎ−モノオレフィンの両方を含む場合は、炭素数３〜５のｎ−パラフィン及び炭素数３〜５のｎ−モノオレフィンの合計含有量を指す。 Using the oxidative dehydrogenation catalyst of the present invention, oxidative dehydrogenation of an n-paraffin having 3 to 5 carbon atoms or an n-monoolefin having 3 to 5 carbon atoms is performed to produce the corresponding n-monoolefin or conjugated diene. In this case, the content of the n-paraffin having 3 to 5 carbon atoms and the n-monoolefin having 3 to 5 carbon atoms in the hydrocarbon raw material is 30% by mass or more, preferably 40% by mass or more, particularly preferably 50% by mass. That's it. In this case, the hydrocarbon raw material may contain hydrocarbons other than n-paraffins having 3 to 5 carbon atoms and n-monoolefins having 3 to 5 carbon atoms. The content of the n-paraffin having 3 to 5 carbon atoms and the n-monoolefin having 3 to 5 carbon atoms in the hydrocarbon raw material means that the hydrocarbon raw material contains n-paraffin having 3 to 5 carbon atoms. When 3-5 n-monoolefins are not included, the total content of n-paraffins having 3 to 5 carbon atoms is indicated, and the hydrocarbon raw material contains 3 to 5 carbon atoms n-monoolefins and 3 to 3 carbon atoms. When it does not contain 5 n-paraffins, it refers to the total content of n-monoolefins having 3 to 5 carbon atoms, and hydrocarbon raw materials are n-paraffins having 3 to 5 carbon atoms and n-paraffins having 3 to 5 carbon atoms. When both monoolefins are included, the total content of n-paraffins having 3 to 5 carbon atoms and n-monoolefins having 3 to 5 carbon atoms is indicated.
本発明の酸化脱水素触媒は、パラフィン又はモノオレフィンを酸化脱水素して、共役ジエンを得る酸化脱水素反応用の触媒として、好適に用いられる。製造目的とする共役ジエンが１，３−ブタジエンの場合、１，３−ブタジエンの原料はｎ−ブタン又はｎ−ブテンであるので、この場合、炭化水素原料中のｎ−ブタン及びｎ−ブテンの含有量は、３０質量％以上、好ましくは４０質量％以上、特に好ましくは５０質量％以上である。なお、炭化水素原料中のｎ−ブタン及びｎ−ブテンの含有量とは、炭化水素原料がｎ−ブタンを含みｎ−ブテンを含まない場合は、ｎ−ブタンの含有量を指し、炭化水素原料がｎ−ブテンを含みｎ−ブタンを含まない場合は、ｎ−ブテンの含有量を指し、炭化水素原料がｎ−ブタン及びｎ−ブテンの両方を含む場合は、ｎ−ブタン及びｎ−ブテンの合計含有量を指す。また、製造目的とする共役ジエンがイソプレンの場合、イソプレンの原料はｉ−ペンタン又はｉ−ペンテンであるので、この場合、炭化水素原料中のｉ−ペンタン及びｉ−ペンテンの含有量は、３０質量％以上、好ましくは４０質量％以上、特に好ましくは５０質量％以上である。なお、炭化水素原料中のｉ−ペンタン及びｉ−ペンテンの含有量とは、炭化水素原料がｉ−ペンタンを含みｉ−ペンテンを含まない場合は、ｉ−ペンタンの含有量を指し、炭化水素原料がｉ−ペンテンを含みｉ−ペンタンを含まない場合は、ｉ−ペンテンの含有量を指し、炭化水素原料がｉ−ペンタン及びｉ−ペンテンの両方を含む場合は、ｉ−ペンタン及びｉ−ペンテンの合計含有量を指す。 The oxidative dehydrogenation catalyst of the present invention is suitably used as a catalyst for an oxidative dehydrogenation reaction in which paraffin or monoolefin is oxidatively dehydrogenated to obtain a conjugated diene. When the conjugated diene to be produced is 1,3-butadiene, the raw material for 1,3-butadiene is n-butane or n-butene. In this case, the n-butane and n-butene in the hydrocarbon raw material Content is 30 mass% or more, Preferably it is 40 mass% or more, Most preferably, it is 50 mass% or more. The contents of n-butane and n-butene in the hydrocarbon raw material refer to the content of n-butane when the hydrocarbon raw material contains n-butane and does not contain n-butene. Refers to the content of n-butene when it contains n-butene and does not contain n-butane, and when the hydrocarbon feed contains both n-butane and n-butene, Refers to the total content. When the conjugated diene to be produced is isoprene, the raw material for isoprene is i-pentane or i-pentene. In this case, the content of i-pentane and i-pentene in the hydrocarbon raw material is 30% by mass. % Or more, preferably 40% by mass or more, particularly preferably 50% by mass or more. The content of i-pentane and i-pentene in the hydrocarbon raw material refers to the content of i-pentane when the hydrocarbon raw material contains i-pentane and does not contain i-pentene. Refers to the content of i-pentene when i-pentene is included but does not include i-pentane, and when the hydrocarbon feedstock includes both i-pentane and i-pentene, Refers to the total content.
炭化水素原料としては、特に制限されないが、例えば、石油精製プロセスにおいて、常圧蒸留で得られるＣ３混合物、Ｃ４混合物、Ｃ５混合物、流動接触分解によって生産されたＣ３混合物、Ｃ４混合物、改質反応によって得られるＣ３混合物、Ｃ４混合物、Ｃ５混合物や、石油化学プロセスにおいてナフサ分解によって生産されたＣ４混合物、Ｃ５混合物から共役ジエンを抽出等により分離して残ったＣ４ラフィネート、Ｃ５ラフィネート等が挙げられる。また、本発明の酸化脱水素触媒を用いて炭化水素原料の酸化脱水素を行い得られる反応生成物から、目的とする成分を取り出した後の回収液も、炭化水素原料として挙げられる。また、炭化水素原料を、そのまま酸化脱水素反応に供しても、これらの炭化水素原料からプロパン、ｎ−ブタン、ｎ−ブテン、ｉ−ペンタン、ｉ−ペンテンを予め分離し、酸化脱水素反応に供してもよい。 Although it does not restrict | limit especially as a hydrocarbon raw material, For example, in a petroleum refining process, C3 mixture obtained by atmospheric distillation, C4 mixture, C5 mixture, C3 mixture produced by fluid catalytic cracking, C4 mixture, and reforming reaction Examples thereof include C3 mixture, C4 mixture, C5 mixture, C4 mixture produced by naphtha cracking in petrochemical process, C4 raffinate remaining after separation of conjugated diene from C5 mixture by extraction, C5 raffinate, and the like. Moreover, the recovered liquid after taking out the target component from the reaction product obtained by performing the oxidative dehydrogenation of the hydrocarbon raw material using the oxidative dehydrogenation catalyst of the present invention is also exemplified as the hydrocarbon raw material. Further, even if the hydrocarbon raw material is directly subjected to an oxidative dehydrogenation reaction, propane, n-butane, n-butene, i-pentane, and i-pentene are separated from these hydrocarbon raw materials in advance and subjected to an oxidative dehydrogenation reaction. May be provided.
本発明の酸化脱水素触媒は、バナジウム原子と、マグネシウム原子と、タングステン原子と、を含有する。本発明の酸化脱水素触媒は、バナジウムと、マグネシウムと、タングステンとを共存させることにより、ブテン等のｎ−オレフィン又はブタジエン等の共役ジエンの選択性が高くなる。 The oxidative dehydrogenation catalyst of the present invention contains vanadium atoms, magnesium atoms, and tungsten atoms. In the oxidative dehydrogenation catalyst of the present invention, the selectivity of n-olefin such as butene or conjugated diene such as butadiene is enhanced by the coexistence of vanadium, magnesium and tungsten.
本発明の酸化脱水素触媒中、バナジウム、マグネシウム及びタングステンの原子換算の合計モル数に対するタングステンの原子換算のモル数の割合（（Ｗ／（Ｖ＋Ｍｇ＋Ｗ））×１００）は、０．３〜２．０モル％、好ましくは０．５〜１．８モル％、より好ましくは０．６〜１．６モル％、さらに好ましくは０．８〜１．４モル％、特に好ましくは１．０〜１．２モル％である。本発明の酸化脱水素触媒中のバナジウム、マグネシウム及びタングステンの原子換算の合計モル数に対するタングステンの原子換算のモル数の割合が、上記範囲内にあることにより、モノオレフィン又は共役ジエンの選択性及び収率が高くなる。一方、本発明の酸化脱水素触媒中の、バナジウム、マグネシウム及びタングステンの原子換算の合計モル数に対するタングステンの原子換算のモル数の割合が、上記範囲未満だと、燃焼反応が抑制されず、ＣＯ又はＣＯ２の生成が多くなり、また、上記範囲を超えると、分解反応が進行し、分解生成物が多くなる。 In the oxidative dehydrogenation catalyst of the present invention, the ratio of the number of moles of tungsten converted to the total number of moles of vanadium, magnesium and tungsten ((W / (V + Mg + W)) × 100) is 0.3-2. 0 mol%, preferably 0.5-1.8 mol%, more preferably 0.6-1.6 mol%, still more preferably 0.8-1.4 mol%, particularly preferably 1.0-1 .2 mol%. When the ratio of the number of moles of tungsten converted to the total number of moles of vanadium, magnesium and tungsten in the oxidative dehydrogenation catalyst of the present invention is within the above range, the selectivity of monoolefin or conjugated diene and The yield is high. On the other hand, if the ratio of the number of moles of tungsten converted to the total number of moles of vanadium, magnesium and tungsten in the oxidative dehydrogenation catalyst of the present invention is less than the above range, the combustion reaction is not suppressed, and CO or generation of CO 2 is increased, also exceeds the above range, the decomposition reaction proceeds, become much degradation products.
本発明の酸化脱水素触媒中、マグネシウムの原子換算のモル数に対するタングステンの原子換算のモル数の割合（（Ｗ／Ｍｇ）×１００）は、好ましくは０．２〜８．０モル％、特に好ましくは０．３〜２．０モル％、より好ましくは１．０〜１．５モル％である。本発明の酸化脱水素触媒中のマグネシウムの原子換算のモル数に対するタングステンの原子換算のモル数の割合が、上記範囲内にあることにより、モノオレフィン又は共役ジエンの選択性及び収率が高くなる。 In the oxidative dehydrogenation catalyst of the present invention, the ratio of the number of moles of tungsten converted to the number of moles of magnesium converted to atoms ((W / Mg) × 100) is preferably 0.2 to 8.0 mol%, particularly Preferably it is 0.3-2.0 mol%, More preferably, it is 1.0-1.5 mol%. When the ratio of the number of moles of tungsten converted to atoms in the oxidative dehydrogenation catalyst of the present invention is within the above range, the selectivity and yield of monoolefin or conjugated diene are increased. .
本発明の酸化脱水素触媒中、バナジウムの原子換算のモル数に対するタングステンの原子換算のモル数の割合（（Ｗ／Ｖ）×１００）は、好ましくは１．０〜１２．０モル％、特に好ましくは２．０〜１０．０モル％、より好ましくは４．０〜８．０モル％である。本発明の酸化脱水素触媒中のバナジウムの原子換算のモル数に対するタングステンの原子換算のモル数の割合が、上記範囲内にあることにより、モノオレフィン又は共役ジエンの選択性及び収率が高くなる。 In the oxidative dehydrogenation catalyst of the present invention, the ratio of the number of moles of tungsten converted to the number of moles of vanadium converted to atoms ((W / V) × 100) is preferably 1.0 to 12.0 mol%, particularly Preferably it is 2.0-10.0 mol%, More preferably, it is 4.0-8.0 mol%. When the ratio of the number of moles of tungsten converted to the number of moles of vanadium in the oxidative dehydrogenation catalyst of the present invention is within the above range, the selectivity and yield of the monoolefin or conjugated diene increase. .
本発明の酸化脱水素触媒中、バナジウム、マグネシウム及びタングステンの原子換算の合計モル数に対するバナジウム及びマグネシウムの原子換算の合計モル数の割合（（（Ｖ＋Ｍｇ）／（Ｖ＋Ｍｇ＋Ｗ））×１００）は、好ましくは９８．２〜９９．７モル％、特に好ましくは９８．４〜９９．５モル％、より好ましくは９８．８〜９９．４モル％である。本発明の酸化脱水素触媒中のバナジウム、マグネシウム及びタングステンの原子換算の合計モル数に対するバナジウム及びマグネシウムの原子換算の合計モル数の割合が、上記範囲内にあることにより、モノオレフィン又は共役ジエンの選択性及び収率が高くなる。 In the oxidative dehydrogenation catalyst of the present invention, the ratio (((V + Mg) / (V + Mg + W)) × 100) of the total molar number of vanadium and magnesium to the total molar number of vanadium, magnesium and tungsten is preferably Is 98.2 to 99.7 mol%, particularly preferably 98.4 to 99.5 mol%, more preferably 98.8 to 99.4 mol%. When the ratio of the total number of moles of vanadium and magnesium in terms of atoms to the total number of moles of vanadium, magnesium and tungsten in the oxidative dehydrogenation catalyst of the present invention is within the above range, the monoolefin or conjugated diene Selectivity and yield are increased.
本発明の酸化脱水素触媒中、マグネシウムの原子換算のモル数に対するバナジウムの原子換算のモル数の割合（（Ｖ／Ｍｇ）×１００）は、好ましくは２．０〜３０．０モル％、特に好ましくは５．０〜２５．０モル％、より好ましくは１０．０〜２０．０モル％である。本発明の酸化脱水素触媒中のマグネシウムの原子換算のモル数に対するバナジウムの原子換算のモル数の割合が、上記範囲内にあることにより、モノオレフィン又は共役ジエンの選択性及び収率が高くなる。 In the oxidative dehydrogenation catalyst of the present invention, the ratio of the number of moles of vanadium converted to atoms ((V / Mg) × 100) relative to the number of moles of magnesium converted to atoms is preferably 2.0 to 30.0 mol%, particularly Preferably it is 5.0-25.0 mol%, More preferably, it is 10.0-20.0 mol%. When the ratio of the number of moles of vanadium in terms of atoms to the number of moles of atoms in magnesium in the oxidative dehydrogenation catalyst of the present invention is within the above range, the selectivity and yield of the monoolefin or conjugated diene are increased. .
本発明の酸化脱水素触媒では、バナジウム原子、マグネシウム原子及びタングステン原子は、単一金属の酸化物の状態で、あるいは、これらの２種の金属からなる複合酸化物の状態で、あるいは、単一金属の酸化物と複合酸化物の両方状態で、存在している。つまり、本発明の酸化脱水素触媒では、各金属原子がどのような状態又は構造で金属酸化物を形成しているかは、特に制限されず、例えば、（ｉ）バナジウムとマグネシウムとタングステンの複合酸化物であっても、（ｉｉ）マグネシウムの酸化物にバナジウムとマグネシウムとタングステンの複合酸化物が担持されたものであっても、（ｉｉｉ）バナジウムとマグネシウムの複合酸化物に、タングステンの酸化物が担持されたものであっても、（ｉｖ）マグネシウムの酸化物に、バナジウムとマグネシウムの複合酸化物とタングステンの酸化物が担持されたものであっても、（ｖ）（ｉ）〜（ｉｖ）の混合物であってもよい。 In the oxidative dehydrogenation catalyst of the present invention, the vanadium atom, the magnesium atom and the tungsten atom are in the state of a single metal oxide or in the state of a complex oxide composed of these two metals, or in a single state. It exists in both metal oxide and composite oxide states. That is, in the oxidative dehydrogenation catalyst of the present invention, the state or structure in which each metal atom forms the metal oxide is not particularly limited. For example, (i) a composite oxidation of vanadium, magnesium and tungsten Or (iii) a composite oxide of vanadium, magnesium and tungsten supported on an oxide of magnesium, or (iii) an oxide of tungsten on the composite oxide of vanadium and magnesium. Even if it is supported (iv) (v) (i) to (iv) (v) (i) to (iv) even if the oxide of magnesium is supported by a composite oxide of vanadium and magnesium and an oxide of tungsten. It may be a mixture of
バナジン酸マグネシウムは、複合酸化物であり、オルト体（Ｍｇ３Ｖ２Ｏ８）、ピロ体及びメタ体が存在する。本発明の酸化脱水素触媒は、マグネシウムの酸化物とバナジン酸マグネシウム複合酸化物とタングステンの酸化物とを含有することが好ましく、マグネシウムの酸化物とオルトバナジン酸マグネシウム複合酸化物とタングステンの酸化物とを含有することが特に好ましい。また、上記（ｉ）〜（ｖ）において、バナジウムとマグネシウムとの複合酸化物としては、オルトバナジン酸マグネシウム複合酸化物が好ましい。 Magnesium vanadate is a complex oxide, and there exist ortho-forms (Mg 3 V 2 O 8 ), pyro-forms, and meta-forms. The oxidative dehydrogenation catalyst of the present invention preferably contains an oxide of magnesium, a magnesium vanadate composite oxide, and an oxide of tungsten, and an oxide of magnesium, an ortho vanadate magnesium composite oxide, and an oxide of tungsten It is particularly preferable to contain In the above (i) to (v), the composite oxide of vanadium and magnesium is preferably a magnesium orthovanadate composite oxide.
本発明の酸化脱水素触媒は、主として、バナジウム原子と、マグネシウム原子と、タングステン原子と、酸素原子と、からなる化合物であるが、本発明の酸化脱水素触媒は、本発明の効果を損なわない範囲で、他の金属原子を含んでいてもよい。また、本発明の酸化脱水素触媒は、本発明の効果を損なわない範囲で、上記金属原子以外を不純物として含有することは許容される。 The oxidative dehydrogenation catalyst of the present invention is a compound mainly composed of vanadium atoms, magnesium atoms, tungsten atoms and oxygen atoms, but the oxidative dehydrogenation catalyst of the present invention does not impair the effects of the present invention. It may contain other metal atoms in the range. In addition, the oxidative dehydrogenation catalyst of the present invention is allowed to contain impurities other than the metal atoms as long as the effects of the present invention are not impaired.
本発明の酸化脱水素触媒は、粉状又は粒状の金属酸化物であるが、そのような粉状又は粒状の本発明の酸化脱水素触媒を、粉状又は粒状のまま用いてもよいし、あるいは、粉状又は粒状の本発明の酸化脱水素触媒を、圧縮成形等により成形して、成形体として用いてもよいし、あるいは、粉状又は粒状の本発明の酸化脱水素触媒を、バインダーを用いて成形して、成形体として用いてもよい。 The oxidative dehydrogenation catalyst of the present invention is a powdered or granular metal oxide, but such a powdery or granular oxidative dehydrogenation catalyst of the present invention may be used in a powdered or granular form, Alternatively, the powdered or granular oxidative dehydrogenation catalyst of the present invention may be molded by compression molding or the like and used as a molded body, or the powdered or granular oxidative dehydrogenation catalyst of the present invention may be used as a binder. May be used as a molded body.
本発明の酸化脱水素触媒が、バインダーを用いて成形された成形体として用いられる場合、成形体全体の質量に対するバナジウムのＶ２Ｏ５換算量、マグネシウムのＭｇＯ換算量及びタングステンのＷＯ３換算量の合計の割合（（（Ｖ２Ｏ５換算量＋ＭｇＯ換算量＋ＷＯ３換算量）／成形体全質量）×１００）は、好ましくは５０質量％以上、特に好ましくは７０質量％で以上ある。成形体全体の質量に対するバナジウムのＶ２Ｏ５換算量、マグネシウムのＭｇＯ換算量及びタングステンのＷＯ３換算量の合計の割合が上記範囲にあることにより、モノオレフィン又は共役ジエンの選択率及び収率が高くなる。なお、本発明において、バナジウムのＶ２Ｏ５換算量とは、成形体中に含有されているバナジウム原子が、全てＶ２Ｏ５として存在しているとして計算した場合のＶ２Ｏ５の質量を指し、また、マグネシウムのＭｇＯ換算量とは、成形体中に含有されているマグネシウム原子が、全てＭｇＯとして存在しているとして計算した場合のＭｇＯの質量を指し、また、タングステンのＷＯ３換算量とは、成形体中に含有されているタングステン原子が、全てＷＯ３として存在しているとして計算した場合のＷＯ３の質量を指す。 When the oxidative dehydrogenation catalyst of the present invention is used as a molded body molded using a binder, the amount of vanadium converted to V 2 O 5, the amount of magnesium converted to MgO and the amount of tungsten converted to WO 3 with respect to the mass of the entire molded body The total ratio (((V 2 O 5 converted amount + MgO converted amount + WO 3 converted amount) / total mass of molded article) × 100) is preferably 50% by mass or more, particularly preferably 70% by mass or more. The ratio of the total amount of vanadium in terms of V 2 O 5, the amount of magnesium in terms of MgO and the amount of tungsten in terms of WO 3 in terms of the total mass of the compact is within the above range, so that the selectivity and yield of monoolefin or conjugated diene Becomes higher. In the present invention, the terms of V 2 O 5 amount of vanadium, vanadium atom contained in the molded body, the mass of V 2 O 5 when calculated as being present as all V 2 O 5 the points, also with the terms of MgO amount of magnesium, a magnesium atom contained in the molded body, refers to the mass of MgO when calculated as being present as all MgO, also WO 3 conversion tungsten the amount and the tungsten atom contained in the molded body, refers to the mass of WO 3 when calculated as being present as all WO 3.
本発明の酸化脱水素触媒が、バインダーを用いて成形された成形体として用いられる場合、成形体中の全金属原子の原子換算の合計モル数に対するバナジウム、マグネシウム及びタングステンの原子換算の合計モル数の割合（（（Ｖ＋Ｍｇ＋Ｗ）／成形体中の全金属原子）×１００）は、好ましくは６０モル％以上、特に好ましくは８０モル％以上である。成形体中の全金属原子の原子換算の合計モル数に対するバナジウム、マグネシウム及びタングステンの原子換算の合計モル数の割合が上記範囲にあることにより、モノオレフィン又は共役ジエンの選択率及び収率が高くなる。 When the oxidative dehydrogenation catalyst of the present invention is used as a molded body molded using a binder, the total number of moles of vanadium, magnesium and tungsten in terms of atoms relative to the total number of moles of atoms in all metal atoms in the shaped body. The ratio (((V + Mg + W) / total metal atoms in the molded body) × 100) is preferably 60 mol% or more, particularly preferably 80 mol% or more. Since the ratio of the total number of moles of vanadium, magnesium and tungsten in terms of atoms to the total number of moles in terms of atoms of all metal atoms in the compact is in the above range, the selectivity and yield of monoolefin or conjugated diene are high. Become.
本発明の酸化脱水素触媒は、以下に述べる本発明の酸化脱水素触媒の製造方法により、好適に製造される。 The oxidative dehydrogenation catalyst of the present invention is preferably produced by the method for producing the oxidative dehydrogenation catalyst of the present invention described below.
本発明の酸化脱水素触媒の製造方法は、バナジウム源と、マグネシウム源と、タングステン源と、が水に溶解又は分散されている原料混合液を調製し、次いで、得られた原料混合液中の水を蒸発させて除去して、原料混合物粉体を得、次いで、得られた原料混合物粉体を焼成することを特徴とする酸化脱水素触媒の製造方法である。 The method for producing an oxidative dehydrogenation catalyst of the present invention comprises preparing a raw material mixed solution in which a vanadium source, a magnesium source, and a tungsten source are dissolved or dispersed in water, and then in the obtained raw material mixed solution. It is a method for producing an oxidative dehydrogenation catalyst, characterized by evaporating and removing water to obtain a raw material mixture powder and then firing the obtained raw material mixture powder.
本発明の酸化脱水素触媒の製造方法では、先ず、バナジウム源と、マグネシウム源と、タングステン源と、が水に溶解又は分散されている原料混合液を調製する。 In the method for producing an oxidative dehydrogenation catalyst of the present invention, first, a raw material mixed solution in which a vanadium source, a magnesium source, and a tungsten source are dissolved or dispersed in water is prepared.
バナジウム源、マグネシウム源、タングステン源とは、酸化脱水素触媒を構成する金属原子の供給源となる金属原子源であり、バナジウム、マグネシウム、タングステンを含有する化合物である。このような金属原子源としては、例えば、バナジウム、マグネシウム、タングステンの塩化物、硝酸塩、硫酸塩、酢酸塩、アンモニウム塩や、これらの金属原子のうちの２種以上からなる複合塩等が挙げられる。 The vanadium source, the magnesium source, and the tungsten source are metal atom sources that serve as a supply source of metal atoms that constitute the oxidative dehydrogenation catalyst, and are compounds containing vanadium, magnesium, and tungsten. Examples of such metal atom sources include vanadium, magnesium, tungsten chlorides, nitrates, sulfates, acetates, ammonium salts, and composite salts composed of two or more of these metal atoms. .
原料混合液を調製する方法としては、特に制限されず、各金属原子源を水に直接添加して撹拌混合してもよいし、あるいは、金属原子源を水に溶解又は分散させたものを水に添加して撹拌混合してもよい。原料混合液の調製の際には、必要に応じて、４０〜６０℃で加熱しながら撹拌混合を行う。 The method of preparing the raw material mixture is not particularly limited, and each metal atom source may be directly added to water and mixed with stirring, or a solution obtained by dissolving or dispersing a metal atom source in water. And may be mixed with stirring. In preparation of the raw material mixture, stirring and mixing are performed while heating at 40 to 60 ° C., if necessary.
原料混合液中の各金属原子の含有量は、製造目的とする酸化脱水素触媒を構成する各金属原子のモル比により、適宜選択される。 Content of each metal atom in a raw material liquid mixture is suitably selected by the molar ratio of each metal atom which comprises the oxidative dehydrogenation catalyst made into a manufacturing objective.
本発明の酸化脱水素触媒の製造方法では、次いで、得られた原料混合液中の水を蒸発させて水を除去して、原料混合物粉体を得る。原料混合液中の水を蒸発させる方法としては、特に制限されず、常圧下又は減圧下で、原料混合液を加熱する方法が挙げられる。原料混合液中の水の蒸発を常圧下で行う場合、加熱温度は、特に制限されないが、好ましくは５０〜１５０℃である。原料混合液中の水の蒸発を減圧下で行う場合、加熱温度は減圧度等に応じて、適宜選択される。また、水の蒸発操作を行った後、必要に応じて、乾燥を行うことができる。乾燥の際の乾燥温度は、特に制限されないが、好ましくは６０〜１５０℃であり、また、乾燥時間は、６〜４８時間程度であればよい。 In the method for producing an oxidative dehydrogenation catalyst of the present invention, the water in the obtained raw material mixture is then evaporated to remove the water to obtain a raw material mixture powder. The method for evaporating water in the raw material mixture is not particularly limited, and examples thereof include a method of heating the raw material mixture under normal pressure or reduced pressure. When evaporation of water in the raw material mixture is performed under normal pressure, the heating temperature is not particularly limited, but is preferably 50 to 150 ° C. When the water in the raw material mixture is evaporated under reduced pressure, the heating temperature is appropriately selected according to the degree of reduced pressure. Moreover, after performing the evaporation operation of water, it can dry as needed. Although the drying temperature in the case of drying is not restrict | limited in particular, Preferably it is 60-150 degreeC, and drying time should just be about 6 to 48 hours.
本発明の酸化脱水素触媒の製造方法では、次いで、得られた原料混合物粉体を焼成して、酸化脱水素触媒を得る。焼成温度は、特に制限されないが、好ましくは４００〜９００℃、特に好ましくは５００〜８００℃である。焼成時間は、特に制限されないが、好ましくは３〜３０時間である。原料混合物粉体の焼成では、一度焼成した物を、同じ温度又は異なる温度で焼成することにより、焼成を複数回行ってもよい。ただし、高温での焼成による触媒のシンタリングによる影響を考慮すれば、焼成の最高温度は、７５０℃以下が好ましい。 In the method for producing an oxidative dehydrogenation catalyst of the present invention, the obtained raw material mixture powder is then fired to obtain an oxidative dehydrogenation catalyst. The firing temperature is not particularly limited, but is preferably 400 to 900 ° C, particularly preferably 500 to 800 ° C. The firing time is not particularly limited, but is preferably 3 to 30 hours. In firing the raw material mixture powder, the fired product may be fired a plurality of times by firing the fired product at the same temperature or at different temperatures. However, in consideration of the influence of sintering of the catalyst due to calcination at high temperature, the maximum temperature of calcination is preferably 750 ° C. or less.
原料混合物粉体の焼成においては、焼成中に焼成対象を十分に磨砕して、焼成時の触媒成分の不均一化を抑制することが好ましい。磨砕には、乳鉢、ボールミル等が用いられ、手動式／自動式のいずれも使用可能である。 In firing the raw material mixture powder, it is preferable that the firing target is sufficiently ground during firing to prevent the catalyst components from becoming uneven during firing. For grinding, a mortar, a ball mill, or the like is used, and either a manual type or an automatic type can be used.
本発明の酸化脱水素方法は、本発明の酸化脱水素触媒の存在下、４００〜７００℃で、炭化水素原料中に含まれる炭素数３〜５のパラフィン又は炭素数３〜５のモノオレフィンの酸化脱水素を行う酸化脱水素反応であり、該炭化水素原料が、炭素数３〜５のパラフィンを含む炭化水素原料、炭素数３〜５のモノオレフィンを含む炭化水素原料又は炭素数３〜５のパラフィンと炭素数３〜５のモノオレフィンを含む炭化水素原料であることを特徴とする酸化脱水素方法である。つまり、本発明の酸化脱水素方法は、炭素数３〜５のパラフィン又は炭素数３〜５のモノオレフィンを含む炭化水素原料を原料にして、触媒として、本発明の酸化脱水素触媒を用いて、酸化脱水素反応を行うものである。 The oxidative dehydrogenation method of the present invention comprises a C3-5 paraffin or a C3-5 monoolefin contained in a hydrocarbon raw material at 400 to 700 ° C. in the presence of the oxidative dehydrogenation catalyst of the present invention. It is an oxidative dehydrogenation reaction in which oxidative dehydrogenation is performed, and the hydrocarbon raw material includes a hydrocarbon raw material containing paraffin having 3 to 5 carbon atoms, a hydrocarbon raw material containing monoolefin having 3 to 5 carbon atoms, or 3 to 5 carbon atoms. It is an oxidative dehydrogenation method characterized by being a hydrocarbon raw material containing paraffin and 3 to 5 carbon monoolefin. That is, the oxidative dehydrogenation method of the present invention uses a hydrocarbon raw material containing a paraffin having 3 to 5 carbon atoms or a monoolefin having 3 to 5 carbon atoms as a raw material, and uses the oxidative dehydrogenation catalyst of the present invention as a catalyst. The oxidative dehydrogenation reaction is performed.
本発明の酸化脱水素方法に係る炭化水素原料は、本発明の酸化脱水素触媒に係る炭化水素原料と同様である。 The hydrocarbon raw material according to the oxidative dehydrogenation method of the present invention is the same as the hydrocarbon raw material according to the oxidative dehydrogenation catalyst of the present invention.
本発明の酸化脱水素方法における酸化脱水素反応の反応温度は、４００〜７００℃、好ましくは５００〜７００℃、特に好ましくは６００〜６７５℃である。酸化脱水素反応の反応温度が、上記範囲にあることにより、ＣＯ又はＣＯ２の生成及びコークの生成が少なく、且つ、モノオレフィン又は共役ジエンの選択率及び収率が高くなる。一方、酸化脱水素反応の反応温度が、上記範囲未満だと、転化率又はモノオレフィン若しくは共役ジエンの収率が低くなり、また、上記範囲を超えると、分解反応が進み過ぎて、ＣＯ又はＣＯ２の生成やコークの生成が多くなる。 The reaction temperature of the oxidative dehydrogenation reaction in the oxidative dehydrogenation method of the present invention is 400 to 700 ° C, preferably 500 to 700 ° C, particularly preferably 600 to 675 ° C. When the reaction temperature of the oxidative dehydrogenation is in the above range, the production of CO or CO 2 and the production of coke are small, and the selectivity and yield of monoolefin or conjugated diene are increased. On the other hand, when the reaction temperature of the oxidative dehydrogenation reaction is less than the above range, the conversion rate or the yield of monoolefin or conjugated diene becomes low. When the reaction temperature exceeds the above range, the decomposition reaction proceeds excessively, and CO or CO 2 generation and coke generation increase.
本発明の酸化脱水素方法の形態例としては、例えば、触媒が充填されている固定床流通式反応装置を用いて、その反応装置に、加熱下、原料ガスを供給する方法が挙げられる。原料ガスは、例えば、パラフィン、あるいは、オレフィン、あるいは、パラフィン又はオレフィンを含む炭化水素と、酸素源と、希釈剤との混合ガスとして供給される。酸素源としては、純酸素又は空気が用いられる。希釈ガスとしては、窒素、ヘリウム又はスチームが用いられるが、原料ガスと酸素源が反応することで生じる発熱を抑制するために、スチームを用いることが好ましい。原料ガスの供給量は、特に制限されず、触媒活性、触媒充填量、接触時間、圧力損失などにより、適宜調節される。原料ガスとして、パラフィン、あるいは、オレフィン、あるいは、パラフィン又はオレフィンを含む炭化水素と酸素の混合ガスを用いる場合、酸素過剰だと、パラフィン又はオレフィンの完全酸化によるＣＯ２の生成が多くなるため、酸素に対するパラフィン又はオレフィンの分圧比（パラフィン又はオレフィン／酸素）が０．５以上であることが好ましい。反応圧力は、特に制限されず、常圧、加圧のいずれでもよい。 As an example of the oxidative dehydrogenation method of the present invention, for example, a method of supplying a raw material gas under heating to a reaction apparatus using a fixed bed flow type reaction apparatus filled with a catalyst can be mentioned. The source gas is supplied, for example, as a mixed gas of paraffin, olefin, or a hydrocarbon containing paraffin or olefin, an oxygen source, and a diluent. Pure oxygen or air is used as the oxygen source. Nitrogen, helium, or steam is used as the dilution gas, but steam is preferably used in order to suppress the heat generated by the reaction between the source gas and the oxygen source. The supply amount of the raw material gas is not particularly limited, and is appropriately adjusted depending on the catalyst activity, the catalyst filling amount, the contact time, the pressure loss, and the like. When paraffin, olefin, or a mixed gas of hydrocarbon and oxygen containing paraffin or olefin is used as a raw material gas, oxygen excess increases the amount of CO 2 produced by complete oxidation of paraffin or olefin. The partial pressure ratio of paraffin or olefin to paraffin (paraffin or olefin / oxygen) is preferably 0.5 or more. The reaction pressure is not particularly limited, and may be normal pressure or increased pressure.
また、本発明の酸化脱水素触媒は、本発明の酸化脱水素触媒の製造方法により得られた酸化脱水素触媒である。すなわち、本発明の酸化脱水素触媒は、バナジウム源と、マグネシウム源と、タングステン源と、が水に溶解又は分散されている原料混合液を調製し、次いで、得られた原料混合液中の水を蒸発させて除去して、原料混合物粉体を得、次いで、得られた原料混合物粉体を焼成することにより得られたものであることを特徴とする酸化脱水素触媒である。 The oxidative dehydrogenation catalyst of the present invention is an oxidative dehydrogenation catalyst obtained by the method for producing an oxidative dehydrogenation catalyst of the present invention. That is, the oxidative dehydrogenation catalyst of the present invention prepares a raw material mixed solution in which a vanadium source, a magnesium source, and a tungsten source are dissolved or dispersed in water, and then the water in the obtained raw material mixed solution. Is an oxidative dehydrogenation catalyst obtained by evaporating and removing a raw material mixture powder and then firing the obtained raw material mixture powder.
以下に実施例を挙げて、本発明を具体的に説明するが、本発明はこれに制限されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
（実施例１）
＜触媒Ａ＞Ｗ−Ｍｇ−Ｖ−Ｏ触媒
蒸留水２００ｍｌに、バナジン酸アンモニウム３．３４０ｇを溶解させ、更に、水酸化マグネシウム８．７６７ｇと、蒸留水１０ｍｌにメタタングステン酸アンモニウム六水和物０．５１０ｇを溶解させた水溶液とを加えて撹拌して、原料混合液を得た。
次いで、得られた原料混合液を、撹拌しながら５０℃で加熱して蒸発乾固させ、次いで、蒸発乾固物を１１０℃で１２時間乾燥して、原料混合物粉体を得た。
次いで、得られた原料混合物粉体を、空気中７００℃で６時間焼成し、触媒Ａを得た。
Example 1
<Catalyst A> W-Mg-V-O catalyst 3.340 g of ammonium vanadate was dissolved in 200 ml of distilled water, and further, 8.767 g of magnesium hydroxide and ammonium metatungstate hexahydrate 0 in 10 ml of distilled water. An aqueous solution in which .510 g was dissolved was added and stirred to obtain a raw material mixture.
Next, the obtained raw material mixture was heated to 50 ° C. with stirring to evaporate to dryness, and then the evaporated dry matter was dried at 110 ° C. for 12 hours to obtain a raw material mixture powder.
Next, the obtained raw material mixture powder was calcined in the air at 700 ° C. for 6 hours to obtain Catalyst A.
（比較例１）
＜触媒Ｂ＞Ｍｇ−Ｖ−Ｏ触媒
蒸留水２００ｍｌに、バナジン酸アンモニウム３．３４０ｇを溶解させ、更に、水酸化マグネシウム８．７６７ｇを加えて撹拌して、原料混合液を得た。
次いで、得られた原料混合液を、撹拌しながら５０℃で加熱して蒸発乾固させ、次いで、蒸発乾固物を１１０℃で１２時間乾燥して、原料混合物粉体を得た。
次いで、得られた原料混合物粉体を、空気中７００℃で６時間焼成し、触媒Ｂを得た。
(Comparative Example 1)
<Catalyst B> Mg-V-O catalyst 3.340 g of ammonium vanadate was dissolved in 200 ml of distilled water, and further 8.767 g of magnesium hydroxide was added and stirred to obtain a raw material mixture.
Next, the obtained raw material mixture was heated to 50 ° C. with stirring to evaporate to dryness, and then the evaporated dry matter was dried at 110 ° C. for 12 hours to obtain a raw material mixture powder.
Next, the obtained raw material mixture powder was calcined in the air at 700 ° C. for 6 hours to obtain Catalyst B.
（触媒性能の評価）
常圧固定床流通式反応装置を用い、下記のようにして酸化的脱水素反応を行い、触媒の性能評価を行った。
上記のようにして得られた触媒０．２５ｇを反応装置に充填した。次いで反応装置に空気を３１．５ｍｌ／ｍｉｎで流通させながら、反応管内部の温度を４５０℃まで昇温させた。４５０℃に到達した後、空気３１．５ｍｌ／ｍｉｎを加え、３０分間流通させて、触媒の前処理（酸化処理）を行った。前処理終了後、スチームを２５５．４ｍｌ／ｍｉｎ、ｎ−ブタンを６．３ｍｌ／ｍｉｎで加えて流通させることにより、ｎ−ブタン：空気：スチーム（モル比）＝１:５:４０．５、全流量が２９３．２ｍｌ／ｍｉｎになるように、原料ガスを流通させて、ｎ−ブタンの酸化的脱水素反応を６０分間行った。反応結果を表２に示す。
(Evaluation of catalyst performance)
Using an atmospheric pressure fixed bed flow type reactor, the oxidative dehydrogenation reaction was performed as follows, and the performance of the catalyst was evaluated.
The reaction apparatus was charged with 0.25 g of the catalyst obtained as described above. Next, the temperature inside the reaction tube was raised to 450 ° C. while allowing air to flow through the reaction apparatus at 31.5 ml / min. After reaching 450 ° C., 31.5 ml / min of air was added and the mixture was circulated for 30 minutes to pretreat the catalyst (oxidation treatment). After completion of the pretreatment, n-butane: air: steam (molar ratio) = 1: 5: 40.5 is obtained by adding and circulating steam at 255.4 ml / min and n-butane at 6.3 ml / min. The raw material gas was circulated so that the total flow rate was 293.2 ml / min, and oxidative dehydrogenation of n-butane was performed for 60 minutes. The reaction results are shown in Table 2.
ｎ−ブタン転化率、ＣＯ、ＣＯ２、炭素数１〜３の炭化水素、ブテン及びブタジエン選択率、ブテン及びブタジエン収率を、以下のようにして計算した。 n- butane conversion, CO, CO 2, hydrocarbons having 1 to 3 carbon atoms, butene and butadiene selectivity, butene and butadiene yield, was calculated as follows.
転化率（％）＝（（原料ガス中のｎ−ブタン炭素モル数−生成ガス中のｎ−ブタンの炭素モル数）／原料ガス中のｎ−ブタン炭素モル数）×１００ Conversion rate (%) = ((number of moles of n-butane carbon in raw material gas−number of carbon moles of n-butane in product gas) / number of moles of n-butane carbon in raw material gas) × 100
生成物選択率（％）＝（生成ガス中の各生成物の炭素モル数／（原料ガス中のｎ−ブタン炭素モル数−生成ガス中のｎ−ブタン炭素モル数））×１００
＊式中、各生成物の炭素モル数とは、選択率の対象となるＣＯ、ＣＯ２、ブテン、ブタジエンのそれぞれの炭素モル数である。
Product selectivity (%) = (number of moles of carbon in each product gas / (number of moles of n-butane carbon in raw material gas−number of moles of n-butane carbon in product gas)) × 100
* In the formula, the number of carbon moles of each product is the number of carbon moles of CO, CO 2 , butene, and butadiene, which are the targets of selectivity.
ブテン収率（％）＝（生成ガス中のブテン炭素モル数／生成ガス中の全炭素モル数）×１００ Butene yield (%) = (number of moles of butene carbon in the product gas / total number of moles of carbon in the product gas) × 100
ブタジエン収率（％）＝（生成ガス中のブタジエンの炭素モル数／生成ガス中の全炭素モル数）×１００ Butadiene yield (%) = (number of moles of butadiene in product gas / total number of moles of carbon in product gas) × 100
原料ガス及び生成ガスの分析を、ＴＣＤガスクロマトグラフ（ジーエルサイエンス ＧＣ−３５３Ｂ）及びＦＩＤガスクロマトグラフ（ジーエルサイエンス ＧＣ−３５３Ｂ）を用いて行った。Ｏ２及びＮ２の分析には、モレキュラーシーブ１３Ｘ、ＣＯ及びＣＯ２の分析には、Ｕｎｉｂｅａｄｓ Ｃ充填カラム（ジーエルサイエンス社製）を用い、炭化水素化合物の分析には、ＨＰ−ＡＬ／Ｓキャピラリーカラム（Ａｇｉｌｅｎｔ ｔｅｃｈｎｏｌｏｇｉｅｓ社製）を用いた。 The analysis of the source gas and the product gas was performed using a TCD gas chromatograph (GL Science GC-353B) and an FID gas chromatograph (GL Science GC-353B). Molecular sieve 13X for analysis of O 2 and N 2 , Unibeads C packed column (manufactured by GL Sciences) is used for analysis of CO and CO 2 , and HP-AL / S capillary column for analysis of hydrocarbon compounds (Manufactured by Agilent Technologies) was used.
なお、以下の表中、Ｃ１〜Ｃ３は炭素数が１から３の炭化水素の合計を指し、ｎ−Ｃ４Ｈ８はｎ−ブテンを指し、１，３−Ｃ４Ｈ８は１，３−ブタジエンを指す。 In the following table, C1 to C3 indicate the total of hydrocarbons having 1 to 3 carbon atoms, n-C 4 H 8 indicates n-butene, 1,3-C 4 H 8 indicates 1,3 -Refers to butadiene.
Claims (4)
該炭化水素原料が、炭素数３〜５のパラフィンを含む炭化水素原料、炭素数３〜５のモノオレフィンを含む炭化水素原料又は炭素数３〜５のパラフィンと炭素数３〜５のモノオレフィンとを含む炭化水素原料であり、
該酸化脱水素触媒が、バナジウム原子と、マグネシウム原子と、タングステン原子と、を含有し、且つ、バナジウム、マグネシウム及びタングステンの原子換算の合計モル数に対するタングステンの原子換算のモル数の割合（（Ｗ／（Ｖ＋Ｍｇ＋Ｗ））×１００）が０．３〜２．０モル％であること、
を特徴とする酸化脱水素触媒。 An oxidative dehydrogenation catalyst for performing oxidative dehydrogenation of paraffins having 3 to 5 carbon atoms or monoolefins having 3 to 5 carbon atoms contained in a hydrocarbon raw material;
The hydrocarbon raw material is a hydrocarbon raw material containing a paraffin having 3 to 5 carbon atoms, a hydrocarbon raw material containing a monoolefin having 3 to 5 carbon atoms, or a paraffin having 3 to 5 carbon atoms and a monoolefin having 3 to 5 carbon atoms, A hydrocarbon feedstock containing
The oxidative dehydrogenation catalyst contains a vanadium atom, a magnesium atom, and a tungsten atom, and the ratio of the number of moles of tungsten in terms of atoms to the total number of moles of atoms in vanadium, magnesium, and tungsten ((W / (V + Mg + W)) × 100) is 0.3 to 2.0 mol%,
An oxidative dehydrogenation catalyst.
該酸化脱水素触媒が、バナジウム原子と、マグネシウム原子と、タングステン原子と、を含有し、且つ、バナジウム、マグネシウム及びタングステンの原子換算の合計モル数に対するタングステンの原子換算のモル数の割合（（Ｗ／（Ｖ＋Ｍｇ＋Ｗ））×１００）が０．３〜２．０モル％であること、
を特徴とする酸化脱水素触媒。 An oxidative dehydrogenation catalyst for producing n-butene and 1,3-butadiene by oxidative dehydrogenation reaction from n-butane contained in a hydrocarbon raw material,
The oxidative dehydrogenation catalyst contains a vanadium atom, a magnesium atom, and a tungsten atom, and the ratio of the number of moles of tungsten in terms of atoms to the total number of moles of atoms in vanadium, magnesium, and tungsten ((W / (V + Mg + W)) × 100) is 0.3 to 2.0 mol%,
An oxidative dehydrogenation catalyst.
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