JPH09221446A - Production of fluorenone - Google Patents
Production of fluorenoneInfo
- Publication number
- JPH09221446A JPH09221446A JP8328701A JP32870196A JPH09221446A JP H09221446 A JPH09221446 A JP H09221446A JP 8328701 A JP8328701 A JP 8328701A JP 32870196 A JP32870196 A JP 32870196A JP H09221446 A JPH09221446 A JP H09221446A
- Authority
- JP
- Japan
- Prior art keywords
- fluorene
- catalyst
- fluorenone
- molecular oxygen
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000007789 gas Substances 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 239000002994 raw material Substances 0.000 abstract description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052936 alkali metal sulfate Inorganic materials 0.000 abstract description 4
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 10
- 239000012808 vapor phase Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 2
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 description 1
- ZVEJRZRAUYJYCO-UHFFFAOYSA-N 9-methyl-9h-fluorene Chemical compound C1=CC=C2C(C)C3=CC=CC=C3C2=C1 ZVEJRZRAUYJYCO-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DKHHWICVJRMJBO-UHFFFAOYSA-F S(=O)(=O)([O-])[O-].[Cs+].[Fe+2].[V+5].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[Cs+].[Fe+2].[V+5].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] DKHHWICVJRMJBO-UHFFFAOYSA-F 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RMJMDPATFSUVKD-UHFFFAOYSA-N [V].[Fe].[Cs] Chemical compound [V].[Fe].[Cs] RMJMDPATFSUVKD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、フルオレノンの製
造方法に関するものである。より詳しくは、本発明は、
フルオレンを接触気相酸化して高選択率及び高転化率で
フルオレノンを製造する方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing fluorenone. More specifically, the present invention
The present invention relates to a method for producing fluorenone with high selectivity and high conversion by subjecting fluorene to catalytic vapor phase oxidation.
【０００２】[0002]
【従来の技術】フルオレノンは、農薬、医薬や機能性高
分子などの原料として工業的に有用な物質である。フル
オレノンの製造方法としては、フルオレンを気相または
液相で酸化して製造する方法が知られている。これらの
方法のうち、フルオレンを気相で分子状酸素により気相
接触酸化してフルオレノンを製造する気相酸化法は、液
相法に比べ高生産性であり、廃液がでない等の利点を有
するものの、高転化率で反応を行うと選択性が低下する
欠点があり、高生産性を維持しつつフルオレンを有効利
用することが困難であった。また、用いるフルオレン原
料によってフルオレノンの選択性が低下したり、また触
媒活性が変化するなどの現象があり安定して高収率でフ
ルオレノンを製造することが困難であった。Fluorenone is an industrially useful substance as a raw material for agricultural chemicals, pharmaceuticals, functional polymers and the like. As a method of producing fluorenone, a method of producing fluorene by oxidizing fluorene in a gas phase or a liquid phase is known. Among these methods, the vapor-phase oxidation method of producing fluorenone by vapor-phase catalytic oxidation of fluorene with molecular oxygen in the vapor phase has high productivity as compared with the liquid-phase method, and has advantages such as no waste liquid. However, when the reaction is carried out at a high conversion rate, there is a drawback that the selectivity is lowered, and it is difficult to effectively use fluorene while maintaining high productivity. Further, it is difficult to stably produce fluorenone in a high yield due to phenomena such as a decrease in fluorenone selectivity and a change in catalyst activity depending on the fluorene raw material used.
【０００３】上述したように、フルオレノンの製造方法
としては液相法及び気相法が知られており、液相法とし
ては、アルカリ水溶液と疎水性有機溶媒および四級アン
モニウム塩等の相間移動触媒を用いた分子状酸素による
液相酸化法について多数の報告がある（特開平７−８２
２０６号公報、特開平７−８２２０７号公報等）。ま
た、気相法としては、フルオレンを３００〜７００℃で
五酸化バナジウムと接触させる方法（米国特許第１，３
７４，６９５号）、バナジン酸鉄および硫酸カリウムよ
りなる触媒を用いる方法（Ｚｈ．Ｐｙｉｒｌ Ｋｈｉｍ
３５、６９３−６９６（１９６２））、五酸化バナジ
ウムおよび錫酸化物よりなる触媒を用いる方法（工化
誌、５６，（６），４１３−４１６（１９５３））、バ
ナジン酸、モリブデン酸またはタングステン酸などの金
属塩及びアルカリ金属硫酸塩などからなる触媒を用いて
通常よりも多量の水蒸気を反応系に加えて気相酸化する
方法（米国特許第１，８９２，７６８号）、五酸化バナ
ジウム、シリカおよび硫酸カリウムよりなる触媒を用い
る方法（米国特許２，９５６，０６５号）、バナジウム
−チタニア−アルカリ金属よりなる触媒を用いる方法
（特開昭６０−２３３０２８号公報）が示されている。
また、バナジウム−鉄−セシウムよりなる触媒を用いる
方法（Ｓｔｕｄ．Ｓｕｒｆ．Ｓｃｉ．Ｃａｔａｌ（１９
９３）、７５（Ｎｅｗ Ｆｒｏｎｔｉｅｒｓ ｉｎ Ｃ
ａｔａｌｙｓｉｓ，Ｐｔ．Ａ），７０７−１７）もまた
開示されている。As mentioned above, the liquid phase method and the gas phase method are known as the method for producing fluorenone. As the liquid phase method, an alkaline aqueous solution, a hydrophobic organic solvent, and a phase transfer catalyst such as a quaternary ammonium salt are used. There have been many reports on a liquid-phase oxidation method using molecular oxygen using TiO2 (JP-A-7-82).
206, JP-A-7-82207, etc.). Further, as a vapor phase method, a method of contacting fluorene with vanadium pentoxide at 300 to 700 ° C. (US Pat.
74,695), a method using a catalyst composed of iron vanadate and potassium sulfate (Zh. Pyrl Khim).
35 , 693-696 (1962)), a method using a catalyst composed of vanadium pentoxide and tin oxide (Kikado, 56, (6), 413-416 (1953)), vanadic acid, molybdic acid or tungstic acid. A method in which a larger amount of water vapor than usual is added to the reaction system and vapor phase oxidation is carried out using a catalyst composed of a metal salt such as an alkali metal sulfate, etc. (US Pat. No. 1,892,768), vanadium pentoxide, silica And a method of using a catalyst composed of potassium sulfate (US Pat. No. 2,956,065) and a method of using a catalyst composed of vanadium-titania-alkali metal (JP-A-60-2333028).
In addition, a method using a catalyst composed of vanadium-iron-cesium (Stud. Surf. Sci. Catal (19
93), 75 (New Frontiers in C)
analysis, Pt. A), 707-17) are also disclosed.
【０００４】しかしながら、上記したような従来公知の
方法では、高転化率で反応を行うとフルオレノンの選択
性が低下し、高収率でかつ安定してフルオレノンを得る
ことは困難であったことから、フルオレノンの生産性を
高めることはできなかった。However, according to the above-mentioned conventionally known methods, when the reaction is carried out at a high conversion rate, the selectivity of fluorenone is lowered, and it is difficult to stably obtain fluorenone in a high yield. , Could not increase the productivity of fluorenone.
【０００５】[0005]
【発明が解決しようとする課題】したがって、本発明の
目的は、フルオレノンの改良された製造方法を提供する
ことにある。Accordingly, it is an object of the present invention to provide an improved process for producing fluorenone.
【０００６】本発明の他の目的は、気相酸化における問
題点を解決し、高選択率を維持しつつ、高転化率でフル
オレノンを製造することを可能にする方法を提供するこ
とにある。Another object of the present invention is to provide a method which solves the problems in gas phase oxidation and makes it possible to produce fluorenone at a high conversion rate while maintaining a high selectivity.
【０００７】[0007]
【課題を解決するための手段】本発明者らの研究によ
り、フルオレンを分子状酸素含有ガスにより接触気相酸
化する際に、フルオレン原料と分子状酸素含有ガスとか
らなる供給原料ガス中のフルオレン濃度を従来方法より
も高い範囲に調整することにより高転化率かつ高選択率
でフルオレノンが得られることを知った。このことは、
通常、接触気相酸化反応において原料ガス濃度を高めた
場合、反応熱によって反応速度が加速され熱点部の温度
が高くなり、その結果、燃焼ガスの生成が増加するため
選択率が低下するのがほとんどであったため、上記した
ような本発明者らの知見のように高い原料ガス濃度条件
下で１００％近い転化率を維持しつつかつ選択率が向上
することは驚くべき事実であった。この知見に基づいて
本発明を完成するに至った。Means for Solving the Problems According to the research conducted by the present inventors, when fluorene is catalytically vapor-phase oxidized with a molecular oxygen-containing gas, fluorene in a feed gas composed of a fluorene raw material and a molecular oxygen-containing gas is used. It was found that fluorenone can be obtained with high conversion and high selectivity by adjusting the concentration to a range higher than that of the conventional method. This means
Generally, when the concentration of the raw material gas is increased in the catalytic gas phase oxidation reaction, the reaction rate is accelerated by the reaction heat to raise the temperature of the hot spot, and as a result, the production rate of the combustion gas is increased and the selectivity is lowered. Therefore, it was a surprising fact that the selectivity is improved while maintaining a conversion rate close to 100% under a high source gas concentration condition as the findings of the present inventors as described above. Based on this finding, the present invention has been completed.
【０００８】すなわち、上記諸目的は、下記により達成
される。フルオレンを分子状酸素含有ガスにより接触気
相酸化してフルオレノンを製造する際に、原料フルオレ
ンと分子状酸素含有ガスとからなる供給原料ガス中のフ
ルオレン／分子状酸素（モル比）を１〜０．１３に調整
することよりなるフルオレノンの製造方法。That is, the above objects are achieved by the following. When fluorenone is produced by catalytic vapor-phase oxidation of fluorene with a gas containing molecular oxygen, the fluorene / molecular oxygen (molar ratio) in the feed gas composed of the raw fluorene and the gas containing molecular oxygen is set to 1 to 0. A method for producing fluorenone, which comprises adjusting the concentration to 0.13.
【０００９】[0009]
【発明の実施の形態】以下、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
【００１０】本発明で用いるフルオレン原料としては、
コールタールより得られるフルオレン含有油から得られ
るフルオレン（タール系のフルオレン）、脱アルキル化
ベンゼン製造プロセスで副生する残油から得られるフル
オレン（石油プロセス系のフルオレン）など各種フルオ
レンを用いることができる。また、本発明において用い
られるフルオレン原料は、フルオレン１００％である必
要はなく、その出発原料、精製法などによって含まれる
各種不純物、例えば、メチルビフェニルなどのビフェニ
ル化合物、メチルナフタレンなどのナフタレン化合物、
９−メチルフルオレンなどのフルオレン派生物、ジベン
ゾフランなどを含んでいてもよい。As the fluorene raw material used in the present invention,
Various fluorenes such as fluorene obtained from fluorene-containing oil obtained from coal tar (tar-based fluorene) and fluorene obtained from residual oil by-produced in the dealkylated benzene production process (fluorene from petroleum process) can be used. . The fluorene raw material used in the present invention does not have to be 100% fluorene, and various impurities contained in the starting raw material, the purification method and the like, for example, biphenyl compounds such as methylbiphenyl, naphthalene compounds such as methylnaphthalene,
Fluorene derivatives such as 9-methylfluorene, dibenzofuran and the like may be included.
【００１１】また、フルオレン原料中のフルオレン濃度
は、６０重量％以下であっても、高収率でフルオレノン
を製造することができるが、その後の精製などを考慮す
ると、フルオレン濃度を７０重量％以上、好ましくは８
０重量％以上に調整したフルオレン原料を用いるのがよ
い。Further, even if the fluorene concentration in the fluorene raw material is 60% by weight or less, fluorenone can be produced in a high yield, but in consideration of the subsequent purification, the fluorene concentration is 70% by weight or more. , Preferably 8
It is preferable to use a fluorene raw material adjusted to 0% by weight or more.
【００１２】本発明の接触気相反応に使用する触媒につ
いては特に制限はなく、フルオレンからフルオレノンヘ
の気相酸化に一般に用いられている触媒を使用すること
ができる。具体的には、前記のような五酸化バナジウム
からなる触媒、バナジン酸鉄及び硫酸カリウムからなる
触媒、五酸化バナジウム及び錫酸化物からなる触媒、バ
ナジン酸、モリブデン酸またはタングステン酸などの金
属塩またはアルカリ金属硫酸塩などからなる触媒、五酸
化バナジウム−シリカ−硫酸カリウムからなる触媒、バ
ナジウム−チタニア−アルカリ金属よりなる触媒、およ
びバナジウム−鉄−硫酸セシウムなどからなる触媒など
を挙げることができる。これらのうち、バナジウム、酸
化チタンおよびアルカリ金属硫酸塩からなる触媒が好適
に用いられる。なお、バナジウム−チタニア−アルカリ
金属よりなる触媒を用いる際に、触媒のアルカリ金属元
素／バナジウム（原子比）は、０．８〜８、より好まし
くは１〜５、特に１〜３であるのが好ましい。特に、上
記のような触媒活性成分を炭化珪素、アルミナ、シリ
カ、シリカ−アルミナ、軽石などの不活性担体上に担持
した担持型触媒が好適に用いられる。なお、該担持型触
媒は、球状、円柱状、サドル状、円筒状等の粒状であ
り、通常、その粒径は３〜１５ｍｍ、好ましくは３〜１
０ｍｍである。The catalyst used in the catalytic gas phase reaction of the present invention is not particularly limited, and a catalyst generally used for gas phase oxidation of fluorene to fluorenone can be used. Specifically, a catalyst composed of vanadium pentoxide as described above, a catalyst composed of iron vanadate and potassium sulfate, a catalyst composed of vanadium pentoxide and tin oxide, vanadic acid, a metal salt such as molybdic acid or tungstic acid, or Examples thereof include a catalyst containing an alkali metal sulfate, a catalyst containing vanadium pentoxide-silica-potassium sulfate, a catalyst containing vanadium-titania-alkali metal, and a catalyst containing vanadium-iron-cesium sulfate. Of these, a catalyst composed of vanadium, titanium oxide and an alkali metal sulfate is preferably used. When a catalyst composed of vanadium-titania-alkali metal is used, the alkali metal element / vanadium (atomic ratio) of the catalyst is 0.8 to 8, more preferably 1 to 5, and especially 1 to 3. preferable. In particular, a supported catalyst in which the above-mentioned catalytically active component is supported on an inert carrier such as silicon carbide, alumina, silica, silica-alumina or pumice is preferably used. The supported catalyst has a granular shape such as a spherical shape, a cylindrical shape, a saddle shape, and a cylindrical shape, and the particle size thereof is usually 3 to 15 mm, preferably 3 to 1
It is 0 mm.
【００１３】本発明の方法によれば、フルオレンと分子
状酸素含有ガスとからなる供給原料ガスを上記のような
触媒と接触させて酸化反応を行う際に、供給原料ガス中
のフルオレン／分子状酸素（モル比）が１〜０．１３、
好ましくは０．９〜０．３、最も好ましくは０．８〜
０．６となるように調整することである。供給原料ガス
中のフルオレン／分子状酸素（モル比）が１を超える場
合は、酸素が不足し転化率が急激に低下するので好まし
くない。なお、分子状酸素含有ガスに空気を用いた場
合、上記条件は、供給原料ガス１Ｎｍ3 中のフルオレン
含有量に換算して、それぞれ、２００〜１２８０ｇ／Ｎ
ｍ3 、４５０〜１１７０ｇ／Ｎｍ3 および９００ｇ／Ｎ
ｍ3 〜１０６０ｇ／Ｎｍ3 である。According to the method of the present invention, when the feedstock gas consisting of fluorene and the molecular oxygen-containing gas is brought into contact with the above catalyst to carry out the oxidation reaction, fluorene / molecular weight in the feedstock gas Oxygen (molar ratio) is 1 to 0.13,
Preferably 0.9-0.3, most preferably 0.8-
The adjustment is to be 0.6. When the fluorene / molecular oxygen (molar ratio) in the feed gas is more than 1, oxygen is insufficient and the conversion rate is drastically reduced, which is not preferable. When air is used as the molecular oxygen-containing gas, the above conditions are converted into the fluorene content in the feed gas 1Nm 3 of 200 to 1280 g / N, respectively.
m 3, 450~1170g / Nm 3 and 900 g / N
m 3 is a ~1060g / Nm 3.
【００１４】本発明において、フルオレン／分子状酸素
は、「純フルオレン（モル）／（原料ガス中の分子状酸
素（モル）−不純物が消費する分子状酸素（モル））」
と定義される。In the present invention, fluorene / molecular oxygen means "pure fluorene (mol) / (molecular oxygen (mol) in raw material gas-molecular oxygen (mol) consumed by impurities)".
Is defined as
【００１５】分子状酸素含有ガスとしては、通常、空気
が用いられるが、そのほかに酸素富化空気、窒素や二酸
化炭素等の不活性ガスと酸素の混合ガスなども使用する
ことができる。なお、供給原料ガスは水蒸気で希釈して
供給してもよい。As the molecular oxygen-containing gas, air is usually used, but oxygen-enriched air, a mixed gas of oxygen with an inert gas such as nitrogen or carbon dioxide, or the like can also be used. The source gas may be diluted with water vapor before being supplied.
【００１６】本発明の方法において、分子状酸素含有ガ
スとして純酸素を用いたとしても、フルオレン／分子状
酸素（モル比）が１〜０．１３という条件から、供給原
料ガス中のフルオレン濃度が３７１０ｇ／Ｎｍ3 を超え
ることはない。また、分子状酸素含有ガスとしては、経
済的な面から通常空気を用いるのが好ましいと考えられ
るが、この場合は、供給原料ガス中のフルオレン濃度は
１２８Ｏｇ／Ｎｍ3 を超えることはない。In the method of the present invention, even if pure oxygen is used as the molecular oxygen-containing gas, the concentration of fluorene in the feed gas is high because of the condition of fluorene / molecular oxygen (molar ratio) of 1 to 0.13. It does not exceed 3710 g / Nm 3 . As the molecular oxygen-containing gas, it is considered that it is usually preferable to use air from the economical point of view, but in this case, the concentration of fluorene in the feed material gas does not exceed 128 Og / Nm 3 .
【００１７】本発明における接触気相酸化反応を実施す
る際の温度、空間速度などの反応条件については特に制
限はなく、使用する触媒の種類などに応じて適宜決定す
ることができる。一般的には、反応温度は、２５０〜４
８０℃、好ましくは３００〜４５０℃の範囲から、空間
速度は、１００〜１０，０００／ｈｒ、好ましくは２０
０〜５，０００／ｈｒの範囲から選ばれる。Reaction conditions such as temperature and space velocity for carrying out the catalytic gas phase oxidation reaction in the present invention are not particularly limited and can be appropriately determined according to the type of catalyst used. Generally, the reaction temperature is 250-4.
From the range of 80 ° C, preferably 300 to 450 ° C, the space velocity is 100 to 10,000 / hr, preferably 20.
It is selected from the range of 0 to 5,000 / hr.
【００１８】[0018]
【実施例】以下、実施例を挙げて本発明を更に具体的に
説明する。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.
【００１９】調製例１ ８０℃の純水１８０ｍｌにバナジン酸アンモニウム１
３．４ｇ、シュウ酸２６．８ｇ、硫酸カリウム２．４ｇ
および硫酸セシウム２５．１ｇを加えて撹拌し均一な溶
液とした。この溶液を室温まで冷却した後、表面積２０
ｍ2 ／ｇのアナターゼ型酸化チタン１２０ｇおよび炭化
ケイ素ウィスカー４．８ｇを加えて十分撹拌し均一なス
ラリーとし、さらにこのスラリーに純水４００ｍｌを加
えて触媒調製スラリーとした。Preparation Example 1 Ammonium vanadate 1 was added to 180 ml of pure water at 80 ° C.
3.4 g, oxalic acid 26.8 g, potassium sulfate 2.4 g
And 25.1 g of cesium sulfate were added and stirred to form a uniform solution. After cooling the solution to room temperature, a surface area of 20
120 g of anatase type titanium oxide of m 2 / g and 4.8 g of silicon carbide whiskers were added and sufficiently stirred to make a uniform slurry, and 400 ml of pure water was added to this slurry to make a catalyst preparation slurry.
【００２０】ステンレス製回転炉に平均直径４ｍｍの球
状の炭化ケイ素担体２００ｇを投入し、炉を回転させ、
炭化ケイ素担体温度を１８０〜２２０℃に保持しつつ、
上記触媒調製スラリー２０ｇを噴霧し把持させた後、空
気流通下５５０℃で５時間焼成した酸化触媒を調製し
た。各添加成分の原子比は下記のとおりである。200 g of a spherical silicon carbide carrier having an average diameter of 4 mm was put into a stainless rotary furnace, and the furnace was rotated,
While maintaining the silicon carbide carrier temperature at 180 to 220 ° C,
After 20 g of the catalyst preparation slurry was sprayed and held, an oxidation catalyst was prepared by firing at 550 ° C. for 5 hours in an air stream. The atomic ratio of each additive component is as follows.
【００２１】Ｖ：Ｃｓ：Ｋ：Ｓ：ＴｉＯ2＝７．６４：
９．２６：ｌ．８４：５．５５：ｌ００ 比較例ｌ 上記酸化触媒を、図１に示すように、内径２０ｍｍのス
テンレス製反応管１のガス出口側に１８０ｍｍの層長で
充填し、この反応管１を４３０℃の溶融塩バス２中に保
持した。図ｌに示す装置を用い、フィーダー３から１４
０℃に保温したパイプを経て供給された石油プロセス系
のフルオレン原料（フルオレン濃度９８重量％）を反応
管の入口部に送り予熱された空気と混合して触媒層４に
導入した。フルオレンの供給速度９．５９ｍｇ／分（純
フルオレン換算）および空気送風量５００ｍｌ／分（０
℃、１気圧換算）で反応を行った。この際の供給原料ガ
ス中のフルオレン濃度は１９．ｌｇ／Ｎｍ3 −供給原料
ガスであった。V: Cs: K: S: TiO 2 = 7.64:
9.26: l. 84: 5.55: 100 Comparative Example 1 As shown in FIG. 1, the above-mentioned oxidation catalyst was filled in a gas outlet side of a stainless steel reaction tube 1 having an inner diameter of 20 mm with a layer length of 180 mm, and the reaction tube 1 was heated to 430 ° C. It was kept in the molten salt bath 2. Using the device shown in FIG.
A petroleum process type fluorene raw material (fluorene concentration 98% by weight) supplied through a pipe kept at 0 ° C. was sent to the inlet of the reaction tube and mixed with preheated air to be introduced into the catalyst layer 4. Fluorene supply rate of 9.59 mg / min (converted to pure fluorene) and air flow rate of 500 ml / min (0
The reaction was carried out at (° C, converted to 1 atm). The fluorene concentration in the feed gas at this time was 19. It was lg / Nm 3 − feedstock gas.
【００２２】反応生成ガスは内径３５ｍｍのガラス製空
冷捕集管（図示せず）および、直列に３つのアセトンを
満たした洗気瓶（図示せず）に通じ捕集を行い、アセト
ン溶液として回収し、ガスクロマトグラフ（島津ＧＣ−
１４Ｂ、カラムＯＶ−１／０．２５ｍｍＩＤ／５０ｍ）
によって分析した。フルオレン転化率９９．２モル％、
フルオレノン選択率８７．４モル％であり、フルオレノ
ン収率は８６．８モル％であった。The reaction product gas is collected as an acetone solution by passing through a glass air-cooled collection tube (not shown) having an inner diameter of 35 mm and an air washing bottle (not shown) filled with three acetones in series. Gas chromatograph (Shimadzu GC-
14B, column OV-1 / 0.25mm ID / 50m)
Was analyzed by Fluorene conversion 99.2 mol%,
The fluorenone selectivity was 87.4 mol% and the fluorenone yield was 86.8 mol%.
【００２３】実施例ｌ〜４ 比較例ｌにおいて、フルオレンの供給速度を変更して供
給原料ガスのフルオレン濃度を２５３ｇ／Ｎｍ3 （実施
例１）、４８２ｇ／Ｎｍ3 （実施例２）、９０１ｇ／Ｎ
ｍ3 （実施例３）および１０３１ｇ／Ｎｍ3 （実施例
４）とした以外は比較例１と同様に酸化反応を行い、そ
の結果を表１に示した。Examples 1 to 4 In Comparative Example 1, the fluorene concentration was changed to 253 g / Nm 3 (Example 1), 482 g / Nm 3 (Example 2), 901 g / N
An oxidation reaction was performed in the same manner as in Comparative Example 1 except that m 3 (Example 3) and 1031 g / Nm 3 (Example 4) were used, and the results are shown in Table 1.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【発明の効果】本発明のフルオレノンの製造方法は、フ
ルオレンを分子状酸素含有ガスにより接触気相酸化して
フルオレノンを製造する際に、原料フルオレンと分子状
酸素含有ガスとからなる供給原料ガス中のフルオレン／
分子状酸素（モル比）を１〜０．１３に調整することよ
りなることを特徴とするものである。本発明の方法によ
れば、フルオレンの接触気相酸化反応により、フルオレ
ノンを高転化率かつ高選択率で製造することができる。
特に、ｌ００％近くの高いフルオレン転化率を維持しつ
つ、高い選択率を達成することができる。Industrial Applicability The method for producing fluorenone of the present invention is a method of producing a fluorenone by catalytic vapor-phase oxidation of fluorene with a gas containing molecular oxygen, in a feed gas comprising a raw material fluorene and a gas containing molecular oxygen. Fluorene /
It is characterized in that the molecular oxygen (molar ratio) is adjusted to 1 to 0.13. According to the method of the present invention, fluorenone can be produced with a high conversion and a high selectivity by the catalytic gas phase oxidation reaction of fluorene.
In particular, it is possible to achieve a high selectivity while maintaining a high fluorene conversion rate near 100%.
【図１】 実施例および比較例で用いた反応装置の概略
図である。FIG. 1 is a schematic diagram of a reaction apparatus used in Examples and Comparative Examples.
Claims (3)
接触気相酸化してフルオレノンを製造する際に、原料フ
ルオレンと分子状酸素含有ガスとからなる供給原料ガス
中のフルオレン／分子状酸素（モル比）を１〜０．１３
に調整することよりなるフルオレノンの製造方法。1. When fluorene is produced by catalytic gas phase oxidation of fluorene with a molecular oxygen-containing gas, fluorene / molecular oxygen (molar ratio in a feed gas consisting of the raw fluorene and the molecular oxygen-containing gas). ) 1 to 0.13
A method for producing fluorenone, which comprises adjusting to.
項１に記載の方法。2. The method according to claim 1, wherein the molecular oxygen-containing gas is air.
ルカリ金属を含有し、アルカリ金属のバナジウムに対す
る原子比がアルカリ金属／バナジウム０．８〜８である
触媒を使用する、請求項１または２に記載の方法。3. The method according to claim 1, wherein a catalyst containing at least vanadium, titania and an alkali metal and having an alkali metal to vanadium atomic ratio of alkali metal / vanadium of 0.8 to 8 is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32870196A JP3187331B2 (en) | 1995-12-11 | 1996-12-09 | Method for producing fluorenone |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32137095 | 1995-12-11 | ||
| JP7-321370 | 1995-12-11 | ||
| JP32870196A JP3187331B2 (en) | 1995-12-11 | 1996-12-09 | Method for producing fluorenone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09221446A true JPH09221446A (en) | 1997-08-26 |
| JP3187331B2 JP3187331B2 (en) | 2001-07-11 |
Family
ID=26570453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32870196A Expired - Fee Related JP3187331B2 (en) | 1995-12-11 | 1996-12-09 | Method for producing fluorenone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3187331B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199627A (en) * | 2005-01-21 | 2006-08-03 | Air Water Chemical Inc | Process for producing 9-fluorenone-2-carboxylic acid |
-
1996
- 1996-12-09 JP JP32870196A patent/JP3187331B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199627A (en) * | 2005-01-21 | 2006-08-03 | Air Water Chemical Inc | Process for producing 9-fluorenone-2-carboxylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3187331B2 (en) | 2001-07-11 |
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