JP2002105078A - Method for producing pyromellitic anhydride - Google Patents
Method for producing pyromellitic anhydrideInfo
- Publication number
- JP2002105078A JP2002105078A JP2000297040A JP2000297040A JP2002105078A JP 2002105078 A JP2002105078 A JP 2002105078A JP 2000297040 A JP2000297040 A JP 2000297040A JP 2000297040 A JP2000297040 A JP 2000297040A JP 2002105078 A JP2002105078 A JP 2002105078A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- pyromellitic anhydride
- surface area
- reaction
- producing pyromellitic
- 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.)
- Pending
Links
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims 1
- 229910006404 SnO 2 Inorganic materials 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000012808 vapor phase Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000002994 raw material Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- LROJZZICACKNJL-UHFFFAOYSA-N Duryl aldehyde Chemical compound CC1=CC(C)=C(C=O)C=C1C LROJZZICACKNJL-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 organic acid salts Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance 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
- 239000002699 waste material Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- FEWANSQOXSIFOK-UHFFFAOYSA-N 1,2,3,4-tetraethylbenzene Chemical compound CCC1=CC=C(CC)C(CC)=C1CC FEWANSQOXSIFOK-UHFFFAOYSA-N 0.000 description 1
- HQWYPEYABTZLAY-UHFFFAOYSA-N 1-ethyl-2,4,5-tri(propan-2-yl)benzene Chemical compound CCC1=CC(C(C)C)=C(C(C)C)C=C1C(C)C HQWYPEYABTZLAY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003570 air Substances 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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229940095064 tartrate Drugs 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
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】 本発明は、無水ピロメリット酸
製造用触媒および無水ピロメリット酸の製造方法に関す
るものである。より詳しくは、２，４，５−トリアルキ
ルベンズアルデヒドの接触気相酸化により無水ピロメリ
ット酸を製造する方法において、好適な触媒系及び、該
触媒系を用いた無水ピロメリット酸の製造方法に関する
ものである。無水ピロメリット酸はポリイミド樹脂原
料、可塑剤、ポリエステル樹脂改質剤等として広範囲に
使用されており工業原料としての重要性も近年ますます
高まってきている。TECHNICAL FIELD The present invention relates to a catalyst for producing pyromellitic anhydride and a method for producing pyromellitic anhydride. More specifically, a method for producing pyromellitic anhydride by catalytic gas phase oxidation of 2,4,5-trialkylbenzaldehyde, which relates to a suitable catalyst system and a method for producing pyromellitic anhydride using the catalyst system It is. Pyromellitic anhydride is widely used as a raw material for a polyimide resin, a plasticizer, a modifier for a polyester resin and the like, and its importance as an industrial raw material has been increasing more and more in recent years.
【０００２】[0002]
【従来の技術】 無水ピロメリット酸の製造方法には大
きく分けて液相酸化法と気相酸化法とがある。2. Description of the Related Art Methods for producing pyromellitic anhydride are roughly classified into a liquid phase oxidation method and a gas phase oxidation method.
【０００３】液相酸化法としては、１，２，４，５−テ
トラメチルベンゼン（以下、デュレンと記すことがあ
る）の硝酸酸化法、２，４，５−トリメチルベンズアル
デヒドの液相空気酸化法が知られているが、いずれも直
接無水ピロメリット酸を得ることはできず、生成したピ
ロメリット酸を無水化する必要がある。この無水化工程
は多大なエネルギーを消費する方法であり、装置腐食も
大きく経済性の面で課題がある。また、これら液相酸化
法は多量の廃液が発生するプロセスであり、環境面でも
課題のある製造方法と言える。As the liquid phase oxidation method, there are a nitric acid oxidation method of 1,2,4,5-tetramethylbenzene (hereinafter sometimes referred to as durene) and a liquid phase air oxidation method of 2,4,5-trimethylbenzaldehyde. However, none of them can directly obtain pyromellitic anhydride, and it is necessary to dehydrate generated pyromellitic acid. This dehydration step is a method that consumes a large amount of energy, causes a large amount of equipment corrosion, and has a problem in terms of economic efficiency. In addition, these liquid phase oxidation methods are processes in which a large amount of waste liquid is generated, and can be said to be production methods that have environmental issues.
【０００４】一方、気相酸化法は直接無水ピロメリット
酸を得ることが可能であり、コストのかかる無水化工程
を必要とせず、廃液もほとんど発生しない優れた方法で
ある。しかしながら、液相酸化法に比べ反応選択率が低
い問題があり、従来から触媒の改良を中心とした数多く
の報告がなされている。[0004] On the other hand, the vapor phase oxidation method is an excellent method that can directly obtain pyromellitic anhydride, does not require a costly dehydration step, and hardly generates waste liquid. However, there is a problem that the reaction selectivity is lower than that of the liquid phase oxidation method, and many reports have been made mainly on improvement of the catalyst.
【０００５】接触気相酸化による無水ピロメリット酸の
製造法はデュレンを原料に用いる方法が最も一般的であ
るが、その他、ペンタアルキルベンゼン、ヘキサアルキ
ルベンゼン（特開昭５５−１２２７８７号公報）、ペン
タアルキルフェノール、テトラアルキルフェノール（特
開昭５５−１５４９６６号公報）、テトラエチルベンゼ
ン（特開平３−２８４６４６号、特開平３−１０９３８
７号、特開平３−２８４６４５号の各公報）、アントラ
セン（特開昭５６−８３８８号公報）、１−エチル−
２,４,５−トリイソプロピルベンゼン（特開平８−１１
９９６９号公報）、２，４，５−トリアルキルベンズア
ルデヒド（特開平７−２８６４号公報）などを原料とし
て用いる例が報告されている。The most common method for producing pyromellitic anhydride by catalytic gas phase oxidation is a method using durene as a raw material. In addition, pentaalkylbenzene, hexaalkylbenzene (JP-A-55-122787), pentaalkylphenol , Tetraalkylphenol (JP-A-55-154966), tetraethylbenzene (JP-A-3-284646, JP-A-3-10938).
7, each of JP-A-3-284645), anthracene (JP-A-56-8388), 1-ethyl-
2,4,5-triisopropylbenzene (JP-A-8-11
No. 9969) and 2,4,5-trialkylbenzaldehyde (Japanese Patent Application Laid-Open No. 7-2864) are reported as raw materials.
【０００６】[0006]
【発明が解決すべき課題】 本発明の目的は、安価に高
純度の無水ピロメリット酸を製造する方法を提供するこ
とにあり、２，４，５−トリアルキルベンズアルデヒド
の接触気相酸化により無水ピロメリット酸を製造するに
当たり、好適な触媒系を用いることにより高収率で無水
ピロメリット酸を得ることである。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing high-purity pyromellitic anhydride at a low cost, and to provide an anhydride by catalytic gas phase oxidation of 2,4,5-trialkylbenzaldehyde. In producing pyromellitic acid, it is to obtain pyromellitic anhydride in high yield by using a suitable catalyst system.
【０００７】２，４，５−トリアルキルベンズアルデヒ
ドの接触気相酸化による無水ピロメリット酸の製造方法
については、特開平７−２８６４号公報において既に開
示されているが、反応収率は高々９０質量％（６１モル
％）と低く満足できるものではなかった。A method for producing pyromellitic anhydride by catalytic gas phase oxidation of 2,4,5-trialkylbenzaldehyde has already been disclosed in JP-A-7-2864, but the reaction yield is at most 90 mass%. % (61 mol%), which was not satisfactory.
【０００８】[0008]
【課題を解決するための手段】 上記目的は、活性成分
の比表面積が５０ｍ 2／ｇ以下の触媒の存在下に、２，
４，５−トリアルキルベンズアルデヒドを分子状酸素含
有ガスにより接触気相酸化する事により達成される。Means for Solving the Problems The object is to provide an active ingredient
Has a specific surface area of 50m Two/ G in the presence of up to
4,5-trialkylbenzaldehyde containing molecular oxygen
This is achieved by catalytic gas phase oxidation with a gas.
【０００９】本発明において用いる触媒は、触媒活性成
分の比表面積が５０ｍ2／ｇ以下の触媒であり、好まし
くは比表面積が１〜４０ｍ2／ｇの範囲のもの、さらに
好ましくは比表面積が５〜３０ｍ2／ｇの範囲の触媒で
ある。触媒の比表面積が５０ｍ2／ｇを越える場合は燃
焼活性が増大し無水ピロメリット酸収率が低下するため
好ましくない。触媒の比表面積は活性物質の分散に用い
る無機酸化物粉体の比表面積によって容易に制御可能で
あるが、無機酸化物粉体は必須ではなく、触媒構成元素
や触媒焼成温度により無機酸化物粉体を含まない場合も
好適な範囲に制御することが可能である。The catalyst used in the present invention has a specific surface area of the catalytically active component of 50 m 2 / g or less, preferably has a specific surface area of 1 to 40 m 2 / g, and more preferably has a specific surface area of 5 to 40 m 2 / g. it is a catalyst in the range of 30 m 2 / g. If the specific surface area of the catalyst exceeds 50 m 2 / g, the combustion activity increases and the yield of pyromellitic anhydride decreases, which is not preferable. Although the specific surface area of the catalyst can be easily controlled by the specific surface area of the inorganic oxide powder used for dispersing the active substance, the inorganic oxide powder is not essential, and the inorganic oxide powder depends on the catalyst constituent elements and the catalyst firing temperature. Even when the body is not included, it can be controlled to a suitable range.
【００１０】本発明の触媒としては、上記比表面積を有
するものであれば良いが、バナジウムを含有するものが
好ましく、さらに、モリブデン、タングステン、リン、
ホウ素、銀、アンチモン、硫黄、ニオブ、アルカリ土類
金属、希土類元素から選ばれた少なくとも１種の元素
（以下、Ａ群元素と記すことがある）を適量添加するこ
とにより収率が向上する。しかしながら、これらＡ群元
素は過剰に用いた場合は触媒活性の低下や燃焼の増大に
つながり、使用量としてはバナジウムに対するＡ群元素
の原子比として３を超えない範囲で用いることが好まし
く、より好ましくは２を越えない範囲である。The catalyst of the present invention may be any catalyst having the above specific surface area, but preferably contains vanadium, and further comprises molybdenum, tungsten, phosphorus,
The yield is improved by adding an appropriate amount of at least one element selected from boron, silver, antimony, sulfur, niobium, an alkaline earth metal, and a rare earth element (hereinafter, sometimes referred to as a group A element). However, when these Group A elements are used in excess, they lead to a decrease in catalytic activity and an increase in combustion, and it is preferable to use them in an amount not exceeding 3 as the atomic ratio of Group A elements to vanadium, more preferably. Is a range not exceeding 2.
【００１１】また、本発明の触媒には、さらに酸化チタ
ン、酸化ジルコニウム、酸化錫から選ばれる少なくとも
１種の無機酸化物を加えることもでき、これらを適量加
えることにより無水ピロメリット酸収率の向上や触媒の
耐熱性の向上が可能となる。これら無機酸化物の好まし
い使用量としては、例えば、前記触媒の構成元素である
バナジウム、Ａ群元素のモル数の総和に対して、加える
無機酸化物粉体の表面積が０を越えかつ１×１０5ｍ2／
モル以下の範囲であり、さらに好ましくは１×１０2〜
１×１０5ｍ2／モル、最も好ましくは１×１０2〜４×
１０4ｍ2／モルとなるように添加するのが良い。The catalyst of the present invention may further contain at least one inorganic oxide selected from titanium oxide, zirconium oxide, and tin oxide. It is possible to improve the heat resistance of the catalyst. The preferred usage of these inorganic oxides is, for example, that the surface area of the inorganic oxide powder to be added exceeds 0 and 1 × 10 5 m 2 /
Mol or less, and more preferably 1 × 10 2 to
1 × 10 5 m 2 / mole, most preferably 1 × 10 2 to 4 ×
It is preferable to add so as to be 10 4 m 2 / mol.
【００１２】ここで、加える無機酸化物粉体の表面積
（ｍ2／モル）とは、使用した酸化物粉体の重量（ｇ）
に該酸化物の比表面積（ｍ2／ｇ）を乗じたものを、触
媒に使用したバナジウム、Ａ群元素の金属状態でのモル
数の総和（モル）で除したものである。また、比表面積
は、ＢＥＴ（Ｂｒｕｎａｅｒ−Ｅｍｍｅｔｔ−Ｔｅｌｌ
ｅｒ）法により測定したものである。Here, the surface area (m 2 / mol) of the inorganic oxide powder to be added means the weight (g) of the oxide powder used.
Is multiplied by the specific surface area (m 2 / g) of the oxide, and is divided by the total (mol) of the number of moles of vanadium and group A elements used in the catalyst in the metal state. The specific surface area is determined by BET (Brunaer-Emmett-Tell).
er) method.
【００１３】これらの触媒の調製方法および原料につい
ては、特に制限されるものではなく従来から一般に用い
られている手法により調製することができる。例えば原
料としては、使用する元素の硝酸塩、硫酸塩、塩酸塩、
リン酸塩、炭酸塩等の無機塩や、蓚酸塩、クエン酸塩、
酒石酸塩等の有機酸塩類の他、錯塩、あるいは酸化物な
どが使用可能である。これらは触媒調製時の焼成等によ
り、対応する酸化物あるいは複合酸化物として触媒中に
存在するものと考えられる。また、酸化チタン、酸化ジ
ルコニウム、酸化錫は、市販の酸化物、あるいは対応す
る塩より調製した酸化物などの粉体が使用でき、ＢＥＴ
比表面積としては５〜１００ｍ2／ｇのものが好適に使
用可能である。The preparation method and raw materials of these catalysts are not particularly limited, and they can be prepared by a conventionally used method. For example, raw materials include nitrates, sulfates, hydrochlorides,
Inorganic salts such as phosphates and carbonates, oxalates, citrates,
In addition to organic acid salts such as tartrate, complex salts or oxides can be used. It is considered that these are present in the catalyst as a corresponding oxide or composite oxide due to calcination during preparation of the catalyst. For titanium oxide, zirconium oxide and tin oxide, commercially available oxides or powders of oxides prepared from corresponding salts can be used.
Those having a specific surface area of 5 to 100 m 2 / g can be suitably used.
【００１４】触媒を調製する際には、これら各元素の原
料化合物をなるべく均一に混合することが好ましく、水
等の分散溶媒中で攪拌混合して、液状、スラリー状、粘
土状とする。またこのときウィスカー等の繊維状物を同
時に混合することによって触媒の強度を高めることも有
効な方法である。In preparing the catalyst, it is preferable to mix the raw material compounds of these elements as uniformly as possible. The mixture is stirred and mixed in a dispersion solvent such as water to form a liquid, slurry, or clay. At this time, it is also effective to increase the strength of the catalyst by simultaneously mixing fibrous materials such as whiskers.
【００１５】触媒に形状を付与する方法としては、従来
公知の方法が使用可能であり、スラリー液を加熱した耐
熱性担体上に噴霧する焼き付け法や、転動造粒法、含浸
法等の担持法や、押し出し成形等の方法を用いることが
できる。As a method for imparting a shape to the catalyst, a conventionally known method can be used, and a baking method in which a slurry liquid is sprayed on a heated heat-resistant carrier, a rolling granulation method, an impregnation method, or the like. And extrusion and other methods.
【００１６】担持法を採用する場合、使用する担体の素
材は特に規定しないが、炭化ケイ素、シリカ、アルミ
ナ、ステアタイト、陶器、磁器等触媒担体として通常使
用される高温酸化雰囲気で安定な不活性担体であればい
ずれでも用いることができるが、好ましくは炭化ケイ素
製のものであり、より好ましくは純度９５%以上の高純
度炭化ケイ素製のものが好適に使用できる。担体の形状
は特に限定されず球、リング、半リング、円柱、円錐、
サドル状等の粒状のものが好適に用いられ、より好まし
くは見かけ外径として平均３〜１５ｍｍ程度のものが使
用できる。When the supporting method is adopted, the material of the carrier to be used is not particularly limited, but it is stable and inert in a high-temperature oxidizing atmosphere usually used as a catalyst carrier such as silicon carbide, silica, alumina, steatite, pottery, and porcelain. Any carrier can be used, but a carrier made of silicon carbide is preferable, and a carrier made of high-purity silicon carbide having a purity of 95% or more is more preferably used. The shape of the carrier is not particularly limited, and a sphere, a ring, a half ring, a cylinder, a cone,
Granules such as saddles are preferably used, and more preferably those having an average outer diameter of about 3 to 15 mm.
【００１７】反応の原料として用いる２，４，５−トリ
アルキルベンズアルデヒドとしては、任意のアルキル基
を持つものが使用可能であるが、アルキル基の炭素数が
大きくなるほど酸化反応時の発熱量が増大するため、ア
ルキル基の炭素数は少ないほうが好ましくＣ１〜Ｃ３の
アルキル基を持つものが好適に使用できる。中でも２，
４，５−トリメチルベンズアルデヒドは、酸化反応時の
発熱量も少なく、比較的安価な１，２，４−トリメチル
ベンゼン（以下、プソイドキュメンと記すことがある）
を、ＨＦ−ＢＦ3、ＨＳＯ3Ｆ−ＳｂＦ5，ＣＦ3ＳＯ3Ｈ
等の存在下、常温で一酸化炭素（ＣＯ）によるカルボニ
ル化反応により高い収率で製造することができるため、
無水ピロメリット酸を安価に製造するための原料として
は特に好ましい。As the 2,4,5-trialkylbenzaldehyde used as a raw material for the reaction, those having an arbitrary alkyl group can be used, but the calorific value during the oxidation reaction increases as the number of carbon atoms in the alkyl group increases. Therefore, it is preferable that the number of carbon atoms of the alkyl group is small, and those having a C1 to C3 alkyl group can be suitably used. Among them 2,
4,5-Trimethylbenzaldehyde generates less heat during the oxidation reaction and is relatively inexpensive 1,2,4-trimethylbenzene (hereinafter sometimes referred to as pseudocumene).
With HF-BF 3 , HSO 3 F-SbF 5 , CF 3 SO 3 H
Can be produced in a high yield by carbonylation reaction with carbon monoxide (CO) at room temperature in the presence of
It is particularly preferable as a raw material for inexpensively producing pyromellitic anhydride.
【００１８】また本発明においては、原料として２，
４，５−トリアルキルベンズアルデヒドと１，２，４，
５−テトラアルキルベンゼンの混合物を用いて反応する
ことも可能であり、これらの混合物は任意の混合比で使
用することができる。Further, in the present invention, as a raw material,
4,5-trialkylbenzaldehyde and 1,2,4
The reaction can be carried out using a mixture of 5-tetraalkylbenzenes, and these mixtures can be used in any mixing ratio.
【００１９】反応は、固定床式反応器に触媒を充填し
２，４，５−トリアルキルベンズアルデヒド、あるいは
２，４，５−トリアルキルベンズアルデヒドと１，２，
４，５−テトラアルキルベンゼンの混合物と、分子状酸
素含有ガスを混合した原料ガスを、所定の温度に制御さ
れた熱媒中に保持された反応管に充填された触媒層に通
じることによって行う。工業的には気相酸化反応に一般
的に用いられる反応ガス入口部空間と出口部空間を共有
する複数の反応管が熱媒中に保持された多管式熱交換器
型の反応器が好適に使用できる。反応管径は特に限定さ
れないが、接触気相酸化反応で通常用いられる内径１５
ｍｍ〜３０ｍｍのものが使用できる。In the reaction, a fixed bed reactor is charged with a catalyst, and 2,4,5-trialkylbenzaldehyde or 2,4,5-trialkylbenzaldehyde and 1,2,5
The reaction is performed by passing a raw material gas obtained by mixing a mixture of 4,5-tetraalkylbenzene and a molecular oxygen-containing gas through a catalyst layer filled in a reaction tube held in a heating medium controlled at a predetermined temperature. Industrially, a multi-tube heat exchanger type reactor in which a plurality of reaction tubes sharing a reaction gas inlet space and an outlet space generally used for a gas phase oxidation reaction are held in a heating medium is preferable. Can be used for The diameter of the reaction tube is not particularly limited.
mm to 30 mm can be used.
【００２０】本発明は、かかる反応管に触媒活性成分の
比表面積が５０ｍ2／ｇ以下である酸化物触媒を充填し
て、原料ガスを流通し接触気相酸化反応を行うものであ
る。According to the present invention, such a reaction tube is filled with an oxide catalyst having a specific surface area of the catalytically active component of 50 m 2 / g or less, and a catalytic gas phase oxidation reaction is carried out by flowing a raw material gas.
【００２１】本発明において、反応条件は特に限定され
るものではないが、好ましい空間速度は５００〜１０，
０００ｈ-1、特に好ましくは１，０００〜８，０００ｈ
-1である。 また、反応温度は、熱媒温度で３００〜５
００℃であり、好ましくは３５０℃〜４５０℃である。
原料ガス濃度は、分子状酸素含有ガス１ｍ3（標準状
態）当りの質量として（以後ｇ／ｍ3と表記する）１０
〜１００ｇ／ｍ3、好ましくは１０〜５０ｇ／ｍ3であ
る。In the present invention, the reaction conditions are not particularly limited, but the preferred space velocity is 500-10,
000 h -1 , particularly preferably 1,000 to 8,000 h
It is -1 . The reaction temperature is 300 to 5 at the temperature of the heating medium.
00 ° C, preferably 350 ° C to 450 ° C.
The raw material gas concentration is expressed as a mass per 1 m 3 (standard state) of the molecular oxygen-containing gas (hereinafter referred to as g / m 3 ).
To 100 g / m 3, preferably 10 to 50 g / m 3.
【００２２】また、分子状酸素含有ガスとしては、空
気、酸素、あるいは窒素や二酸化炭素など反応に関与し
ない不活性ガスと酸素との混合ガスを用いることができ
る。As the molecular oxygen-containing gas, air, oxygen, or a mixed gas of oxygen and an inert gas not involved in the reaction such as nitrogen or carbon dioxide can be used.
【実施例】 以下、実施例を用いて、本発明をさらに具
体的に説明する。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples.
【００２３】なお、実施例および比較例中の無水ピロメ
リット酸の収率（モル％）は、液体クロマトグラフによ
り測定した値であり、以下の式により定義される。
［（生成した無水ピロメリット酸のモル数）／（供給原
料のモル数）］×１００The yield (mol%) of pyromellitic anhydride in Examples and Comparative Examples is a value measured by liquid chromatography and is defined by the following equation.
[(Mol number of generated pyromellitic anhydride) / (mol number of feed material)] × 100
【００２４】［触媒調製］ 触媒Ａ 脱イオン水４００ｍｌ中に蓚酸２４０ｇを溶解させ、こ
れにメタバナジン酸アンモニウム１００ｇを加え均一に
溶解した後、第1リン酸アンモニウム３．０７ｇを加え
均一に混合した。ここにさらに表面積２０ｍ2／ｇのア
ナターゼ型酸化チタン２１４ｇ、炭化珪素ウィスカー１
７ｇを加えて均一なスラリーとなるまで十分攪拌混合
し、６００ｍｌの触媒成分スラリーを調製した。外部加
熱式の回転炉中に外径７ｍｍ、長さ７ｍｍのリング状炭
化ケイ素担体２００ｍｌを入れて２００〜３５０℃に予
熱しておき、先に調製した触媒成分スラリーを噴霧して
触媒物質１０ｇを担持させた。ついで焼成炉にて５００
℃で６時間焼成し触媒Aを得た。担持された触媒活性物
質粉体を剥離回収して比表面積を湯浅アイオニクス製４
−ソープ Ｕ２Ｃで測定したところ１４．５ｍ2／ｇで
あった。[Preparation of Catalyst] Catalyst A 240 g of oxalic acid was dissolved in 400 ml of deionized water, and 100 g of ammonium metavanadate was added and dissolved uniformly. Then, 3.07 g of ammonium monophosphate was added and mixed. Here, 214 g of anatase-type titanium oxide having a surface area of 20 m 2 / g and silicon carbide whisker 1
7 g was added, and the mixture was sufficiently stirred and mixed until a uniform slurry was obtained, thereby preparing a catalyst component slurry of 600 ml. 200 ml of a ring-shaped silicon carbide carrier having an outer diameter of 7 mm and a length of 7 mm was placed in an externally heated rotary furnace, preheated to 200 to 350 ° C., and the previously prepared catalyst component slurry was sprayed to obtain 10 g of a catalyst substance. Supported. Then in a firing furnace 500
Calcination was performed at 6 ° C. for 6 hours to obtain a catalyst A. The supported catalytically active substance powder is peeled and collected, and the specific surface area is made by Yuasa Ionics.
-Soap It was 14.5 m < 2 > / g as measured by U2C.
【００２５】触媒Ｂ 比表面積２０ｍ2／ｇの酸化チタンに代えて、比表面積6
４ｍ2／ｇの酸化チタンを用いた以外は触媒Aと同様にし
て触媒Ｂを調製した。 担持された触媒活性物質粉体を
剥離回収して比表面積を測定したところ５２ｍ2／ｇで
あった。Catalyst B The specific surface area was 6 instead of titanium oxide having a specific surface area of 20 m 2 / g.
A catalyst B was prepared in the same manner as the catalyst A except that 4 m 2 / g of titanium oxide was used. The supported catalytically active substance powder was peeled and collected, and the specific surface area was measured to be 52 m 2 / g.
【００２６】触媒Ｃ 脱イオン水４００ｍｌ中に蓚酸２４０ｇを溶解させ、こ
れにメタバナジン酸アンモニウム１００ｇおよびパラモ
リブデン酸アンモニウム１５．１ｇを加え均一に混合し
た後、第1リン酸アンモニウム３．０７ｇおよびあらか
じめ少量の脱イオン水に溶解した硝酸銀６．５３ｇを加
え均一に混合した。ここにさらに表面積２０ｍ2／ｇの
アナターゼ型酸化チタン２１４ｇ、炭化珪素ウィスカー
１７ｇを加えて均一なスラリーとなるまで十分攪拌混合
し、６００ｍｌの触媒成分スラリーを調製した。外部加
熱式の回転炉中に外径７ｍｍ、長さ７ｍｍのリング状炭
化ケイ素担体２００ｍｌを入れて２００〜３５０℃に予
熱しておき、先に調製した触媒成分スラリーを噴霧して
触媒物質１０ｇを担持させた。ついで焼成炉にて５００
℃で６時間焼成し触媒Aを得た。担持された触媒活性物
質粉体を剥離回収して比表面積を測定したところ１８．
４ｍ2／ｇであった。Catalyst C 240 g of oxalic acid was dissolved in 400 ml of deionized water, and 100 g of ammonium metavanadate and 15.1 g of ammonium paramolybdate were added thereto and mixed uniformly. 6.53 g of silver nitrate dissolved in deionized water was added and mixed uniformly. Further, 214 g of anatase-type titanium oxide having a surface area of 20 m 2 / g and 17 g of silicon carbide whiskers were added thereto and sufficiently stirred and mixed until a uniform slurry was obtained, thereby preparing a catalyst component slurry of 600 ml. 200 ml of a ring-shaped silicon carbide carrier having an outer diameter of 7 mm and a length of 7 mm was placed in an externally heated rotary furnace, preheated to 200 to 350 ° C., and the previously prepared catalyst component slurry was sprayed to obtain 10 g of a catalyst substance. Supported. Then in a firing furnace 500
Calcination was performed at 6 ° C. for 6 hours to obtain a catalyst A. 17. The supported catalytically active substance powder was peeled and collected, and the specific surface area was measured.
It was 4 m 2 / g.
【００２７】触媒Ｄ 表面積２０ｍ2／ｇのアナターゼ型酸化チタン２１４ｇ
を使用しない以外は触媒Ｃと同様に触媒Ｄを調製した。
担持された触媒活性物質粉体を剥離回収して比表面積を
測定したところ１６．７ｍ2／ｇであった。Catalyst D 214 g of anatase type titanium oxide having a surface area of 20 m 2 / g
Catalyst D was prepared in the same manner as Catalyst C except that was not used.
The carried catalytically active substance powder was peeled and collected, and the specific surface area was measured to be 16.7 m 2 / g.
【００２８】実施例１ 触媒Ａを、内径２５ｍｍ、長さ４００ｍｍのステンレス
鋼製の反応管に触媒層長２００ｍｍとなるように充填
し、さらに予熱層として平均粒子径５ｍｍのガラス玉を
層長約１００ｍｍ充填した。この触媒層に３０ｇ／ｍ3
の濃度の２，４，５−トリメチルベンズアルデヒドおよ
び残部が空気である原料混合ガスを６．３Ｌ／分で通じ
て反応を行った。反応温度３７０℃の時、最も高い無水
ピロメリット酸収率が得られ無水ピロメリット酸収率は
７０．７モル％（１０４．１質量％）であった。Example 1 Catalyst A was filled into a stainless steel reaction tube having an inner diameter of 25 mm and a length of 400 mm so as to have a catalyst layer length of 200 mm, and a glass ball having an average particle diameter of 5 mm was further used as a preheating layer. 100 mm was filled. 30 g / m 3 of the catalyst layer
The reaction was carried out by passing 2,4,5-trimethylbenzaldehyde having a concentration of 5% and a raw material mixed gas whose balance was air at 6.3 L / min. At the reaction temperature of 370 ° C., the highest yield of pyromellitic anhydride was obtained, and the yield of pyromellitic anhydride was 70.7 mol% (104.1% by mass).
【００２９】比較例１ 実施例１において触媒Ａに代え触媒Ｂを用いた以外は実
施例１と同様に２，４，５−トリメチルベンズアルデヒ
ドの接触気相酸化反応を行った。反応温度３７０℃の
時、最も高い無水ピロメリット酸収率が得られ無水ピロ
メリット酸収率は６６．４モル％（９７．８質量％）で
あった。Comparative Example 1 A catalytic gas phase oxidation reaction of 2,4,5-trimethylbenzaldehyde was carried out in the same manner as in Example 1 except that catalyst B was used instead of catalyst A. At the reaction temperature of 370 ° C., the highest yield of pyromellitic anhydride was obtained, and the yield of pyromellitic anhydride was 66.4 mol% (97.8% by mass).
【００３０】実施例２ 実施例１において触媒Ａに代え触媒Ｃを用いた以外は実
施例１と同様に２，４，５−トリメチルベンズアルデヒ
ドの接触気相酸化反応を行った。反応温度３９０℃の
時、最も高い無水ピロメリット酸収率が得られ無水ピロ
メリット酸収率は７６．０モル％（１１１．９質量％）
であった。Example 2 A catalytic gas phase oxidation reaction of 2,4,5-trimethylbenzaldehyde was carried out in the same manner as in Example 1 except that the catalyst C was used in place of the catalyst A. When the reaction temperature is 390 ° C., the highest yield of pyromellitic anhydride is obtained, and the yield of pyromellitic anhydride is 76.0 mol% (111.9 mass%).
Met.
【００３１】実施例３ 実施例１において触媒Aに代え触媒Ｄを用いた以外は実
施例1と同様に反応を行った結果７６．５モル％（１１
２．６質量％）の収率で無水ピロメリット酸が得られ
た。Example 3 A reaction was carried out in the same manner as in Example 1 except that catalyst D was used instead of catalyst A. As a result, 76.5 mol% (11
Pyromellitic anhydride was obtained in a yield of 2.6 mass%).
【００３２】実施例４ 反応原料を２，４，５−トリメチルベンズアルデヒドと
デュレン（１：１モル比）の混合物を用いた以外は実施
例２と同様にして反応を行ったところ６８．１モル％の
収率で無水ピロメリット酸が得られた。Example 4 The reaction was carried out in the same manner as in Example 2 except that a mixture of 2,4,5-trimethylbenzaldehyde and durene (1: 1 molar ratio) was used as a reaction raw material. Pyromellitic anhydride was obtained in a yield of 1.
【００３３】比較例２ 実施例４において触媒Ｃに代え触媒Ｂを用いた以外は実
施例４と同様に反応を行った結果６０．７モル％の収率
で無水ピロメリット酸が得られた。Comparative Example 2 The reaction was carried out in the same manner as in Example 4 except that catalyst B was used instead of catalyst C. As a result, pyromellitic anhydride was obtained in a yield of 60.7 mol%.
【００３４】[0034]
【発明の効果】 無水ピロメリット酸を製造する際に、
本発明の触媒の存在下に２，４，５−トリアルキルベン
ズアルデヒドあるいは２，４，５−トリアルキルベンズ
アルデヒドと１，２，４，５−テトラアルキルベンゼン
の混合物を接触気相酸化することにより、高純度の無水
ピロメリット酸を安価に製造することができる。Effect of the Invention When producing pyromellitic anhydride,
By subjecting 2,4,5-trialkylbenzaldehyde or a mixture of 2,4,5-trialkylbenzaldehyde and 1,2,4,5-tetraalkylbenzene to catalytic gas phase oxidation in the presence of the catalyst of the present invention, high catalytic oxidation is achieved. Pyromellitic anhydride of high purity can be produced at low cost.
フロントページの続き Ｆターム(参考） 4C071 AA01 AA08 BB01 CC12 EE05 FF15 KK03 LL07 4G069 AA03 AA08 AA09 AA11 AA12 BA04A BA04B BA04C BA05A BB04A BB04B BB04C BB15B BC08A BC22A BC26A BC32A BC32B BC32C BC38A BC54A BC54B BC54C BC55A BC59A BC59B BC59C BC60A BD03A BD05B BD07A BD07B BD07C BD08A CB07 DA06 EA02Y EC02X EC02Y FA02 FA03 FB24 FB57 4H039 CA65 CC90 Continuation of the front page F term (reference) 4C071 AA01 AA08 BB01 CC12 EE05 FF15 KK03 LL07 4G069 AA03 AA08 AA09 AA11 AA12 BA04A BA04B BA04C BA05A BB04A BB04B BB04C BB15B BC08A BC22 BCBC BCA BCBC BC BC BC BC BC BC BC BC BD07B BD07C BD08A CB07 DA06 EA02Y EC02X EC02Y FA02 FA03 FB24 FB57 4H039 CA65 CC90
Claims (4)
媒活性成分の比表面積が５０ｍ2／ｇ以下である触媒の
存在下に、２，４，５−トリアルキルベンズアルデヒド
を分子状酸素含有ガスで接触気相酸化することを特徴と
する無水ピロメリット酸の製造方法。When producing pyromellitic anhydride, a 2,4,5-trialkylbenzaldehyde is added to a molecular oxygen-containing gas in the presence of a catalyst having a specific surface area of a catalytically active component of 50 m 2 / g or less. A process for producing pyromellitic dianhydride by catalytic gas phase oxidation.
んでなる請求項1に記載の無水ピロメリット酸製造方
法。2. The method for producing pyromellitic anhydride according to claim 1, comprising vanadium as an active component of the catalyst.
ン、タングステン、リン、ホウ素、銀、アンチモン、硫
黄、ニオブ、アルカリ土類金属、希土類元素からなる群
から選ばれた少なくとも１つの元素を含んでなる請求項
２に記載の無水ピロメリット酸製造方法。3. The active component of the catalyst further includes at least one element selected from the group consisting of molybdenum, tungsten, phosphorus, boron, silver, antimony, sulfur, niobium, alkaline earth metals, and rare earth elements. The method for producing pyromellitic anhydride according to claim 2.
ＺｒＯ2、ＳｎＯ2よりなる群から選ばれた少なくとも１
種の無機酸化物粉体を含有してなる請求項２または３に
記載の無水ピロメリット酸の製造方法。4. The catalyst according to claim 1, wherein the active component is TiO 2 ,
At least one selected from the group consisting of ZrO 2 and SnO 2
The method for producing pyromellitic anhydride according to claim 2 or 3, wherein the method comprises containing at least one inorganic oxide powder.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000297040A JP2002105078A (en) | 2000-09-28 | 2000-09-28 | Method for producing pyromellitic anhydride |
| US09/963,402 US6452021B1 (en) | 2000-09-28 | 2001-09-27 | Process for producing pyromellitic anhydride |
| EP01122618A EP1193241B1 (en) | 2000-09-28 | 2001-09-27 | Process for producing pyromellitic anhydride |
| CNB011411465A CN1159279C (en) | 2000-09-28 | 2001-09-27 | Method for preparing 1,2,4,5-pyromellitic anhydride |
| DE60115797T DE60115797T2 (en) | 2000-09-28 | 2001-09-27 | Process for the preparation of pyromellitic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000297040A JP2002105078A (en) | 2000-09-28 | 2000-09-28 | Method for producing pyromellitic anhydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002105078A true JP2002105078A (en) | 2002-04-10 |
Family
ID=18779214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000297040A Pending JP2002105078A (en) | 2000-09-28 | 2000-09-28 | Method for producing pyromellitic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002105078A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2135671A2 (en) | 2008-06-19 | 2009-12-23 | Mitsubishi Gas Chemical Company, Inc. | Catalyst and method for producing carboxylic acid and/or carboxylic anhydride in the presence of the catalyst |
-
2000
- 2000-09-28 JP JP2000297040A patent/JP2002105078A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2135671A2 (en) | 2008-06-19 | 2009-12-23 | Mitsubishi Gas Chemical Company, Inc. | Catalyst and method for producing carboxylic acid and/or carboxylic anhydride in the presence of the catalyst |
| US8357625B2 (en) | 2008-06-19 | 2013-01-22 | Mitsubishi Gas Chemical Company, Inc. | Catalyst and method for producing carboxylic acid and/or carboxylic anhydride in the presence of the catalyst |
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