JPS62201645A - Production of catalyst for producing pyromellitic acid anhydride - Google Patents
Production of catalyst for producing pyromellitic acid anhydrideInfo
- Publication number
- JPS62201645A JPS62201645A JP61042130A JP4213086A JPS62201645A JP S62201645 A JPS62201645 A JP S62201645A JP 61042130 A JP61042130 A JP 61042130A JP 4213086 A JP4213086 A JP 4213086A JP S62201645 A JPS62201645 A JP S62201645A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- vanadium
- carrier
- oxalic acid
- acid
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 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 14
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 63
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 15
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 14
- 239000011975 tartaric acid Substances 0.000 claims abstract description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000010412 oxide-supported catalyst Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 150000007524 organic acids Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 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 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- WGSMMQXDEYYZTB-UHFFFAOYSA-N 1,2,4,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C)C=C1C.CC1=CC(C)=C(C)C=C1C WGSMMQXDEYYZTB-UHFFFAOYSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- JBXYCUKPDAAYAS-UHFFFAOYSA-N methanol;trifluoroborane Chemical compound OC.FB(F)F JBXYCUKPDAAYAS-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- 150000002913 oxalic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 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
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は１，２，４．５−テトラアルキルベンゼン類、
たとえばジュレン（１，２，４，５−テトラメチルベン
ゼン）を気相接触酸化して無水ピロメリット酸を製造す
る時に用いる触媒の製造方法に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to 1,2,4,5-tetraalkylbenzenes,
For example, the present invention relates to a method for producing a catalyst used when producing pyromellitic anhydride by catalytically oxidizing durene (1,2,4,5-tetramethylbenzene) in a gas phase.
無水ピロメリット酸は、耐熱性樹脂の可塑剤、耐熱性樹
脂原料としての用途がある。Pyromellitic anhydride is used as a plasticizer for heat-resistant resins and as a raw material for heat-resistant resins.
〈従来技術およびその問題点〉
空気あるいは分子状酸素含存ガスで１．２，４．５−テ
トラアルキルベンゼン類、たとえばジュレン等を接触気
相酸化して無水ピロメリット酸を製造する場合、通常五
酸化バナジウムを主触媒成分とする金属酸化物触媒が用
いられる。<Prior art and its problems> When pyromellitic anhydride is produced by catalytic gas phase oxidation of 1,2,4,5-tetraalkylbenzenes, such as durene, with air or molecular oxygen-containing gas, A metal oxide catalyst containing vanadium oxide as the main catalyst component is used.
これら五酸化バナジウム系触媒は、粒径２〜５ＩＩ１１
程度の熔融アルミナ、あるいは炭化ケイ素など表面積が
ｌｒｎ”７ｇ以下の担体に担持させて使用するが、担体
に担持させる際、難溶性の金属酸化物および金属酸化物
の塩（主に五酸化バナジウムおよびまたはメタバナジウ
ム酸アンモニウム）に有機酸（シュウ酸およびまた酒石
酸）を加えて水溶性に変え、均一溶液として担体に噴霧
して乾燥させ担持するか、濃縮乾固により担持する。These vanadium pentoxide catalysts have a particle size of 2 to 5II11.
It is used by supporting it on a carrier with a surface area of 7 g or less, such as molten alumina or silicon carbide. Or ammonium metavanadate) is made water-soluble by adding an organic acid (oxalic acid and also tartaric acid), and the homogeneous solution is sprayed onto a carrier and dried and supported, or supported by concentration to dryness.
あるいは、４１機酸を用いず、金属酸化物およびまたは
金属酸化物の塩をスラリー状あるいは多量の溶媒を用い
て溶解させて濃縮乾固させ、担体に担持させる。Alternatively, the metal oxide and/or metal oxide salt is dissolved in a slurry form or using a large amount of solvent, concentrated to dryness, and supported on a carrier without using a 41-organic acid.
前者の例では、たとえば特公昭４５−４９７８号公報に
開示されているように、水に対して難溶性の五酸化バナ
ジウムまたはメタバナジウム酸アンモニウムを溶解させ
るため、バナジウムに対して１０倍モルのシュウ酸を加
えて均一溶液とし、リン酸およびまたはタングステン酸
等の助触媒成分とともに、半融アルミナ、シリコンカー
バイト等の担体に担持させた後、空気気流中で約４５０
℃で数時間焼成して触媒を得るが、大量に使用したシュ
ウ酸が焼成時に二酸化炭素、−酸化炭素ガスとなって盛
んにガス化するため、触媒成分が担体から剥離しゃすい
状態となっている。In the former example, as disclosed in Japanese Patent Publication No. 45-4978, in order to dissolve vanadium pentoxide or ammonium metavanadate, which are sparingly soluble in water, 10 times the molar amount of sulfur to vanadium is used. After adding an acid to make a homogeneous solution and supporting it on a carrier such as semi-fused alumina or silicon carbide together with a cocatalyst component such as phosphoric acid and/or tungstic acid, it is heated to about 450 ml in an air stream.
The catalyst is obtained by calcination at ℃ for several hours, but the oxalic acid used in large quantities becomes carbon dioxide and carbon oxide gas during calcination and is actively gasified, making it easy for the catalyst components to peel off from the carrier. There is.
この触媒を使って反応を行うと、反応時間が３０時間を
超えると急速に反応性が低下するため、実用触媒として
使えない。When a reaction is carried out using this catalyst, the reactivity rapidly decreases when the reaction time exceeds 30 hours, so it cannot be used as a practical catalyst.
また、特公昭４３−２６４９７号公報では、五酸化バナ
ジウムに対して２．５倍モルのシュウ酸を加え、０．ｌ
８Ｎｂ／ＶとなるようにＮｂ分を加えて触媒水溶液を調
製し、この触媒水溶液を熔融アルミナに加えて蒸発乾固
した後、５００℃で焼成し、触媒を得ており、用いたシ
ュウ酸量は上記例に比べかなり抑えているが、焼成時の
ガス化反応が起こり、そのため活性の低下がある。Furthermore, in Japanese Patent Publication No. 43-26497, 2.5 times mole of oxalic acid is added to vanadium pentoxide, and 0. l
A catalyst aqueous solution was prepared by adding Nb to give a concentration of 8Nb/V, and this catalyst aqueous solution was added to molten alumina, evaporated to dryness, and then calcined at 500°C to obtain a catalyst.The amount of oxalic acid used was Although this is considerably suppressed compared to the above example, a gasification reaction occurs during firing, resulting in a decrease in activity.
後者の例では、たとえば特公昭４２−２８５５８号公報
に開示されているように、メタバナジウム酸アンモニウ
ムとクロム酸アンモニウムを用い、バナジウムとクロム
（原子比でＶ：ｌ；ｒ＝４＋３）を主触媒成分とした触
媒であるが、この触媒の調製法は、シュウ酸などの溶解
助剤を用いずに多量の熱水を用いてメタバナジウム酸ア
ンモニウムを溶解させ、熔融アルミナあるいは炭化ケイ
素に担持させることを特徴としている。これによれば、
シュウ酸を用いていないため焼成時にガス化反応はみら
れないが、触媒水溶液の濃縮時に難溶性のメタバナジウ
ム酸アンモニウムの析出があるため、不均一な状態で担
体に担持され、その上メタバナジウム酸アンモニウムの
析出する速度は、水が蒸発する速度により微妙に変化し
、そのことにより触媒の活性に大きな影響を与え、再現
性が出ないという欠点がある。In the latter example, as disclosed in Japanese Patent Publication No. 42-28558, ammonium metavanadate and ammonium chromate are used, and vanadium and chromium (atomic ratio V:l; r=4+3) are used as main catalysts. The method for preparing this catalyst is to dissolve ammonium metavanadate using a large amount of hot water without using a dissolution aid such as oxalic acid, and to support it on molten alumina or silicon carbide. It is characterized by According to this,
Since oxalic acid is not used, no gasification reaction is observed during calcination. However, since sparingly soluble ammonium metavanadate is precipitated when the aqueous catalyst solution is concentrated, metavanadium is supported on the carrier in a non-uniform state, and metavanadium The rate at which ammonium acid is precipitated varies slightly depending on the rate at which water evaporates, which has a major effect on the activity of the catalyst and has the disadvantage of not being reproducible.
すなわち、有機酸を用いて均一溶液として担持した場合
、触媒の賦活のために空気流通下において４５０〜６０
０℃で焼成する必要があるが、この時有機酸が分解して
二酸化炭素、−酸化炭素ガスとなる激しいガス化反応の
ため、触媒成分がかなり剥離しやすくなってしまい、長
時間の反応後にかなりの活性低下がみられる。That is, when supported as a homogeneous solution using an organic acid, 450 to 60
It is necessary to calcinate at 0℃, but at this time, the organic acid decomposes into carbon dioxide and -carbon oxide gas due to the intense gasification reaction, which makes the catalyst component quite easy to peel off. A considerable decrease in activity is observed.
また有機酸を用いない場合は、焼成時にそのようなガス
化反応はみられないが、担体に担持させる時、水の蒸発
の速度、攪拌等の諸条件によって触媒成分の担持状態が
異なり、再現性が出ないという欠点がある。In addition, when an organic acid is not used, such a gasification reaction is not observed during calcination, but when supported on a carrier, the supported state of the catalyst component varies depending on various conditions such as the rate of water evaporation and stirring, and it is difficult to reproduce it. It has the disadvantage of not being sexual.
〈発明の目的〉
本発明は上記事情に鑑みてなされたもので、上記欠点を
解消し、長時間活性が持続し、かつ再現性のある無水ピ
ロメリット酸製造用触媒の製造方法を提供することを目
的とする。<Objective of the Invention> The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for producing a catalyst for producing pyromellitic anhydride that eliminates the above drawbacks, maintains activity for a long time, and has reproducibility. With the goal.
〈発明の構成〉
従来、有機酸を用いて触媒を均一化する方法においては
、触媒調製時、五酸化バナジウムまたはメタバナジウム
酸アンモニウムを水溶性にするためシュウ酸を用いてい
たが、バナジウムに対して用いるシュウ酸量を変えた場
合、初期活性にも差があったが、それ以上に、長時間使
用すると活性に大きな差が出たことから１本発明者らは
バナジウムに対して用いるシュウ酸の量比を変えること
と、使用有機酸としてシュウ酸だけでなく酒石酸につい
ても検討した。その結果、有機酸としてシュウ酸および
または酒石酸を用いることと、該有機酸をバナジウムに
対して０．５〜１．５倍モル使用すればよいという知見
を得た。<Structure of the Invention> Conventionally, in the method of homogenizing a catalyst using an organic acid, oxalic acid was used to make vanadium pentoxide or ammonium metavanadate water-soluble during catalyst preparation. When the amount of oxalic acid used for vanadium was changed, there was a difference in the initial activity, but even more so, there was a large difference in activity when used for a long time. We also investigated not only oxalic acid but also tartaric acid as the organic acid used. As a result, it was found that oxalic acid and/or tartaric acid should be used as the organic acid, and that the organic acid should be used in a molar amount of 0.5 to 1.5 times that of vanadium.
本発明によりば、空気あるいは分子状酸素含存ガスで１
．２，４．５−テトラアルキルベンゼン類を接触気相酸
化して無水ピロメリット酸を製造する時に用いる酸化バ
ナジウム担持触媒を調製するにあたり、五酸化バナジウ
ムおよびまたはメタバナジウム酸アンモニウムに、シュ
ウ酸およびまたは酒石酸をバナジウムに対して０．５〜
１．５倍モル添加することを特徴とする無水ピロメリッ
ト酸製造用触媒の製造方法が提供される。According to the present invention, air or molecular oxygen-containing gas is used to
．． In preparing a vanadium oxide supported catalyst used for producing pyromellitic anhydride by catalytic gas phase oxidation of 2,4.5-tetraalkylbenzenes, oxalic acid and/or tartaric acid are added to vanadium pentoxide and/or ammonium metavanadate. 0.5 to vanadium
Provided is a method for producing a catalyst for producing pyromellitic anhydride, characterized in that the catalyst is added 1.5 times in mole.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
五酸化バナジウムまたはメタバナジウム酸アンモニウム
は水に対して難溶性であるため、水中でシュウ酸および
または酒石酸を加えることにより、水に可溶な状態に変
える。Since vanadium pentoxide or ammonium metavanadate is sparingly soluble in water, it is made soluble in water by adding oxalic acid and/or tartaric acid to the water.
この均一溶液に助触媒となる金属酸化物、金属の塩（ア
ンモニウム塩、炭酸塩、塩化物）等を添加した後、溶融
アルミナまたは炭化ケイ素等の表面積が１ｍ″／ｇ以下
の担体に担持した後、空気流通下４５０℃〜６００℃で
焼成し、触媒を得る。After adding metal oxides, metal salts (ammonium salts, carbonates, chlorides), etc. as co-catalysts to this homogeneous solution, the mixture was supported on a carrier with a surface area of 1 m''/g or less, such as molten alumina or silicon carbide. Thereafter, it is calcined at 450°C to 600°C under air circulation to obtain a catalyst.
用いる有機酸（シュウ酸およびまた酒石酸）はバナジウ
ムに対して０．５〜１．５倍モルならば焼成時に発生す
る二酸化炭素および一酸化炭素ガスの量が少量であるた
め、無視することができ、長時間使用しても触媒活性の
低下がみられないが１．５倍超にすると焼成後には触媒
成分がかなり剥離しており、また長時間使用すると酸化
活性が低下する。これは空気およびまたは分子状酸素含
有ガスにより触媒成分が剥離してしまうためであると思
ねれる。逆に０．５倍未満にするとバナジウムを含んだ
スラリーが水溶液中に析出したままで、担体に均一に担
持することはできない上、担持にむらが生じ、製造した
触媒の再現性が低くなる。If the organic acids (oxalic acid and tartaric acid) used are 0.5 to 1.5 times the mole of vanadium, the amount of carbon dioxide and carbon monoxide gas generated during firing is small and can be ignored. Although no decrease in catalytic activity is observed even when used for a long time, when the ratio exceeds 1.5 times, the catalyst component is considerably peeled off after firing, and the oxidation activity decreases when used for a long time. This seems to be because the catalyst component is peeled off by air and/or molecular oxygen-containing gas. On the other hand, if it is less than 0.5 times, the vanadium-containing slurry will remain precipitated in the aqueous solution, and it will not be possible to support it uniformly on the carrier, and the support will be uneven, resulting in low reproducibility of the produced catalyst.
なお、前記有機酸をバナジウムに対して０．５〜１倍モ
ル加える場合は、ごく少量のスラリーが残るが、量的に
無視することができる程度の量である。Note that when the organic acid is added in an amount of 0.5 to 1 mole relative to vanadium, a very small amount of slurry remains, but the amount is negligible in terms of quantity.
また有機酸として使用されるシュウ酸と酒石酸を比べて
みると、シュウ酸はカルボキシル基のみを持つが、酒石
酸はカルボキシル基以外に水酸基を持っているため、シ
且つ酸よりもより少量でバナジウムを水溶性にすること
ができる。バナジウムに対する量は０．８〜１．５倍モ
ルが最適で、酒石酸については０．５〜１．２倍モルが
最適である。Furthermore, when comparing oxalic acid and tartaric acid, which are used as organic acids, oxalic acid has only carboxyl groups, but tartaric acid has hydroxyl groups in addition to carboxyl groups, so it contains vanadium in a smaller amount than oxalic acids. Can be made water soluble. The optimal amount for vanadium is 0.8 to 1.5 times the mole, and the optimal amount for tartaric acid is 0.5 to 1.2 times the mole.
触媒の評価は以下のようにして行った。The catalyst was evaluated as follows.
触媒を内径２８ｍａ＋φの反応管に３０１１ｊ！充填し
、塩浴温度３７０〜ｓｏｏ”ｃで空間速度（ＳＶ）３０
００〜１５０００ｈｒ−’、モ／Ｌ／比（ジュレン／空
気）０．１〜０．４で酸化を行い、得られた生成物をメ
タノール−三フッ化ホウ素錯塩にてメチルエステル化物
に変換した後、ガスクロマトグラフィーにより生成物の
分析を行い、触媒の活性を評価した。3011j to put the catalyst in a reaction tube with an inner diameter of 28mm + φ! Filled, space velocity (SV) 30 at salt bath temperature 370~soo”c
00 to 15,000 hr-', oxidation was carried out at a mo/L/ratio (durene/air) of 0.1 to 0.4, and the obtained product was converted into a methyl ester with methanol-boron trifluoride complex salt. The product was analyzed by gas chromatography to evaluate the activity of the catalyst.
次に本発明の実施例について述べる。Next, examples of the present invention will be described.
（実施例１）
五酸化バナジウム６ｇに等モルのシュウ酸を加え２００
ｃｃの水溶液としてＶ／Ｔｉ＝１０１０．３５となるよ
うに四塩化チタン（ＴｉにＩＬ４ ）を加え、この触媒
水溶液を湯浴上の粒径が３０１１１の熔融アルミナ６０
ｇに徐々に注加し、濃縮乾固後、空気流通下ＳＯＯ℃で
３時間焼成した。(Example 1) Add equimolar amount of oxalic acid to 6 g of vanadium pentoxide and add 200 g of vanadium pentoxide.
Titanium tetrachloride (IL4 to Ti) was added as an aqueous solution of cc so that V/Ti = 1010.35, and this catalyst aqueous solution was poured into molten alumina 60 with a particle size of 30111 on a hot water bath.
After concentrating to dryness, the mixture was calcined at SOO° C. for 3 hours under air circulation.
上記の触媒３０ＩＩＩＬを用いて内径２８ｍｍφの反応
管に充填し、ＳＶ＝ １２０００ ｈｒ’、モル比（ジ
ュレン／空気） ＝０．１ 、反応温度４ｏｏ℃で実験
を行ったところ、反応初期のＰＭＤＡ（ｊ％水ピロメリ
ット酸）の重量収率は９８％で、１００時間後もこの収
率はほとんど変化しなかった。Using the catalyst 30IIIL described above, a reaction tube with an inner diameter of 28 mm was filled, and an experiment was conducted at SV = 12000 hr', molar ratio (durene/air) = 0.1, and reaction temperature of 40°C. The weight yield of j% water pyromellitic acid) was 98%, and this yield hardly changed even after 100 hours.
（実施例２）
メタバナジウム酸アンモニウム７．７ｇに７．９ｇの酒
石酸（バナジウムに対して約０．８倍モル）を加え、２
００ｃｃ（７）水溶液としテＶ／Ｎｂ−１０／Ｉ 、４
となるようにシュウ酸ニオブを加え、この触媒を湯浴上
の粒径が２〜３ｏ＋ｍの炭化ケイ素に徐々に注加し、濃
縮乾固後、空気流通下５３０℃で３時間焼成し、実施例
１と同一の条件下で実験を行ったところ、２００時間後
もＰＭＤＡの重量収率は１０３％であった。(Example 2) 7.9 g of tartaric acid (approximately 0.8 times the mole of vanadium) was added to 7.7 g of ammonium metavanadate, and 2
00cc (7) aqueous solution teV/Nb-10/I, 4
Add niobium oxalate so that When an experiment was conducted under the same conditions as in Example 1, the weight yield of PMDA was 103% even after 200 hours.
（比較例）
五酸化バナジウム６ｇにシュウ酸および酒石酸２４．１
ｇ （バナジウムに対して３倍モル）を加え、２００ｃ
ｃ（７）水溶液Ｖ／Ｔｉ−１０７０，３５とナルヨうニ
四塩化チタン（Ｔｉ（：ＩＬ４ ）を加え、この触媒水
溶液を湯浴上の粒径３ＩＩＩＩｌの熔融アルミナ６０ｇ
に徐々に注加し、濃縮乾固後、空気流通下５００℃で３
時間焼成したところ、触媒成分の剥離がみられ、重量を
測定すると担持後酸化バナジウムの５％に相当した。(Comparative example) Oxalic acid and tartaric acid 24.1 g to 6 g of vanadium pentoxide
g (3 times the mole relative to vanadium) and 200c
c(7) Add aqueous solution V/Ti-1070,35 and titanium tetrachloride (Ti(:IL4)), and pour this catalyst aqueous solution into 60g of molten alumina with a particle size of 3IIIL on a hot water bath.
After concentrating to dryness, it was heated at 500℃ under air circulation for 3 hours.
When calcined for a period of time, peeling of the catalyst component was observed, and when the weight was measured, it was equivalent to 5% of the vanadium oxide after being supported.
この触媒３０ｎｌを用いて、実施例１と同一の条件下で
実験を行ったところ、反応初期でも実施例１に比べＰＭ
Ｄへの重量収率は８５％と低く、３０時間経過すると６
０％にまで収率は低下した。When an experiment was conducted using 30 nl of this catalyst under the same conditions as in Example 1, it was found that even in the early stage of the reaction, PM was smaller than in Example 1.
The weight yield to D was as low as 85%, and after 30 hours, 6
The yield decreased to 0%.
〈発明の効果〉
以上詳述したように本発明によれば、五酸化バナジウム
およびまたはメタバナジウム酸アンモニウムに、シュウ
酸およびまたは酒石酸をバナジウムに対して０．５〜１
．５倍モル添加するようにしたので、長時間活性が持続
し、かつ再現性を有し、工業的利用価値の高い無水ピロ
メリット酸製造用触媒が得られるという効果がある。<Effects of the Invention> As detailed above, according to the present invention, oxalic acid and/or tartaric acid is added to vanadium pentoxide and/or ammonium metavanadate in an amount of 0.5 to 1 with respect to vanadium.
．． Since it was added in a 5-fold molar amount, it is possible to obtain a catalyst for producing pyromellitic anhydride that maintains its activity for a long time, has reproducibility, and has high industrial utility value.
Claims (1)
５−テトラアルキルベンゼン類を接触気相酸化して無水
ピロメリット酸を製造する時に用いる酸化バナジウム担
持触媒を調製するにあたり、五酸化バナジウムおよびま
たはメタバナジウム酸アンモニウムに、シュウ酸および
または酒石酸をバナジウムに対して０．５〜１．５倍モ
ル添加することを特徴とする無水ピロメリット酸製造用
触媒の製造方法。(1) 1, 2, 4, with air or molecular oxygen-containing gas
In preparing a vanadium oxide supported catalyst used for producing pyromellitic anhydride by catalytic gas phase oxidation of 5-tetraalkylbenzenes, oxalic acid and/or tartaric acid are added to vanadium pentoxide and/or ammonium metavanadate to vanadium. A method for producing a catalyst for producing pyromellitic anhydride, the method comprising adding 0.5 to 1.5 times the mole of pyromellitic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61042130A JPS62201645A (en) | 1986-02-27 | 1986-02-27 | Production of catalyst for producing pyromellitic acid anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61042130A JPS62201645A (en) | 1986-02-27 | 1986-02-27 | Production of catalyst for producing pyromellitic acid anhydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62201645A true JPS62201645A (en) | 1987-09-05 |
Family
ID=12627350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61042130A Pending JPS62201645A (en) | 1986-02-27 | 1986-02-27 | Production of catalyst for producing pyromellitic acid anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62201645A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891250A (en) * | 2010-06-25 | 2010-11-24 | 华东师范大学 | Phase change material and preparation method of compound strip-shaped VO2 nanoflower structure on silicon substrate |
-
1986
- 1986-02-27 JP JP61042130A patent/JPS62201645A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891250A (en) * | 2010-06-25 | 2010-11-24 | 华东师范大学 | Phase change material and preparation method of compound strip-shaped VO2 nanoflower structure on silicon substrate |
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