JPH0824848B2 - Method for producing catalyst for synthesizing formaldehyde - Google Patents
Method for producing catalyst for synthesizing formaldehydeInfo
- Publication number
- JPH0824848B2 JPH0824848B2 JP2002495A JP249590A JPH0824848B2 JP H0824848 B2 JPH0824848 B2 JP H0824848B2 JP 2002495 A JP2002495 A JP 2002495A JP 249590 A JP249590 A JP 249590A JP H0824848 B2 JPH0824848 B2 JP H0824848B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- molybdenum
- solution
- powder
- nitric 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.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 38
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 230000002194 synthesizing effect Effects 0.000 title claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- -1 organic acid salts Chemical class 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はメチラール又はメタノールの酸化反応により
ホルムアルデヒドを合成する触媒の製造方法に関するも
のである。TECHNICAL FIELD The present invention relates to a method for producing a catalyst for synthesizing formaldehyde by the oxidation reaction of methylal or methanol.
（従来の技術） メチラール又はメタノールの酸化反応によりホルムア
ルデヒドを合成する触媒の製造方法は、特公昭39−1030
4号公報、特公昭50−4358号公報に開示されているが如
く、第２図のフロー工程図に示されるように、基本的に
はモリブデン及び鉄の塩の希薄溶液の混合により錯塩沈
澱物を得、この沈澱物を濾過、洗浄、乾燥、粉砕、成
形、焼成等の工程を経て製造されている。(Prior Art) A method for producing a catalyst for synthesizing formaldehyde by an oxidation reaction of methylal or methanol is disclosed in JP-B-39-1030.
As disclosed in Japanese Patent Publication No. 4 and Japanese Patent Publication No. 50358/1975, as shown in the flow chart of FIG. 2, basically, a complex salt precipitate is obtained by mixing dilute solutions of molybdenum and iron salts. And the precipitate is subjected to steps such as filtration, washing, drying, crushing, molding, and calcination.
（発明が解決しようとする課題） しかしながら、上記の方法は錯塩を生成させる条件が
反応活性に影響するために、反応活性の一定した触媒を
製造する事が難しい。また、生成した錯塩を濾過、洗
浄、乾燥及び粉砕する工程があり、煩雑な触媒製造工程
となっている。(Problems to be Solved by the Invention) However, in the above method, it is difficult to produce a catalyst having a constant reaction activity because the conditions for forming a complex salt affect the reaction activity. Further, there is a step of filtering, washing, drying and crushing the produced complex salt, which is a complicated catalyst manufacturing step.
本発明の目的は、メチラール又はメタノールの酸化反
応によりホルムアルデヒドを合成する触媒を製造するに
当たり、簡略な触媒製造方法を提供することである。An object of the present invention is to provide a simple catalyst production method for producing a catalyst for synthesizing formaldehyde by an oxidation reaction of methylal or methanol.
（課題を解決するための手段） 本発明は、メチラール又はメタノールの酸化反応によ
りホルムアルデヒドを合成する触媒を製造するに当た
り、モリブデン及び鉄、又はモリブデン及び鉄に加えア
ルカリ金属、アンチモン、アルミニウム、インジウム、
クロム、ケイ素、コバルト、タングステン、ニッケル及
びビスマスの群の中から選ばれた１種又はそれ以上の元
素から成る酸化物触媒を得るために、モリブデンに対し
て1.7倍モル以上、好ましくは2.0倍モル以上の硝酸を添
加して調製した液を噴霧乾燥し、得られた粉体を250〜6
00℃で焼成した後に、打錠成形する簡略化した触媒の製
造方法に関するものである。また、本発明の方法では、
打錠成形後に400〜600℃の温度で焼成を行っても良い。(Means for Solving the Problems) The present invention, in producing a catalyst for synthesizing formaldehyde by an oxidation reaction of methylal or methanol, molybdenum and iron, or molybdenum and iron, in addition to alkali metal, antimony, aluminum, indium,
In order to obtain an oxide catalyst composed of one or more elements selected from the group consisting of chromium, silicon, cobalt, tungsten, nickel and bismuth, the molar ratio is 1.7 times or more, preferably 2.0 times, the mol of molybdenum. The liquid prepared by adding the above nitric acid is spray-dried and the obtained powder is
The present invention relates to a method for producing a simplified catalyst which is tablet-molded after firing at 00 ° C. Further, in the method of the present invention,
Baking may be performed at a temperature of 400 to 600 ° C. after tableting.
本発明において、触媒の元素源としては水又は硝酸に
可溶なアンモニウム塩、硝酸塩、塩酸塩、硫酸塩、有機
酸塩、酸化物等の形で用いることが望ましい。特に、モ
リブデン、及びタングステンについてはアンモニウム塩
の形で、鉄、アルカリ金属、アルミニウム、インジウ
ム、クロム、コバルト、ニッケル及びビスマスは硝酸塩
の形で、ケイ素はシリカゾルの形で、アンチモンは酸化
物の形で用いるのが好適である。In the present invention, the element source of the catalyst is preferably used in the form of ammonium salts, nitrates, hydrochlorides, sulfates, organic acid salts, oxides, etc. which are soluble in water or nitric acid. In particular, molybdenum and tungsten in the form of ammonium salts, iron, alkali metals, aluminum, indium, chromium, cobalt, nickel and bismuth in the form of nitrates, silicon in the form of silica sols, antimony in the form of oxides. It is preferably used.
液の調製は、下記の２種類の液を混合する方法で行
う。The liquid is prepared by mixing the following two types of liquids.
Ａ液：パラモリブデン酸アンモニウム〔（NH4）6Mo7O
24・4H2O〕を水に溶解した液を用いる。溶解は約80℃で
行うことが好ましく、溶解後の液は室温まで放冷する。
タングステン源はＡ液に添加する。Liquid A: Ammonium paramolybdate [(NH 4 ) 6 Mo 7 O
24 · 4H the 2 O] using a solution obtained by dissolving in water. The dissolution is preferably performed at about 80 ° C., and the solution after the dissolution is allowed to cool to room temperature.
The tungsten source is added to the liquid A.
Ｂ液：硝酸鉄〔Fe（NO3）３・9H2O〕及びＡ液中の溶
解したモリブデンに対して1.7倍モル以上、好ましくは
2.0倍モル以上の硝酸を水に溶解した液を用いる。アル
カリ金属、アンチモン、アルミニウム、インジウム、ク
ロム、ケイ素、コバルト、ニッケル及びビスマスについ
ても、その元素源となる塩又は酸化物はＢ液に添加す
る。Solution B: iron nitrate [Fe (NO 3) 3 · 9H 2 O ] and 1.7-fold mole or more relative to the dissolved molybdenum A solution, preferably
Use a solution prepared by dissolving 2.0 times or more molar amount of nitric acid in water. Regarding alkali metals, antimony, aluminum, indium, chromium, silicon, cobalt, nickel and bismuth, salts or oxides serving as element sources thereof are added to the liquid B.
Ａ液及びＢ液の混合は、Ｂ液にＡ液を混合しても、ま
たＡ液にＢ液を混合しても良いが、好ましくはＢ液にＡ
液を混合する。混合する時には、液を十分撹拌しながら
行うことが必要である。The solutions A and B may be mixed with the solution B with the solution A or with the solution A with the solution B, but the solution B is preferably mixed with the solution A.
Mix the liquids. When mixing, it is necessary to stir the liquid sufficiently.
このとき、硝酸の量がモリブデンに対して1.7倍モル
未満では混合した液がゲル化し、噴霧乾燥できない。硝
酸の量がモリブデンに対して1.7倍モル以上では液が得
られる。この場合、モリフデンの一部がモリブデン酸塩
と成って沈澱することもあるが、触媒の製造工程上特に
問題は無い。At this time, if the amount of nitric acid is less than 1.7 times the molar amount of molybdenum, the mixed solution gels and cannot be spray-dried. A liquid is obtained when the amount of nitric acid is 1.7 times mol or more with respect to molybdenum. In this case, a part of the molyfden may be formed as a molybdate and precipitate, but there is no particular problem in the production process of the catalyst.
硝酸の量の上限は特に無いが、経済上の観点からモリ
ブデンに対して10倍モル程度が妥当である。There is no particular upper limit to the amount of nitric acid, but from an economic point of view, a molar ratio of about 10 times that of molybdenum is appropriate.
本発明において硝酸の代わりに塩酸又は硫酸を用いて
液を調製することもできるが、噴霧乾燥工程における腐
食等の問題が発生するため、硝酸を使用することが好適
である。In the present invention, a solution can be prepared by using hydrochloric acid or sulfuric acid instead of nitric acid, but nitric acid is preferably used because it causes problems such as corrosion in the spray drying step.
次に、この調製した液は噴霧乾燥により乾燥粉体とさ
れる。噴霧乾燥器は、通常、噴霧化装置、高温ガス供給
装置、乾燥室及び排出ガスから乾燥粉体を分離する装置
からなる。噴霧乾燥工程における本発明の調製した液の
噴霧化は通常工業的に実施される遠心方式、二流体ノズ
ル方式及び高圧ノズル方式のいずれによっても行いう
る。Next, the prepared liquid is spray-dried into a dry powder. The spray dryer usually consists of an atomizer, a hot gas supply, a drying chamber and a device for separating the dry powder from the exhaust gas. Atomization of the prepared liquid of the present invention in the spray-drying step can be carried out by any of a centrifugal system, a two-fluid nozzle system and a high-pressure nozzle system which are usually carried out industrially.
液を噴霧乾燥するための空気の熱源としては、間接水
蒸気、電気ヒーター等が用いられる。乾燥器入口温度は
150〜400℃、好ましくは200〜300℃の範囲である。Indirect steam, an electric heater, or the like is used as a heat source of air for spray-drying the liquid. The dryer inlet temperature is
It is in the range of 150 to 400 ° C, preferably 200 to 300 ° C.
噴霧乾燥で生成する粉体粒子の形状はほぼ球形であ
る。得られる粉体は上記の球体粒子とその破砕物の混合
物である。この粉体の大きさは、通常或る範囲に分布す
る。The shape of the powder particles produced by spray drying is almost spherical. The powder obtained is a mixture of the above spherical particles and their crushed products. The size of this powder is usually distributed in a certain range.
粉体粒子の粒径分布は、例えば、遠心方式による噴霧
乾燥では、液の供給速度、噴霧化装置の回転子の大きさ
及び回転数等によって希望する範囲に制御することがで
きる。本発明の方法によって得られる粉体粒子の大きさ
は５〜150μの範囲の分布が好ましい。The particle size distribution of the powder particles can be controlled in a desired range by the liquid supply rate, the size of the rotor of the atomizing device, the number of rotations, and the like in, for example, centrifugal spray drying. The size of the powder particles obtained by the method of the present invention is preferably in the range of 5 to 150 μm.
この様にして得られた粉体は、250〜600℃の温度で焼
成する。焼成温度が250℃未満では硝酸塩等の分解が不
十分であり、次工程以降で問題が起きる。また、焼成温
度が600℃を越えると触媒の結晶化が起き、表面積が低
下して反応活性が小さくなり、実用的でない。The powder thus obtained is fired at a temperature of 250 to 600 ° C. If the firing temperature is less than 250 ° C., decomposition of nitrates and the like is insufficient, causing problems in the subsequent steps. Further, if the calcination temperature exceeds 600 ° C., crystallization of the catalyst occurs, the surface area decreases and the reaction activity decreases, which is not practical.
得られた触媒粉体は離型剤として黒鉛、ステアリン酸
等を0.1〜10％に加えた後、打錠成形器により、通常、
径5mm、高さ4mmの円柱形又はラシヒリング形に打錠成型
されるが、これら成形された触媒の見掛け密度は1.5〜
2.8g/cm2であり、好ましくは2.0〜2.3g/cm3である。見
掛け密度が1.5g/cm2未満では成形品の強度が弱く、取扱
下が困難である。また、見掛け密度が2.8g/cm2を越える
と反応活性及び選択性が低下する。The obtained catalyst powder is added with graphite, stearic acid or the like as a release agent to 0.1 to 10%, and then, usually, with a tablet molding machine,
It is molded into a cylinder or Raschig ring shape with a diameter of 5 mm and a height of 4 mm, but the apparent density of these molded catalysts is 1.5-
It is 2.8 g / cm 2 , and preferably 2.0 to 2.3 g / cm 3 . If the apparent density is less than 1.5 g / cm 2 , the strength of the molded product is weak and it is difficult to handle. On the other hand, if the apparent density exceeds 2.8 g / cm 2 , the reaction activity and selectivity decrease.
また、打錠成形後に400〜600℃の温度で焼成を行って
も良い。本発明における触媒の粉体及び打錠成形体の焼
成時間は１〜10時間が好適である。In addition, firing may be performed at a temperature of 400 to 600 ° C. after tableting. The firing time of the powder of the catalyst and the tablet compacts in the present invention is preferably 1 to 10 hours.
以上、本発明の方法は、要約すると第１図に示される
フロー工程から構成される。In summary, the method of the present invention comprises the flow steps shown in FIG.
本発明においては、触媒が粉体として得られるため
に、粉体工程は必要としない利点がある。In the present invention, since the catalyst is obtained as a powder, there is an advantage that a powder step is not necessary.
（実施例） 次に本発明の実施例を具体的に説明するが、本発明は
これらに制限されない。(Examples) Next, examples of the present invention will be specifically described, but the present invention is not limited thereto.
（実施例１） （NH4）6Mo7O24・4H2O 1926gを水4800mlに溶解した
Ａ液とFe（NO3）３・9H2O 1700g及びCr（NO3）３・9H2
O 557gを水5,000mlに溶解し、更に62％硝酸を2,200g加
えてＢ液を調製する。硝酸／モリブデンの比は2.0であ
る。このＡ液を十分に撹拌しているＢ液に加えてＣ液を
つくる。このＣ液を、搭頂に円板型のアトマイザーを有
するサイクロン型噴霧乾燥器（直径1.4m）に８/Hrで
フィードした。円板の直径は80mmであり、回転数10,000
rpmで噴霧化した。空気の噴霧器入口温度は250℃に保っ
た。サイクロンの下部から触媒の粉体が得られ、これを
電気炉を用いて400℃で３時間焼成し、1,700gの触媒粉
体を得た。(Example 1) (NH 4) 6 Mo 7 O 24 · 4H 2 the O 1926G dissolved in water 4800 ml A solution and Fe (NO 3) 3 · 9H 2 O 1700g and Cr (NO 3) 3 · 9H 2
Dissolve 557 g of O in 5,000 ml of water, and further add 2,200 g of 62% nitric acid to prepare solution B. The nitric acid / molybdenum ratio is 2.0. This solution A is added to solution B which is sufficiently stirred to prepare solution C. This C liquid was fed at 8 / Hr into a cyclone type spray dryer (diameter 1.4 m) having a disk type atomizer at the top. The diameter of the disk is 80 mm and the rotation speed is 10,000.
Atomized at rpm. The air atomizer inlet temperature was maintained at 250 ° C. Catalyst powder was obtained from the lower part of the cyclone, and this was calcined in an electric furnace at 400 ° C. for 3 hours to obtain 1,700 g of catalyst powder.
この粉体の粒径は10〜120μに分布しており、平均粒
径は40μであった。The particle size of this powder was distributed in the range of 10 to 120μ, and the average particle size was 40μ.
この触媒粉体を打錠成形器で外径5mm、内径2mm、高さ
4mmのラシヒリング形に成型した。更に、この成型した
触媒を電気炉を用いて500℃で３時間焼成し、Mo2Fe0.75
Cr0.25Ｏ7.5の組成物を有する触媒を得た。Using a tablet press, this catalyst powder was compressed to an outer diameter of 5 mm, an inner diameter of 2 mm, and a height.
Molded into a 4mm Raschig ring. Furthermore, this molded catalyst was calcined in an electric furnace at 500 ° C. for 3 hours to give Mo 2 Fe 0.75
A catalyst having a composition of Cr 0.25 O 7.5 was obtained.
（実施例２） （NH4）6Mo7O24・4H2O 1,870gを水5,000mlに溶解し
たＡ液とFe（NO3）３・9H2O 1,224g及びCr（NO3）３・
9H2O 1,211g、KNO3 5g及び30％シリカゾル350gを水6,
000mlに溶解し、更に62％硝酸を3,500g加えたＢ液を調
製する。このＡ液を十分撹拌しているＢ液に加えてＣ液
をつくる。硝酸／モリブデンの比は3.3である。このＣ
液を実施例１と同じサイクロン型噴霧乾燥器に６/Hr
でフィードした。噴霧器の回転数は8,500rpm、空気の噴
霧器入口温度は275℃に保った。サイクロンの下部から
得られた触媒粉体を電気炉を用いて550℃で３時間焼成
して、1,750gの触媒粉体を得た。この粉体の粒径は15〜
150ミクロンに分布しており、平均粒径は45ミクロンで
あった。この触媒粉体を打錠成型器にて径5mm、高さ4mm
の円柱型に成型し、Mo1.75Fe0.5Cr0.5Ｋ0.008Si0.29の
組成を有する酸化物触媒を得た。(Example 2) (NH 4) 6 Mo 7 O 24 · 4H 2 O 1,870g and A solution prepared by dissolving in water 5,000ml Fe (NO 3) 3 · 9H 2 O 1,224g and Cr (NO 3) 3 ·
9H 2 O 1,211g, KNO 3 5g and 30% silica sol 350g in water 6,
Dissolve in 000 ml, and further add 3,500 g of 62% nitric acid to prepare solution B. This solution A is added to solution B which is sufficiently stirred to prepare solution C. The nitric acid / molybdenum ratio is 3.3. This C
The liquid was placed in the same cyclone type spray dryer as in Example 1 at 6 / Hr.
It was fed with. The number of revolutions of the atomizer was 8,500 rpm, and the inlet temperature of the air atomizer was maintained at 275 ° C. The catalyst powder obtained from the lower part of the cyclone was calcined in an electric furnace at 550 ° C. for 3 hours to obtain 1,750 g of catalyst powder. The particle size of this powder is 15 ~
It was distributed over 150 microns and had an average particle size of 45 microns. Using a tablet press, this catalyst powder is 5 mm in diameter and 4 mm in height.
To obtain an oxide catalyst having a composition of Mo 1.75 Fe 0.5 Cr 0.5 K 0.008 Si 0.29 .
（実施例３） 実施例１で製造した触媒を内径１インチの反応管に充
填し、メチラール:O2:N2＝1.2:22の混合ガスをSV＝20,0
00Hr-1で通過させて、270℃の熱媒の中で反応を行った
ところ、メチラールの転化率は100％、ホルムアルデヒ
ドの収率，は86,0％であった。(Example 3) The catalyst produced in Example 1 was filled in a reaction tube having an inner diameter of 1 inch, and a mixed gas of methylal: O 2 : N 2 = 1.2: 22 was added with SV = 20,0.
When the reaction was carried out in a heating medium at 270 ° C by passing it at 00Hr -1 , the conversion of methylal was 100% and the yield of formaldehyde was 86.0%.
また、フィードガスをメタノール:O2:N2＝1:1.5:14の
混合ガスに変え、SV＝15,000Hr-1で通過させて、260℃
の熱媒の中で反応を行ったところ、メタノールの転化率
は94％、ホルムアルデヒドの収率は85.5％であった。Also, the feed gas was changed to a mixed gas of methanol: O 2 : N 2 = 1: 1.5: 14 and passed at SV = 15,000Hr −1 , 260 ℃
When the reaction was carried out in a heating medium, the conversion of methanol was 94% and the yield of formaldehyde was 85.5%.
（比較例１） 実施例１において硝酸を1,100gにした以外は同じ条件
によりＣ液を調製した。硝酸／モリブデンの比は1.0で
あった。このＣ液はゲル化が著しく、噴霧乾燥すること
ができなかった。(Comparative Example 1) A liquid C was prepared under the same conditions as in Example 1 except that nitric acid was changed to 1,100 g. The nitric acid / molybdenum ratio was 1.0. This C liquid was extremely gelled and could not be spray dried.
（比較例２） 実施例２において、62％硝酸を1,600gにした以外は同
じ条件によりＣ液を調製した。硝酸／モリブデンの比は
1.5であった。このＣ液はゲル化し、噴霧乾燥できなか
った。(Comparative Example 2) A liquid C was prepared under the same conditions as in Example 2, except that 62% nitric acid was changed to 1,600 g. The ratio of nitric acid / molybdenum is
1.5. This C liquid gelled and could not be spray dried.
（実施例４〜13） 表に示す種々の組成の酸化物触媒について実施例１と
類似の方法で触媒を調製した。また、実施例３のメチラ
ールの酸化反応を行い、ホルムアルデヒドの収率を求め
た。(Examples 4 to 13) Oxide catalysts having various compositions shown in the table were prepared in the same manner as in Example 1. Further, the methylal oxidation reaction of Example 3 was performed to determine the yield of formaldehyde.
（比較例３） 実施例１の組成の触媒を特公昭39−10304号公報に記
載されている方法に準じて調製した。 Comparative Example 3 A catalyst having the composition of Example 1 was prepared according to the method described in JP-B-39-10304.
溶液Ａは（NH4）6Mo7O24・4H2O 145.0gを水1.4に
溶解したもので、塩酸を加えてPH4.4にした。Solution A (NH 4) a 6 Mo 7 O 24 · 4H 2 O 145.0g which was dissolved in water 1.4, and the PH4.4 by adding hydrochloric acid.
溶液Ｂ液は、FeCl3・6H2O 81.3gとCrCl3、6H2O 26.
5gを水2.2に溶解し、セルロース粉末20gを加えたもの
で、塩酸でPHを1.0に調節した。Solution B is FeCl 3 .6H 2 O 81.3g and CrCl 3 , 6H 2 O 26.
5 g was dissolved in 2.2 water, 20 g of cellulose powder was added, and the pH was adjusted to 1.0 with hydrochloric acid.
この２つの溶液を92℃に加熱し、溶液Ａを溶液Ｂに、
強く撹拌しながら徐々に注いだ。この懸濁液を18時間撹
拌した後に濾過した。この濾過物を濾過器の上で水１
で洗浄し、それからビーカーに移して水２を加えて混
合し、再び濾過した。濾過物を室温で１日、70℃で１日
そして110℃で１日乾燥した。The two solutions are heated to 92 ° C., solution A is solution B,
It was gradually poured with vigorous stirring. The suspension was stirred for 18 hours and then filtered. This filtered material is filtered on a filter to remove water 1
Washed with water, then transferred to a beaker, mixed with water 2 and filtered again. The filtrate was dried at room temperature for 1 day, 70 ° C for 1 day and 110 ° C for 1 day.
この生成物を16mesh（1.0mm）以下に粉砕し、実施例
１と同じラシヒリング形に打錠成型した。この触媒を電
気炉を用いて500℃で３時間焼成した。The product was crushed to 16 mesh (1.0 mm) or less and tableted into the same Raschig ring shape as in Example 1. The catalyst was calcined in an electric furnace at 500 ° C for 3 hours.
この触媒を実施例３と同じ方法でメチラールの酸化反
応を行った。メチラールの転化率は100％、ホルムアル
デヒドの収率は82.3％であった。また、メタノールの酸
化反応では、転化率91％、ホルムアルデヒドの収率は8
1.9％であった。This catalyst was subjected to the methylal oxidation reaction in the same manner as in Example 3. The conversion of methylal was 100% and the yield of formaldehyde was 82.3%. In the methanol oxidation reaction, the conversion rate was 91% and the formaldehyde yield was 8%.
It was 1.9%.
（発明の効果） 本発明では、モリブデン及び鉄を主要構成元素とす
る、ホルムアルデヒド製造用酸化物触媒の製造に当た
り、特定モル比の硝酸を添加したので、粉末状触媒が容
易に得られ、粉砕工程を要せず、高性能の酸化物系触媒
を簡略に製造できる。(Effect of the invention) In the present invention, nitric acid having a specific molar ratio was added in the production of an oxide catalyst for producing formaldehyde, which contains molybdenum and iron as main constituent elements, so that a powdery catalyst can be easily obtained, and a pulverization step can be performed. And a high-performance oxide-based catalyst can be simply manufactured.
第１図は、本発明の方法を要約的に説明するフロー工程
図である。 第２図は、従来例の方法を要約的に説明するフロー工程
図である。FIG. 1 is a flow process diagram for schematically explaining the method of the present invention. FIG. 2 is a flow process diagram that summarizes the method of the conventional example.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 23/16 Ｚ 23/74 Ｚ Ｃ０７Ｃ 47/04 9049−4Ｈ 47/052 9049−4Ｈ // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location B01J 23/16 Z 23/74 Z C07C 47/04 9049-4H 47/052 9049-4H // C07B 61/00 300
Claims (2)
りホルムアルデヒドを合成する触媒の製造方法であっ
て、モリブデン及び鉄、又はモリブデン及び鉄に加えア
ルカリ金属、アンチモン、アルミニウム、インジウム、
クロム、ケイ素、コバルト、タングステン、ニッケル及
びビスマスの群の中から選ばれた１種又はそれ以上の元
素から成る酸化物触媒を得るために、モリブデンに対し
て1.7倍モル以上の硝酸を添加して調製した液を噴霧乾
燥し、得られた粉体を250〜600℃で焼成した後に、打錠
成形することを特徴とする、ホルムアルデヒド合成用触
媒の製造方法。1. A method for producing a catalyst for synthesizing formaldehyde by the oxidation reaction of methylal or methanol, which comprises molybdenum and iron, or in addition to molybdenum and iron, alkali metal, antimony, aluminum, indium,
In order to obtain an oxide catalyst consisting of one or more elements selected from the group of chromium, silicon, cobalt, tungsten, nickel and bismuth, 1.7 times mole or more nitric acid is added to molybdenum. A method for producing a catalyst for synthesizing formaldehyde, which comprises spray-drying the prepared liquid, firing the obtained powder at 250 to 600 ° C., and then tableting.
る、請求項（１）記載の方法。2. The method according to claim 1, wherein the tablet-molded catalyst is calcined at 400 to 600 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002495A JPH0824848B2 (en) | 1990-01-11 | 1990-01-11 | Method for producing catalyst for synthesizing formaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002495A JPH0824848B2 (en) | 1990-01-11 | 1990-01-11 | Method for producing catalyst for synthesizing formaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03207450A JPH03207450A (en) | 1991-09-10 |
| JPH0824848B2 true JPH0824848B2 (en) | 1996-03-13 |
Family
ID=11530940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002495A Expired - Lifetime JPH0824848B2 (en) | 1990-01-11 | 1990-01-11 | Method for producing catalyst for synthesizing formaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0824848B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413584C (en) * | 2003-12-09 | 2008-08-27 | 南化集团研究院 | Fe-Mo catalyst for preparing formaldehyde through methanol oxidation and preparation process thereof |
| FR2997397B1 (en) * | 2012-10-29 | 2014-11-07 | Arkema France | PROCESS FOR THE DIRECT SYNTHESIS OF UNSATURATED ALDEHYDES FROM ALCOHOL MIXTURES |
| CN115845865B (en) * | 2022-12-13 | 2024-04-30 | 西南化工研究设计院有限公司 | Iron-molybdenum catalyst for preparing formaldehyde by methanol oxidation and preparation method thereof |
-
1990
- 1990-01-11 JP JP2002495A patent/JPH0824848B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03207450A (en) | 1991-09-10 |
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