JPS6320037A - Production of iron molybdate catalyst for oxidation - Google Patents
Production of iron molybdate catalyst for oxidationInfo
- Publication number
- JPS6320037A JPS6320037A JP61165234A JP16523486A JPS6320037A JP S6320037 A JPS6320037 A JP S6320037A JP 61165234 A JP61165234 A JP 61165234A JP 16523486 A JP16523486 A JP 16523486A JP S6320037 A JPS6320037 A JP S6320037A
- Authority
- JP
- Japan
- Prior art keywords
- iron
- catalyst
- iron molybdate
- reaction
- molybdate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000007254 oxidation reaction Methods 0.000 title claims description 13
- 230000003647 oxidation Effects 0.000 title claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000002506 iron compounds Chemical class 0.000 claims description 10
- 239000005078 molybdenum compound Substances 0.000 claims description 10
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 10
- 239000005909 Kieselgur Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 15
- 239000011733 molybdenum Substances 0.000 abstract description 15
- 239000007787 solid Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 37
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 36
- 238000001027 hydrothermal synthesis Methods 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 10
- 239000000725 suspension Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 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
- 241000755266 Kathetostoma giganteum Species 0.000 description 1
- 241000283986 Lepus Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- -1 iron molybdate Chemical class 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はモリブデン酸鉄からなる、又はモリブデン酸鉄
な活性成分とする酸化用触媒の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an oxidation catalyst consisting of iron molybdate or having iron molybdate as the active component.
酸化反応、例えば、メタノールを酸化してホルムアルデ
ヒドを得る方法としては、従来より金属特に金属銀を触
媒として用いる方法と、金属酸化物を用いる方法とが知
られており、画法とも工業的に実施されている。後者の
触媒として金属酸化物を用いる方法は、金属銀を用いる
方法に比べ、ホルムアルデヒドの収率が高く、またメタ
ノールの転化率が高いので実質上メタノールを含まない
ホルムアルデヒド水溶液が得られる点などですぐれてい
る。For oxidation reactions, for example, methods to obtain formaldehyde by oxidizing methanol, two methods have been known: one using a metal, especially metallic silver, as a catalyst, and the other using a metal oxide. has been done. The latter method using a metal oxide as a catalyst is superior to the method using metallic silver in that it has a higher yield of formaldehyde and a higher conversion rate of methanol, making it possible to obtain an aqueous formaldehyde solution that is substantially free of methanol. ing.
この目的で好ましい金属酸化物は鉄とモリブデンの酸化
物である。鉄の酸化物は、活性は高いが殆ど選択性がな
く、一方モリブデンの酸化物は、選択性は良いものの活
性が極めて低いため、鉄又はモリブデンの酸化物を単独
で使うことは好ましくない。メタノールのホルムアルデ
ヒドへの酸化において活性な触媒種は、モリブデン酸鉄
（Ｆｅｗ（ＭＯＯ４）ｓ）であることは良く知られてお
り、従って、モリブデンと鉄の原子比は／、ｊｔである
。しかしながら、実際に工業上用いられている触媒は、
常にかなり高い割合で過剰の三酸化モリブデンを含んで
いる。この理由は、メタノールをホルムアルデヒドへ酸
化する際に選択性の悪い、モリブデンの欠乏した触媒の
形成を防ぐためであるといわれている。また、三酸化モ
リブデンの存在は、最終生成触媒の、機械的特性を保つ
上でも、必要といわれている。Preferred metal oxides for this purpose are iron and molybdenum oxides. Iron oxides have high activity but almost no selectivity, while molybdenum oxides have good selectivity but very low activity, so it is not preferable to use iron or molybdenum oxides alone. It is well known that the active catalytic species in the oxidation of methanol to formaldehyde is iron molybdate (Few(MOO4)s), and therefore the atomic ratio of molybdenum to iron is /, jt. However, the catalysts actually used industrially are
It always contains a fairly high proportion of excess molybdenum trioxide. The reason for this is said to be to prevent the formation of a molybdenum-deficient catalyst with poor selectivity when methanol is oxidized to formaldehyde. Furthermore, the presence of molybdenum trioxide is said to be necessary to maintain the mechanical properties of the final catalyst.
このような過剰の三酸化モリブデンを含む触媒の問題点
は、反応条件下で三酸化モリブデンが気化し触媒床下部
に沈着することで、これによシ触媒の活性及び選択性が
低下し、また触媒の崩壊や触媒床の閉塞が起こり、事実
上反応の継続が困難となることである。また、反応に余
シ関与しない高価な三酸化モリブデンを多量に含むこと
自体経済的に好ましいことではない。The problem with such catalysts containing excess molybdenum trioxide is that under the reaction conditions the molybdenum trioxide vaporizes and deposits at the bottom of the catalyst bed, which reduces the activity and selectivity of the catalyst and also The catalyst collapses and the catalyst bed becomes clogged, making it virtually impossible to continue the reaction. Furthermore, it is not economically desirable to contain a large amount of expensive molybdenum trioxide, which does not take any part in the reaction.
特公昭３９．−１０３０ダ号によれば、追加的にクロム
を含む触媒が開示されている。これＫよれば、触媒の安
定性が増すことが示されているが、触媒の基本的組成は
変わらず、上記の問題点を十分解決してはいない。尚、
これら従来の触媒の調製方法は、鉄及びモリブデンの可
溶性塩を含む溶液から複合塩の沈澱を形成させ、成形後
高温で焼成する方法である。この場合の生成沈澱は実質
上無定形の固体であシ、これを焼成することＫより、メ
タノールのホルムアルデヒドへの酸化に活性なモリブデ
ン酸鉄を含む触媒が形成される。Tokuko Showa 39. No. 1030-1030 discloses catalysts which additionally contain chromium. According to K, it has been shown that the stability of the catalyst is increased, but the basic composition of the catalyst remains unchanged and the above-mentioned problems have not been sufficiently solved. still,
These conventional catalyst preparation methods involve forming a complex salt precipitate from a solution containing soluble salts of iron and molybdenum, forming the precipitate, and then calcining the precipitate at a high temperature. The precipitate produced in this case is a substantially amorphous solid, and by calcining it, a catalyst containing iron molybdate active in the oxidation of methanol to formaldehyde is formed.
一方、特開昭！；／−３３４９０号には、モリブデンの
鉄に対する原子比かへＳ−八りであるモリブデン酸鉄を
水溶液中で生成させる方法が開示されている。これによ
れば、触媒は以下の方法により製造される：
ａ）ｐＨ／、♂−ｊ、Ｊの可溶性モリブデン酸塩溶液と
可溶性第二鉄塩溶液をモリブデンの鉄に対する原子比が
少なくとも八Ｓとなるような割合で２０−１０℃の温度
で混合することばよシ無定形沈澱物を得、
ｂ） この懸濁液を７０℃から沸点までの温度で少なく
とも３０分加熱して、無定形の沈澱物を少なくともり０
チの結晶化度を有するモリブデン酸鉄に変成させ、
Ｃ）得られた沈澱物を洗浄して固体分のモリブデンの鉄
に対する原子比をへ！；−／、７とし、ｄ）該洗浄物を
１２０℃を超えない温度で少なくとも３０分間乾燥する
。On the other hand, Tokukai Akira! ;/-33490 discloses a method for producing iron molybdate in an aqueous solution in which the atomic ratio of molybdenum to iron is S-8. According to this, the catalyst is prepared by the following method: a) A soluble molybdate solution and a soluble ferric salt solution at pH/,♂-j,J are mixed in such a manner that the atomic ratio of molybdenum to iron is at least 8S. b) heating this suspension for at least 30 minutes at a temperature from 70°C to the boiling point to obtain an amorphous precipitate; At least 0
C) The resulting precipitate is washed to reduce the atomic ratio of molybdenum to iron in the solid content. ;-/, 7, and d) drying the washed product at a temperature not exceeding 120° C. for at least 30 minutes.
このような方法で得られる触媒は、遊離の三酸化モリブ
デンを殆ど含まず実質的にモリブデン酸鉄から成シ立っ
ている点で従来の触媒とは異なる。The catalyst obtained by such a method differs from conventional catalysts in that it contains almost no free molybdenum trioxide and consists essentially of iron molybdate.
しかしながら、上記に示されたように、触媒を調製する
だめの実施態様は極めて煩雑であるばかりでなく、原料
となる可溶性モリブデン酸塩及び第二鉄塩溶液のｐＨは
、それぞれへＳ−２、ｇ、ｉ、ｉ−八Ｓのように限定さ
れる。However, as shown above, not only is the implementation of the catalyst preparation extremely complicated, but the pH of the starting soluble molybdate and ferric salt solutions is adjusted to S-2, S-2, and S-2, respectively. g, i, i-8S.
また、生成した無定形沈澱物をモリブデン酸鉄に変成す
るに際しては、ｐＨ値や温度の他、モリブデンと鉄の比
、水の分量や水の還流比などが影響を与え、場合により
目的とするモリブデン酸鉄が生成しないこともあり、こ
の操作は限定条件が多く煩雑であシ、かつ再現性に乏し
いものであった。In addition, when converting the generated amorphous precipitate into iron molybdate, in addition to the pH value and temperature, the ratio of molybdenum to iron, the amount of water, the reflux ratio of water, etc. have an influence, and depending on the case, the purpose Iron molybdate may not be produced, and this operation is complicated with many limited conditions and has poor reproducibility.
本発明者等は、上記問題点に鑑み種々検討した結果、モ
リブデン化合物及び鉄化合物を水熱合成することにより
、容易にかつ再現性良くモリブデン酸鉄が得られ、かつ
このモリブデン酸鉄は酸化用触媒として適していること
を見出し本発明に到達した。As a result of various studies in view of the above problems, the present inventors have found that iron molybdate can be easily and reproducibly obtained by hydrothermally synthesizing a molybdenum compound and an iron compound, and that this iron molybdate can be used for oxidation. The present invention was achieved by discovering that it is suitable as a catalyst.
すなわち、本発明の要旨は、モリブデン化合物及び鉄化
合物から酸化用モリブデン酸鉄触媒を製造する方法にお
いて、モリブデン化合物及び鉄化合物を、１００℃を越
える温度及び加圧下で水熱合成することによりモリブデ
ン酸鉄な生成せしめることを特徴とする酸化用モリブデ
ン酸鉄触媒の製造方法に存する。That is, the gist of the present invention is to provide a method for producing an iron molybdate catalyst for oxidation from a molybdenum compound and an iron compound by hydrothermally synthesizing a molybdenum compound and an iron compound at a temperature exceeding 100° C. and under pressure. The present invention relates to a method for producing an iron molybdate catalyst for oxidation, which is characterized in that it produces iron.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明におけるモリブデン酸鉄の合成の原料としては、
モリブデン及び鉄の化合物が用いられる。モリブデン化
合物としては、バラモリブデン酸アンモニウムやジモリ
ブデン酸アンモニウムのような水溶性モリブデン酸塩が
好適に用いられるが、その他の水溶性または不溶性のモ
リブデン化合物、例えば三酸化モリブデンのようなもの
もまた使用可能であり、これは本法の大きな利点の一つ
である。Raw materials for the synthesis of iron molybdate in the present invention include:
Compounds of molybdenum and iron are used. As molybdenum compounds, water-soluble molybdates such as ammonium rosemolybdate and ammonium dimolybdate are preferably used, but other water-soluble or insoluble molybdenum compounds such as molybdenum trioxide can also be used. This is one of the major advantages of this method.
鉄化合物としては、これも特にその種類を限定するもの
ではないが、通常、硝酸第二鉄、塩化第二鉄等の可溶性
塩から選ばれる。The type of iron compound is not particularly limited, but it is usually selected from soluble salts such as ferric nitrate and ferric chloride.
原料におけるモリブデン化合物と鉄化合物の使用量は、
通常、モリブデンの鉄に対する原子比／からコの間で選
択される。モリブデン酸鉄の原子比は／、Ｊであるので
、好ましくは八３がら八７である。原子比かこれより大
きくても水熱法では、モリブデン酸鉄の生成が妨げられ
る訳ではないがモリブデン酸鉄の他に三酸化モリブデン
などが共存する結果となる。The amount of molybdenum compounds and iron compounds used in raw materials is
Typically, the atomic ratio of molybdenum to iron is selected between / and . Since the atomic ratio of iron molybdate is /, J, it is preferably 83 to 87. Even if the atomic ratio is larger than this, in the hydrothermal method, the production of iron molybdate is not hindered, but molybdenum trioxide and the like coexist in addition to iron molybdate.
上記モリブデン化合物及び鉄化合物を水熱合成し、モリ
ブデン酸鉄を生成せしめる。The molybdenum compound and iron compound are hydrothermally synthesized to produce iron molybdate.
モリブデン化合物及び鉄化合物は、通常、水性溶液とし
て反応に供給するが、この溶液の調製方法は特に限定さ
れない。例えばモリブデン１ヒ金物及び鉄の化合物の各
々の水溶液をっくシ、これらを混合して不溶性の沈澱物
を得、この懸一方の化合物が不溶性であれば、他方の化
合物の水溶液にこれを加えてそのまま用いつる。The molybdenum compound and iron compound are usually supplied to the reaction as an aqueous solution, but the method for preparing this solution is not particularly limited. For example, prepare an aqueous solution of molybdenum, an arsenic compound, and an iron compound, mix them to obtain an insoluble precipitate, and if one compound is insoluble, add this to an aqueous solution of the other compound. Use it as is.
これら化合物に加える水の量には特に制限はない。また
、水溶液あるいは、懸濁液に例えば鉱酸等を加え所望の
ｐＨに調節してもよいが、これは必ずしも必須ではない
。There is no particular limit to the amount of water added to these compounds. Furthermore, it is possible to adjust the pH to a desired level by adding, for example, a mineral acid to the aqueous solution or suspension, but this is not always essential.
水熱合成の温度は１００℃を越える温度とし、通常−０
０℃以下の温度で行なう。反応は加圧下に行なうが、こ
れは通常自生圧、即ち水の蒸気正分で十分である。水熱
合成の際、攪拌は必ずしも必須ではないが、モリブデン
酸鉄の生成速度を速めるうえで好ましい。また、反応時
間は、約３０分程度から数日間のあいだで適宜選択され
る。The temperature for hydrothermal synthesis is over 100℃, usually -0
Carry out at a temperature below 0°C. The reaction is carried out under pressure, which is usually autogenous pressure, ie, a positive vapor fraction of water is sufficient. Although stirring is not necessarily essential during hydrothermal synthesis, it is preferable in order to speed up the production rate of iron molybdate. Further, the reaction time is appropriately selected from about 30 minutes to several days.
水熱合成から得られる固形物はモリブデン酸鉄な主成分
とし、これに対して次に水洗を十分におこなう。必要な
らば酸性の水あるいは熱水を用いるのも良い方法である
。洗浄された固形物は次いで約ｉｏｏ℃から２００℃程
度で乾燥され、最終的にモリブデン酸鉄の結晶からなる
固体がえられる。このものがモリブデン酸鉄（Ｆｅ２
（ＭＯ０４）ｓ ）であることはＸ線解析によシ確認さ
れる。The solid material obtained from hydrothermal synthesis has iron molybdate as its main component, and is then thoroughly washed with water. It is also a good idea to use acidic water or hot water if necessary. The washed solid material is then dried at about 100° C. to about 200° C. to finally obtain a solid consisting of crystals of iron molybdate. This material is iron molybdate (Fe2
(MO04)s ) is confirmed by X-ray analysis.
このようにして合成されたモリブデン酸鉄は、これをこ
のまま、あるいは成形して触媒として使用しつる。ある
いはこれを３００ ’（：、から１．．００℃程度の温
度で焼成してから使用しても良い。The iron molybdate thus synthesized can be used as a catalyst as it is or after being shaped. Alternatively, this may be used after being fired at a temperature of about 300°C to 1.00°C.
特に好ましい焼成温度は３ Ｊ Ｏ’Ｃからｌ！、、ｔ
Ｏ’Ｃである。Particularly preferred firing temperatures range from 3 J O'C to l! ,,t
It's O'C.
合成されたモリブデン酸鉄沈反応に不活性な担体成分を
加えて成形し、適当な粒径として反応に供するのは、反
応のコントロール、触媒粒子への機械的強度の賦与、経
済的見地などから云って好ましいことである。The reason for adding an inert carrier component to the synthesized iron molybdate precipitation reaction and molding it into particles of an appropriate size for the reaction is to control the reaction, impart mechanical strength to the catalyst particles, and from an economic standpoint. That's a good thing.
担体成分としては、アルミナ、シリカ、シリカ−アルミ
ナ、チタニア、ジルコニア、珪藻土、天然粘土、合成粘
土あるいはゼオライトなどが好適に使用できる。珪藻土
は特に好ましい担体成分である。担体成分の触媒全体に
対する添加量は特に限定されないが、１０％ないしｑＯ
％程度から選ばれる。モリブデン酸鉄に担体成分を加え
るにあたっては、更に追加的に結合剤や滑剤などを加え
ても良い。また、成形方法としては打錠、押出しなど各
種の公知の方法がとりつる。As the carrier component, alumina, silica, silica-alumina, titania, zirconia, diatomaceous earth, natural clay, synthetic clay, or zeolite can be suitably used. Diatomaceous earth is a particularly preferred carrier component. The amount of the carrier component added to the entire catalyst is not particularly limited, but is between 10% and qO
Selected from approximately %. When adding a carrier component to iron molybdate, a binder, a lubricant, etc. may be additionally added. In addition, various known methods such as tableting and extrusion can be used as the molding method.
担体成分と混合せられた触媒を調製するに当たって、担
体となるべき成分を予め加えた形で水熱合成を行うこと
もまた可能である。このような方法は触媒製造ｉ程を短
縮できるという意味でも有利なことである。In preparing a catalyst mixed with a carrier component, it is also possible to carry out hydrothermal synthesis with the component to be a carrier added in advance. Such a method is also advantageous in the sense that the catalyst production steps can be shortened.
また、水熱合成時、あるいはその後の過程で触媒として
有効な第三の成分例えばクロムの化合物などを小量添加
しても良い。Further, a small amount of a third component effective as a catalyst, such as a chromium compound, may be added during hydrothermal synthesis or in a subsequent process.
本発明の触媒は、酸化反応、特にメタノールの接触酸化
によるホルムアルデヒドの製造に極めて有効である。反
応に当たっては、まず触媒を上記した手法によシ所望の
大きさの粒子にするのが好ましい。反応形式としては、
通常固定床が用いられる。また反応が発熱反応であるの
で、除熱の為通常外部に循環流体を配した管状反応器を
用いるのが好ましい。The catalyst of the present invention is extremely effective in oxidation reactions, particularly in the production of formaldehyde by catalytic oxidation of methanol. In carrying out the reaction, it is preferable to first form the catalyst into particles of a desired size by the method described above. The reaction format is
A fixed bed is usually used. Furthermore, since the reaction is exothermic, it is preferable to use a tubular reactor with a circulating fluid provided outside for heat removal.
反応に際しては、メタノール、酸素、窒素な含むガス状
混合物を、普通、触媒／ ｍｌに対し毎時Ｓ〜／！；Ｍ
ｌ程度の割合で本発明の触媒に供給する。本反応は、通
常酸素過剰の条件下で行うが、爆発の危険を避ける為爆
発限界外で操作する必要がある。During the reaction, a gaseous mixture containing methanol, oxygen, and nitrogen is normally added at a rate of S~/!/ml of catalyst per hour. ;M
1 of the catalyst of the present invention. This reaction is normally carried out under conditions of excess oxygen, but must be operated outside the explosive limits to avoid the risk of explosion.
反応温度は、２００℃からダＳθ℃、好ましくは２ＳＯ
℃からｑ ｏ Ｏ’Ｃの間で行なわれる。The reaction temperature is from 200°C to 2SO°C, preferably 2SO
It is carried out between ℃ and q o O'C.
本発明方法が酸化用触媒としてのモリブデン酸鉄生成に
効果がある理由は必ずしも明らかではないが、水熱条件
が平衡的にモリブデン酸鉄生成に有利である為と思われ
る。The reason why the method of the present invention is effective in producing iron molybdate as an oxidation catalyst is not necessarily clear, but it is thought to be because the hydrothermal conditions are equilibriumally favorable to producing iron molybdate.
本発明における触媒の製造方法は、従来の技術に較べ著
しく簡単である。また、得られた触媒の機械的強度も大
きく、余分な三酸化モリブデンを含まないので反応中の
モリブデンの気化沈着が起こらず、従って触媒の粉化や
反応器の閉塞と云った問題が避けられ、長期間安定した
運転が続けられ、優れた触媒が得られる。The method for producing a catalyst according to the present invention is significantly simpler than conventional techniques. In addition, the resulting catalyst has high mechanical strength and does not contain excess molybdenum trioxide, so molybdenum vaporization and deposition during the reaction does not occur, thus avoiding problems such as catalyst pulverization and reactor clogging. , stable operation can be continued for a long period of time, and an excellent catalyst can be obtained.
特に、メタノールの酸化によるホルムアルデヒドの製造
に用いた場合、メタノールの転化率が高く同時にホルム
アルデヒドへの選択率が高いので、工業的に優れたもの
である。In particular, when used in the production of formaldehyde by oxidizing methanol, the conversion rate of methanol is high and at the same time the selectivity to formaldehyde is high, so it is industrially excellent.
以下、実施例をあげて本発明を更に詳しく説明するが、
これによって本発明の範囲を限定するものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples.
This is not intended to limit the scope of the invention.
実施例／ 市販のバラモリブデン酸アンモニウム（ＣＩＪ＆）。Example/ Commercially available ammonium rosemolybdate (CIJ&).
ＭＯ？Ｏｔａ ”ＩＨｘＯ） ９− ’ｌ ｊ Ｆを脱
イオン水１００ｍ１に溶解し、水溶液を調製する。この
水溶液に硝酸を加えてｐＨを八７とした。別に硝酸第二
鉄（Ｆｅ（ＮＯＩ）Ｓ−９ＨｔＯ） ／ ｒ、 Ｏｐを
脱イオン水ｉｏ。MO? Prepare an aqueous solution by dissolving Ota"IHxO) 9-'lj F in 100 ml of deionized water. Nitric acid was added to this aqueous solution to adjust the pH to 87. Separately, ferric nitrate (Fe(NOI)S- 9HtO)/r, Op deionized water io.
ｍｌに溶解し、更に硝酸を加えてｐＨを八／３とした。ml and further added nitric acid to adjust the pH to 8/3.
このモリブデンの水溶液に、鉄の水溶液を室温で攪拌下
ゆっくり添加し、更に３０分攪拌を続けた。この操作で
黄色の沈澱物が生じた。この時の原料のＭＯ／／Ｆ′ｅ
比は八りｔであり、またｐＨはｉ、ｓｓであった。An aqueous iron solution was slowly added to this aqueous molybdenum solution at room temperature with stirring, and stirring was continued for an additional 30 minutes. This operation produced a yellow precipitate. MO of raw material at this time //F'e
The ratio was 8 t, and the pH was i, ss.
この沈澱物を含む懸濁液を攪拌機を備えたチタン製の／
ｌオートクレーブに入れ密閉し、電気炉中で昇温、攪拌
下／ ！ ０ ’Ｃ１３時間水熱合成を行った。The suspension containing this precipitate was stirred in a titanium/
l Place in an autoclave, seal it, raise the temperature in an electric furnace, and stir/! Hydrothermal synthesis was carried out at 0'C for 13 hours.
反応を停止後、室温に戻し、固形分をろ過により取得し
、これを熱水で洗浄ろ過を数回繰り返した。After stopping the reaction, the temperature was returned to room temperature, solid content was obtained by filtration, and washing and filtration with hot water were repeated several times.
このようにして得られた固形分を／ ００ ’（：で−
昼夜乾燥した。収量￥ｉｇ、ざｊＩであった。The solid content obtained in this way is / 00' (: -
Dry day and night. The yield was ¥ig, zajI.
ｔた、コレのＸ線回折を測定したところ、モＨｏへ
リプデン酸鉄（Ｆｅ、（蜘−３）であり、実質上三酸化
゛モリブデン（ＭＯＯ，）を含んでいないことがわかっ
た。When X-ray diffraction of this was measured, it was found that it was iron molybdate (Fe, (Spider-3)) and did not substantially contain molybdenum trioxide (MOO,).
実施例２
モリブデン及び鉄の水溶液の硝酸によるｐＨ調節をおこ
なわなかった以外は、実＃Ｊ例／と同様にして水熱合成
及びその後の処理をおこなった。収量はｑ、ｓ、ｙｉで
あった。Example 2 Hydrothermal synthesis and subsequent treatments were carried out in the same manner as Example #J, except that the pH of the aqueous solution of molybdenum and iron was not adjusted with nitric acid. The yield was q, s, yi.
このもののＸ線回折を測定したところ、モリプデン酸鉄
であシ、三酸化モリブデンは含んでいなかった。When X-ray diffraction of this material was measured, it was found that it was iron molybdate and did not contain molybdenum trioxide.
実施例３
硝酸によるｐＨ調節は行わない以外は実施倒れを実施例
／と同様にしてオートクレーブで／！；Ｏ”Ｑ、！；時
間水熱合成を行った。但し、反応中攪拌は行わなかった
。Example 3 The procedure was carried out in the same manner as in Example except that the pH was not adjusted with nitric acid, but in an autoclave. ;O''Q,!;Hydrothermal synthesis was carried out for an hour. However, stirring was not performed during the reaction.
得られた固形物を実施例／と同様に処理して、ワ、７７
ｙの固体を得た。The obtained solid was treated in the same manner as in Example 77.
y solid was obtained.
この固体物質は、外見の色調から不均一であったがＸ線
回折からもモリブデン酸鉄以外にも小量の三酸化モリブ
デン等が認められた。This solid substance was non-uniform in appearance, but X-ray diffraction revealed small amounts of molybdenum trioxide in addition to iron molybdate.
実施例亭
水熱合成を３０時間とした以外は実施例３と同様にして
水熱合成を行った。Example Tei Hydrothermal synthesis was carried out in the same manner as in Example 3, except that the hydrothermal synthesis was carried out for 30 hours.
得られたもの（収量ｇ、ｈ ｏ ｇ）のＸ線回折測定結
果は、モリブデン酸鉄であり実質上三酸化モリブデンが
含まれていないことを示した。X-ray diffraction measurement results of the obtained product (yield g, h o g) showed that it was iron molybdate and substantially free of molybdenum trioxide.
無攪拌下であっても、時間を十分にとればモリブデン酸
鉄が容易に生成することがわかる。It can be seen that iron molybdate can be easily produced even without stirring if sufficient time is allowed.
実施例Ｓ
実施例Ｊと同様に懸濁液を作った。次に、これに市販の
珪藻土を３７．３ｊ９加えてからオートクレーブに仕込
み、／ ！； ０ ℃、／Ｓ時間水熱合成を行った。Example S A suspension was made as in Example J. Next, add 37.3j9 of commercially available diatomaceous earth to this and place it in an autoclave, /! ; Hydrothermal synthesis was performed at 0° C. for /S hours.
これを実施例／と同様に処理して得られたもののＸ線回
折を行なったところ、珪藻土以外にはモリブデン酸鉄の
みであった。This was treated in the same manner as in Example 1, and when X-ray diffraction was performed on the obtained product, only iron molybdate was found in addition to diatomaceous earth.
実施例６
硝酸第二鉄ｉｓ、ｏｇを水２００ｍ１に溶解した水溶液
を作った。これに三酸化モリブデン７．７３成を行った
。以下同様に処理して得られたもの（収量？、Ｊ Ｊ
ｉ ）のＸ線回折は、これがモリブデン酸鉄であシ実質
的に三酸化モリブデンが含まれていないことを示した。Example 6 An aqueous solution was prepared by dissolving ferric nitrate is, og in 200 ml of water. This was subjected to 7.73% molybdenum trioxide formation. The following was obtained by the same treatment (yield?, J J
X-ray diffraction of i) showed that it was iron molybdate and was essentially free of molybdenum trioxide.
実施例７
バラモリブデン酸アンモニウムｌθ、ｌｂ＆を脱イオン
水１００ｍ１ｌ／Ｃ溶解した水溶液に硝酸第二鉄ｉｓ、
ｏｏｉを脱イオン水ｉｏｏｍｔに溶解した水溶液を加え
懸濁液を得た。この時のＭｏ／Ｐ ｅ比はｉ、ｓｓであ
った。Example 7 Ferric nitrate is,
An aqueous solution of ooi dissolved in deionized water ioomt was added to obtain a suspension. The Mo/P e ratio at this time was i, ss.
この懸濁液を／ｌのチタン製オートクレーブに仕込み、
攪拌下、ｉｓｏ℃、３時間水熱合成を行った。反応停止
後室温に戻し、沈澱物をろ過し、更にこれを熱水で洗浄
ろ過を数回繰シ返したのち、１００℃で一昼夜乾燥した
。収量はｑ、ｓｏｇであった。This suspension was charged into a /l titanium autoclave.
Hydrothermal synthesis was carried out at iso° C. for 3 hours while stirring. After the reaction was stopped, the temperature was returned to room temperature, the precipitate was filtered, and the precipitate was washed and filtered several times with hot water, and then dried at 100° C. for a day and a night. The yield was q, sog.
このもののＸ線回折測定結果はこれがモリブデン酸鉄で
あり、実質的に三酸化モリブデンを含まないことを示し
た。X-ray diffraction measurements of this material showed it to be iron molybdate and substantially free of molybdenum trioxide.
実施例ｇ
バラモリブデン酸アンモニウムがｉｏ、ｓｏｇであシ、
硝酸第二鉄が／ ！；、００１であること以外は実施例
りと同様にして懸濁液を作った。この時のＭｏ／Ｆｅ比
は八６０であった。この懸濁液を実施例７と同様にして
水熱合成とその後の処理を行い１０．／！；！の固体粉
末物質を得た。Example g Ammonium baramolybdate is io, sog,
Ferric nitrate/! ;,001, a suspension was prepared in the same manner as in Example. The Mo/Fe ratio at this time was 860. This suspension was subjected to hydrothermal synthesis and subsequent treatments in the same manner as in Example 7. 10. /! ;! A solid powder material was obtained.
このものはＸ線回折によると大部分がモリブデン酸鉄で
あったが、小量の三酸化モリブデンを含んでいることが
わかった。According to X-ray diffraction, this material was mostly iron molybdate, but it was found that it contained a small amount of molybdenum trioxide.
実施例？
バラモリブデン酸アンモニウム１０．／Ａｔ／ヲ脱イオ
ン水１００尼に溶解し、更に硝酸を加えてｐＨを八ｇｏ
にした。一方、塩化第二鉄（ＦｅＣ！１ｓ−ＡＨ，Ｏ）
／ ０．０、．７ ＆を脱イオン水１００ｍ１に溶解
し、アンモニア水でｐＨを／、３ｏとした。この二つの
液を併せて懸濁液を作った。この時のＭＯ７’Ｆ ｅ比
は八ＳＳであった。Example? Ammonium rosemolybdate 10. /At/ was dissolved in 100% deionized water and the pH was adjusted to 80% by adding nitric acid.
I made it. On the other hand, ferric chloride (FeC!1s-AH,O)
/ 0.0,. 7& was dissolved in 100 ml of deionized water and the pH was adjusted to 3o with aqueous ammonia. These two solutions were combined to make a suspension. The MO7'Fe ratio at this time was 8SS.
以下この懸濁液を実施例りと全く同様にして水熱合成及
びその後の処理を行いｉｏ、ｉｇｇの固体粉末物質を得
た。Thereafter, this suspension was subjected to hydrothermal synthesis and subsequent treatments in exactly the same manner as in the example to obtain solid powder substances of io and igg.
このもののＸ線回折結果はモリブデン酸鉄であり、実質
的に三酸化モリブデンを含んでいなかった。The X-ray diffraction results of this material showed that it was iron molybdate, and it contained substantially no molybdenum trioxide.
参考例／
実施例コで得られたモリブデン酸鉄からなる触媒を打錠
成形し、空気流中で’１００′Ｃ，２時間焼成した。こ
れを破砕して粒径を約２龍に揃えた。この触媒ｓ、ｘｍ
ｌ （ａ、／ｂ ｇ ）に、はぼ等量のガラスピーズ（
３朋径〕をまぜて希釈した後、これを内径ユ２朋のガラ
ス製反応器に配置した。反応器にメタノール、空気及び
窒素を各々１１．３９／ｈｒ、 ／ ！；、６Ｎｌ／ｈ
ｒ、 ／ ７．９ Ｎ７／ｈｒの流量で供給した。混合
ガス中のメタノール及び酸素のモル分率は各々ｇ及び９
チであシ、またカス空間速度（ＧＨ３Ｖ）はｑｏｏｏ／
ｈｒであった。Reference Example/The catalyst made of iron molybdate obtained in Example 1 was molded into tablets and calcined in an air stream at 100°C for 2 hours. This was crushed to have a particle size of about 2 dragons. This catalyst s, xm
l (a, /b g ), add approximately the same amount of glass peas (
3 mm diameter] were mixed and diluted, and then placed in a glass reactor with an internal diameter of 2 mm. Methanol, air and nitrogen were added to the reactor at 11.39/hr each, /! ;, 6Nl/h
r,/7.9 N7/hr. The molar fractions of methanol and oxygen in the mixed gas are g and 9, respectively.
It's a good idea, and the space velocity (GH3V) is qoooo/
It was hr.
電気炉にて所定温度まで昇温し反応を開始した。生成物
はガスクロマトグラフィーによシ分析した。The reaction was started by raising the temperature to a predetermined temperature in an electric furnace. The product was analyzed by gas chromatography.
反応開始後７０時間における成績は次の通りであった。The results 70 hours after the start of the reaction were as follows.
（反応器入口温度：２９０℃ 触媒床最高温度：３６０
℃）
メタノール転化率：ざ９チ
転化したメタノールからホルムアルデヒドへの選択率＝
り９％
参考例−
実施例７で得られたモリブデン酸鉄からなる触媒を参考
例１と同様に成形、焼成、破砕し、この触媒ｓ、ｓｍｌ
を等量のガラスピーズで希釈後反応器に充填した。次い
で参考例／と同様な反応条件で反応を行った。(Reactor inlet temperature: 290℃ Maximum catalyst bed temperature: 360℃
°C) Methanol conversion rate: Selectivity from converted methanol to formaldehyde =
Reference Example - The catalyst made of iron molybdate obtained in Example 7 was molded, calcined, and crushed in the same manner as in Reference Example 1, and the catalyst s, sml
was diluted with an equal amount of glass beads and charged into a reactor. Next, a reaction was carried out under the same reaction conditions as in Reference Example.
反応開始後７０時間での成績は次の通りであった。The results 70 hours after the start of the reaction were as follows.
（反応器入口温度：コ！；Ｏ’Ｃ触媒床最高温度： 、
？ ｌＩＯ’Ｃ）
メタノール転化率＝９６％
ホルムアルデヒド選択率：ｇｑｑ６
参考例３
実施例りで得られたモリブデン酸鉄からなる触媒を参考
例１と同様に成形、焼成、破砕し、この触媒３．２ ｍ
ｌを等量のガラスピーズで希釈後反応器沈充填した。次
いで参考例／と同様な反応条件で反応を行った。(Reactor inlet temperature: Ko!; O'C catalyst bed maximum temperature: ,
? lIO'C) Methanol conversion rate = 96% Formaldehyde selectivity: gqq6 Reference Example 3 The catalyst made of iron molybdate obtained in Example 1 was molded, calcined, and crushed in the same manner as Reference Example 1, and this catalyst 3.2 m
1 was diluted with an equal amount of glass beads and charged into the reactor. Next, a reaction was carried out under the same reaction conditions as in Reference Example.
反応開始後７２時間での成績は次の通シであった。The results 72 hours after the start of the reaction were as follows.
（反応器入口温度：２６０℃ 触媒床最高温度＝３７３
℃〕
メタノール転化率Ｈｑｇチ
ホルムアルデヒド選択率：９３チ
参考例ダ
実施例ｔで得られたモリブデン酸鉄からなる触媒１０部
と市販の珪藻±２０部とを良く混合したのち、参考例／
と同様に成形、焼成、破砕を行い、この触媒ｓ、 ｓ
ｍｌを等量のガラスピーズで希釈後反応器に充填した。(Reactor inlet temperature: 260℃ Maximum catalyst bed temperature = 373
°C] Methanol conversion Hqg Thiformaldehyde selectivity: 93 Chi Reference Example DA After thoroughly mixing 10 parts of the catalyst made of iron molybdate obtained in Example t and ±20 parts of commercially available diatom, Reference Example/
The catalysts s, s are molded, fired, and crushed in the same manner as
ml was diluted with an equal amount of glass beads and then filled into the reactor.
次いで参考例／と同様な反応条件で反応を行った。Next, a reaction was carried out under the same reaction conditions as in Reference Example.
反応成績は次の通りであった。The reaction results were as follows.
反応時間 ３６時間（入ロ温度＝２６０℃最高温度：３
ＳＯ℃）
メタノール転化率＝９θ％
ホルムアルデヒド選択ｉ ： ｇ ９ ％反応時間 ６
５時間（入口温度：２９０℃最高温度：３ｇＯ℃）
メタノール転化率＝９９％
ホルムアルデヒド選択率：９／％
参考例Ｓ
実施例ワで得られたモリブデン酸鉄を参考例３と同様な
手法で触媒化した後、この／ ｍｌを内径Ａ ｍｍのガ
ラス製反応器に充填した。これにコチのｎ−ブタンと空
気とを供給して反応を行った。空間速度（ＧＨ８Ｖ）は
コ０００／ｈｒとした。Reaction time: 36 hours (inlet temperature = 260℃ maximum temperature: 3
SO℃) Methanol conversion rate = 9θ% Formaldehyde selection i: g 9% Reaction time 6
5 hours (Inlet temperature: 290°C Maximum temperature: 3gO°C) Methanol conversion rate = 99% Formaldehyde selectivity: 9/% Reference Example S The iron molybdate obtained in Example W was catalyzed in the same manner as in Reference Example 3. After cooling, this /ml was filled into a glass reactor with an internal diameter of A mm. Flathead n-butane and air were supplied to this to carry out a reaction. The space velocity (GH8V) was set to 000/hr.
ｐｓｏ℃でのｎ−ブタン転化率は９．／ｑ６、！；００
℃でのｎ−ブタン転化率は３コ、θチであった。The n-butane conversion rate at pso°C is 9. /q6,! ;00
The n-butane conversion rate at °C was 3 and θ.
生成物は一酸化炭素及び二酸化炭素であった。The products were carbon monoxide and carbon dioxide.
出 願 人 三菱化成工業株式会社 代 理 人 弁理士 長谷用 − （ほか／名〕Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - (other/name)
Claims (5)
デン酸鉄触媒を製造する方法において、モリブデン化合
物及び鉄化合物を、１００℃を越える温度及び加圧下で
水熱合成することによりモリブデン酸鉄を生成せしめる
ことを特徴とする、酸化用モリブデン酸鉄触媒の製造方
法。(1) In a method for producing an iron molybdate catalyst for oxidation from a molybdenum compound and an iron compound, iron molybdate is produced by hydrothermally synthesizing a molybdenum compound and an iron compound at a temperature exceeding 100°C and under pressure. A method for producing an iron molybdate catalyst for oxidation, characterized by:
ることを特徴とする特許請求の範囲第１項記載の方法。(2) The method according to claim 1, characterized in that a carrier component is mixed with the produced iron molybdate.
ることを特徴とする特許請求の範囲第１項記載の方法。(3) The method according to claim 1, characterized in that iron molybdate is produced in the coexistence of a carrier component.
ナ、チタニア、ジルコニア、珪藻土、天然粘土、合成粘
土及びゼオライトからなる群から選ばれた一種以上であ
ることを特徴とする特許請求の範囲第２項又は第３項記
載の方法。(4) Claim 2, characterized in that the carrier component is one or more selected from the group consisting of alumina, silica, silica-alumina, titania, zirconia, diatomaceous earth, natural clay, synthetic clay, and zeolite. or the method described in paragraph 3.
求の範囲第２項ないし第４項のいずれかに記載の方法。(5) The method according to any one of claims 2 to 4, wherein the carrier component is diatomaceous earth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61165234A JPH0763625B2 (en) | 1986-07-14 | 1986-07-14 | Method for producing iron molybdate catalyst for oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61165234A JPH0763625B2 (en) | 1986-07-14 | 1986-07-14 | Method for producing iron molybdate catalyst for oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6320037A true JPS6320037A (en) | 1988-01-27 |
| JPH0763625B2 JPH0763625B2 (en) | 1995-07-12 |
Family
ID=15808407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61165234A Expired - Fee Related JPH0763625B2 (en) | 1986-07-14 | 1986-07-14 | Method for producing iron molybdate catalyst for oxidation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0763625B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108114744A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | One kind supports sections catalyst with base of molybdenum and its preparation and application |
| CN112850788A (en) * | 2021-01-25 | 2021-05-28 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Monoclinic structure Fe2(MoO4)3Nanowire and preparation method and application thereof |
| CN114618509A (en) * | 2022-03-21 | 2022-06-14 | 上海尼普敦环境科技有限公司 | Carbon dioxide hydrogenation reduction catalyst and preparation method thereof |
| CN115072791A (en) * | 2022-06-24 | 2022-09-20 | 陕西科技大学 | FeMoO 4 Superfine nano particle, preparation method and application |
| CN115487816A (en) * | 2022-08-16 | 2022-12-20 | 中国地质大学（武汉） | Vermiculite-based iron molybdate nano enzyme and preparation method and application thereof |
| CN115818722A (en) * | 2022-12-30 | 2023-03-21 | 浙江工业大学 | Preparation method of square sheet iron molybdate |
-
1986
- 1986-07-14 JP JP61165234A patent/JPH0763625B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108114744A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | One kind supports sections catalyst with base of molybdenum and its preparation and application |
| CN112850788A (en) * | 2021-01-25 | 2021-05-28 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Monoclinic structure Fe2(MoO4)3Nanowire and preparation method and application thereof |
| CN114618509A (en) * | 2022-03-21 | 2022-06-14 | 上海尼普敦环境科技有限公司 | Carbon dioxide hydrogenation reduction catalyst and preparation method thereof |
| CN115072791A (en) * | 2022-06-24 | 2022-09-20 | 陕西科技大学 | FeMoO 4 Superfine nano particle, preparation method and application |
| CN115487816A (en) * | 2022-08-16 | 2022-12-20 | 中国地质大学（武汉） | Vermiculite-based iron molybdate nano enzyme and preparation method and application thereof |
| CN115487816B (en) * | 2022-08-16 | 2023-08-04 | 中国地质大学（武汉） | Vermiculite-based ferric molybdate nano enzyme and preparation method and application thereof |
| CN115818722A (en) * | 2022-12-30 | 2023-03-21 | 浙江工业大学 | Preparation method of square sheet iron molybdate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0763625B2 (en) | 1995-07-12 |
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