JPS63188640A - Production of formaldehyde by oxidizing methylal - Google Patents
Production of formaldehyde by oxidizing methylalInfo
- Publication number
- JPS63188640A JPS63188640A JP62020400A JP2040087A JPS63188640A JP S63188640 A JPS63188640 A JP S63188640A JP 62020400 A JP62020400 A JP 62020400A JP 2040087 A JP2040087 A JP 2040087A JP S63188640 A JPS63188640 A JP S63188640A
- Authority
- JP
- Japan
- Prior art keywords
- iron
- tube
- methylal
- oxide catalyst
- molybdenum
- 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 92
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000006227 byproduct Substances 0.000 description 13
- 229910002090 carbon oxide Inorganic materials 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 108010038629 Molybdoferredoxin Proteins 0.000 description 2
- HBELESVMOSDEOV-UHFFFAOYSA-N [Fe].[Mo] Chemical compound [Fe].[Mo] HBELESVMOSDEOV-UHFFFAOYSA-N 0.000 description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HZNPCLUBXJLRAA-UHFFFAOYSA-N iron;oxomolybdenum Chemical compound [Fe].[Mo]=O HZNPCLUBXJLRAA-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- JQBLKHRODWOBSM-UHFFFAOYSA-N [O-2].[Cr+3].[Mo+4].[Fe+2] Chemical compound [O-2].[Cr+3].[Mo+4].[Fe+2] JQBLKHRODWOBSM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- -1 caddium Chemical compound 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000007086 side reaction 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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）
本発明はメチノールの酸化反応によりホルムアルデヒド
を製造する方法に関する。さらに詳細には、メチノール
を気相において、酸素を含有するガスによって、酸化触
媒の存在下で酸化させることにより、ホルムアルデヒド
を製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing formaldehyde by an oxidation reaction of methanol. More specifically, the present invention relates to a method for producing formaldehyde by oxidizing methanol in the gas phase with an oxygen-containing gas in the presence of an oxidation catalyst.
（従来の技術）
従来、ホルムアルデヒドの製造はメタノールを銀又は鉄
〜モリブデン触媒の存在下で酸化することにより行なわ
れている。しかし、この方法により得られるホルマリン
の濃度は量論的に反応したとしても、たかだか６３重量
％である。それに対してメチノール酸化反応により得ら
れるホルマリン濃度は量論的に反応すれば、８３重量％
であり、メチノールの酸化に比べて生成か人中の水の量
が非常に少ないという特徴を有する。メチノールの酸化
反応に有効な触媒として銀、酸化銅、およびモリブデン
三基本として鉄、マンガン、マグネシウム、カドシウム
、カルシウム等を加えた触媒が知られている。しかしな
がら、これらの触媒では一酸化炭素、ジメチルエーテル
およびギ酸メチルの副生が多く、高選択性でホルムアル
デヒドを得ることは困難であり、酸化活性が低いため高
温での運転を必要とする。本出願人は先に、鉄、そりブ
デン及びアルカリ金属、ビスマス、クロム、タングステ
ン、ニッケル、コバルトから選ばれた１種又はそれ以上
の金属元素を有効成分とする触媒が上記の副生物が少な
く高選択性を有することを見出し、特許出願をした（特
開昭５７−１３４４３２号公報）。(Prior Art) Conventionally, formaldehyde has been produced by oxidizing methanol in the presence of a silver or iron-molybdenum catalyst. However, the concentration of formalin obtained by this method is at most 63% by weight even if the reaction is stoichiometric. On the other hand, if the formalin concentration obtained by methynol oxidation reaction is stoichiometric, it is 83% by weight.
It has the characteristic that the amount of water produced is very small compared to the oxidation of methanol. Catalysts containing silver, copper oxide, and molybdenum to which iron, manganese, magnesium, caddium, calcium, etc. are added are known as effective catalysts for the oxidation reaction of methanol. However, these catalysts produce many byproducts of carbon monoxide, dimethyl ether, and methyl formate, making it difficult to obtain formaldehyde with high selectivity, and requiring operation at high temperatures due to low oxidation activity. The present applicant has previously discovered that a catalyst containing iron, tributene, and one or more metal elements selected from alkali metals, bismuth, chromium, tungsten, nickel, and cobalt is highly effective, with few of the above-mentioned by-products. They found that it had selectivity and filed a patent application (Japanese Patent Application Laid-Open No. 134432/1983).
更に又、これら金属元素の含有割合が金属原子比で鉄工
に対してモリブデン１．５〜３．０．アルカリ金属、ビ
スマス、クロム、タングステン、コバルト。Furthermore, the content ratio of these metal elements is 1.5 to 3.0 in molybdenum to ironwork in metal atomic ratio. Alkali metals, bismuth, chromium, tungsten, cobalt.
ニッケルの合計が０．００１〜０．１である改良発明の
特許出願をした（特開昭６０−２５１９３２号公報）。A patent application was filed for an improved invention in which the total amount of nickel is 0.001 to 0.1 (Japanese Patent Laid-Open No. 60-251932).
（本発明が解決しようとする問題点）
本発明者らはメチノールの酸化によりホルムアルデヒド
の製造法について鋭意検討を重ねた結果ホルムアルデヒ
ドを効率よく製造する方法を見出し、本発明を完成する
に至った。本発明は、メチノールの酸化によるホルムア
ルデヒドの製造に関して、反応初期の転化率、選択率が
高いばかりでなく、長期にわたり反応特性に変化がなく
、高生産性を与える製造方法を提供するものである。(Problems to be Solved by the Present Invention) The present inventors have conducted extensive studies on a method for producing formaldehyde by oxidizing methyleneol, and as a result, have found a method for efficiently producing formaldehyde, and have completed the present invention. The present invention provides a production method for producing formaldehyde by oxidizing methanol, which not only has a high conversion rate and selectivity at the initial stage of the reaction, but also has no change in reaction characteristics over a long period of time, and provides high productivity.
（問題点を解決するための手段）
本発明は、鉄およびモリブデン又はそれらに加えて、ア
ルカリ金属、ビスマス、クロム、タングステン、コバル
トニッケルから選ばれた１種またはそれ以上の金属元素
を有効成分とする酸化物を使用して、メチラールの酸化
によりホルムアルデヒドを製造するに当り、使用する酸
化触媒がチューブ中に固定化されており、この触媒層中
をメチラールおよび酸素を含むガスが流れることにより
ホルムアルデヒドが生成されることを特徴とする。この
際に、反応器に供給されるメチラール濃度と酸素濃度と
が以下の関係式を満たすことを特徴とする。(Means for Solving the Problems) The present invention uses iron and molybdenum, or in addition to them, one or more metal elements selected from alkali metals, bismuth, chromium, tungsten, and cobalt nickel as active ingredients. When formaldehyde is produced by oxidation of methylal using an oxide of It is characterized by being generated. At this time, the methylal concentration and oxygen concentration supplied to the reactor are characterized in that they satisfy the following relational expression.
７．０≧Ｘ≧２．０ において、
１．０４Ｙ −３，９≧Ｘ≧１．０４Ｙ−５，９・・・
・・・・・・ ＴＩ）但し、ここでＸは反応器に供給さ
れるガス状のメチラールの容積％、Ｙは反応器に供給さ
れる酸素の容積％とする。7.0≧X≧2.0, 1.04Y −3,9≧X≧1.04Y−5,9...
...... TI) However, here, X is the volume % of gaseous methylal supplied to the reactor, and Y is the volume % of oxygen supplied to the reactor.
〈作 用〉
ここでの具体的触媒の例として、モリブデン酸鉄、モリ
ブデン酸鉄と三酸化モリブデンとの混合物、更には、そ
れら混合物に加えて、アルカリ金属、ビスマス、クロム
、タングステン、コバルトニッケルから選ばれた１種も
しくは２種以上の金属酸化物を含む触媒が含まれる。<Function> Examples of specific catalysts include iron molybdate, a mixture of iron molybdate and molybdenum trioxide, and in addition to these mixtures, alkali metals, bismuth, chromium, tungsten, and cobalt nickel. Catalysts containing one or more selected metal oxides are included.
この際使用される触媒のモリブデンと鉄との原子比Ｍｏ
／Ｐｅは通常１．５〜４．５の範囲にある。The atomic ratio of molybdenum and iron in the catalyst used at this time is Mo
/Pe is usually in the range of 1.5 to 4.5.
好ましくは１．５〜３．０．更に好ましくは１．６〜２
．３゜特に好ましくは１．６〜１．９の範囲にある。Preferably 1.5 to 3.0. More preferably 1.6-2
．． 3° is particularly preferably in the range of 1.6 to 1.9.
ここで、反応器に供給される酸素濃度とメチラール濃度
との関係が、本式より逸脱する場合には、安定にホルム
アルデヒドを製造する事が困難である。たとえば、メチ
ラール濃度（容積％）Ｘと酸素濃度（容積％）Ｙとの関
係においてメチラール濃度が１．０４Ｙ−３，９よりも
大きくなると反応の活性を長期的に維持する事が困難と
なる。経時的な選択率の低下、例えば−酸化炭素の副生
が増大する等の減少が認められる。Here, if the relationship between the oxygen concentration and methylal concentration supplied to the reactor deviates from this formula, it is difficult to stably produce formaldehyde. For example, in the relationship between methylal concentration (volume %) A decrease in selectivity over time, such as an increase in carbon oxide by-products, is observed.
また、逆に、メチラール濃度が１．０４Ｙ−５，９より
も低くなると、爆発の危険性等の問題があり酸化反応を
安定的に行なうことが困難である。Conversely, if the methylal concentration is lower than 1.04Y-5,9, there are problems such as the danger of explosion, and it is difficult to carry out the oxidation reaction stably.
本発明において、メチラールの酸化反応は、通常２５０
℃〜４００℃の範囲で行なわれる。好ましい方式は、チ
ューブ内に充填した触媒層中をメチラール、および酸素
を含むガスが通過させる。工業的には反応器は通常５，
０００〜５０，０００本のチューブから構成されており
、そのチューブは内径は１５〜２５ｍｍ、長さ６００〜
２，０００ ｍｍから成る。反応器中のチューブの外側
に熱媒体を通して、チューブ内の反応物に熱を与えるか
、あるいは反応物から熱を除くことにより、反応温度を
制御する。In the present invention, the oxidation reaction of methylal is usually carried out at 250
The temperature range is 400°C to 400°C. A preferred method is to allow a gas containing methylal and oxygen to pass through a catalyst layer filled in a tube. Industrially, reactors are usually 5,
It consists of 000 to 50,000 tubes, each with an inner diameter of 15 to 25 mm and a length of 600 to 50,000.
It consists of 2,000 mm. The reaction temperature is controlled by passing a heating medium outside the tube in the reactor to impart heat to or remove heat from the reactants within the tube.
熱媒体としては、無機塩、耐熱性の有機媒体等が使用さ
れる。熱媒体の温度は通常２４０℃から３００°Ｃの範
囲で使用される。As the heat medium, an inorganic salt, a heat-resistant organic medium, etc. are used. The temperature of the heat medium used is usually in the range of 240°C to 300°C.
チューブ内に充填される触媒の形状は粒状、シリンダ状
、ラシヒリング状、スポークリング状等の形状のものが
使用される。The shape of the catalyst filled in the tube may be granular, cylindrical, Raschig ring, spoke ring, or the like.
本発明反応でのメチラールからホルムアルデヒドへの転
化収率は、反応条件によるが通常は８５〜９５％である
。反応温度が低すぎる場合には収率が低下する。又逆に
、高すぎる場合にも、−酸化炭素等への副反応のために
も、収率は低下する。好ましい、反応温度は３００℃か
ら３８０℃であり、特に好ましくは、最高温度を３７０
℃以下とする。The conversion yield of methylal to formaldehyde in the reaction of the present invention is usually 85 to 95%, although it depends on the reaction conditions. If the reaction temperature is too low, the yield will decrease. Conversely, if the temperature is too high, the yield decreases due to side reactions to -carbon oxide, etc. Preferably, the reaction temperature is 300°C to 380°C, and particularly preferably the maximum temperature is 370°C.
The temperature shall be below ℃.
本反応では、反応器に供給するガス相中の酸素濃度、メ
チラール濃度も、第（１）式で示される範囲に制御する
必要がある。通常使用される方法は、反応後のホルマリ
ンガスを含む反応物を、水を含む吸収塔にてホルマリン
を吸収させた後の酸素濃度の低いガスと空気、およびメ
チラールを混合することにより調製される。In this reaction, it is also necessary to control the oxygen concentration and methylal concentration in the gas phase supplied to the reactor within the range shown by equation (1). The commonly used method is to mix the reactant containing formalin gas after the reaction with a gas with a low oxygen concentration after the formalin has been absorbed in an absorption tower containing water, air, and methylal. .
通常、反応器中での線速度は１．０〜２．５Ｎｍ’／ｎ
ｒＳｅｃの範囲で使用される。Usually, the linear velocity in the reactor is 1.0 to 2.5 Nm'/n
Used in the rSec range.
〈実施例さ 以下、実施例にて、本発明を更に詳細に説明する。<Example Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
内径１５鶴、長さ７００ｆｌのチューブ中に、スポーク
リング状の鉄〜モリブデン酸化物触媒（モリブデン−鉄
原子比Ｍｏ／Ｆｅ＝１．９）を充填し、耐熱有機熱媒を
２８０℃に保ち、チューブの外側も循環さセせる。触媒
層に供給されるガス組成として、＋１）より計算される
範囲として、酸素８容積％１メチラール４容積％のガス
を選定し、線速度１ ｍ、’ ／ ｒｄ ＳｓＣにて供
給した。なお、この供給ガス中には水が２容積％含まれ
ていた。ホルムアルデヒドへの転化収率は９３％であっ
た。また副生した一酸化炭素は生成したホルムアルデヒ
ドの２％であった。Example 1 A spoke ring-shaped iron-molybdenum oxide catalyst (molybdenum-iron atomic ratio Mo/Fe = 1.9) was filled in a tube with an inner diameter of 15 mm and a length of 700 fl, and a heat-resistant organic heating medium was heated at 280°C. keep it cool and circulate the outside of the tube as well. As the gas composition supplied to the catalyst layer, a gas containing 8% by volume of oxygen and 4% by volume of 1-methylal was selected as the range calculated from +1), and was supplied at a linear velocity of 1 m, '/rd SsC. Note that this supplied gas contained 2% by volume of water. The conversion yield to formaldehyde was 93%. Furthermore, the amount of carbon monoxide produced as a by-product was 2% of the formaldehyde produced.
６ケ付反応させた後の成績も、ホルムアルデヒドへの転
化収率は９３％、副生じた一酸化炭素は２％であった。The results after the 6-addition reaction also showed that the conversion yield to formaldehyde was 93%, and the amount of carbon monoxide produced as a by-product was 2%.
比較例１
（１１式より計算される範囲外として、酸素８容積％、
メチシール５容積％のガスを選定した他は実施例１と同
様の操作を行なった。反応直後の成績はホルムアルデヒ
ドへの転化収率９２％、−酸化炭素の副生は１０％であ
ったが６ケ月の反応成績は、ホルムアルデヒドへの転化
収率８４％、−酸化炭素の副生は１０％であった。Comparative Example 1 (Oxygen 8% by volume, outside the range calculated from Equation 11,
The same operation as in Example 1 was performed except that a gas containing 5% by volume of methisil was selected. Immediately after the reaction, the conversion yield to formaldehyde was 92%, and the by-product of carbon oxide was 10%, but the reaction results after 6 months were that the conversion yield to formaldehyde was 84%, and the by-product of carbon oxide was 10%. It was 10%.
実施例２
内径２０ｉｓ、長さ８００１１のチューブ中に、ラシヒ
リング状の鉄〜モリブデン酸化物触媒（モリブデン−鉄
原子比Ｍｏ／Ｆｅ＝２．２）を充填し、耐熱有機熱媒を
２６０℃に保ち、チューブの外側を循環させる。Example 2 A Raschig ring-shaped iron-molybdenum oxide catalyst (molybdenum-iron atomic ratio Mo/Fe = 2.2) was filled in a tube with an inner diameter of 20 is and a length of 80011, and the heat-resistant organic heat medium was maintained at 260°C. , circulate the outside of the tube.
触媒層に供給されるガス組成として、（１）式より計算
される範囲として酸素８．５容積％、メチラール４．５
容積％のガスを選定し、線速度１．５ｍ３／ ｍ５ｅｃ
にて供給した。なお、この供給ガス中には、水分が２容
積％含まれていた。ホルムアルデヒドへの転化収率は９
２％であった。また副生した一酸化炭素は生成したホル
ムアルデヒドの４％であった。As for the gas composition supplied to the catalyst layer, the range calculated from equation (1) is 8.5% by volume of oxygen and 4.5% of methylal.
Select volume% gas and linear velocity 1.5m3/m5ec
Supplied by. Note that this supplied gas contained 2% by volume of water. The conversion yield to formaldehyde is 9
It was 2%. Furthermore, the amount of carbon monoxide produced as a by-product was 4% of the formaldehyde produced.
６ケ月反応させた後の成績も、ホルムアルデヒドへの転
化収率は９１％、副生した一酸化炭素は４％であった。After 6 months of reaction, the conversion yield to formaldehyde was 91%, and the amount of by-product carbon monoxide was 4%.
比較例２
（１）式より計算される範囲外として、酸素７．５容積
％、メチシール４．５容積％を選定した他は実施例２と
同様の操作を行なった。反応直後の成績は、ホルムアル
デヒドへの転化収率９２％、−酸化炭素の副生４％であ
った。しかしながら、６ケ月後の反応成績はホルムアル
デヒドへの転化収率は８３％、−酸化炭素の副生は９％
であった。Comparative Example 2 The same operation as in Example 2 was carried out, except that 7.5% by volume of oxygen and 4.5% by volume of methisil were selected as outside the range calculated by formula (1). Immediately after the reaction, the conversion yield to formaldehyde was 92%, and the by-product of -carbon oxide was 4%. However, the reaction results after 6 months showed that the conversion yield to formaldehyde was 83%, and the by-product of carbon oxide was 9%.
Met.
実施例３
ラシヒリング状の鉄〜モリブデン〜クロム酸化物より成
る触媒（原子比： Ｍｏ／Ｆｅ−Ｃｒ＝２．１／１１０
．０２）を使用して実施例２と同様の操作を行なった。Example 3 Catalyst consisting of Raschig ring-shaped iron-molybdenum-chromium oxide (atomic ratio: Mo/Fe-Cr=2.1/110
．． The same operation as in Example 2 was carried out using 02).
得られた成績は、ホルムアルデヒドへの転化収率９２％
、−酸化炭素の副生は３％であった。なお、６ケ月の反
応成績もホルムアルデヒドへの転化収率９２％、−酸化
炭素への副生も３％であった。The results obtained were a conversion yield of 92% to formaldehyde.
, -The amount of carbon oxide by-product was 3%. The reaction results after 6 months showed that the conversion yield to formaldehyde was 92%, and the by-product of -carbon oxide was 3%.
（発明の効果）
以上述べた様に、本発明の方法はメチラールの酸化によ
り、ホルムアルデヒドを製造するに当り、長期的に安定
な製造方法を提供するものであり工業的な意義は極めて
大きい。(Effects of the Invention) As described above, the method of the present invention provides a long-term stable production method for producing formaldehyde by oxidizing methylal, and has extremely great industrial significance.
Claims (1)
金属、ビスマス、クロム、タングステン、コバルト、ニ
ッケルから選ばれた１種またはそれ以上の金属元素を有
効成分とする酸化物を使用して、メチラールの酸化によ
りホルムアルデヒドを製造するに当り、使用する酸化物
触媒がチューブ中に固定化されており、この触媒層中を
メチラールおよび酸素を含むガスが流れることによりホ
ルムアルデヒドが生成されるに際して、反応系に供給す
るメチラール濃度と酸素濃度とが以下の関係式を満すこ
とを特徴とするホルムアルデヒドの製造方法 ７．０≧Ｘ≧２．０において、 １．０４Ｙ−３．９≧Ｘ≧１．０４Ｙ−５．９ 但し、Ｘは反応器に供給されるガス状のメチラールの容
積％、Ｙは反応器に供給される酸素の容積％とする。 （２）酸化物触媒が、モリブデン酸鉄より成る特許請求
の範囲第１項記載の方法 （３）酸化物触媒がモリブデン酸鉄および三酸化モリブ
デンより成ることを特徴とする特許請求の範囲第１項記
載の方法 （４）酸化物触媒が、モリブデン酸鉄に加えて、更に、
アルカリ金属、ビスマス、クロム、タングステン、コバ
ルト、ニッケルから選ばれた１種もしくは２種以上の金
属酸化物より成ることを特徴とする特許請求の範囲第１
項記載の方法 （５）酸化物触媒が、モリブデン酸鉄、三酸化モリブデ
ンに加えて、更にアルカリ金属、ビスマス、クロム、タ
ングステン、コバルト、ニッケルから選ばれた１種もし
くは２種以上の金属酸化物より成ることを特徴とする特
許請求の範囲第１項記載の方法 （６）チューブ中に固定化される酸化物触媒の形状が粒
状であることを特徴とする特許請求の範囲第３項もしく
は第５項記載の方法 （７）チューブ中に固定される酸化物触媒の形状がラシ
ヒリング状又はスポークリング状であることを特徴とす
る特許請求の範囲第３項もしくは第５項記載の方法 （８）チューブ中に固定される酸化物触媒の形状がシリ
ンダー状であることを特徴とする特許請求の範囲第３項
もしくは第５項記載の方法 （９）チューブの形状が内径１５〜２５ｍｍ、長さ６０
０〜２０００ｍｍの範囲であることを特徴とする特許請
求の範囲第６項、第７項、又は第９項記載の方法 （１０）反応器のチューブの本数が５，０００〜５０，
０００本より成ることを特徴とする第９項記載の方法 （１１）反応器中のチューブの外側に熱媒体を通してチ
ューブに熱を与えるか、あるいはチューブから熱をうば
うことにより成る特許請求の範囲第１０項記載の方法 （１２）熱媒体が、無機塩、耐熱性の有機媒体より成る
特許請求の範囲第１１記載の方法 （１３）使用する熱媒体の温度が２４０℃〜３００℃で
あることを特徴とする特許請求の範囲第１２項記載の方
法 （１４）使用する酸化物触媒のモリブデンと鉄との原子
比Ｍｏ／Ｆｅが１．５から４．５の範囲である特許請求
の範囲第１項〜第１３項いずれかに記載の方法 （１５）使用する酸化物触媒のモリブデンと鉄との原子
比Ｍｏ／Ｆｅが１．５から３．０の範囲である特許請求
の範囲第１４項記載の方法 （１６）使用する酸化物触媒のモリブデンと鉄との原子
比Ｍｏ／Ｆｅが１．６から２．３の範囲である特許請求
の範囲第１５項記載の方法 （１７）使用する酸化物触媒のモリブデンと鉄との原子
比Ｍｏ／Ｆｅが１．６から１．９の範囲である特許請求
の範囲第１６項記載の方法[Claims] (1) Use of an oxide containing iron and molybdenum, or one or more metal elements selected from alkali metals, bismuth, chromium, tungsten, cobalt, and nickel as active ingredients in addition to them. When producing formaldehyde by oxidizing methylal, the oxide catalyst used is fixed in a tube, and when a gas containing methylal and oxygen flows through this catalyst layer, formaldehyde is produced. , a formaldehyde production method characterized in that the methylal concentration and oxygen concentration supplied to the reaction system satisfy the following relational expression 7.0≧X≧2.0, 1.04Y-3.9≧X≧ 1.04Y-5.9 However, X is the volume % of gaseous methylal supplied to the reactor, and Y is the volume % of oxygen supplied to the reactor. (2) The method according to claim 1, wherein the oxide catalyst is made of iron molybdate. (3) The method according to claim 1, wherein the oxide catalyst is made of iron molybdate and molybdenum trioxide. In addition to iron molybdate, the oxide catalyst (method (4)) described in Section 4 further comprises:
Claim 1 comprising one or more metal oxides selected from alkali metals, bismuth, chromium, tungsten, cobalt, and nickel.
Method (5) as described in Section 5, wherein the oxide catalyst is one or more metal oxides selected from alkali metals, bismuth, chromium, tungsten, cobalt, and nickel in addition to iron molybdate and molybdenum trioxide. (6) The method according to claim 1, characterized in that the oxide catalyst immobilized in the tube has a granular shape. (7) The method (8) as set forth in claim 3 or 5, wherein the shape of the oxide catalyst fixed in the tube is a Raschig ring shape or a spoke ring shape. The method according to claim 3 or 5, characterized in that the shape of the oxide catalyst fixed in the tube is cylindrical (9) The shape of the tube is 15 to 25 mm in inner diameter and 60 mm in length.
(10) The method according to claim 6, 7, or 9, characterized in that the number of tubes in the reactor is in the range of 5,000 to 50,
(11) The method according to claim 9, characterized in that the method (11) comprises applying heat to the tube by passing a heat medium to the outside of the tube in the reactor, or extracting heat from the tube. Method according to claim 10 (12) The heating medium comprises an inorganic salt and a heat-resistant organic medium Method according to claim 11 (13) The temperature of the heating medium used is 240°C to 300°C The method (14) according to claim 12, characterized in that the oxide catalyst used has an atomic ratio of molybdenum to iron, Mo/Fe, in the range of 1.5 to 4.5. (15) The method according to any one of claims 1 to 13, wherein the oxide catalyst used has an atomic ratio Mo/Fe of molybdenum and iron in a range of 1.5 to 3.0. Method (16) The method according to claim 15, wherein the oxide catalyst used has an atomic ratio Mo/Fe of molybdenum and iron in the range of 1.6 to 2.3 (17) The oxide used The method according to claim 16, wherein the atomic ratio Mo/Fe of molybdenum and iron in the catalyst is in the range of 1.6 to 1.9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62020400A JPS63188640A (en) | 1987-02-02 | 1987-02-02 | Production of formaldehyde by oxidizing methylal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62020400A JPS63188640A (en) | 1987-02-02 | 1987-02-02 | Production of formaldehyde by oxidizing methylal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63188640A true JPS63188640A (en) | 1988-08-04 |
| JPH0342253B2 JPH0342253B2 (en) | 1991-06-26 |
Family
ID=12025970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62020400A Granted JPS63188640A (en) | 1987-02-02 | 1987-02-02 | Production of formaldehyde by oxidizing methylal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63188640A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0327343A2 (en) * | 1988-02-03 | 1989-08-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing formaldehyde and derivatives thereof |
-
1987
- 1987-02-02 JP JP62020400A patent/JPS63188640A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0327343A2 (en) * | 1988-02-03 | 1989-08-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing formaldehyde and derivatives thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0342253B2 (en) | 1991-06-26 |
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