JPH10218878A - Production of trioxane - Google Patents
Production of trioxaneInfo
- Publication number
- JPH10218878A JPH10218878A JP9023901A JP2390197A JPH10218878A JP H10218878 A JPH10218878 A JP H10218878A JP 9023901 A JP9023901 A JP 9023901A JP 2390197 A JP2390197 A JP 2390197A JP H10218878 A JPH10218878 A JP H10218878A
- Authority
- JP
- Japan
- Prior art keywords
- formaldehyde
- trioxane
- group
- catalyst
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ホルムアルデヒドを環
状３量体化（環化）してトリオキサンを効率的に製造す
る方法に関する。トリオキサンはエンジニアリングプラ
スチックであるポリアセタール樹脂のモノマーとして工
業的に多量に生産されている有用な化学物質である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing trioxane by subjecting formaldehyde to cyclic trimerization (cyclization). Trioxane is a useful chemical substance which is industrially produced in large quantities as a monomer of polyacetal resin which is an engineering plastic.
【０００２】[0002]
【従来の技術】従来、トリオキサンの製造方法として
は、硫酸、スルホン酸基を有する陽イオン交換樹脂、ゼ
オライト等の酸触媒の存在下でホルムアルデヒド水溶液
を加熱し、生成するトリオキサンを含む成分を留出物と
して得、ついで得られたトリオキサンを含むホルムアル
デヒド水溶液から、ベンゼン等の水に難溶性の溶剤によ
りトリオキサンを抽出する方式が提案されている。2. Description of the Related Art Conventionally, as a method for producing trioxane, a formaldehyde aqueous solution is heated in the presence of an acid catalyst such as sulfuric acid, a cation exchange resin having a sulfonic acid group, or zeolite to distill a component containing trioxane produced. A method has been proposed in which trioxane is extracted from an aqueous formaldehyde solution containing trioxane using a solvent having low solubility in water such as benzene.
【０００３】工業的なトリオキサンの製造方法として
は、硫酸を用いる方法が一般的であるが、強酸による装
置の腐食対策として高価な装置材料を使用する必要があ
り、更にパラホルムアルデヒドが析出しやすい、副生物
が多く選択率が低い等の問題がある。またスルホン酸基
を有する陽イオン交換樹脂やゼオライト等の固体酸触媒
を用いた場合には、腐食の問題に対しては有効である
が、副反応による選択率の低下や、パラホルムアルデヒ
ド析出による触媒層の圧力損失の増加等の問題がある。As an industrial method for producing trioxane, sulfuric acid is generally used. However, expensive equipment materials must be used as a countermeasure against corrosion of the equipment by a strong acid, and paraformaldehyde is easily precipitated. There are problems such as many by-products and low selectivity. When a solid acid catalyst such as a cation exchange resin having a sulfonic acid group or zeolite is used, it is effective for the problem of corrosion, but the selectivity is reduced by a side reaction and the catalyst is precipitated by paraformaldehyde precipitation. There are problems such as an increase in pressure loss in the bed.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、ホルムアル
デヒド水溶液を酸性触媒と接触させトリオキサンを製造
する方法において、装置材料の腐食、副生成物の生成が
少ない効率的なトリオキサンの製造方法を提供すること
を目的とするものである。SUMMARY OF THE INVENTION The present invention provides a method for producing trioxane by contacting an aqueous formaldehyde solution with an acidic catalyst to provide an efficient method for producing trioxane with less corrosion of equipment materials and less generation of by-products. The purpose is to do so.
【０００５】[0005]
【課題を解決するための手段】本発明者は、上記の課題
を解決するために鋭意研究をした結果、酸性触媒下トリ
オキサンを製造する方法において、触媒として下記式
（１）Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, in a method for producing trioxane under an acidic catalyst, the following formula (1)
【化２】 で表される３Ａ族金属塩触媒を使用する事により、装置
材質の腐食もなく、かつ、副生成物であるジオキシメチ
レンジメトキシド、トリオキシメチレンジメトキシド等
の生成が少ないトリオキサンの製造方法を見い出し、本
発明を完成するに至った。Embedded image By using a Group 3A metal salt catalyst represented by the following formula, there is provided a method for producing trioxane that does not corrode equipment materials and generates little by-products such as dioxymethylene dimethoxide and trioxymethylene dimethoxide. They have found and completed the present invention.
【０００６】すなわち、本発明は、ホルムアルデヒド水
溶液を酸性触媒と接触させトリオキサンを製造する方法
において、触媒として上記式（１）で表される３Ａ族金
属塩触媒を使用する事を特徴とするトリオキサンの製造
法である。この３Ａ族金属塩触媒は強いルイス酸性を有
するが、ブレンステッド酸性は比較的弱いことから、装
置材質の腐食が起こりにくい。さらに、水中でほとんど
加水分解されないため反応液中で安定して存在すること
ができ、取り扱いが容易である。これらの３Ａ族金属塩
触媒の特徴を利用したこの新規なトリオキサン製造方法
は、装置材質の腐食もなく、かつ、副生成物の生成量が
少ない極めて工業的に有意義な方法である。That is, the present invention provides a method for producing trioxane by bringing an aqueous formaldehyde solution into contact with an acidic catalyst, wherein a catalyst of a Group 3A metal salt represented by the above formula (1) is used as a catalyst. It is a manufacturing method. Although the Group 3A metal salt catalyst has strong Lewis acidity, the Bronsted acidity is relatively weak, so that the material of the apparatus hardly corrodes. Furthermore, since it is hardly hydrolyzed in water, it can be stably present in the reaction solution, and is easy to handle. This novel method for producing trioxane utilizing the characteristics of these Group 3A metal salt catalysts is an industrially significant method that does not corrode equipment materials and generates a small amount of by-products.
【０００７】以下本発明のトリオキサン製造方法を詳細
に説明する。本発明において、使用されるホルムアルデ
ヒド水溶液とは、濃度３５〜８０重量％のものが好まし
く、さらに好ましくは６０〜７５重量％のものである。
ホルムアルデヒド水溶液の濃度が３５重量％未満では、
ホルムアルデヒドからトリオキサンへの転化率が低く、
８０重量％を越えると、パラホルムアルデヒドの発生が
あり操作が困難となるためである。なお、ホルムアルデ
ヒド水溶液中には、メタノール、メチラール、蟻酸、蟻
酸メチル、トリオキサンなどが含まれていても反応にさ
しつかえない。Hereinafter, the method for producing trioxane of the present invention will be described in detail. In the present invention, the formaldehyde aqueous solution used preferably has a concentration of 35 to 80% by weight, more preferably 60 to 75% by weight.
If the concentration of the aqueous formaldehyde solution is less than 35% by weight,
Low conversion of formaldehyde to trioxane,
If the content exceeds 80% by weight, paraformaldehyde is generated and the operation becomes difficult. Note that even if the aqueous formaldehyde solution contains methanol, methylal, formic acid, methyl formate, trioxane, etc., the reaction may not be affected.
【０００８】前記（１）式で表される３Ａ族金属塩触媒
の３Ａ族金属原子Ｍとしては、スカンジウム、イットリ
ウム、ランタン、プラセオジム、ネオジム、サマリウ
ム、ユウロピウム、ガドリニウム、テルビウム、ジスプ
ロシウム、ホルミウム、エルビウム、ツリウム、イッテ
ルビウム、ルテチウム等が好適に使用でき、これらの３
Ａ族金属原子Ｍはその一種のみであってもよく、また二
種類以上を含むものであってもよい。またＲｆとして
は、トリフルオロメチル基、ペンタフルオロエチル基、
ノナフルオロブチル基等のアルキル基の水素が全てＦで
置換されたペルフルオロアルキル基が挙げられるが、炭
素数１〜４のペルフルオロアルキル基が特に好ましい。The group 3A metal atom M of the group 3A metal salt catalyst represented by the above formula (1) includes scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, Thulium, ytterbium, lutetium and the like can be preferably used.
The group A metal atom M may be only one kind, or may contain two or more kinds. As Rf, a trifluoromethyl group, a pentafluoroethyl group,
A perfluoroalkyl group in which all hydrogens of an alkyl group such as a nonafluorobutyl group are substituted with F is mentioned, and a perfluoroalkyl group having 1 to 4 carbon atoms is particularly preferable.
【０００９】これらの３Ａ族金属塩触媒は、例えば３Ａ
族金属原子の酸化物とトリフルオロメタンスルホン酸を
混合後、水溶液中で加熱することによって容易に調製さ
れる。These Group 3A metal salt catalysts include, for example, 3A
It is easily prepared by mixing an oxide of a group metal atom with trifluoromethanesulfonic acid and then heating in an aqueous solution.
【００１０】本発明における触媒の使用量は特に限定さ
れるものではなく、また反応液中のホルムアルデヒド濃
度にもよるが、一般的にはホルムアルデヒドに対し重量
比で０．００１〜１０が適当であり、好ましくは０．０
１〜０．１の範囲である。[0010] The amount of the catalyst used in the present invention is not particularly limited and depends on the formaldehyde concentration in the reaction solution, but is generally 0.001 to 10 by weight based on the formaldehyde. , Preferably 0.0
It is in the range of 1 to 0.1.
【００１１】本発明の実施において、反応温度は、６０
〜１２５℃の間で設定される。反応温度が低すぎる場合
は、パラホルムアルデヒドの析出が起こり、高すぎる場
合には選択率の低下が起こる。また、パラホルムアルデ
ヒドの析出を防止する添加剤を加えて反応させることも
できる。In the practice of the present invention, the reaction temperature is 60
Set between １２５125 ° C. If the reaction temperature is too low, precipitation of paraformaldehyde will occur, and if it is too high, the selectivity will decrease. Further, the reaction can be carried out by adding an additive for preventing precipitation of paraformaldehyde.
【００１２】また、本発明における反応圧力は、反応系
を液相に保てる圧力であれば特に制限はなく、減圧、常
圧、加圧いずれでもよい。The reaction pressure in the present invention is not particularly limited as long as the reaction system can be maintained in a liquid phase, and may be any of reduced pressure, normal pressure and pressurized pressure.
【００１３】[0013]
【発明の効果】上述した実施例にて明らかなように、本
発明のトリオキサンの製造方法によれば、ホルムアルデ
ヒド水溶液からトリオキサンを製造する工程において、
装置材料の腐食がなく、副生物が少なく効率的にトリオ
キサンを製造することができる。As is clear from the above-described embodiments, according to the method for producing trioxane of the present invention, in the step of producing trioxane from an aqueous formaldehyde solution,
Trioxane can be produced efficiently with little corrosion of equipment materials and few by-products.
【００１４】[0014]
【実施例】以下、実施例及び比較例により本発明をさら
に具体的に説明する。但し、本発明はこれらの実施例に
より限定されるものではない。The present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited by these examples.
【００１５】実施例１ 撹拌機、温度計、ジムロート冷却器をつけた100ml 容量
の４つ口フラスコに６５重量％ホルムアルデヒド水溶液
７０ｇ、トリフルオロメタンスルホン酸スカンジウム
（Ｓｃ( ＯＴｆ)3、ＯＴｆ＝ＯＳＯ2 ＣＦ3 ）の５０重
量％水溶液を１０ｇ仕込み１０５℃にて反応をおこなっ
た。このときのＳｃ( ＯＴｆ)3の反応液中濃度は６重量
％であった。５１分後フラスコ内の反応液をガスクロマ
トグラフィーにて分析し、組成を求めた。反応の結果
を、表１に示した。なお、反応液中にパラホルムアルデ
ヒドの析出は見られなかった。また反応液中にＳＵＳ３
０４のテストピースを設置し、１０日間経過後の腐食状
態を、目視にて観察した。Example 1 70 g of a 65% by weight aqueous solution of formaldehyde, scandium trifluoromethanesulfonate (Sc (OTf) 3 , OTf = OSO 2 CF 3) were placed in a 100 ml four-necked flask equipped with a stirrer, thermometer and Dimroth condenser. 10 g of a 50% by weight aqueous solution of the above was charged and reacted at 105 ° C. At this time, the concentration of Sc (OTf) 3 in the reaction solution was 6% by weight. After 51 minutes, the reaction solution in the flask was analyzed by gas chromatography to determine the composition. The results of the reaction are shown in Table 1. Note that no paraformaldehyde was precipitated in the reaction solution. SUS3 in the reaction solution
The test piece No. 04 was placed, and the corrosion state after 10 days had elapsed was visually observed.
【００１６】実施例２〜５ 触媒の量、種類を変更する以外は、実施例１と同様に行
った。その結果を表１に示した。Examples 2 to 5 The same procedure as in Example 1 was carried out except that the amount and type of the catalyst were changed. The results are shown in Table 1.
【００１７】比較例１ 実施例１と同様の装置で、硫酸触媒を使用してトリオキ
サンを合成した。その結果を表１に示す。Comparative Example 1 Trioxane was synthesized in the same apparatus as in Example 1 using a sulfuric acid catalyst. Table 1 shows the results.
【００１８】[0018]
【表１】 [Table 1]
Claims (2)
式で表される触媒と接触させることを特徴とするトリオ
キサンの製造方法。 【化１】 1. An aqueous formaldehyde solution comprising:
A method for producing trioxane, which is brought into contact with a catalyst represented by the formula: Embedded image
トリウム、サマリウム、ネオジムおよびユウロピウムか
らなる群からえらばれる少なくとも１種以上のものであ
る請求項１記載のトリオキサンの製造方法。2. The process for producing trioxane according to claim 1, wherein M in the formula (1) is at least one member selected from the group consisting of scandium, yttrium, samarium, neodymium and europium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9023901A JPH10218878A (en) | 1997-02-06 | 1997-02-06 | Production of trioxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9023901A JPH10218878A (en) | 1997-02-06 | 1997-02-06 | Production of trioxane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10218878A true JPH10218878A (en) | 1998-08-18 |
Family
ID=12123379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9023901A Pending JPH10218878A (en) | 1997-02-06 | 1997-02-06 | Production of trioxane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10218878A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749164A (en) * | 2016-10-27 | 2017-05-31 | 苏州双湖化工技术有限公司 | Concentrated formaldehyde is the apparatus and method that raw material continuously prepares metaformaldehyde |
-
1997
- 1997-02-06 JP JP9023901A patent/JPH10218878A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749164A (en) * | 2016-10-27 | 2017-05-31 | 苏州双湖化工技术有限公司 | Concentrated formaldehyde is the apparatus and method that raw material continuously prepares metaformaldehyde |
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