JPH0329770B2 - - Google Patents
Info
- Publication number
- JPH0329770B2 JPH0329770B2 JP61101324A JP10132486A JPH0329770B2 JP H0329770 B2 JPH0329770 B2 JP H0329770B2 JP 61101324 A JP61101324 A JP 61101324A JP 10132486 A JP10132486 A JP 10132486A JP H0329770 B2 JPH0329770 B2 JP H0329770B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acid
- hexadiene
- dimethyl
- isobutyraldehyde
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 89
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 70
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- DZPCYXCBXGQBRN-UHFFFAOYSA-N 2,5-Dimethyl-2,4-hexadiene Chemical compound CC(C)=CC=C(C)C DZPCYXCBXGQBRN-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 239000011973 solid acid Substances 0.000 claims description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 10
- 239000011707 mineral Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 claims description 5
- MWTPBEVCVOHWSX-UHFFFAOYSA-N 6-methylhepta-2,4-diene Chemical compound CC=CC=CC(C)C MWTPBEVCVOHWSX-UHFFFAOYSA-N 0.000 claims 1
- 239000003377 acid catalyst Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- -1 alumina Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 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
Description
〈産業上の利用分野〉
本発明はイソブチレンおよび／またはターシヤ
リーブチルアルコールとイソブチルアルデヒドか
ら２，５−ジメチル−２，４−ヘキサジエンを製
造する方法に関するものである。２，５−ジメチ
ル−２，４−ヘキサジエンは農薬、殺虫剤、医薬
あるいは各種有機合成の中間体として非常に有用
なものである。
〈従来の技術〉
イソブチレンおよび／またはターシヤリーブチ
ルアルコールとイソブチルアルデヒドから２，５
−ジメチル−２，４−ヘキサジエンを製造する方
法としては鉱酸、スルホン酸、ヘテロポリ酸等を
触媒として液相加圧下に反応させる方法が知られ
ている（特開昭48−34108号公報）。
しかしながらこの方法では２，５−ジメチル−
２，４−ヘキサジエンの収率は40％以下と低く、
多量の幅生物が生成する。また鉱酸、スルホン酸
等は材質に対する腐食性が強く、材質腐食による
トラブルに常に注意して運転しなければならない
欠点があつた。
〈発明が解決しようとする問題点〉
本発明はイソブチレンおよび／またはターシヤ
リーブチルアルコールとイソブチルアルデヒドか
ら２，５−ジメチル−２，４−ヘキサジエンを製
造する方法において、従来の技術の欠点、即ち幅
生成物が多量に生成し収率が低いこと、装置の材
質に対する腐食性が強いこと等の問題点を解決
し、収率よく２，５−ジメチル−２，４−ヘキサ
ジエンを得る工業的に有利な方法を提供しようと
するものである。
〈問題点を解決するための手段〉
本発明者らはイソブチレンおよび／またはター
シヤリーブチルアルコールとイソブチルアルデヒ
ドから２，５−ジメチル−２，４−ヘキサジエン
を収率よく得るための工業的に有利な方法につい
て鋭意研究を行ない本発明に到達したものであ
る。すなわち本発明はイソブチレンおよび／また
はターシヤリーブチルアルコールとイソブチルア
ルデヒドを固体酸触媒の存在下に150〜350℃の温
度条件で気相で反応させることを特徴とする、
２，５−ジメチル−２，４−ヘキサジエンの製造
方法である。
本発明方法に用いられる原料はイソブチレンお
よび／またはターシヤリーブチルアルコールとイ
ソブチルアルデヒドである。イソブチレンはその
純度について特に制約を受けることなく、純度の
高いイソブチレンをそのまま用いてもよく、ある
いはいわゆるスペントＢ−Ｂ留分として取得され
るものを用いてもよい。ターシヤリーブチルアル
コールについても同様に純度について特に制約を
受けることはない。また原料としてイソブチレン
とターシヤリーブチルアルコールの混合物を使用
することもできる。イソブチルアルデヒドについ
てもその純度について特に制約を受けることはな
い。
イソブチレンまたはターシヤリーブチルアルコ
ールとイソブチルアルデヒドとの比率あるいはイ
ソブチレンとターシヤリーブチルアルコールの混
合物とイソブチルアルデヒドとの比率は任意に選
択することができるが、イソブチルアルデヒドに
対するイソブチレンまたはターシヤリーブチルア
ルコールあるいはイソブチレンとターシヤリーブ
チルアルコールの混合物がモル比で１〜10の範囲
がもつとも有効に用いられる。
本発明方法に用いられる触媒は固体酸触媒であ
る。固体酸触媒としては酸性白土、ベントナイ
ト、モンモリロナイト等の天然粘土鉱物、シリ
カ・アルミナ、シリカ・マグネシア、シリカ・ボ
リア等の複合酸化物、アルミナ、シリカ、チタニ
ア、ニオブ酸等の金属酸化物それに合成ゼオライ
ト等がある。また多孔性担体にリン酸を担持した
固体リン酸も本発明方法の固体酸触媒として用い
ることができる。
好ましくは最高酸強度がHo関数の値で−5.6よ
り強い酸点を有している固体酸触媒が用いられ
る。これらの具体的なものとしてシリカ・アルミ
ナ、酸性白土、合成ゼオライト、ニオブ酸等があ
げられるが、これらの中でニオブ酸触媒が最も好
ましく用いられる。ニオブ酸は含水酸化ニオブと
も呼ばれる固体酸であり、その調整法については
特開昭60−44039号公報に記載されている。
ニオブ酸触媒は、そのまま用いてもよいが鉱酸
特に硫酸又はリン酸等で処理を行つた後に用いる
とさらに高い活性と、２，５−ジメチル−２，４
−ヘキサジエンの選択性が得られる。
ニオブ酸触媒を鉱酸で処理する方法としては通
常ニオブ酸を鉱酸水溶液に浸漬した後、水洗する
という方法で行なわれる。また場合によればニオ
ブ酸を充填した塔に鉱酸水溶液を通して、その後
純水で洗浄するという方法が採用される。鉱酸と
してはリン酸又は硫酸が好ましく用いられる。硫
酸又はリン酸水溶液の濃度は硫酸又はリン酸処理
方法によつても異なるが、通常は0.01モル／〜
1.0モル／である。またその使用量は浸漬法の
場合はニオブ酸に対して通常２〜10倍（容積比）
である。硫酸又はリン酸処理したニオブ酸は通常
100〜500℃で焼成した後、触媒として使用され
る。
このような硫酸で処理したニオブ酸触媒は未処
理のニオブ酸触媒に比べて、活性が高いばかりで
なく、２，５−ジメチル−２，４−ヘキサジエン
の選択性も高い。そのために硫酸又はリン酸処理
ニオブ酸触媒を用いることにより、未処理のニオ
ブ酸触媒を用いる場合と比べて、さらに高い収率
で２，５−ジメチル−２，４−ヘキサジエンを得
ることができる。
本発明方法は気相で反応が行なわれる。
反応温度は150〜350℃の温度範囲が有効に用い
られ、好ましくは200〜300℃の温度範囲が用いら
れる。反応温度が350℃以上になると重合物等の
高沸点物の生成が多くなり、また反応温度が150
℃以下になると反応速度が非常に遅くなる。
反応圧力は反応系が気相に保たれる圧力であれ
ば特に限定されないが、通常は大気圧ないし加圧
条件下で反応が行なわれ、好ましくは２〜10絶対
気圧の圧力範囲で反応が行なわれる。
反応形式としては固体酸触媒が充填された充填
層に原料を連続的に供給するいわゆる固定床流通
反応型の形式が一般的に採用されるが、場合によ
れば流動床型の反応形式を採用しても差支えがな
い。
以下に実施例によつて本発明方法をさらに具体
的に説明するが、本発明の範囲はこれによつて制
限を受けるものではない。
〈実施例〉
実施例 １
反応管系17mm石英製反応管にニオブ酸触媒
（CBMM社製）20mlを充填し、この反応管を電気
炉で250℃に加熱した。この反応管にイソブチレ
ンを22.4ｇ／hrで、イソブチルアルデヒドを14.4
ｇ／hrで通じて常圧条件下に反応を行なつた。反
応器を出たガスは氷水で冷却し、さらに未反応イ
ソブチレン等の軽沸化合物をドライアイス−メタ
ノールで冷却した。このようにして得られた反応
液をガスクロマトグラフイーで分析した。反応成
績はイソブチルアルデヒド基準（モル）により、
イソブチルアルデヒドの軽化率（％）２，５−ジ
メチル−２，４−ヘキサジエンの選択率（％）及
び収率（％）をそれぞれ算出した。又この値は特
に断わつたとき以外は反応開始後８時間経過時の
値を示した。
以下の各実施例についても同様である。
反応成績はイソブチルアルデヒド転化率89.3％
２，５−ジメチル−２，４−ヘキサジエンの選
択率は65.3％、収率は58.3％であつた。
実施例 ２〜４
実施例１で用いたニオブ酸のかわりに第１表に
記載した触媒20mlを反応管に充填し、２，５−ジ
メチル−２，４−ヘキサジエンの合成反応を行な
い、第１表に記載した結果を得た。なお触媒以外
の反応条件はすべて実施例１に記載した条件と同
じである。
<Industrial Application Field> The present invention relates to a method for producing 2,5-dimethyl-2,4-hexadiene from isobutylene and/or tert-butyl alcohol and isobutyraldehyde. 2,5-dimethyl-2,4-hexadiene is extremely useful as an agrochemical, an insecticide, a medicine, or an intermediate in various organic syntheses. <Prior art> From isobutylene and/or tert-butyl alcohol and isobutyraldehyde.
As a method for producing -dimethyl-2,4-hexadiene, a method is known in which a mineral acid, a sulfonic acid, a heteropolyacid, etc. are used as a catalyst and the reaction is carried out under pressure in a liquid phase (Japanese Unexamined Patent Publication No. 34108/1983). However, in this method, 2,5-dimethyl-
The yield of 2,4-hexadiene is low at less than 40%.
A large amount of breadth organisms are generated. Additionally, mineral acids, sulfonic acids, and the like are highly corrosive to materials, and there is a drawback in that operators must always be careful about troubles caused by material corrosion. <Problems to be Solved by the Invention> The present invention solves the drawbacks of the conventional technology, namely the width It is industrially advantageous for obtaining 2,5-dimethyl-2,4-hexadiene in good yield by solving problems such as large amounts of products produced, low yields, and strong corrosiveness to equipment materials. This is an attempt to provide a method. <Means for Solving the Problems> The present inventors have developed an industrially advantageous method for obtaining 2,5-dimethyl-2,4-hexadiene in good yield from isobutylene and/or tert-butyl alcohol and isobutyraldehyde. The present invention was achieved through intensive research on the method. That is, the present invention is characterized by reacting isobutylene and/or tertiary butyl alcohol with isobutyraldehyde in the gas phase at a temperature of 150 to 350°C in the presence of a solid acid catalyst.
This is a method for producing 2,5-dimethyl-2,4-hexadiene. The raw materials used in the process of the invention are isobutylene and/or tert-butyl alcohol and isobutyraldehyde. The purity of isobutylene is not particularly limited, and highly pure isobutylene may be used as it is, or one obtained as a so-called spent B-B fraction may be used. Tertiary butyl alcohol is similarly not subject to any particular restrictions on purity. It is also possible to use a mixture of isobutylene and tert-butyl alcohol as a raw material. There are no particular restrictions on the purity of isobutyraldehyde. The ratio of isobutylene or tertiary-butyl alcohol to isobutyraldehyde or the ratio of isobutylene and tertiary-butyl alcohol to isobutyraldehyde can be arbitrarily selected. A mixture of l-butyl alcohols having a molar ratio of 1 to 10 is also effectively used. The catalyst used in the process of the invention is a solid acid catalyst. Solid acid catalysts include natural clay minerals such as acid clay, bentonite, and montmorillonite, composite oxides such as silica/alumina, silica/magnesia, and silica/boria, metal oxides such as alumina, silica, titania, and niobic acid, and synthetic zeolites. etc. Further, solid phosphoric acid in which phosphoric acid is supported on a porous carrier can also be used as the solid acid catalyst in the method of the present invention. Preferably, a solid acid catalyst is used which has an acid point whose maximum acid strength is stronger than −5.6 as a value of the Ho function. Specific examples of these catalysts include silica/alumina, acid clay, synthetic zeolite, and niobic acid, among which niobic acid catalysts are most preferably used. Niobic acid is a solid acid also called hydrous niobium oxide, and its preparation method is described in JP-A-60-44039. The niobic acid catalyst may be used as it is, but if it is used after being treated with a mineral acid, especially sulfuric acid or phosphoric acid, it will have even higher activity and 2,5-dimethyl-2,4
- Hexadiene selectivity is obtained. A method for treating a niobic acid catalyst with a mineral acid is generally to immerse the niobic acid in an aqueous mineral acid solution and then wash it with water. In some cases, a method may be adopted in which an aqueous mineral acid solution is passed through a tower filled with niobic acid, and then washed with pure water. As the mineral acid, phosphoric acid or sulfuric acid is preferably used. The concentration of sulfuric acid or phosphoric acid aqueous solution varies depending on the sulfuric acid or phosphoric acid treatment method, but it is usually 0.01 mol/~
It is 1.0 mol/. In addition, in the case of the immersion method, the amount used is usually 2 to 10 times that of niobic acid (volume ratio).
It is. Niobic acid treated with sulfuric acid or phosphoric acid is usually
After calcining at 100-500℃, it is used as a catalyst. Such a niobic acid catalyst treated with sulfuric acid has not only higher activity but also higher selectivity for 2,5-dimethyl-2,4-hexadiene than an untreated niobic acid catalyst. Therefore, by using a niobic acid catalyst treated with sulfuric acid or phosphoric acid, 2,5-dimethyl-2,4-hexadiene can be obtained in a higher yield than when using an untreated niobic acid catalyst. In the method of the invention, the reaction is carried out in the gas phase. As for the reaction temperature, a temperature range of 150 to 350°C is effectively used, preferably a temperature range of 200 to 300°C. When the reaction temperature exceeds 350℃, high-boiling substances such as polymers will be produced, and if the reaction temperature exceeds 150℃,
At temperatures below ℃, the reaction rate becomes very slow. The reaction pressure is not particularly limited as long as the reaction system is maintained in the gas phase, but the reaction is usually carried out under atmospheric pressure or pressurized conditions, preferably in a pressure range of 2 to 10 absolute atmospheres. It will be done. As for the reaction format, a so-called fixed bed flow reaction format is generally adopted in which raw materials are continuously supplied to a packed bed filled with a solid acid catalyst, but in some cases a fluidized bed type reaction format is adopted. There is no harm in doing so. The method of the present invention will be explained in more detail with reference to Examples below, but the scope of the present invention is not limited thereby. <Examples> Example 1 Reaction tube system A 17 mm quartz reaction tube was filled with 20 ml of a niobic acid catalyst (manufactured by CBMM), and the reaction tube was heated to 250° C. in an electric furnace. Into this reaction tube was added isobutylene at 22.4 g/hr and isobutyraldehyde at 14.4 g/hr.
The reaction was carried out under normal pressure conditions at a flow rate of g/hr. The gas exiting the reactor was cooled with ice water, and unreacted low-boiling compounds such as isobutylene were further cooled with dry ice-methanol. The reaction solution thus obtained was analyzed by gas chromatography. Reaction results are based on isobutyraldehyde (mol).
The reduction rate (%) of isobutyraldehyde, the selectivity (%) of 2,5-dimethyl-2,4-hexadiene, and the yield (%) were calculated, respectively. Also, unless otherwise specified, these values are the values obtained 8 hours after the start of the reaction. The same applies to each of the following examples. The reaction results were that the conversion of isobutyraldehyde was 89.3%, the selectivity of 2,5-dimethyl-2,4-hexadiene was 65.3%, and the yield was 58.3%. Examples 2 to 4 Instead of the niobic acid used in Example 1, 20 ml of the catalyst listed in Table 1 was charged into a reaction tube, and a synthesis reaction of 2,5-dimethyl-2,4-hexadiene was carried out. The results listed in the table were obtained. Note that all reaction conditions other than the catalyst were the same as those described in Example 1.
【表】
実施例５〜８、比較例１
実施例１で用いたのと同じニオブ酸触20mlを用
い、第２表に記載した反応条件で反応を行ない、
第２表に記載した反応成績を得た。なお第２表に
記載した以外の反応条件については実施例１に記
載したのと同じ条件で反応を行なつた。[Table] Examples 5 to 8, Comparative Example 1 Using 20 ml of the same niobium acid catalyst used in Example 1, the reaction was carried out under the reaction conditions listed in Table 2.
The reaction results listed in Table 2 were obtained. The reaction conditions other than those listed in Table 2 were the same as those described in Example 1.
【表】
実施例 ９
実施例１で用いたイソブチレンのかわりにター
シヤリーブチルアルコールを29.6ｇ／hrで供給し
て反応を行なつた。なおイソブチレンのかわりに
ターシヤリーブチルアルコールを用いること以外
の条件はすべて実施例１に記載したのと同じ条件
で反応を行なつた。
この時に得られたイソブチルアルデヒドの転化
率は65.3％であり、２，５−ジメチル−２，４−
ヘキサジエンの選択率は65.2％、収率は42.4％で
あつた。
実施例 10
反応管径23mmのSUS製反応管にニオブ酸触媒
（CBMM社製）20mlを充填し、この反応管を電気
炉で250℃に加熱した。この反応管にイソブチレ
ンを44.8ｇ／hrで、イソブチルアルデヒドを14.4
ｇ／hrで通じ、反応圧力５Kg／cm2（ゲージ圧）で
反応を行つた。反応器を出たガスは常圧に減圧し
た後、ドライアイス−メタノールで冷却した。こ
のようにして得られた反応液をガスクロマトグラ
フイーで分析した。反応開始８時間後のイソブチ
ルアルデヒドの転化率は95.3％２，５−ジメチル
−２，４−ヘキサジエンの選択率は79.5％、収率
は75.8％であつた。
またジイソブチレンの生成はまつたく認められ
ず、過剰のイソブチレンはほとんど回収された。
さらに反応を続けて反応開始300時間後のイソ
ブチルアルデヒドの転化率、２，５−ジメチル−
２，４−ヘキサジエンの選択率及び収率を求めた
ところ、イソブチルアルデヒド基準でそれぞれ
92.1％、78.9％、72.7％であり、この間触媒の活
性はほとんど低下しなかつた。
実施例 11〜14
実施例10で用いたのと同じニオブ酸触媒20mlを
用いて第３表に記載した反応条件で反応を行な
い、第３表に記載した反応結果を得た。なお第３
表に記載した反応条件以外の反応条件については
実施例10に記載したのと同じ条件で反応を行なつ
た。[Table] Example 9 In place of the isobutylene used in Example 1, tertiary butyl alcohol was supplied at a rate of 29.6 g/hr to carry out the reaction. The reaction was carried out under the same conditions as described in Example 1 except that tertiary butyl alcohol was used instead of isobutylene. The conversion rate of isobutyraldehyde obtained at this time was 65.3%, and 2,5-dimethyl-2,4-
The selectivity of hexadiene was 65.2% and the yield was 42.4%. Example 10 A SUS reaction tube with a diameter of 23 mm was filled with 20 ml of a niobic acid catalyst (manufactured by CBMM), and the reaction tube was heated to 250° C. in an electric furnace. Isobutylene was added to this reaction tube at a rate of 44.8g/hr, and isobutyraldehyde was added at a rate of 14.4g/hr.
The reaction was carried out at a reaction pressure of 5 Kg/cm 2 (gauge pressure). The gas exiting the reactor was reduced to normal pressure and then cooled with dry ice-methanol. The reaction solution thus obtained was analyzed by gas chromatography. Eight hours after the start of the reaction, the conversion rate of isobutyraldehyde was 95.3%, the selectivity of 2,5-dimethyl-2,4-hexadiene was 79.5%, and the yield was 75.8%. Furthermore, no diisobutylene was observed to be produced, and most of the excess isobutylene was recovered. Continuing the reaction, the conversion rate of isobutyraldehyde 300 hours after the start of the reaction, 2,5-dimethyl-
When the selectivity and yield of 2,4-hexadiene were determined, they were each based on isobutyraldehyde.
They were 92.1%, 78.9%, and 72.7%, and the activity of the catalyst hardly decreased during this period. Examples 11-14 Using 20 ml of the same niobic acid catalyst used in Example 10, a reaction was carried out under the reaction conditions listed in Table 3, and the reaction results listed in Table 3 were obtained. Furthermore, the third
The reaction was carried out under the same conditions as described in Example 10 except for the reaction conditions listed in the table.
【表】
実施例 15
実施例10で用いたイソブチレンのかわりにター
シヤリーブチルアルコールを59.2ｇ／hrで供給し
て反応を行なつた。なおイソブチレンのかわりに
ターシヤリーブチルアルコールを用いること以外
の条件は実施例10に記載したのと同じ条件で反応
を行なつた。この時に得られたイソブチルアルデ
ヒドの転化率、２，５−ジメチル−２，４−ヘキ
サジエンの選択率および収率はイソブチルアルデ
ヒド基準でそれぞれ69.6％、68.8％、48.2％であ
つた。
実施例 16
リン酸処理ニオブ酸触媒を次の如く調製した。
ニオブ酸（CBMM社製）100mlを0.1モル／リ
ン酸水溶液500mlに２時間室温で浸漬した。その
後１の純水で５回水洗を繰り返した後、350℃
で４時間焼成を行なつた。このようにして調製し
たリン酸処理ニオブ酸触媒を用いて以下の反応を
行なつた。
反応管径23mmのSUS製反応管にリン酸処理ニ
オブ酸触媒20mlを充填し、この反応管を電気炉で
250℃に加熱した。この反応管にイソブチレンを
44.8ｇ／hrで、イソブチルアルデヒドを14.4ｇ／
hrで通じ、反応圧力５Kg／cm2（ゲージ圧）で反応
を行なつた。反応器を出たガスは常圧に減圧した
後、ドライアイス−メタノールで冷却した。この
ようにした得られた反応液をガスクロマトグラフ
イーで分析した。反応開始８時間後のイソブチル
アルデヒド転化率、２，５−ジメチル−２，４−
ヘキサジエンの選択率及び収率はイソブチルアル
デヒド基準で、それぞれ97.8％、83.3％、81.6％
であつた。
さらに反応を続けて反応開始300時間後のイソ
ブチルアルデヒド転化率、２，５−ジメチル−
２，４−ヘキサジエンの選択率及び収率を求めた
ところ、イソブチルアルデヒド基準でそれぞれ
93.2％、83.9％、78.2％であり、この間触媒の活
性、選択性はほとんど低下しなかつた。
実施例 17〜19
実施例16で調製したリン酸処理ニオブ酸触媒20
mlを用いて第４表に記載した反応条件で反応を行
ない、第４表に記載した反応結果を得た。
なお第４表に記載した反応条件以外の反応条件
については、実施例16に記載したのと同じ条件で
反応を行なつた。[Table] Example 15 In place of the isobutylene used in Example 10, tertiary butyl alcohol was supplied at a rate of 59.2 g/hr to carry out the reaction. The reaction was carried out under the same conditions as described in Example 10, except that tertiary butyl alcohol was used instead of isobutylene. The conversion rate of isobutyraldehyde, selectivity and yield of 2,5-dimethyl-2,4-hexadiene obtained at this time were 69.6%, 68.8%, and 48.2%, respectively, based on isobutyraldehyde. Example 16 A phosphoric acid treated niobic acid catalyst was prepared as follows.
100 ml of niobic acid (manufactured by CBMM) was immersed in 500 ml of a 0.1 mol/phosphoric acid aqueous solution for 2 hours at room temperature. After that, after repeating water washing 5 times with pure water from step 1, 350℃
Baking was carried out for 4 hours. The following reaction was carried out using the phosphoric acid-treated niobic acid catalyst thus prepared. A SUS reaction tube with a diameter of 23 mm was filled with 20 ml of phosphoric acid-treated niobic acid catalyst, and the reaction tube was placed in an electric furnace.
Heated to 250°C. Add isobutylene to this reaction tube.
44.8g/hr and 14.4g/hr of isobutyraldehyde.
hr, and the reaction was carried out at a reaction pressure of 5 Kg/cm 2 (gauge pressure). The gas exiting the reactor was reduced to normal pressure and then cooled with dry ice-methanol. The reaction solution thus obtained was analyzed by gas chromatography. Isobutyraldehyde conversion rate 8 hours after the start of the reaction, 2,5-dimethyl-2,4-
The selectivity and yield of hexadiene are 97.8%, 83.3%, and 81.6%, respectively, based on isobutyraldehyde.
It was hot. Continuing the reaction, the isobutyraldehyde conversion rate 300 hours after the start of the reaction, 2,5-dimethyl-
When the selectivity and yield of 2,4-hexadiene were determined, they were each based on isobutyraldehyde.
They were 93.2%, 83.9%, and 78.2%, and the activity and selectivity of the catalyst hardly decreased during this period. Examples 17-19 Phosphoric acid treated niobic acid catalyst prepared in Example 16 20
ml under the reaction conditions listed in Table 4, and the reaction results listed in Table 4 were obtained. The reaction conditions other than those listed in Table 4 were the same as those described in Example 16.
【表】
実施例 20
実施例16で用いたイソブチレンのかわりにター
シヤリーブチルアルコールを59.2ｇ／hrで供給し
て反応を行なつた。なおイソブチレンのかわりに
ターシヤリーブチルアルコールを用いること以外
の条件は実施例16に記載したのと同じ条件で反応
を行なつた。この時に得られたイソブチルアルデ
ヒド転化率、２，５−ジメチル−２，４−ヘキサ
ジエンの選択率及び収率はイソブチルアルデヒド
基準でそれぞれ79.4％、80.4％、63.8％であつた。
実施例 21
硫酸処理ニオブ酸触媒を次の如く調製した。
ニオブ酸（CBMM社製）100mlを0.1モル／
硫酸水溶液500mlに２時間室温で浸漬した。その
後１の純水で５回水洗を繰り返した後350℃で
４時間焼成を行なつた。このようにして調製した
硫酸処理ニオブ酸触媒を用いて以下の反応を行な
つた。
反応管径23mmのSUS製反応管に硫酸処理ニオ
ブ酸触媒20mlを充填し、この反応管を電気炉で
250℃に加熱した。この反応管にイソブチレンを
44.8ｇ／hrで、イソブチルアルデヒドを14.4ｇ／
hrで通じ、反応圧力５Kg／cm2（ゲージ圧）で反応
を行なつた。反応器を出たガスは常圧した後、ド
ライアイス−メタノールで冷却した。このように
した得られた反応液をガスクロマトグラフイーで
分析した。反応開始８時間後のイソブチルアルデ
ヒド転化率、２，５−ジメチル−２，４−ヘキサ
ジエンの選択率及び収率はイソブチルアルデヒド
基準でそれぞれ96.6％、83.3％、80.5％であつた。
さらに反応を続けて反応開始300時間後のイソ
ブチルアルデヒド転化率、２，５−ジメチル−
２，４−ヘキサジエンの選択率及び収率を求めた
ところ、イソブチルアルデヒド基準でそれぞれ
94.1％、84.1％、79.1％であり、この間触媒の活
性、選択性はほとんど低下しなかつた。
実施例 22〜24
実施例21で調製した硫酸処理ニオブ酸触媒20ml
を用いて、第５表に記載した反応条件で反応を行
ない、第５表に記載した反応結果を得た。
なお第５表に記載した反応条件以外の反応条件
については実施例21に記載したのと同じ条件で反
応を行なつた。[Table] Example 20 In place of the isobutylene used in Example 16, tertiary butyl alcohol was supplied at a rate of 59.2 g/hr to carry out the reaction. The reaction was carried out under the same conditions as described in Example 16 except that tertiary butyl alcohol was used instead of isobutylene. The isobutyraldehyde conversion, 2,5-dimethyl-2,4-hexadiene selectivity and yield obtained at this time were 79.4%, 80.4% and 63.8%, respectively, based on isobutyraldehyde. Example 21 A sulfuric acid treated niobic acid catalyst was prepared as follows. Niobic acid (manufactured by CBMM) 100ml 0.1mol/
It was immersed in 500 ml of sulfuric acid aqueous solution for 2 hours at room temperature. Thereafter, the product was washed 5 times with pure water from step 1 and then fired at 350° C. for 4 hours. The following reaction was carried out using the sulfuric acid-treated niobic acid catalyst thus prepared. A SUS reaction tube with a diameter of 23 mm was filled with 20 ml of sulfuric acid-treated niobic acid catalyst, and the reaction tube was placed in an electric furnace.
Heated to 250°C. Add isobutylene to this reaction tube.
44.8g/hr and 14.4g/hr of isobutyraldehyde.
hr, and the reaction was carried out at a reaction pressure of 5 Kg/cm 2 (gauge pressure). The gas exiting the reactor was brought to normal pressure and then cooled with dry ice-methanol. The reaction solution thus obtained was analyzed by gas chromatography. Eight hours after the start of the reaction, the conversion rate of isobutyraldehyde, the selectivity and yield of 2,5-dimethyl-2,4-hexadiene were 96.6%, 83.3%, and 80.5%, respectively, based on isobutyraldehyde. Continuing the reaction, the isobutyraldehyde conversion rate 300 hours after the start of the reaction, 2,5-dimethyl-
When the selectivity and yield of 2,4-hexadiene were determined, they were each based on isobutyraldehyde.
They were 94.1%, 84.1%, and 79.1%, and the activity and selectivity of the catalyst hardly decreased during this period. Examples 22-24 20 ml of sulfuric acid-treated niobic acid catalyst prepared in Example 21
The reaction was carried out under the reaction conditions listed in Table 5 using the following formula, and the reaction results listed in Table 5 were obtained. The reaction was carried out under the same conditions as described in Example 21 except for the reaction conditions listed in Table 5.
【表】
実施例 25
実施例21で用いたイソブチレンのかわりにター
シヤリーブチルアルコールを59.2ｇ／hrで供給し
て反応を行なつた。なおイソブチレンのかわりに
ターシヤリーブチルアルコールを用いること以外
の条件は実施例21に記載したのと同じ条件で反応
を行なつた。この時に得られたイソブチルアルデ
ヒド転化率、２，５−ジメチル−２，４−ヘキサ
ジエンの選択率及び収率はイソブチルアルデヒド
基準でそれぞれ80.4％、82.6％、66.4％であつた。
〈発明の効果〉
以上の如く本発明によりイソブチレンおよび／
またはターシヤリーブチルアルコールとイソブチ
ルアルデヒドを固体酸触媒存在下に気相で反応さ
せることにより２，５−ジメチル−２，４−ヘキ
サジエンが高収率で得ることができるようにな
り、さらに固体酸としてニオブ酸あるいはニオブ
酸を鉱酸で処理した触媒を用いることにより一層
の高収率を得ることができ、工業的に有利な２，
５−ジメチル−２，４−ヘキサジエンの製造方法
を確立した。[Table] Example 25 In place of the isobutylene used in Example 21, tertiary butyl alcohol was supplied at a rate of 59.2 g/hr to carry out the reaction. The reaction was carried out under the same conditions as described in Example 21 except that tert-butyl alcohol was used instead of isobutylene. The isobutyraldehyde conversion rate, 2,5-dimethyl-2,4-hexadiene selectivity, and yield obtained at this time were 80.4%, 82.6%, and 66.4%, respectively, based on isobutyraldehyde. <Effects of the Invention> As described above, according to the present invention, isobutylene and/or
Alternatively, by reacting tertiary-butyl alcohol and isobutyraldehyde in the gas phase in the presence of a solid acid catalyst, 2,5-dimethyl-2,4-hexadiene can be obtained in high yield, and further as a solid acid. By using niobic acid or a catalyst prepared by treating niobic acid with a mineral acid, even higher yields can be obtained, which is industrially advantageous.
A method for producing 5-dimethyl-2,4-hexadiene was established.
Claims (1)
チルアルコールとイソブチルアルデヒドを固体酸
触媒の存在下に150〜350℃の温度条件で気相で反
応させることを特徴とする２，５−ジメチル−
２，４−ヘキサジエンの製造方法。 ２ 固体酸触媒としてニオブ酸を用いることを特
徴とする特許請求の範囲第１項に記載の２，５−
ジメチル−２，４−ヘキサジエンの製造方法。 ３ ニオブ酸を鉱酸で処理した触媒を用いること
を特徴とする特許請求の範囲第１項又は第２項記
載の２，５−ジメチル−２，４−ヘキサジエンの
製造方法。 ４ ニオブ酸を処理する鉱酸が、硫酸又はリン酸
であることを特徴とする特許請求の範囲第３項記
載の２，５−ジメチル−２，４−ヘキサジエンの
製造方法。 ５ 気相加圧条件下で反応を行うことを特徴とす
る特許請求の範囲第１項に記載の２，５−ジメチ
ル−２，４−ヘキサジエンの製造方法。[Claims] 1. 2,5-dimethyl-, which is characterized by reacting isobutylene and/or tert-butyl alcohol with isobutyraldehyde in the gas phase at a temperature of 150 to 350°C in the presence of a solid acid catalyst.
A method for producing 2,4-hexadiene. 2. 2,5- as set forth in claim 1, characterized in that niobic acid is used as the solid acid catalyst.
A method for producing dimethyl-2,4-hexadiene. 3. A method for producing 2,5-dimethyl-2,4-hexadiene according to claim 1 or 2, characterized in that a catalyst obtained by treating niobic acid with a mineral acid is used. 4. The method for producing 2,5-dimethyl-2,4-hexadiene according to claim 3, wherein the mineral acid used to treat the niobic acid is sulfuric acid or phosphoric acid. 5. The method for producing 2,5-dimethyl-2,4-hexadiene according to claim 1, wherein the reaction is carried out under pressurized gas phase conditions.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000514727A CA1253888A (en) | 1985-08-07 | 1986-07-25 | Production of 2,5-dimethyl-2,4-hexadiene |
| US06/891,173 US4684758A (en) | 1985-08-07 | 1986-07-31 | Production of 2,5-dimethyl-2,4-hexadiene |
| EP86306095A EP0215567B1 (en) | 1985-08-07 | 1986-08-07 | Production of 2,5-dimethyl-2,4-hexadiene |
| DE8686306095T DE3672423D1 (en) | 1985-08-07 | 1986-08-07 | METHOD FOR PRODUCING 2,5-DIMETHYL-2,4-HEXADIEN. |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17381585 | 1985-08-07 | ||
| JP60-173815 | 1985-08-07 | ||
| JP60-297283 | 1985-12-27 | ||
| JP61-21697 | 1986-02-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62281829A JPS62281829A (en) | 1987-12-07 |
| JPH0329770B2 true JPH0329770B2 (en) | 1991-04-25 |
Family
ID=15967665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61101324A Granted JPS62281829A (en) | 1985-08-07 | 1986-04-30 | Production of 2,5-dimethyl-2,4-hexadiene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62281829A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4834108A (en) * | 1971-09-06 | 1973-05-16 | ||
| JPS6044039A (en) * | 1983-08-17 | 1985-03-08 | シ−ビ−エムエム・インタ−ナシヨナル・リミタ−ダ | Hydrated niobium oxide solid acid catalyst |
-
1986
- 1986-04-30 JP JP61101324A patent/JPS62281829A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4834108A (en) * | 1971-09-06 | 1973-05-16 | ||
| JPS6044039A (en) * | 1983-08-17 | 1985-03-08 | シ−ビ−エムエム・インタ−ナシヨナル・リミタ−ダ | Hydrated niobium oxide solid acid catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62281829A (en) | 1987-12-07 |
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