JP2007126450A - Method for synthesizing etbe by microwave - Google Patents
Method for synthesizing etbe by microwave Download PDFInfo
- Publication number
- JP2007126450A JP2007126450A JP2006272189A JP2006272189A JP2007126450A JP 2007126450 A JP2007126450 A JP 2007126450A JP 2006272189 A JP2006272189 A JP 2006272189A JP 2006272189 A JP2006272189 A JP 2006272189A JP 2007126450 A JP2007126450 A JP 2007126450A
- Authority
- JP
- Japan
- Prior art keywords
- etbe
- reaction
- synthesizing
- microwave
- catalyst
- 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
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、燃料もしくは燃料用添加剤として有用なエチルターシャリーブチルエーテル（以下「ＥＴＢＥ」と略す。）の合成方法に関する。 The present invention relates to a method for synthesizing ethyl tertiary butyl ether (hereinafter abbreviated as “ETBE”) useful as a fuel or fuel additive.
ＥＴＢＥはガソリン代替燃料として欧米（特に欧州）で使用されている物質であり、特にバイオマス原料を用いて合成したものは地球温暖化対策のバイオマス燃料として注目され、国内でも導入が検討されている。ＥＴＢＥは、（１）メチルターシャリーブチルエーテル（以下、「ＭＴＢＥ」と略す。）と同様、オクタン価向上効果があり、（２）ＭＴＢＥに比較すると毒性が低い（ＭＴＢＥはハイオクガソリンに添加されていたが、毒性の問題から２００４年以降、添加中止となっている。）、（３）エタノールに比べてガソリンへの影響（蒸気圧の上昇や水分混入によるエンジン腐食、ＮＯｘ増加）が少ない、（４）エタノール添加ガソリンと同等の発熱量で比較した場合、若干のコスト高となる、などの特徴がある。フランスやスペインでは、ＥＴＢＥをガソリンに１５％程度添加して使用している。 ETBE is a substance used in Europe and the United States (especially Europe) as an alternative fuel for gasoline, and especially synthesized using biomass raw materials is attracting attention as a biomass fuel for combating global warming, and its introduction is also being studied in Japan. ETBE, like (1) methyl tertiary butyl ether (hereinafter abbreviated as “MTBE”), has an effect of improving octane number, and (2) is less toxic than MTBE (MTBE was added to high-octane gasoline) Due to toxicity problems, the addition has been discontinued since 2004.) (3) Compared with ethanol, there is less impact on gasoline (elevated steam pressure, engine corrosion due to moisture mixing, NOx increase), (4) When compared with the calorific value equivalent to ethanol-added gasoline, there are features such as a slight increase in cost. In France and Spain, about 15% of ETBE is added to gasoline.
従来ＥＴＢＥは、ｔ−ブチルアルコールとエタノールを、触媒とする強酸性イオン交換樹脂を充填した反応蒸留塔で反応させることにより、製造している。 Conventionally, ETBE is produced by reacting t-butyl alcohol and ethanol in a reactive distillation column packed with a strong acidic ion exchange resin as a catalyst.
また、同時にｔ−ブチルアルコールの分解反応によりイソブテンが生成するため、イソブテンリッチガスを使用して、下記の反応によりＥＴＢＥを製造できる。 At the same time, isobutene is produced by the decomposition reaction of t-butyl alcohol, so that ETBE can be produced by the following reaction using isobutene-rich gas.
特許文献１、２には、固体触媒の反応ステージを備えた反応装置を用いて、イソブチレンをエタノール及び水と化学量論的に加圧下で液相反応させて、ＥＴＢＥとともにｔ−ブチルアルコールを合成する方法が提案されている。
しかし、ＥＴＢＥの合成方法においては、反応容器を外部加熱するため余分なエネルギーを必要とし、また、加熱にむらがあるため副反応が起こりやすく、ＥＴＢＥの収率を下げていた。このため、製造コストが高くなるという問題があった。一方、反応時間の短縮化には、マイクロ波照射が有効であることは知られているが、ＥＴＢＥの合成にマイクロ波を使用した例はない。 However, in the method for synthesizing ETBE, extra energy is required to heat the reaction vessel to the outside, and side reactions are likely to occur due to uneven heating, reducing the yield of ETBE. For this reason, there existed a problem that manufacturing cost became high. On the other hand, it is known that microwave irradiation is effective for shortening the reaction time, but there is no example of using microwave for the synthesis of ETBE.
本発明は、このような現状に鑑みてなされたものであり、余分なエネルギーを必要とせず、短時間に簡易かつ低コストにＥＴＢＥを合成できるＥＴＢＥの合成方法を提供することを目的とする。 The present invention has been made in view of such a situation, and an object of the present invention is to provide a method for synthesizing ETBE that can synthesize ETBE easily and at low cost in a short time without requiring extra energy.
前記課題を解決するため、本発明者らは鋭意検討した結果、マイクロ波照射により外部加熱よりも短時間でＥＴＢＥを合成でき、また副反応生成物を低く抑えられることを見出し、本発明に到達した。 In order to solve the above-mentioned problems, the present inventors have intensively studied and found that ETBE can be synthesized in a shorter time than external heating by microwave irradiation, and that side reaction products can be suppressed to a low level. did.
すなわち、本発明は以下のとおりである。
１）エタノールとターシャリーブチルアルコールとを含有する混合物からＥＴＢＥを合成する方法であって、触媒の存在下、マイクロ波照射により加熱することを特徴とするＥＴＢＥの合成方法、
２）触媒が強酸性イオン交換樹脂である前記１）に記載のＥＴＢＥの合成方法、
３）反応温度が４０〜１００℃である前記１）又は２）に記載のＥＴＢＥの合成方法。
That is, the present invention is as follows.
1) A method for synthesizing ETBE from a mixture containing ethanol and tertiary butyl alcohol, which comprises heating by microwave irradiation in the presence of a catalyst,
2) The method for synthesizing ETBE according to 1) above, wherein the catalyst is a strongly acidic ion exchange resin,
3) The method for synthesizing ETBE according to 1) or 2) above, wherein the reaction temperature is 40 to 100 ° C.
本発明によれば、余分なエネルギーを必要としないため所要エネルギーが少なく、簡易にしかも短時間にＥＴＢＥを合成することができ、また、副反応生成物を低く抑えることができる。よって、低価格のＥＴＢＥの提供が可能になる。 According to the present invention, since no extra energy is required, less energy is required, ETBE can be synthesized easily and in a short time, and side reaction products can be kept low. Therefore, it is possible to provide low-cost ETBE.
本発明に係るＥＴＢＥの合成方法は、エタノールとターシャリーブチルアルコールとを含有する混合物からＥＴＢＥを合成する方法であって、触媒の存在下、マイクロ波照射により加熱することを特徴とする。 The method for synthesizing ETBE according to the present invention is a method for synthesizing ETBE from a mixture containing ethanol and tertiary butyl alcohol, characterized by heating by microwave irradiation in the presence of a catalyst.
本発明における前記エタノールとｔ−ブチルアルコールの割合は、エタノール１モルに対して、ｔ−ブチルアルコール０．２〜２０モル、好ましくは０．５〜１０モルである。ｔ−ブチルアルコールが０．２モル未満であると、ジエチルエーテルの副生が多くなる。一方、２０モルを超えると、ｔ−ブチルアルコールがコストに占める割合が高くなり、ＥＴＢＥの製造コストが高くなるからである。 The ratio of the said ethanol and t-butyl alcohol in this invention is 0.2-20 mol, Preferably it is 0.5-10 mol with respect to 1 mol of ethanol. When t-butyl alcohol is less than 0.2 mol, a by-product of diethyl ether increases. On the other hand, when the amount exceeds 20 mol, the proportion of t-butyl alcohol in the cost increases and the production cost of ETBE increases.
前記混合物には、エタノールとｔ−ブチルアルコールのほかに、モレキュラーシーブ、無水硫酸ナトリウム、無水硫酸カルシウム、酸無水物などの脱水剤や、ベンゼン、シクロヘキサンなどの溶媒が添加されていてもよい。 In addition to ethanol and t-butyl alcohol, a dehydrating agent such as molecular sieve, anhydrous sodium sulfate, anhydrous calcium sulfate, and acid anhydride, and a solvent such as benzene and cyclohexane may be added to the mixture.
前記混合物をマイクロ波照射により加熱してＥＴＢＥを合成する場合、触媒存在下で反応させるが、触媒としてはカチオン交換樹脂、硫酸などの強酸性触媒が好ましい。これらの触媒のなかでも、強酸性イオン交換樹脂は触媒回収が容易である点より好ましく、強酸性触媒として使用可能である触媒用の強酸性イオン交換樹脂を使用することができる。好ましい強酸性イオン交換樹脂としては、例えば、イオン交換基がスルフォン酸基（ＳＯ３Ｈ）等の強酸基が導入された多孔質タイプ（ＭＲ形）のスチレン系樹脂、触媒・非水溶液陽イオン交換樹脂として「アンバーリスト(Amberlyst)１５ＪＷＥＴ」（登録商標）の商品名で、ローム・アンド・ハース(Roam and Hass)社から製造・販売されているものなどを挙げることができる。 When the mixture is heated by microwave irradiation to synthesize ETBE, the reaction is carried out in the presence of a catalyst. The catalyst is preferably a strongly acidic catalyst such as a cation exchange resin or sulfuric acid. Among these catalysts, strong acid ion exchange resins are preferred from the viewpoint of easy catalyst recovery, and strong acid ion exchange resins for catalysts that can be used as strong acid catalysts can be used. Preferred strong acidic ion exchange resins include, for example, porous type (MR type) styrene resins in which strong acid groups such as sulfonic acid groups (SO 3 H) are introduced as ion exchange groups, and catalyst / non-aqueous cation exchange. Examples of the resin include those manufactured and sold by Roam and Hass under the trade name “Amberlyst 15JWET” (registered trademark).
触媒使用量は、エタノール１モルに対して、１〜２０ｇ、好ましくは３〜９ｇである。触媒量が１ｇ未満であると、反応が完結しなくなる。一方、２０ｇを超えても触媒効果は頭打ちとなり、コスト高となるからである。 The amount of catalyst used is 1 to 20 g, preferably 3 to 9 g, per 1 mol of ethanol. If the amount of catalyst is less than 1 g, the reaction will not be completed. On the other hand, even if it exceeds 20 g, the catalytic effect reaches its peak and the cost increases.
本発明のＥＴＢＥの合成方法の好ましい一実施形態では、前記の特定の量比で、エタノールとｔ−ブチルアルコールを混合し、これらに必要に応じて上記した脱水剤や溶媒などを配合して液体混合物を調製し、得られた混合物を、触媒存在下で、マイクロ波照射により加熱する。 In a preferred embodiment of the method for synthesizing ETBE of the present invention, ethanol and t-butyl alcohol are mixed at the specific amount ratio described above, and the above-described dehydrating agent and solvent are blended as necessary. A mixture is prepared and the resulting mixture is heated by microwave irradiation in the presence of a catalyst.
照射するマイクロ波の出力や周波数、照射方法は、特に限定されるものではなく、反応温度が所定の範囲に保持できるよう電気的に制御すればよい。出力が低すぎる場合はＥＴＢＥ転化率が低くなり、一方、出力が高すぎる場合はマイクロ波の利用率が悪くなったり、生成物や反応物の蒸発が起こり、効率が悪くなる。マイクロ波の周波数は、通常、１ＧＨｚ〜３００ＧＨｚである。１ＧＨｚ未満又は３００ＧＨｚを超える周波数範囲では、反応促進効果が不十分となる。 The output, frequency, and irradiation method of the microwave to be irradiated are not particularly limited, and may be electrically controlled so that the reaction temperature can be maintained within a predetermined range. When the output is too low, the ETBE conversion rate is low. On the other hand, when the output is too high, the utilization rate of the microwave is deteriorated, and evaporation of products and reactants occurs, resulting in poor efficiency. The frequency of the microwave is usually 1 GHz to 300 GHz. In the frequency range below 1 GHz or above 300 GHz, the reaction promoting effect is insufficient.
マイクロ波の照射は連続照射、間欠照射のいずれの方法であってもよい。照射時間及び照射停止時間は、ＥＴＢＥの生成状況に応じて適宜に決定することができる。 Microwave irradiation may be either continuous irradiation or intermittent irradiation. The irradiation time and the irradiation stop time can be appropriately determined according to the generation state of ETBE.
マイクロ波発振器としては、マグネトロン等のマイクロ波発振器や、固体素子を用いたマイクロ波発振器等を適宜用いることができる As the microwave oscillator, a microwave oscillator such as a magnetron, a microwave oscillator using a solid element, or the like can be used as appropriate.
ＥＴＢＥ合成反応における反応温度は、４０〜１００℃である。反応は前記の温度範囲内であれば逐次進行するが、前記混合物の還流条件下で実施するのが、ＥＴＢＥ転化率を高められる点より好ましい。反応圧力は、常圧で行うことができるが、これに限定されない。 The reaction temperature in the ETBE synthesis reaction is 40 to 100 ° C. Although the reaction proceeds successively within the above temperature range, it is preferable to carry out the reaction under reflux conditions of the mixture from the viewpoint of increasing the ETBE conversion rate. The reaction pressure can be performed at normal pressure, but is not limited thereto.
反応時間は特に限定されないが、通常、０．５〜１０時間程度、好ましくは０．５〜４時間程度反応させるのが良い。 Although reaction time is not specifically limited, Usually, it is good to make it react about 0.5 to 10 hours, Preferably about 0.5 to 4 hours.
以下、本発明の実施例について図面を参照して説明するが、本発明は以下の実施例にのみ限定されるものではない。 Hereinafter, examples of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following examples.
（実施例１）
図１に示したマイクロ波照射装置（１）内に設置された、３００ｍＬ容のガラス製三つ口フラスコに、エタノール１モル、ターシャリーブチルアルコール１モル、強酸性触媒として、「アンバーリスト(Amberlyst)１５ＪＷＥＴ」８ｇを入れた。上記の混合液を、スターラーで攪拌しながら、２．４５ＧＨｚのマイクロ波を照射して混合液の温度を７０℃まで昇温させた後、マイクロ波制御装置（２）を用いて、ＰＩＤ制御により反応温度を７０℃に保持しながらマイクロ波を２時間連続照射し、ＥＴＢＥの合成反応を行った。なお、三口フラスコの中央口には凝縮器（３）を取り付け、ブラインで冷却しながら、開放系で実験を行った。
Example 1
In a 300 mL glass three-necked flask installed in the microwave irradiation apparatus (1) shown in FIG. 1, 1 mol of ethanol, 1 mol of tertiary butyl alcohol and “Amberlyst (Amberlyst) ) 15JWET "8g. While stirring the above-mentioned mixed liquid with a stirrer, the microwave of 2.45 GHz was irradiated to raise the temperature of the mixed liquid to 70 ° C., and then the microwave control device (2) was used to perform PID control. While maintaining the reaction temperature at 70 ° C., microwaves were continuously irradiated for 2 hours to carry out an ETBE synthesis reaction. In addition, the condenser (3) was attached to the center neck of the three-neck flask, and the experiment was conducted in an open system while cooling with brine.
反応後の液体を、島津製作所製ガスクロマトグラフィーＧＣ−２０１０ＡＦ／ＡＯＣで分析し、同定・定量した。ＥＴＢＥに換算したときの転化率を、下記式により求めた。 The liquid after the reaction was analyzed and identified / quantified by gas chromatography GC-2010AF / AOC manufactured by Shimadzu Corporation. The conversion rate when converted to ETBE was determined by the following formula.
転化率(%)＝〔ＥＴＢＥ合成量(mol)/初期エタノール量(mol)〕×100 Conversion rate (%) = [ETBE synthesis amount (mol) / initial ethanol amount (mol)] × 100
（実施例２）
マイクロ波を３時間連続照射した以外は、実施例１と同様な方法によりＥＴＢＥの合成反応を行った。
(Example 2)
An ETBE synthesis reaction was carried out in the same manner as in Example 1 except that microwave irradiation was continued for 3 hours.
（実施例３）
マイクロ波を４時間連続照射した以外は、実施例１と同様な方法によりＥＴＢＥの合成反応を行った。
(Example 3)
An ETBE synthesis reaction was carried out in the same manner as in Example 1 except that microwave irradiation was continued for 4 hours.
（実施例４〜５）
マイクロ波を０．５時間、１時間連続照射した以外は、実施例１と同様な方法によりＥＴＢＥの合成反応を行った。
(Examples 4 to 5)
An ETBE synthesis reaction was carried out in the same manner as in Example 1 except that microwave irradiation was continued for 0.5 hour and 1 hour.
（比較例１）
加熱手段をマイクロ波照射ではなく７０℃の温浴を用い、２時間反応させた以外は、実施例１と同様な方法によりＥＴＢＥの合成反応を行った。なお。三口フラスコの中央口には凝縮器（３）を取り付け、ブラインで冷却しながら、開放系で実験を行った
(Comparative Example 1)
A synthetic reaction of ETBE was carried out in the same manner as in Example 1 except that the heating means was not microwave irradiation but a 70 ° C. warm bath was used and the reaction was performed for 2 hours. Note that. A condenser (3) was attached to the center neck of the three-neck flask, and the experiment was conducted in an open system while cooling with brine.
（比較例２）
加熱手段をマイクロ波照射ではなく７０℃の温浴を用い、３時間反応させた以外は、実施例１と同様な方法によりＥＴＢＥの合成反応を行った。
(Comparative Example 2)
A synthetic reaction of ETBE was carried out by the same method as in Example 1 except that the heating means was not microwave irradiation but a 70 ° C. warm bath was used and the reaction was performed for 3 hours.
（比較例３）
加熱手段をマイクロ波照射ではなく７０℃の温浴を用い、４時間反応させた以外は、実施例１と同様な方法によりＥＴＢＥの合成反応を行った。
(Comparative Example 3)
A synthetic reaction of ETBE was carried out in the same manner as in Example 1 except that the heating means was not microwave irradiation but a 70 ° C. warm bath was used and the reaction was performed for 4 hours.
（比較例４〜５）
加熱手段をマイクロ波照射ではなく７０℃の温浴を用い、０．５時間、１時間反応させた以外は、実施例１と同様な方法によりＥＴＢＥの合成反応を行った。
(Comparative Examples 4-5)
An ETBE synthesis reaction was carried out in the same manner as in Example 1 except that the heating means was not microwave irradiation but a 70 ° C. warm bath was used and the reaction was carried out for 0.5 hour and 1 hour.
実施例及び比較例の結果を表１にまとめて示す。 The results of Examples and Comparative Examples are summarized in Table 1.
表１の結果から、マイクロ波照射した方が、温浴加熱に比べて短時間でＥＴＢＥを合成できることがわかった。 From the results shown in Table 1, it was found that microwave irradiation could synthesize ETBE in a shorter time than warm bath heating.
また、図２は、マイクロ波加熱（触媒あり、なし）した場合と、温浴加熱した場合における、混合物の温度上昇曲線を示している。図２から、マイクロ波と温浴の温度上昇傾向に差はほとんどなかった。また、マイクロ波の触媒の有無でも差がほとんどなく、触媒そのものは加熱していないものと思われた。 FIG. 2 shows the temperature rise curves of the mixture when microwave heating (with or without catalyst) and when heated in a warm bath. From FIG. 2, there was almost no difference in the temperature rising tendency of the microwave and the warm bath. Moreover, there was almost no difference in the presence or absence of the microwave catalyst, and the catalyst itself was not heated.
（実施例６）
ＣＥＭ社製マイクロ波フォーカスドＤｉｓｃｏｖｅｒ Ｂｅｎｃｈ Ｍａｔｅ合成システムに設置された、１００ｍＬ容のガラス製三口フラスコに、エタノール０．５モル、ターシャリーブチルアルコール０．５モル、強酸性触媒「アンバーリスト（Amberlyst）１５ＪＷＥＴ」４ｇを入れた。その後の試験・分析手順は実施例１と同一とし、マイクロ波による加熱試験を行った。反応時間は２時間とした。
(Example 6)
In a 100 mL glass three-necked flask installed in the microwave focused Discover Bench Mate synthesis system manufactured by CEM, 0.5 mol of ethanol, 0.5 mol of tertiary butyl alcohol, a strongly acidic catalyst “Amberlyst” 4 g of “15 JWET” was added. Subsequent test and analysis procedures were the same as in Example 1, and a microwave heating test was performed. The reaction time was 2 hours.
（実施例７）
実施例６と同様な手順でマイクロ波による加熱試験を行った。ただし、試験装置のキャビティに冷却空気を噴射し、反応部を周囲から冷却しながらマイクロ波で加熱した。実施例６と同じく反応温度は７０℃、反応時間は２時間とした。
(Example 7)
A microwave heating test was performed in the same procedure as in Example 6. However, cooling air was injected into the cavity of the test apparatus, and the reaction part was heated with microwaves while cooling from the surroundings. As in Example 6, the reaction temperature was 70 ° C., and the reaction time was 2 hours.
（比較例６）
１００ｍＬ容のがラス製三口フラスコに、エタノール０．５モル、ターシャリーブチルアルコール０．５モル、強酸性触媒「アンバーリスト（Amberlyst）１５ＪＷＥＴ」４ｇを入れ、温浴による試験を行った。実施例６と同じく反応温度は７０℃、反応時間は２時間とした。
(Comparative Example 6)
A 100 mL volume flask made of Las was charged with 0.5 mol of ethanol, 0.5 mol of tertiary butyl alcohol, and 4 g of a strongly acidic catalyst “Amberlyst 15 JWET”, and a test using a warm bath was conducted. As in Example 6, the reaction temperature was 70 ° C., and the reaction time was 2 hours.
実施例６、７及び比較例６の結果を表２に示す。表２の結果から、反応温度は同じ７０℃でも、冷却しながらマイクロ波を多く当てた方が、ＥＴＢＥを多く合成できることが分かった。また、マイクロ波方式の方が温浴に比べ２００倍程度省エネルギーであることがわかった。 The results of Examples 6 and 7 and Comparative Example 6 are shown in Table 2. From the results of Table 2, it was found that even when the reaction temperature was the same 70 ° C., more ETBE could be synthesized by applying more microwaves while cooling. Further, it was found that the microwave method is about 200 times more energy saving than the warm bath.
本発明の合成方法で得られるＥＴＢＥは、低価格の含酸素燃料として単独で、または自動車ガソリンやディーゼルエンジン燃料の添加剤として使用することができる。 ETBE obtained by the synthesis method of the present invention can be used alone as an inexpensive oxygen-containing fuel or as an additive for automobile gasoline or diesel engine fuel.
１ マイクロ波照射装置
２ マイクロ波制御装置
３ 凝縮器
1
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006272189A JP2007126450A (en) | 2005-10-04 | 2006-10-03 | Method for synthesizing etbe by microwave |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005291495 | 2005-10-04 | ||
| JP2006272189A JP2007126450A (en) | 2005-10-04 | 2006-10-03 | Method for synthesizing etbe by microwave |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2007126450A true JP2007126450A (en) | 2007-05-24 |
Family
ID=38149396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006272189A Pending JP2007126450A (en) | 2005-10-04 | 2006-10-03 | Method for synthesizing etbe by microwave |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2007126450A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011016747A (en) * | 2009-07-08 | 2011-01-27 | National Institute Of Advanced Industrial Science & Technology | Method for producing hydroxy aromatic derivative |
| CN115872843A (en) * | 2022-10-24 | 2023-03-31 | 南通瑞合达医药科技有限公司 | Novel synthesis process of ethyl tert-butyl ether |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07330667A (en) * | 1994-06-10 | 1995-12-19 | Koichi Shinozaki | Production of esters by heating with microwave |
| US5527970A (en) * | 1995-02-02 | 1996-06-18 | Texaco Chemical Inc. | Synthesis of ethyl t-butyl ether from t-butanol in one step using acid catalysts |
| JPH1036294A (en) * | 1996-07-25 | 1998-02-10 | Agency Of Ind Science & Technol | Production of acid amide or acid imide or ester compound |
| JP2002532239A (en) * | 1998-12-17 | 2002-10-02 | パーソナル ケミストリー イ ウプサラ アーベー | Microwave device and method for performing a chemical reaction |
| WO2004002617A1 (en) * | 2002-06-26 | 2004-01-08 | Cem Corporation | Reaction and temperature control for high power microwave-assisted chemistry techniques |
| JP2004307435A (en) * | 2003-04-10 | 2004-11-04 | Nihon Gas Kk | Method for preparing dimethyl ether and apparatus for carrying out synthetic reaction of dimethyl ether |
| JP2005162669A (en) * | 2003-12-02 | 2005-06-23 | Suzuki Takahiro | Method of synthesizing etbe |
| JP2006225275A (en) * | 2005-02-15 | 2006-08-31 | Tokyo Electric Power Co Inc:The | Method for synthesizing dimethyl ether |
| JP2007277179A (en) * | 2006-04-07 | 2007-10-25 | Tokyo Electric Power Co Inc:The | Method for synthesizing dimethyl ether using microwave |
-
2006
- 2006-10-03 JP JP2006272189A patent/JP2007126450A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07330667A (en) * | 1994-06-10 | 1995-12-19 | Koichi Shinozaki | Production of esters by heating with microwave |
| US5527970A (en) * | 1995-02-02 | 1996-06-18 | Texaco Chemical Inc. | Synthesis of ethyl t-butyl ether from t-butanol in one step using acid catalysts |
| JPH1036294A (en) * | 1996-07-25 | 1998-02-10 | Agency Of Ind Science & Technol | Production of acid amide or acid imide or ester compound |
| JP2002532239A (en) * | 1998-12-17 | 2002-10-02 | パーソナル ケミストリー イ ウプサラ アーベー | Microwave device and method for performing a chemical reaction |
| WO2004002617A1 (en) * | 2002-06-26 | 2004-01-08 | Cem Corporation | Reaction and temperature control for high power microwave-assisted chemistry techniques |
| JP2004307435A (en) * | 2003-04-10 | 2004-11-04 | Nihon Gas Kk | Method for preparing dimethyl ether and apparatus for carrying out synthetic reaction of dimethyl ether |
| JP2005162669A (en) * | 2003-12-02 | 2005-06-23 | Suzuki Takahiro | Method of synthesizing etbe |
| JP2006225275A (en) * | 2005-02-15 | 2006-08-31 | Tokyo Electric Power Co Inc:The | Method for synthesizing dimethyl ether |
| JP2007277179A (en) * | 2006-04-07 | 2007-10-25 | Tokyo Electric Power Co Inc:The | Method for synthesizing dimethyl ether using microwave |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011016747A (en) * | 2009-07-08 | 2011-01-27 | National Institute Of Advanced Industrial Science & Technology | Method for producing hydroxy aromatic derivative |
| CN115872843A (en) * | 2022-10-24 | 2023-03-31 | 南通瑞合达医药科技有限公司 | Novel synthesis process of ethyl tert-butyl ether |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Teng et al. | A review on the performance of glycerol carbonate production via catalytic transesterification: Effects of influencing parameters | |
| Cintas et al. | Glycerol: a solvent and a building block of choice for microwave and ultrasound irradiation procedures | |
| Peng et al. | Facile and efficient conversion of furfuryl alcohol into n-butyl levulinate catalyzed by extremely low acid concentration | |
| Wang et al. | Microwave-assisted transesterification of glycerol with dimethyl carbonate over sodium silicate catalyst in the sealed reaction system | |
| Okoye et al. | A review on recent trends in reactor systems and azeotrope separation strategies for catalytic conversion of biodiesel-derived glycerol | |
| CN103394372B (en) | Heteropoly ionic liquid catalyst with Br*nsted-Lewis dual acidity | |
| CN106495105B (en) | A method of synthesis nanometer selenium material | |
| CN113788793B (en) | Sulfonic acid functionalized imidazole ionic liquid catalyst and preparation method and application thereof | |
| CN101850244B (en) | Preparation method of Al2O3-SiO3 solid acid catalyst in nuclear shell structure | |
| Chen et al. | A donor–acceptor complex enables the synthesis of E-olefins from alcohols, amines and carboxylic acids | |
| Bartoli et al. | Reaction of dicarbonates with carboxylic acids catalyzed by weak Lewis acids: general method for the synthesis of anhydrides and esters | |
| CA2919220C (en) | Method for catalytic conversion of ketoacids and hydrotreatment to hydrocarbons | |
| Desai et al. | Synthesis of energy rich fuel additive from biomass derived levulinic acid and furfuryl alcohol using novel tin-exchanged heteropoly acid supported on titania nanotubes as catalyst | |
| EP3250541A1 (en) | Methods for preparing glycerol tert-butyl ethers | |
| Yang et al. | NaZSM-5-catalyzed dimethyl carbonate synthesis via the transesterification of ethylene carbonate with methanol | |
| JP2007126450A (en) | Method for synthesizing etbe by microwave | |
| Bernal et al. | AQUIVION® perfluorosulfonic acid resin for butyl levulinate production from furfuryl alcohol | |
| Kumar et al. | Synthesis of an oxygenated fuel additive from a waste biomass derived aldehyde using a green catalyst: an experimental and DFT study | |
| TWI267505B (en) | Method for the catalytic conversion of alkylene carbonate with Mg, Al mixed (hydr)oxide catalyst and its use therefore | |
| Zhang et al. | Low-temperature production of 5-hydroxymethylfurfural from fructose using choline chloride–ethylene glycol–maleic acid ternary deep eutectic solvents | |
| Zainol et al. | Ethyl Levulinate synthesis from Levulinic acid and Furfuryl alcohol by Using modified carbon Cryogels | |
| Umrigar et al. | Optimization of process parameters for oleic acid esterification using microwave reactor: Catalytic activity, product distribution and reactor energy model | |
| Sert et al. | Application of green catalysts for the esterification of benzoic acid with different alcohols | |
| Gao et al. | Enhanced conversion of furfuryl alcohol to alkyl levulinates catalyzed by synergy of CrCl 3 and H 3 PO 4 | |
| Chen et al. | Novel route for the synthesis of methyl propionate from 3-pentanone with dimethyl carbonate over solid bases |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090901 |
|
| A977 | Report on retrieval |
Effective date: 20120307 Free format text: JAPANESE INTERMEDIATE CODE: A971007 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120313 |
|
| A521 | Written amendment |
Effective date: 20120417 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120523 |
|
| A02 | Decision of refusal |
Effective date: 20121002 Free format text: JAPANESE INTERMEDIATE CODE: A02 |