JP2001172272A - Method for producing ethylene oxide - Google Patents
Method for producing ethylene oxideInfo
- Publication number
- JP2001172272A JP2001172272A JP35408499A JP35408499A JP2001172272A JP 2001172272 A JP2001172272 A JP 2001172272A JP 35408499 A JP35408499 A JP 35408499A JP 35408499 A JP35408499 A JP 35408499A JP 2001172272 A JP2001172272 A JP 2001172272A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene oxide
- carbon dioxide
- gas
- reaction
- ethylene
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はエチレンを気相で接
触酸化してエチレンオキシドを製造する方法に関するも
のである。特に本発明は、高濃度の二酸化炭素を含む雰
囲気中で、エチレンオキシドを高い選択率で製造する方
法に関するものである。The present invention relates to a method for producing ethylene oxide by catalytically oxidizing ethylene in a gas phase. In particular, the present invention relates to a method for producing ethylene oxide with high selectivity in an atmosphere containing a high concentration of carbon dioxide.
【０００２】[0002]
【従来の技術】エチレンを気相で接触酸化してエチレン
オキシドを製造することは大規模に行われている。触媒
としては、今日では専ら銀が用いられている。この反応
にはエチレンが完全燃焼して二酸化炭素が生成する副反
応が付随する。そしてエチレンの反応率が高くなるほ
ど、エチレンオキシドに対する二酸化炭素の生成比率が
増加し、エチレンオキシドの選択率は低下する。エチレ
ンオキシドの選択率を向上させる一つの方法は反応に供
するエチレンに二塩化エチレン等の有機ハロゲン化物を
同伴させることである。しかし有機ハロゲン化物は同時
に触媒の活性を低下させるという問題がある。特公昭４
２−２３５６４号公報には、反応に供するガス中の二塩
化エタン濃度を０．００１〜２ｐｐｍとすることによ
り、触媒活性の低下を抑制し、かつエチレンオキシドの
選択率を向上させることが記載されている。2. Description of the Related Art Catalytic oxidation of ethylene in the gas phase to produce ethylene oxide is performed on a large scale. Today, silver is used exclusively as a catalyst. This reaction is accompanied by a side reaction in which ethylene is completely burned to form carbon dioxide. As the reaction rate of ethylene increases, the ratio of carbon dioxide to ethylene oxide increases, and the selectivity of ethylene oxide decreases. One method for improving the selectivity of ethylene oxide is to allow ethylene to be reacted with an organic halide such as ethylene dichloride. However, there is a problem that the organic halide simultaneously reduces the activity of the catalyst. Tokiko 4
JP-A-2-23564 describes that by controlling the concentration of ethane dichloride in a gas to be subjected to a reaction to 0.001 to 2 ppm, a decrease in catalytic activity is suppressed and an ethylene oxide selectivity is improved. I have.
【０００３】エチレンオキシドの選択率を高くする他の
方法は、反応を穏和な条件下で行ってエチレンの反応率
を低くし、反応生成ガスから生成したエチレンオキシド
を回収したのち、未反応エチレンを反応系に戻す循環方
法であり、エチレンオキシド製造プロセスの多くはこの
循環方法を採用している。Another method for increasing the selectivity of ethylene oxide is to carry out the reaction under mild conditions to lower the reaction rate of ethylene, recover the ethylene oxide generated from the reaction product gas, and then convert the unreacted ethylene to the reaction system. The ethylene oxide production process has adopted this circulation method.
【０００４】[0004]
【発明が解決しようとする課題】循環方法の問題点の一
つは、反応に供するガス中に二酸化炭素が高濃度で含ま
れていると触媒活性が低下するので、エチレンオキシド
回収後のガス中の未反応エチレンを再利用するためこの
ガスを反応系に戻す際に、ガス中の二酸化炭素を除去し
なければならないことである。反応に供するガスは、爆
発範囲を避け、かつ反応温度の制御が容易なように、大
量の不活性ガスで稀釈されているので、反応生成ガスか
らエチレンオキシドを回収した後の残存ガスは大量の不
活性ガスを含んでおり、これから二酸化炭素を除去する
ことは工業的には大きな負担である。何故ならば二酸化
炭素の除去には、二酸化炭素を含むガスを吸収液と接触
させて二酸化炭素を吸収液中に吸収する方法が専ら用い
られているが、この方法では二酸化炭素の濃度が低いほ
ど同一量の二酸化炭素を除去するに要する費用は増加す
るからである。One of the problems of the circulation method is that if the gas to be subjected to the reaction contains a high concentration of carbon dioxide, the catalytic activity is reduced. When this gas is returned to the reaction system to reuse unreacted ethylene, carbon dioxide in the gas must be removed. The gas used for the reaction is diluted with a large amount of inert gas so as to avoid the explosion range and to control the reaction temperature easily.Therefore, the residual gas after the ethylene oxide is recovered from the reaction product gas is a large amount. Since it contains an active gas, removing carbon dioxide therefrom is a heavy industrial burden. Because carbon dioxide is removed exclusively by contacting a gas containing carbon dioxide with the absorbing solution to absorb the carbon dioxide into the absorbing solution, the lower the concentration of carbon dioxide in this method, This is because the cost required to remove the same amount of carbon dioxide increases.
【０００５】反応条件を厳しくして、二酸化炭素濃度の
高い状態でエチレンと酸素とを反応させてエチレンオキ
シドを製造する方法も検討されている。例えば特公昭５
８−４９５５１号公報には、二酸化炭素７５〜８５％、
エチレン５〜１５％、酸素１０〜１５％のガスを反応帯
域に供給し、２９０〜３００℃、３５〜５０気圧で反応
させてエチレンオキシドを製造することが記載されてい
る。しかし、この方法におけるエチレンオキシドの選択
率は７０％未満である。従って本発明は、高い二酸化炭
素濃度のガスを反応に供しても高い選択率でエチレンオ
キシドを製造することのできる方法を提供しようとする
ものである。[0005] A method for producing ethylene oxide by reacting ethylene and oxygen in a state of high carbon dioxide concentration under severe reaction conditions has also been studied. For example, Shoko 5
No. 8-49551 discloses that carbon dioxide is 75 to 85%,
It is described that a gas containing 5 to 15% of ethylene and 10 to 15% of oxygen is supplied to a reaction zone and reacted at 290 to 300 ° C and 35 to 50 atm to produce ethylene oxide. However, the selectivity of ethylene oxide in this process is less than 70%. Accordingly, an object of the present invention is to provide a method capable of producing ethylene oxide with high selectivity even when a gas having a high carbon dioxide concentration is subjected to a reaction.
【０００６】[0006]
【課題を解決するための手段】本発明によれば、銀触媒
が収容されている反応帯域に、エチレン１〜４５％、酸
素１〜２０％、二酸化炭素１５〜７５％、メタン及び／
又は不活性ガス０〜４０％、及び有機ハロゲン化物０．
１〜５０ｐｐｍを含むガス混合物を連続的に供給して、
０．１〜３．５ＭＰａで反応させることにより高い選択
率でエチレンオキシドを製造することができる。According to the present invention, a reaction zone containing a silver catalyst is provided with 1 to 45% of ethylene, 1 to 20% of oxygen, 15 to 75% of carbon dioxide, methane and / or
Alternatively, 0 to 40% of an inert gas, and 0.
Continuously supplying a gas mixture comprising 1 to 50 ppm,
By reacting at 0.1 to 3.5 MPa, ethylene oxide can be produced with high selectivity.
【０００７】[0007]
【発明の実施の形態】本発明について詳細に説明する
と、本発明ではエチレン１〜４５％（体積％、本明細書
においてガス組成の％及びｐｐｍは全て体積基準であ
る）、酸素１〜２０％、二酸化炭素１５〜７５％、メタ
ン及び／又は不活性ガス０〜４０％、及び有機ハロゲン
化物０．１〜５０ｐｐｍを含むガス混合物を反応に供す
る。エチレンオキシドの生産性の観点からしてエチレン
の濃度は１０％以上であるのが好ましい。エチレンの最
も好ましい濃度は１０〜４０％、特に２０〜４０％であ
る。またエチレンの反応率を高める観点から、酸素の濃
度は２％以上、特に３％以上であるのが好ましい。酸素
濃度の好ましい濃度は２〜１０．５％であり、３〜１０
％、特に３〜９．５％であれば更に好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail. In the present invention, ethylene is 1 to 45% (volume%, in this specification,% and ppm of gas composition are all by volume), and oxygen is 1 to 20%. , 15 to 75% of carbon dioxide, 0 to 40% of methane and / or an inert gas, and 0.1 to 50 ppm of an organic halide are subjected to the reaction. From the viewpoint of the productivity of ethylene oxide, the concentration of ethylene is preferably 10% or more. The most preferred concentration of ethylene is 10 to 40%, especially 20 to 40%. From the viewpoint of increasing the reaction rate of ethylene, the oxygen concentration is preferably 2% or more, particularly preferably 3% or more. A preferred oxygen concentration is 2 to 10.5%, and 3 to 10%.
%, Particularly preferably 3 to 9.5%.
【０００８】二酸化炭素は前述のように触媒活性を低下
させるが、本発明では他の条件を適正に選択することに
より、二酸化炭素が高濃度で存在していても、高い選択
率でエチレンオキシドを生成させることができる。本発
明では供給ガス中の二酸化炭素濃度は、反応生成ガスか
らの二酸化炭素の除去を容易にする観点から３０％以上
であるのが好ましい。反応生成ガス中の二酸化炭素は、
供給ガス中の二酸化炭素と反応により副生した二酸化炭
素とから成っているが、反応生成ガス中の未反応エチレ
ンを反応系に戻す際には、この副生量に見合う量の二酸
化炭素を除去するに止めるのが操作上有利である。供給
ガス中の二酸化炭素の最も好ましい濃度は４０〜６０％
である。なお、所望ならば供給ガス中には循環されてく
る反応生成ガス中の二酸化炭素に加えて、外部から二酸
化炭素を供給してもよい。例えば反応生成ガスからエチ
レンオキシドと二酸化炭素の混合物を回収してエチレン
カーボネートを製造する場合には、外部から二酸化炭素
を補給する必要がある。Although carbon dioxide reduces the catalytic activity as described above, in the present invention, by appropriately selecting other conditions, even if carbon dioxide is present at a high concentration, ethylene oxide can be produced with a high selectivity even if carbon dioxide is present at a high concentration. Can be done. In the present invention, the concentration of carbon dioxide in the supply gas is preferably 30% or more from the viewpoint of facilitating removal of carbon dioxide from the reaction product gas. Carbon dioxide in the reaction product gas is
It is composed of carbon dioxide in the feed gas and carbon dioxide by-produced by the reaction.When returning unreacted ethylene in the reaction product gas to the reaction system, the amount of carbon dioxide corresponding to the amount of this by-product is removed. It is operationally advantageous to stop it. The most preferred concentration of carbon dioxide in the feed gas is 40-60%
It is. If desired, carbon dioxide may be externally supplied to the supply gas in addition to the carbon dioxide in the circulated reaction product gas. For example, when producing a mixture of ethylene oxide and carbon dioxide from a reaction product gas to produce ethylene carbonate, it is necessary to supply carbon dioxide from the outside.
【０００９】有機ハロゲン化物としては二塩化エチレ
ン、二塩化エタン、塩化ビニル、塩化メチル、塩化エチ
ル等の脂肪族炭化水素のハロゲン置換体や、クロロベン
ゼン、塩化ジフェニル等の芳香族炭化水素のハロゲン置
換体などを用いればよい。供給ガス中の有機ハロゲン化
物の好ましい濃度は１〜２０ｐｐｍ、特に１〜１５ｐｐ
ｍである。メタンや不活性ガスなどは稀釈剤であり、供
給ガス中に占める比率は３０％以下であるのが好まし
い。不活性ガスとしては通常は窒素が用いられる。Examples of the organic halide include halogen-substituted aliphatic hydrocarbons such as ethylene dichloride, ethane dichloride, vinyl chloride, methyl chloride and ethyl chloride, and halogen-substituted aromatic hydrocarbons such as chlorobenzene and diphenyl chloride. Etc. may be used. The preferred concentration of organic halide in the feed gas is 1-20 ppm, especially 1-15 pp
m. Methane, inert gas, and the like are diluents, and preferably account for 30% or less of the supply gas. Usually, nitrogen is used as the inert gas.
【００１０】銀触媒としては、エチレンオキシドの製造
用触媒として知られているもののなかから適宜選択して
用いればよい。好ましくは担体付の触媒を用いる。例え
ばα−アルミナに銀とアルカリ金属とを担体してなる触
媒を用いればよい。反応は０．１〜３．５ＭＰａの圧力
下に行う。好ましい反応圧力は０．２〜３ＭＰａ、特に
０．５〜２．５ＭＰａである。また反応温度は通常１８
０〜３５０℃であり、好ましくは２００〜３００℃であ
る。供給ガスの空間速度（ＧＨＳＶ）は２０００〜８０
００ｈ-1が好ましい。反応はエチレンの反応率が１〜２
０％、特に５〜１５％となるように行うのが好ましい。
反応生成ガスはエチレンオキシドを回収したのち、副生
量見合いの二酸化炭素を除去して反応系に循環する。The silver catalyst may be appropriately selected from those known as catalysts for producing ethylene oxide. Preferably, a catalyst with a carrier is used. For example, a catalyst in which silver and an alkali metal are supported on α-alumina may be used. The reaction is performed under a pressure of 0.1 to 3.5 MPa. Preferred reaction pressure is 0.2 to 3 MPa, especially 0.5 to 2.5 MPa. The reaction temperature is usually 18
It is 0-350 degreeC, Preferably it is 200-300 degreeC. Space velocity (GHSV) of supply gas is 2000 to 80
00h -1 is preferred. In the reaction, the conversion of ethylene is 1-2.
It is preferable to carry out the reaction so as to be 0%, particularly 5 to 15%.
After recovering ethylene oxide, the reaction product gas removes carbon dioxide corresponding to the amount of by-products and circulates the reaction system.
【００１１】[0011]
【実施例】以下に実施例により本発明を更に具体的に説
明するが、本発明は以下の実施例に限定されるものでは
ない。 実施例１〜３及び比較例１〜２ 内径７．５ｍｍのＳＵＳ製反応管に触媒３ｍｌを充填
し、これに表１の組成の原料ガスをＧＨＳＶ＝４３００
ｈｒ-1、圧力約０．８ＭＰａで供給し、酸素の反応率が
４０％となるように反応温度を調節した。反応管から流
出したガスをガスクロマトグラフィーで分析してエチレ
ンオキシドの選択率を算出した。結果を表１に示す。な
お触媒としては、特開平９−１５００５８号公報の実施
例１に準じて調製した触媒を、６〜１０メッシュに破砕
して用いた。また有機ハロゲン化物としては塩化ビニル
を用いた。EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. Examples 1 to 3 and Comparative Examples 1 and 2 3 ml of a catalyst was filled in a SUS reaction tube having an inner diameter of 7.5 mm, and a raw material gas having the composition shown in Table 1 was added to the GHSV = 4300.
The reaction temperature was adjusted so that the reaction rate of oxygen was 40% by supplying at hr -1 and a pressure of about 0.8 MPa. The gas flowing out of the reaction tube was analyzed by gas chromatography to calculate the selectivity of ethylene oxide. Table 1 shows the results. As the catalyst, a catalyst prepared according to Example 1 of JP-A-9-150058 was crushed to 6 to 10 mesh and used. Vinyl chloride was used as the organic halide.
【００１２】[0012]
【表１】 [Table 1]
Claims (5)
チレン１〜４５％、酸素１〜２０％、二酸化炭素１５〜
７５％、メタン及び／又は不活性ガス０〜４０％、及び
有機ハロゲン化物０．１〜５０ｐｐｍを含むガス混合物
を連続的に供給して、０．１〜３．５ＭＰａで反応させ
てエチレンオキシドを生成させることを特徴とするエチ
レンオキシドの製造法。A reaction zone containing a silver catalyst contains 1 to 45% of ethylene, 1 to 20% of oxygen, and 15 to 25% of carbon dioxide.
A gas mixture containing 75%, 0 to 40% of methane and / or an inert gas, and 0.1 to 50 ppm of an organic halide is continuously supplied and reacted at 0.1 to 3.5 MPa to produce ethylene oxide. A process for producing ethylene oxide.
０〜４０％、酸素の比率が２〜１０．５％であることを
特徴とする請求項１記載のエチレンオキシドの製造法。2. The ratio of ethylene in the gas mixture is 1
The method for producing ethylene oxide according to claim 1, wherein the ratio of oxygen is 0 to 40% and the ratio of oxygen is 2 to 10.5%.
比率が１〜２０ｐｐｍであることを特徴とする請求項１
又は２記載のエチレンオキシドの製造方法。3. The gas mixture according to claim 1, wherein the ratio of the organic halide is 1 to 20 ppm.
Or the method for producing ethylene oxide according to 2.
を特徴とする請求項１ないし３のいずれかに記載のエチ
レンオキシドの製造法。4. The method for producing ethylene oxide according to claim 1, wherein the reaction is carried out at 0.5 to 2.5 MPa.
収液と接触させて、生成したエチレンオキシドを吸収液
中に吸収し、未反応エチレン及び二酸化炭素を含む残存
ガスを、これから二酸化炭素の一部を除去したのち、反
応帯域に循環することを特徴とする請求項１ないし４の
いずれかに記載のエチレンオキシドの製造法。5. A reaction product gas flowing out of a reaction zone is brought into contact with an absorbing solution to absorb the generated ethylene oxide into the absorbing solution, and a residual gas containing unreacted ethylene and carbon dioxide is partially removed from the carbon dioxide. The method for producing ethylene oxide according to any one of claims 1 to 4, wherein the mixture is circulated to a reaction zone after removing the ethylene oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35408499A JP2001172272A (en) | 1999-12-14 | 1999-12-14 | Method for producing ethylene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35408499A JP2001172272A (en) | 1999-12-14 | 1999-12-14 | Method for producing ethylene oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001172272A true JP2001172272A (en) | 2001-06-26 |
Family
ID=18435193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35408499A Pending JP2001172272A (en) | 1999-12-14 | 1999-12-14 | Method for producing ethylene oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001172272A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010540536A (en) * | 2007-09-26 | 2010-12-24 | エスデー リ−ツェンスフェルヴェールトゥングスゲゼルシャフト エムベーハー ウント コー． カーゲー | Start-up process of highly selective ethylene oxide catalyst |
| CN110201487A (en) * | 2019-06-24 | 2019-09-06 | 浙江天采云集科技股份有限公司 | High-purity high-yield methane causes steady gas purification and reuse method in a kind of ethylene process epoxy ethane |
| WO2022049638A1 (en) | 2020-09-01 | 2022-03-10 | 千代田化工建設株式会社 | Method for producing ethylene oxide |
-
1999
- 1999-12-14 JP JP35408499A patent/JP2001172272A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010540536A (en) * | 2007-09-26 | 2010-12-24 | エスデー リ−ツェンスフェルヴェールトゥングスゲゼルシャフト エムベーハー ウント コー． カーゲー | Start-up process of highly selective ethylene oxide catalyst |
| KR101464711B1 (en) * | 2007-09-26 | 2014-11-24 | 에스데 리젠츠페어베르퉁스게젤샤프트 엠베하 엔 코. 카게 | Process for initiating a highly selective ethylene oxide catalyst |
| CN110201487A (en) * | 2019-06-24 | 2019-09-06 | 浙江天采云集科技股份有限公司 | High-purity high-yield methane causes steady gas purification and reuse method in a kind of ethylene process epoxy ethane |
| WO2022049638A1 (en) | 2020-09-01 | 2022-03-10 | 千代田化工建設株式会社 | Method for producing ethylene oxide |
| TWI795890B (en) * | 2020-09-01 | 2023-03-11 | 日商千代田化工建設股份有限公司 | How to make ethylene oxide |
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