JPS61126036A - Purification and separation of olefinic hydrocarbon - Google Patents
Purification and separation of olefinic hydrocarbonInfo
- Publication number
- JPS61126036A JPS61126036A JP59247935A JP24793584A JPS61126036A JP S61126036 A JPS61126036 A JP S61126036A JP 59247935 A JP59247935 A JP 59247935A JP 24793584 A JP24793584 A JP 24793584A JP S61126036 A JPS61126036 A JP S61126036A
- Authority
- JP
- Japan
- Prior art keywords
- adsorption
- gas
- adsorbent
- purge
- adsorption tower
- 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.)
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Classifications
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
Description
【発明の詳細な説明】
倉栗上皇五尻光！
本発明は吸着分離方法によってオレフィン類を含む原料
ガスよ、リオレフィン系炭化水素、特にエチレン、プロ
ピレン、ブチレン、ペンテンナト（以下エチレン等とい
う）を回収する方法に関するものである。[Detailed description of the invention] Kurakuri Retired Emperor Gojiri Hikaru! The present invention relates to a method for recovering lyolefin-based hydrocarbons, particularly ethylene, propylene, butylene, and pentenato (hereinafter referred to as ethylene, etc.) from a raw material gas containing olefins by an adsorption separation method.
エチレン等のオレフィン系炭化水素類が石油化学製品で
あるエタノール、エチレンオキサイド、アセトアルデヒ
ド、塩化ビニル、スチレン、酢酸ビニル、エチレングリ
コール、（１１度リニアーポリエチレン、プロパツール
、プロピレンオキサイド、アセトン、ポリプロピレン、
ブタノール、ブタジェン、ポリブテン、ブチルゴム等の
原料として有用なものであることは周知の通りである。Olefinic hydrocarbons such as ethylene are petrochemical products such as ethanol, ethylene oxide, acetaldehyde, vinyl chloride, styrene, vinyl acetate, ethylene glycol, (11 degree linear polyethylene, propatool, propylene oxide, acetone, polypropylene,
It is well known that it is useful as a raw material for butanol, butadiene, polybutene, butyl rubber, etc.
ｌ米東扱歪
従来のオレフィン類の一般的な製造法について簡単に説
明すると、先ず原料ナフサとスチームを混合して、熱分
解炉に送入し、ナフサの熱分解を行ない、次に生成ガス
を直ちに水との熱交換及び重質油の注入によって１２０
℃付近まで急冷し、液化した０５以上の炭化水素成分を
分離する。次にこの非液化ガスは圧縮して不純物を除去
した後、エチレンやプロピレンなどの冷媒を用いて液化
し、蒸留によってエチレン、Ｐ−Ｆ）留分、Ｃ４留分、
残ガス、エタンなどの留分に分離する。To briefly explain the general manufacturing method of conventional olefins, raw material naphtha and steam are first mixed and sent to a pyrolysis furnace to thermally decompose the naphtha, and then the generated gas is 120 by immediately exchanging heat with water and injecting heavy oil.
It is rapidly cooled to around ℃ and the liquefied hydrocarbon components of 05 or higher are separated. Next, this non-liquefied gas is compressed to remove impurities, then liquefied using a refrigerant such as ethylene or propylene, and distilled to produce ethylene, P-F) fraction, C4 fraction,
Separate into fractions such as residual gas and ethane.
以上説明したように、ナフサの熱分解ガス中からオレフ
ィン類などの有用成分を分離、精製する時の基本原理は
低温加圧蒸留（深冷分離法）である。この方法は原料ガ
スを冷却液化し一１００℃〜−２００℃で分留するもの
である。As explained above, the basic principle for separating and purifying useful components such as olefins from naphtha pyrolysis gas is low temperature pressurized distillation (cryogenic separation method). In this method, the raw material gas is cooled and liquefied and fractionated at -100°C to -200°C.
■が”しようとする間６点
しかしながら、上記の方法においては、原料ガス中に水
分や二酸化炭素が存在すると、これらが低温管システム
内で固化して閉塞事故を起すので前処理によりこれらを
十分に除去しなければならないという問題がある。■ However, in the above method, if moisture or carbon dioxide exists in the raw material gas, these will solidify in the cryogenic tube system and cause a blockage accident, so pretreatment is sufficient to remove these. The problem is that it must be removed.
更に前記した従来の方法には、複雑な冷凍及び熱回収シ
ステムの使用が必要であり、しかも装置に特殊な金属材
料などの高級材料を使用することが必要なために装置が
高価となり、また冷凍用コンプレッサーの使用が必要な
どのために運転経費も高いなどの問題がある。Furthermore, the conventional methods described above require the use of complex refrigeration and heat recovery systems, require the use of high-grade materials such as special metal materials in the equipment, making the equipment expensive, and There are problems such as high operating costs due to the need to use a commercial compressor.
本発明者等は前記した従来のオレフィン類の製造方法に
おける問題点を解決すべく検討を重ねた結果、オレフィ
ンを含む原料ガスからオレフィンを選択的に吸着する銅
化合物−活性炭から成る吸着剤を使用してエチレン、プ
ロピレンなどのオレフィン系炭化水素ｉｔ効率よく分離
する方法を見出した。As a result of repeated studies to solve the problems in the conventional olefin production methods described above, the present inventors used an adsorbent consisting of a copper compound and activated carbon that selectively adsorbs olefins from a raw material gas containing olefins. We have discovered a method for efficiently separating olefinic hydrocarbons such as ethylene and propylene.
問題点を”決するための手段及びその作用効果本発明に
従ったオレフィン系炭化水素類の精製分離方法はオレフ
ィン類を含む原料ガスから、吸着分離方法によりオレフ
ィン系炭化水素類を回収する方法において、銅化合物−
活性炭系吸着剤を充填した２つ以上の吸着塔を用い、
（１１原料ガスを吸着塔に流して、オレフィン系炭化水
素類を吸着させる吸着工程、
（２）吸着工程の終了した吸着塔へ製品ガスを導入して
、難吸着成分をパージするパージ工程及び（３）吸着塔
内を減圧又は加熱することによって吸着剤に吸着されて
いるオレフィン系炭化水素を脱着回収する回収工程を、
２つ以上の吸着塔において操り返し実施することを特徴
とした方法に関するものである。A method for refining and separating olefinic hydrocarbons according to the present invention is a method for recovering olefinic hydrocarbons from a raw material gas containing olefins by an adsorption separation method. Copper compounds
Using two or more adsorption towers filled with activated carbon adsorbent, (11) an adsorption step in which the raw material gas is passed through the adsorption tower to adsorb olefinic hydrocarbons; (2) the product is transferred to the adsorption tower after the adsorption step has been completed; A purge step in which gas is introduced to purge difficult-to-adsorb components; and (3) a recovery step in which the olefinic hydrocarbons adsorbed on the adsorbent are desorbed and recovered by reducing or heating the inside of the adsorption tower.
The present invention relates to a method characterized in that it is repeatedly carried out in two or more adsorption towers.
本発明における前記行程（１）は吸着塔内に原料ガスを
流通させることによって、オレフィン類を吸着剤に吸着
させる吸着工程である。この吸着工程では吸着塔内の圧
力を常圧で運転することにより十分な効果が得られるが
、加圧状態で操作することも可能であり、この場合は吸
着量が増加したり高温ガスでも処理できるなどの利点が
ある。加圧状態で運転する場合においても高い吸着圧は
必要ではなく １０ ｋｇ／ｃＪ以下、好ましくは、２
〜５ ｋｇ／ｄの吸着圧で十分である。The step (1) in the present invention is an adsorption step in which olefins are adsorbed on an adsorbent by circulating a raw material gas in an adsorption tower. In this adsorption process, sufficient effects can be obtained by operating the adsorption tower at normal pressure, but it is also possible to operate it under pressurized conditions, in which case the amount of adsorption increases and high temperature gas can also be processed. There are advantages such as being able to Even when operating under pressure, a high adsorption pressure is not necessary; it is less than 10 kg/cJ, preferably 2
An adsorption pressure of ~5 kg/d is sufficient.
原料ガスの吸着塔内への流入は吸着塔出口においてオレ
フィン成分が検出されはじめる時点から吸着塔入口にお
ける濃度に達する時点までの間の任意の時点まで行なう
。又、吸着操作時の温度は常圧下の場合で一４０〜９０
℃、好ましくは０〜６０’Ｃであり、加圧下では一１０
℃〜１２０℃、好ましくは２０℃〜８０℃である。The raw material gas is allowed to flow into the adsorption tower at any point between the time when the olefin component begins to be detected at the outlet of the adsorption tower and the time when the concentration reaches the concentration at the entrance of the adsorption tower. In addition, the temperature during adsorption operation is -40 to -90 °C under normal pressure.
°C, preferably 0 to 60'C, and -10'C under pressure.
℃~120℃, preferably 20℃~80℃.
前記工程（２）は吸着工程が終了した吸着塔内に製品ガ
スを導入して塔内の空隙に残留する難吸着成分をパージ
する工程である。かかる工程（２）の実施により有用成
分であるオレフィン系炭化水素類の回収純度が向上する
という利点が得られ、この工程は本発明におい”Ｃ必須
の工程である。製品ガスの導入の終点は例えば吸着塔出
口のガス分析を実施して有用成分濃度を検知して定める
ことができる。The step (2) is a step of introducing the product gas into the adsorption tower after the adsorption step and purging the difficult-to-adsorb components remaining in the voids in the tower. Implementation of this step (2) has the advantage of improving the recovery purity of olefinic hydrocarbons, which are useful components, and this step is an essential step in the present invention.The end point of introducing the product gas is For example, the concentration of useful components can be detected and determined by analyzing the gas at the outlet of the adsorption tower.
前記工程（３）はパージ工程が終った吸着塔を減圧又は
加熱することにより、吸着剤に吸着されているオレフィ
ン類を脱着させ、空隙に残留するパージガスと共に回収
する工程である。減圧によって脱着を行なう場合は、例
えば真空ポンプにより塔内を１００ｔｏｒｒ以下に減圧
して運転するのが好まし。The step (3) is a step in which the olefins adsorbed by the adsorbent are desorbed and recovered together with the purge gas remaining in the voids by reducing the pressure or heating the adsorption tower after the purge step. When desorption is carried out under reduced pressure, it is preferable to operate the column by reducing the pressure inside the column to 100 torr or less using, for example, a vacuum pump.
い。また加熱による場合は塔内湯度４０〜２５０℃好ま
しくは６０〜１８０℃に加熱して運転するのが好ましい
。stomach. In the case of heating, it is preferable to operate the column by heating it to a temperature of 40 to 250°C, preferably 60 to 180°C.
本発明で使用する銅化合物−活性炭吸着剤は銅（Ｉ）の
ハライド塩もしくは酸化銅（１）又は銅（ＩＩ）のハラ
イド塩、カルボン酸塩、硫酸塩、塩基性塩もしくはアン
ミン錯塩或いは酸化銅（ｎ）などの銅化合物を適当な溶
媒に溶解または′Ｑ濁し、これに活性炭を加えて十分に
攪拌した後、液相を減圧留去などの方法で除去すること
により得ることができる。The copper compound-activated carbon adsorbent used in the present invention is copper(I) halide salt or copper(1) oxide or copper(II) halide salt, carboxylate, sulfate, basic salt or ammine complex salt or copper oxide. It can be obtained by dissolving a copper compound such as (n) in an appropriate solvent or making it cloudy, adding activated carbon to the solution, stirring thoroughly, and removing the liquid phase by a method such as distillation under reduced pressure.
吸着剤に用いられる活性炭には特に限定はないが、形状
的には成形炭及び破砕炭からなる粒状炭及び粉末炭もし
くは繊維状のものが好ましい。かかる活性炭の原料とし
ては、木材、ヤシ殻、石炭石油系ピッチ及び合成繊維な
どが用いることができる。本発明に用いる吸着剤中の活
性炭と銅化合物との重量比（活性炭／銅化合物）は一般
には０．５〜６０．０、好ましくは２．０〜１０．０と
する。The activated carbon used in the adsorbent is not particularly limited, but in terms of shape, granular carbon, powdered carbon, or fibrous carbon consisting of compacted carbon and crushed carbon are preferable. As raw materials for such activated carbon, wood, coconut shell, coal and petroleum pitch, synthetic fibers, etc. can be used. The weight ratio of activated carbon to copper compound (activated carbon/copper compound) in the adsorbent used in the present invention is generally 0.5 to 60.0, preferably 2.0 to 10.0.
以下、本発明の具体的について図面を参照して説明する
。第１図は２塔の吸着塔からなり、減圧脱着によって原
料ガスからオレフィン類を吸着回収する装置図である。Hereinafter, specific details of the present invention will be explained with reference to the drawings. FIG. 1 is a diagram of an apparatus that consists of two adsorption towers and adsorbs and recovers olefins from a raw material gas by vacuum desorption.
吸着塔Ａ及びＢにはオレフィン類を選択的に吸着する銅
化合物−活性炭系吸着剤を充填する。Adsorption towers A and B are filled with a copper compound-activated carbon adsorbent that selectively adsorbs olefins.
かかる装置の運転について説明すると、先ずバルブ（１
）、（３）及び（５）を開き、吸着塔Ａ内に原料ガスを
流通させ、オレフィンガスを吸着剤に吸着させる。この
際バルブ（２）、（４）、（６）、（７）及び（８）は
閉じた状態である。吸着工程終了後パルプ（１）を閉じ
、吸着塔Ａ内の空隙に残留する難吸着性ガスをパージす
るため、バルブ（２）を開き製品ガスを吸着塔Ａ内に導
入し非吸着性成分をパージする。To explain the operation of such a device, first, the valve (1
), (3), and (5) are opened to allow the raw material gas to flow through the adsorption tower A, and the olefin gas is adsorbed by the adsorbent. At this time, valves (2), (4), (6), (7) and (8) are in a closed state. After the adsorption process is completed, the pulp (1) is closed, and in order to purge the poorly adsorbed gas remaining in the voids in the adsorption tower A, the valve (2) is opened to introduce the product gas into the adsorption tower A and remove non-adsorbable components. Purge.
パージ工程終了後はバルブ（２）、（３）及び（５）を
閉じ、バルブ（７）を開き、吸着されたオレフィンガス
及び空隙内に残留するパージガスを真空ポンプによって
吸引して回収する。After the purging process is completed, valves (2), (3), and (5) are closed, valve (7) is opened, and the adsorbed olefin gas and the purge gas remaining in the void are sucked and recovered by a vacuum pump.
吸着塔Ａでの回収工程の間に、吸着塔Ｂでは吸着工程及
びパージ工程を実施する。即ち吸着塔Ａ内のオレフィン
ガスを真空ポンプで吸引回収する間、バルブ（１１、（
４）及び（６）を開き、吸着塔Ｂ内に原料ガスを流通さ
せ、オレフィンガスを吸着させる。During the recovery process in adsorption tower A, adsorption tower B performs an adsorption process and a purge process. That is, while the olefin gas in the adsorption tower A is being sucked and recovered by the vacuum pump, the valves (11, (
4) and (6) are opened, the raw material gas is allowed to flow into the adsorption tower B, and the olefin gas is adsorbed.
ついでバルブ（１）を閉じ、バルブ（２）を開いて製品
′ガスを吸着塔Ｂ内に流通させ、塔内に残留する難吸着
性ガスをパージする。パージ工程終了後はバルブ（２）
、（４）及び（６）を閉じ、同時にバルブ（８）を開き
吸着塔Ｂ内のオレフィンガスを吸引回収する。吸着塔Ｂ
の回収工程が開始すると同時に、回収工程を終えた吸着
塔Ａは吸着工程へと移行する。以上のように吸着塔Ａ及
びＢを交互に吸着−パージ−回収の工程順で運転するこ
とによりオレフィンガスの吸脱着を連続的に行ない、オ
レフィン系炭化水素類を高純度でしかも効率的に精製分
離することができる。なお、上記説明は吸着塔工程の場
合について説明したが、これを３塔以上設けて実施する
こともできることはいうまでもない。 。Then, the valve (1) is closed and the valve (2) is opened to allow the product' gas to flow into the adsorption tower B, thereby purging the poorly adsorbable gas remaining in the tower. After the purge process is completed, press the valve (2)
, (4) and (6) are closed, and at the same time, the valve (8) is opened to suck and recover the olefin gas in the adsorption tower B. Adsorption tower B
At the same time as the recovery process starts, the adsorption tower A that has completed the recovery process shifts to the adsorption process. As described above, by operating adsorption towers A and B alternately in the process order of adsorption, purge, and recovery, olefin gas is adsorbed and desorbed continuously, and olefinic hydrocarbons are efficiently purified with high purity. Can be separated. In addition, although the above description has been made regarding the case of an adsorption tower step, it goes without saying that this can be carried out by providing three or more towers. .
更に、本発明に従えば、前記方法によって回収したオレ
フィンガスを同様の吸着システムに少なくとも一回以上
流通させることにより製品ガス中のオレフィン純度を更
に一層向上させることができるが、かかる態様も本発明
の技術的範囲に属するものである。Further, according to the present invention, the olefin purity in the product gas can be further improved by passing the olefin gas recovered by the above method through a similar adsorption system at least once, but such an embodiment is also included in the present invention. It belongs to the technical scope of
去狙勇
以下に本発明の詳細な説明するが、本発明の範囲をこれ
らの実施例に限定するものでないことはいうまでもない
。Although the present invention will be described in detail below, it goes without saying that the scope of the present invention is not limited to these Examples.
スｌ■江Ｌ
５１容量の加熱減圧蒸留装置の反応釜に賦活処理を施し
たヤシ殻を原料とした活性炭（４〜１０メソシュ破砕品
）２ｋｇを装填し、真空ポンプを用いて減圧（３ｔｏｒ
ｒ）脱気を行なった。一方、同時に付帯溶解層を用いて
６ＮＨＣＩ ３Ｉｌに塩化銅（Ｉ）０、３ ｋｇを窒素
ガス雰囲気下で攪拌溶解して塩化銅塩酸溶液を調製した
。次に調製した塩化銅溶液を脱気した反応釜に注入し、
更に３時間反応釜内を減圧下（５ｔｏｒｒ）に保った後
、温度１６０℃に加熱して水及び塩化水素を除去して黒
色粒状の活性炭。2 kg of activated carbon made from activated coconut shells (crushed product of 4 to 10 mesh) was loaded into the reaction pot of a 51-capacity heating and vacuum distillation device, and the pressure was reduced (3 torr) using a vacuum pump.
r) Deaeration was performed. On the other hand, at the same time, 0.3 kg of copper chloride (I) was dissolved in 3Il of 6NHCl with stirring under a nitrogen gas atmosphere to prepare a copper chloride hydrochloric acid solution. Next, pour the prepared copper chloride solution into the degassed reaction vessel,
After keeping the inside of the reaction vessel under reduced pressure (5 torr) for an additional 3 hours, it was heated to a temperature of 160°C to remove water and hydrogen chloride to form black granular activated carbon.
−塩化銅吸着剤を得た。- A copper chloride adsorbent was obtained.
次にこの吸着剤を用いてオレフィン系炭化水素類を含む
混合ガス（Ｃ２Ｈ４，＝ ３３．５％、ＣｚＨ６＝３３
．２％、Ｃ１，、＝３３．３％）の精製を試みた。Next, using this adsorbent, a mixed gas containing olefinic hydrocarbons (C2H4, = 33.5%, CzH6 = 33
．． 2%, C1,, = 33.3%).
精製は前記した第１図に示した２塔式吸脱着装置を用い
、表−１に記載した吸着−バージー血着のサイクルに基
づいて実施した。Purification was carried out using the two-column adsorption/desorption apparatus shown in FIG. 1 described above, based on the adsorption-vergie blood adsorption cycle shown in Table 1.
表−１
吸着塔Ａ 吸着塔Ｂ
１ 吸着工程 脱着工程
２ パージ工程 〃
３ 脱着工程 吸着工程
４ 〃 パージ工程
第１図に示す吸着塔Ａ及びＢに、それぞれ、前記吸着剤
０．５ ｋｇを充填し、バルブ（７）及び（８）を開と
し、真空ポンプを用いて両塔を１０ ｔｏｒｒに真空排
気した後、バルブ（７）及び（８）を閉とした。Table-1 Adsorption tower A Adsorption tower B 1 Adsorption process Desorption process 2 Purge process 〃 3 Desorption process Adsorption process 4 〃 Purge process Adsorption towers A and B shown in Figure 1 were each filled with 0.5 kg of the above adsorbent. Then, valves (7) and (8) were opened, and both columns were evacuated to 10 torr using a vacuum pump, and then valves (7) and (8) were closed.
（ｉ） 体Ａ＝ロ 、パージ、ＩＩ −塔Ｂ−次に
バルブ＋１）及び（３）を開として前記原料ガス（Ｃｚ
Ｈｎ ＝３３．５％、ＣＪ＆＝３３．２％、ｃｏ、＝３
３．３％）を吸着塔Ａにガス流速３．６１／ｍｉｎ、で
導入塔内が大気圧まで昇圧した後、更にバルブ（５）を
開として引き続き原料ガスを吸着塔Ａに流通させ、浴出
口においてガス中のエチレンガス濃度を測定し、出ロガ
スＣＪａ１１１度が原料ガスＣｚｌ１４？ｉ度の１５％
になった時点でバルブ（１１を閉じた（吸着工程終了）
。(i) Body A = B, purge, II - Column B - Then valves +1) and (3) are opened and the raw material gas (Cz
Hn = 33.5%, CJ & = 33.2%, co, = 3
3.3%) was introduced into the adsorption tower A at a gas flow rate of 3.61/min. After the pressure inside the tower was raised to atmospheric pressure, the valve (5) was further opened to allow the raw material gas to continue to flow through the adsorption tower A. The ethylene gas concentration in the gas was measured at the outlet, and the output log gas CJa111 degrees was found to be the source gas Czl14? 15% of i degree
Valve (11) was closed when the temperature reached (adsorption process completed).
.
次にバルブ（２）を開き製品ガスを流速１．５１／ｍｉ
ｎ。Next, open the valve (2) and let the product gas flow at a flow rate of 1.51/mi.
n.
で吸着塔Ａに導入し、空隙内に残留する難吸着性ガスを
パージした。この製品ガスパージは浴出口におけるガス
中のエチレン濃度が約３５％に到達した時点で停止した
。The gas was introduced into the adsorption tower A, and the hardly adsorbable gas remaining in the voids was purged. This product gas purge was stopped when the ethylene concentration in the gas at the bath outlet reached approximately 35%.
以上の吸着塔Ａによる吸着−パージ工程の間にバルブ（
８）を開として前工程で吸着塔Ｂに吸着されたガスを真
空ポンプによって大気圧から１０ ｔｏｒｒまで減圧脱
着させ製品ガスタンクに回収した。During the adsorption-purge process using adsorption tower A, the valve (
8) was opened, and the gas adsorbed in the adsorption tower B in the previous step was desorbed under reduced pressure from atmospheric pressure to 10 torr using a vacuum pump and collected into the product gas tank.
（ｉｉ） ｐ：Ａ＝ 、ロ 塔ＬＪ 、パー
ジ次にバルブ（３）、（５）及び（２）を閉とすると共
にバルブ（１）及び（４）を開として吸着塔Ａでの脱着
工程並びに吸着塔Ｂでの吸着工程へと移行した。(ii) p:A= , b Column LJ, purge, then close valves (3), (5), and (2), and open valves (1) and (4) to perform desorption step in adsorption column A. Then, the adsorption step in adsorption tower B was started.
吸着塔Ｂの塔内が原料ガスにより１０ ｔｏｒｒから大
気圧まで昇圧するとバルブ（６）を開として塔内を大気
圧に保ちつつ原料ガスを流通させた。吸着工 ′
程は浴出口におけるガス中のＣ，Ｈ，濃度が原料ガス中
のＣｔＨａ濃度の１５％になった時点でバルブ１１）を
閉じて終了させた。次にバルブ（２）を開き製品ガスに
より塔内をパージした。この製品ガスパージは浴出口に
おけるガス中のエチレン濃度が約３５％に到達した時点
で停止した。When the pressure inside the adsorption tower B was increased from 10 torr to atmospheric pressure by the raw material gas, the valve (6) was opened to allow the raw material gas to flow while maintaining the inside of the tower at atmospheric pressure. Suction work ′
The process was terminated by closing the valve 11) when the concentration of C, H, and gas in the gas at the bath outlet reached 15% of the CtHa concentration in the source gas. Next, the valve (2) was opened to purge the inside of the column with the product gas. This product gas purge was stopped when the ethylene concentration in the gas at the bath outlet reached approximately 35%.
以上の様に吸着塔Ａ及びＢを交互に吸着−パージ−脱着
工程を繰り返して原料ガスのエチレン精製を行なった。As described above, the adsorption-purge-desorption process was repeated alternately in the adsorption towers A and B to purify the raw material gas with ethylene.
この時の回収製品ガス中のエチレン濃度は８７．２％で
回収率は６２．４％であった。At this time, the ethylene concentration in the recovered product gas was 87.2%, and the recovery rate was 62.4%.
且較五上
実施例１において製品ガスパージ工程を省略した以外は
同様に操作したところ、回収製品ガス中のエチレン濃度
は５４．２％で回収率は９１．０％であった。即ち、本
発明においてパージ工程は回収製品ガス純度を向上させ
るために不可欠な工程であることがこの結果から明らか
であろう。For comparison, the same procedure as in Example 1 was performed except that the product gas purge step was omitted, and the ethylene concentration in the recovered product gas was 54.2%, and the recovery rate was 91.0%. That is, it is clear from these results that the purge step is an essential step for improving the purity of the recovered product gas in the present invention.
皇血斑主
実施例１に記載した同一手法、原料を用いて活性炭に対
する塩化銅（１）の重量比を０．３ （ｗｔ／ｗｔ）と
して吸着剤を調製した。An adsorbent was prepared using the same method and raw materials as described in Example 1, with a weight ratio of copper (1) chloride to activated carbon of 0.3 (wt/wt).
賦活処理を施した活性炭（４〜１０メツシユ）２ｋｇを
反応釜に充填し、真空ポンプを用いて減圧、脱気を行な
い、一方、溶解槽を用いて６ ＮＨＣｌ ３ ／に塩化
銅（［）０．６ｋｇを窒素ガス雰囲気下で攪拌、溶解し
て塩化銅塩酸溶液を調製した後、前記活性炭に含浸、溶
媒を除去して固体吸着剤を得た。2 kg of activated carbon (4 to 10 meshes) subjected to activation treatment was charged into a reaction vessel, and the pressure was reduced and degassed using a vacuum pump.Meanwhile, copper chloride ([)0 After stirring and dissolving .6 kg in a nitrogen gas atmosphere to prepare a copper chloride hydrochloric acid solution, the activated carbon was impregnated and the solvent was removed to obtain a solid adsorbent.
このようにして得られた吸着剤０．５ ｋｇを実施例１
に記載した２塔式吸脱着精製装置を用いてエチレン含有
原料ガス（ｃ！ｌｌａ ＝３３．５％、Ｃ２Ｈｈ−３３
，２％、ＣＨ４，−３３，３％）からエチレンの精製分
離を行なった。0.5 kg of the adsorbent thus obtained was used in Example 1.
Ethylene-containing raw material gas (c!lla = 33.5%, C2Hh-33
, 2%, CH4, -33, 3%).
この時の回収ガスのエチレン濃度は９１．３％で回収率
は７６．４％であった。The ethylene concentration of the recovered gas at this time was 91.3%, and the recovery rate was 76.4%.
叉止五ユ
実施例１に記載した同一手法、原料を用いて活性炭に対
する塩化銅（１）の重量比を０．６ （ｗｔ／ｗｔ）と
して、又塩化銅（１）溶媒である塩酸濃度を１２Ｎとし
て吸着剤を調製した。Using the same method and raw materials as described in Example 1, the weight ratio of copper chloride (1) to activated carbon was set to 0.6 (wt/wt), and the concentration of hydrochloric acid, which is the copper chloride (1) solvent, was The adsorbent was prepared as 12N.
賦活処理を施した活性炭（４〜１０メソシユ）２ｋｇを
反応釜に装填し、真空ポンプを用いて減圧脱気を行ない
、一方溶解槽を用いて１２ＮＦＩＣＩ ３ｊ！に塩化銅
（ｒ）１．２ｋｇを窒素ガス雰囲気下で攪拌溶解して塩
化銅塩酸溶液を調製した後、前記活性炭に含浸、減圧、
加熱により溶媒を除去して固体吸着剤を得た。2 kg of activated carbon (4 to 10 mSO) subjected to activation treatment was loaded into a reaction vessel, degassed under reduced pressure using a vacuum pump, and 12 NFICI 3j! After stirring and dissolving 1.2 kg of copper chloride (r) in a nitrogen gas atmosphere to prepare a copper chloride hydrochloric acid solution, it was impregnated with the activated carbon, reduced pressure,
The solvent was removed by heating to obtain a solid adsorbent.
得られた吸着剤０．５ ｋｇを実施例１及び２に記載し
た２塔式吸脱着装置を用いてエチレン含有原料ガス（Ｃ
ｚＨ＊＝３３．５％、ＣＪｉ＝３３．２％、ＣＨ４，＝
３３．３％）からエチレンの精製分離を行なった。0.5 kg of the obtained adsorbent was added to an ethylene-containing raw material gas (C
zH*=33.5%, CJi=33.2%, CH4,=
33.3%) was purified and separated from ethylene.
この時の回収ガスのエチレン濃度は９３．３％でエチレ
ン回収率は８６．２％であった。The ethylene concentration of the recovered gas at this time was 93.3%, and the ethylene recovery rate was 86.2%.
大嵐■土
実施例３で得られた回収ガスを実施例３に記載した同一
吸着剤、装置にリサイクルして高純度エチレンの分離回
収を試みた。なお、この時の製品ガスパージは塔出口に
おけるガス中のエチレン濃度が９５％で停止した。この
時の回収ガスエチレン濃度は９９．５％であり、回収率
は８４．１％であった。The recovered gas obtained in Example 3 was recycled using the same adsorbent and equipment described in Example 3 to attempt to separate and recover high-purity ethylene. Note that the product gas purge at this time stopped when the ethylene concentration in the gas at the tower outlet was 95%. At this time, the concentration of recovered gas ethylene was 99.5%, and the recovery rate was 84.1%.
即ち、本発明では多段分離回収することにより容易に回
収ガス純度の向上が図れることが判明した。That is, it has been found that in the present invention, the purity of the recovered gas can be easily improved by performing multi-stage separation and recovery.
スｍ
実施例１に記載した塩化銅（Ｉ）の代りに塩化銅（■）
２水和物を用い、又６ ＮＨＣｌの代りに純水を用いた
以外は同−原料及び装置により吸着剤をＩＨｌ製した。Copper chloride (■) instead of copper chloride (I) described in Example 1
An adsorbent was prepared using the same raw materials and equipment except that dihydrate was used and pure water was used instead of 6 NHCl.
５１反応釜に賦活処理を施した活性炭２ ｋｇを装填し
真空ポンプを用いて真空脱気（３ｔｏｒｒ） した。2 kg of activated carbon subjected to activation treatment was loaded into a reaction vessel No. 51, and vacuum degassed (3 torr) using a vacuum pump.
又、溶解槽に塩化銅（■）２水和物２ ｋｓｒを純水３
１に溶解し、塩化第２銅水溶液を調製した後、前記減圧
下に保持した反応釜に溶液を注入して含浸し、更に、１
６０℃加熱、減圧（５ｔｏｒｒ）条件下で溶媒を充分除
去して吸着剤を得た。Also, add 2 ksr of copper chloride (■) dihydrate to the dissolution tank and 3 ksr of pure water.
1 to prepare a cupric chloride aqueous solution, the solution was poured into the reaction vessel kept under reduced pressure to impregnate it, and further, 1
The solvent was sufficiently removed under conditions of heating at 60° C. and reduced pressure (5 torr) to obtain an adsorbent.
得られた吸着剤を吸着塔Ａ及びＢにそれぞれ０、５ ｋ
ｇづつ充填し、実施例１に記載した手順によリエチレン
含有原料ガス（ＣＪＩ４＝３３．５％、ＣｔＨｈ ＝３
３．２％、ＣＨ４＝３３．３％）のエチレンの精製分離
を行なった。The obtained adsorbent was placed in adsorption towers A and B at 0 and 5 k, respectively.
g at a time, and added lyethylene-containing raw material gas (CJI4 = 33.5%, CtHh = 3) according to the procedure described in Example 1.
3.2%, CH4=33.3%) was purified and separated.
この時のエチレン純度は９２．５％で、回収率は８１．
３％であった。The ethylene purity at this time was 92.5%, and the recovery rate was 81.
It was 3%.
去Ｊ１九１
実施例３に記載した同一吸着剤、装置を用いて下記原料
ガス条件でプロピレンの精製を行なった。Propylene was purified using the same adsorbent and equipment described in Example 3 under the following raw gas conditions.
ガス組成 Ｃ：ＩＨｌ、 ３４．ＯＶｏ１％
ＣＪｚ ３４．４ Ｖｏ１％
ＣＨ＊ ３１．６ Ｖｏ１％
吸着剤 ０．５ ｋｇ Ｘ ２運転温度
３０℃
吸着圧力 １．０ｋｇ／ｃｎｌＧ原料供給量
１４．４１／ｃｙｃｌｅパージガスｌｔ３．０７！／
ｃｙｃｌｅ （ＣｓＨａ）この時のプロピレンの回収
純度は９２．７％であり、回収率は８６．４％であった
。Gas composition C: IHL, 34. OVo1%
CJz 34.4 Vo1% CH* 31.6 Vo1% Adsorbent 0.5 kg X 2 Operating temperature
30℃ Adsorption pressure 1.0kg/cnlG raw material supply amount
14.41/cycle purge gas lt3.07! /
cycle (CsHa) The recovery purity of propylene at this time was 92.7%, and the recovery rate was 86.4%.
１釦［
実施例３に記載した同一吸着材、装置を用いて下記原料
ガス条件でブテン−１（ＣＨユＣＨｚＣＨ＝ Ｃ１ｈ）
の精製を行なった。1 button [Butene-1 (CHyuCHzCH=C1h) using the same adsorbent and equipment described in Example 3 under the following raw material gas conditions
was purified.
ガス組成 １−ＣａｌＩｓ ３５．２ Ｖ
ｏ１％ｎ−ＣＪｔｏ ３４．７ Ｖｏ１％Ｃｌ
１ａ ３０．１ Ｖｏ１％吸着剤
０．５ ｋｇ
運転温度 ３０℃
吸着圧力 １．Ｏｋｇ／ｃｄＧ
原料供給量 １２．６Ｊ ／ｃｙｃｌｅパージガス
５１ ３．０１ ／ｃｙｃｌｅ （１−ＣａＨａ）こ
の時のブテン−１の回収純度は９１．２％であり、回収
率は８２．５％であった。Gas composition 1-CalIs 35.2 V
o1%n-CJto 34.7 Vo1%Cl
1a 30.1 Vo1% adsorbent
0.5 kg Operating temperature 30℃ Adsorption pressure 1. Okg/cdG Raw material supply amount 12.6 J/cycle Purge gas 51 3.01/cycle (1-CaHa) The recovery purity of butene-1 at this time was 91.2%, and the recovery rate was 82.5%. .
ル較医又
実施例で用いたヤシ殻を原料として活性Ｒ（４〜１０メ
ツシュ破砕品）を前記吸着塔Ａ及びＢにそれぞれ０．５
ｋｇづつ充填し、実施例１に記載した手順によりエチ
レン含有原料ガス（ＣＺＨ，＝３３．５％、ｃｚｎａ＝
３３．２％、Ｃ１，＝３３．３％）のエチレン精製を行
なった。この時の回収ガスの純度はｃｚＨａ＝６７゜５
％、ＣｚＨｈ＝ ３２．１％、Ｃ１ｌ ４＝０．４％で
、エチレン回収率は６８．２％であった。In addition, using the coconut shells used in the examples as a raw material, 0.5% of the active R (4 to 10 mesh crushed product) was added to the adsorption towers A and B, respectively.
kg each, and by the procedure described in Example 1, ethylene-containing raw material gas (CZH, = 33.5%, czna =
33.2%, C1, = 33.3%). The purity of the recovered gas at this time is czHa=67°5
%, CzHh=32.1%, C1l4=0.4%, and the ethylene recovery rate was 68.2%.
即ち、この例から塩化銅を含まない活性炭では本発明の
吸着剤に比べ吸着選択性が著しく劣ることが明らかであ
る。That is, it is clear from this example that activated carbon containing no copper chloride has significantly inferior adsorption selectivity compared to the adsorbent of the present invention.
得られた結果を第２表に示す。The results obtained are shown in Table 2.
（以下余白）(Margin below)
第１図は本発明方法を実施するための吸着装置の一例を
示す図面である。
Ａ、Ｂ・・・吸着塔、 １〜８・・・バルブ。FIG. 1 is a drawing showing an example of an adsorption apparatus for carrying out the method of the present invention. A, B...Adsorption tower, 1-8...Valve.
Claims (1)
系炭化水素を吸着分離方法によって回収する方法におい
て、 銅化合物−活性炭系からなる吸着剤を充填させた２つ以
上の吸着塔を用い、 （１）原料ガスを吸着塔に流通させてオレフィン系炭化
水素類を吸着剤に吸着させる吸着行程、（２）吸着工程
を終了した吸着塔へ製品ガスを導入して、難吸着性成分
をパージするパージ工程及び （３）吸着塔内を加熱又は減圧することにより、吸着剤
に吸着されているオレフィン系炭化水素類を回収する回
収行程を２つ以上の吸着塔において繰り返し実施するこ
とを特徴とする方法。[Claims] 1. A method for recovering olefinic hydrocarbons from a raw material gas containing multi-component hydrocarbons by an adsorption separation method, comprising two or more adsorbents filled with a copper compound-activated carbon adsorbent. Using an adsorption tower, (1) an adsorption process in which the raw material gas is passed through the adsorption tower and olefinic hydrocarbons are adsorbed on the adsorbent; (2) the product gas is introduced into the adsorption tower after the adsorption process, and the A purge step for purging adsorbent components and (3) a recovery step for recovering olefinic hydrocarbons adsorbed by the adsorbent by heating or reducing the pressure inside the adsorption tower are repeated in two or more adsorption towers. A method characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59247935A JPS61126036A (en) | 1984-11-26 | 1984-11-26 | Purification and separation of olefinic hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59247935A JPS61126036A (en) | 1984-11-26 | 1984-11-26 | Purification and separation of olefinic hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61126036A true JPS61126036A (en) | 1986-06-13 |
| JPH0259808B2 JPH0259808B2 (en) | 1990-12-13 |
Family
ID=17170741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59247935A Granted JPS61126036A (en) | 1984-11-26 | 1984-11-26 | Purification and separation of olefinic hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61126036A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01167371U (en) * | 1988-05-11 | 1989-11-24 | ||
| JP2010163388A (en) * | 2009-01-15 | 2010-07-29 | Kobe Steel Ltd | Separation purification method of hydrocarbon |
| JP2010532317A (en) * | 2007-04-25 | 2010-10-07 | コリア インスティチュート オブ エナジー リサーチ | Method for producing high purity butene-1 from C4 olefin / paraffin mixed gas |
| JP2010532316A (en) * | 2007-03-29 | 2010-10-07 | コリア インスティチュート オブ エナジー リサーチ | Technology to separate olefin from olefin / paraffin mixed gas |
| JP2013536223A (en) * | 2010-08-26 | 2013-09-19 | コリア インスティチュート オブ エナジー リサーチ | Substitution desorption process for separation of hard olefins |
| JP2013540707A (en) * | 2010-08-26 | 2013-11-07 | コリア インスティチュート オブ エナジー リサーチ | Method and apparatus for recovering ethylene from fluid catalytic cracking exhaust gas |
| US9034185B2 (en) | 2007-03-29 | 2015-05-19 | Korea Institute Of Energy Research | Separation of olefins from olefins/paraffins mixed gas |
| CN106268645A (en) * | 2016-09-27 | 2017-01-04 | 华南理工大学 | A kind of preparation method of the Fluorin doped carbon back adsorbing material of Preferential adsorption ethane |
| CN109012576A (en) * | 2018-07-02 | 2018-12-18 | 昆明理工大学 | A kind of preparation method and application loading cuprous oxide particle active carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06320214A (en) * | 1993-05-11 | 1994-11-22 | Saikawa:Kk | Continuous wire drawing/rolling method and device therefor |
-
1984
- 1984-11-26 JP JP59247935A patent/JPS61126036A/en active Granted
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH053253Y2 (en) * | 1988-05-11 | 1993-01-26 | ||
| JPH01167371U (en) * | 1988-05-11 | 1989-11-24 | ||
| JP2010532316A (en) * | 2007-03-29 | 2010-10-07 | コリア インスティチュート オブ エナジー リサーチ | Technology to separate olefin from olefin / paraffin mixed gas |
| US8436223B2 (en) | 2007-03-29 | 2013-05-07 | Korea Institute Of Energy Research | Separation of olefins from olefins/paraffins mixed gas |
| US9034185B2 (en) | 2007-03-29 | 2015-05-19 | Korea Institute Of Energy Research | Separation of olefins from olefins/paraffins mixed gas |
| JP2014051496A (en) * | 2007-03-29 | 2014-03-20 | Korea Institute Of Energ Reserch | Technology for separating olefin from olefin/paraffin gas mixture |
| JP2014088366A (en) * | 2007-04-25 | 2014-05-15 | Korea Institute Of Energ Reserch | Method for producing high-purity butene-1 from c4 olefin/paraffin mixed gas |
| JP2010532317A (en) * | 2007-04-25 | 2010-10-07 | コリア インスティチュート オブ エナジー リサーチ | Method for producing high purity butene-1 from C4 olefin / paraffin mixed gas |
| US8431762B2 (en) | 2007-04-25 | 2013-04-30 | Korea Institute Of Energy Research | Production of high purity butene-1 from C4 olefins/paraffins mixed gas |
| JP2010163388A (en) * | 2009-01-15 | 2010-07-29 | Kobe Steel Ltd | Separation purification method of hydrocarbon |
| JP2013540707A (en) * | 2010-08-26 | 2013-11-07 | コリア インスティチュート オブ エナジー リサーチ | Method and apparatus for recovering ethylene from fluid catalytic cracking exhaust gas |
| JP2013536223A (en) * | 2010-08-26 | 2013-09-19 | コリア インスティチュート オブ エナジー リサーチ | Substitution desorption process for separation of hard olefins |
| US9090522B2 (en) | 2010-08-26 | 2015-07-28 | Korea Institute Of Energy Research | Method and apparatus for recovering ethylene from fluidized catalytic cracking (FCC) off-gas |
| US9376354B2 (en) | 2010-08-26 | 2016-06-28 | Korea Institute Of Energy Research | Displacement desorption process for light olefin separation |
| CN106268645A (en) * | 2016-09-27 | 2017-01-04 | 华南理工大学 | A kind of preparation method of the Fluorin doped carbon back adsorbing material of Preferential adsorption ethane |
| CN106268645B (en) * | 2016-09-27 | 2019-04-09 | 华南理工大学 | A kind of preparation method of the carbon-based adsorbent material of Fluorin doped of Preferential adsorption ethane |
| CN109012576A (en) * | 2018-07-02 | 2018-12-18 | 昆明理工大学 | A kind of preparation method and application loading cuprous oxide particle active carbon |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0259808B2 (en) | 1990-12-13 |
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