JPH111454A - Method for producing diacetoxybutene - Google Patents
Method for producing diacetoxybuteneInfo
- Publication number
- JPH111454A JPH111454A JP10057892A JP5789298A JPH111454A JP H111454 A JPH111454 A JP H111454A JP 10057892 A JP10057892 A JP 10057892A JP 5789298 A JP5789298 A JP 5789298A JP H111454 A JPH111454 A JP H111454A
- Authority
- JP
- Japan
- Prior art keywords
- acetic acid
- diacetoxybutene
- distillation column
- heat exchanger
- tube
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(57)【要約】
【課題】 貴金属触媒の存在下に、ブタジエン、酢酸及
び酸素を反応させて得たジアセトキシブテンを含む反応
生成液から、蒸留により酢酸を回収するに際し、蒸留塔
のリボイラーが重合物により閉塞するのを防止する。
【解決手段】 リボイラーチューブ入口における流速が
０．７ｍ／秒以上となる流速でリボイラーに塔底液を供
給する。PROBLEM TO BE SOLVED: To recover acetic acid by distillation from a reaction product solution containing diacetoxybutene obtained by reacting butadiene, acetic acid and oxygen in the presence of a noble metal catalyst, a reboiler of a distillation column is used. Prevents clogging by polymer. SOLUTION: The bottom liquid is supplied to the reboiler at a flow rate at which the flow rate at the inlet of the reboiler tube is 0.7 m / sec or more.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ジアセトキシブテ
ンの製造方法に関する。詳しくは、ブタジエンをアセト
キシ化してジアセトキシブテンを製造する方法の改良に
関する。ジアセトキシブテンは、ポリウレタン等の原料
である１，４−ブタンジオール及び高性能溶剤であるテ
トラヒドロフランの重要な中間体である。The present invention relates to a method for producing diacetoxybutene. More specifically, the present invention relates to an improvement in a method for producing diacetoxybutene by acetoxylation of butadiene. Diacetoxybutene is an important intermediate between 1,4-butanediol, a raw material for polyurethane and the like, and tetrahydrofuran, a high-performance solvent.
【０００２】[0002]
【従来の技術】１，４−ブタンジオールの中間体である
ジアセトキシブテンは、貴金属触媒の存在下、ブタジエ
ン、酢酸及び酸素を反応させて製造される（特開昭５２
−７９０７号公報等）。得られたジアセトキシブテン
は、次いでパラジウム触媒又はニッケル触媒等を用いて
水添されてジアセトキシブタンとなり、更に加水分解さ
れて１，４−ブタンジオールとなる（特開昭５２−１３
３９１２号公報等）。2. Description of the Related Art Diacetoxybutene, which is an intermediate of 1,4-butanediol, is produced by reacting butadiene, acetic acid and oxygen in the presence of a noble metal catalyst (Japanese Patent Application Laid-Open (JP-A) 52).
-7907). The obtained diacetoxybutene is then hydrogenated using a palladium catalyst or a nickel catalyst to form diacetoxybutane, and further hydrolyzed to 1,4-butanediol (JP-A-52-13).
No. 3912).
【０００３】このブタジエンを原料とする１，４−ブタ
ンジオールの製造方法では、工程中で多量の酢酸及び水
が使用され、且つ反応により酢酸及び水が副生する。従
って、製品純度を高く保持しながら、これらを回収して
再使用する各種の提案がなされている（上記各公報参
照）。これらの方法では、通常、目的物と酢酸との分離
は蒸留によりなされている。即ち、ブタジエン、酢酸及
び酸素を反応させてジアセトキシブテンを生成させる反
応で得られるアセトキシ化反応の生成液は、脱ガス処理
して未反応ブタジエン等を除去した後、蒸留塔で蒸留し
て、水、酢酸を塔頂から留去し、塔底からジアセトキシ
ブテンを含む成分を抜出している。またジアセトキシブ
タンを加水分解して得られる反応生成物は、蒸留塔で蒸
留して水と酢酸及び他の軽沸物を塔頂から留去し、塔底
から１，４−ブタンジオールを含む成分を抜出してい
る。In this method for producing 1,4-butanediol using butadiene as a raw material, a large amount of acetic acid and water are used in the process, and acetic acid and water are by-produced by the reaction. Therefore, various proposals have been made for recovering and reusing these while maintaining high product purity (see the above publications). In these methods, separation of the target substance and acetic acid is usually performed by distillation. That is, the product liquid of the acetoxylation reaction obtained by reacting butadiene, acetic acid and oxygen to produce diacetoxybutene is subjected to degassing treatment to remove unreacted butadiene and the like, and then distilled in a distillation column. Water and acetic acid are distilled off from the top of the column, and components containing diacetoxybutene are extracted from the bottom of the column. The reaction product obtained by hydrolyzing diacetoxybutane is distilled in a distillation column to distill water, acetic acid and other light-boiling substances from the top, and contains 1,4-butanediol from the bottom. The ingredients have been extracted.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、アセト
キシ化反応生成液から酢酸を回収する蒸留を、リボイラ
ーとして常用のシェル−チューブ型の多管式熱交換器を
備えた蒸留塔で行うと、比較的短期間の運転によりリボ
イラーチューブ内に重合物の付着がおこり、運転を中断
しなければならないことがしばしば起こった。本発明の
課題は、アセトキシ化反応生成液からの酢酸の蒸留分離
において、長期間の運転をしてもリボイラーチューブ内
の重合物の付着を抑制することができる、改良されたア
セトキシ化反応生成液の蒸留方法を提供することにあ
る。However, when the distillation for recovering acetic acid from the acetoxylation reaction product is performed in a distillation column equipped with a conventional shell-tube type multi-tube heat exchanger as a reboiler, the distillation is relatively difficult. Short-term operation often resulted in polymer deposition in the reboiler tube, and the operation often had to be interrupted. It is an object of the present invention to provide an improved acetoxylation reaction product which can suppress the adhesion of a polymer in a reboiler tube even after a long-term operation in the separation of acetic acid from an acetoxylation reaction product by distillation. To provide a distillation method.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記課題
を解決するために鋭意検討した結果、アセトキシ化反応
で得られる反応生成液から、酢酸等を蒸留分離する蒸留
塔のリボイラーチューブ内の液流速を一定の値以上にす
ることにより、長期間の運転においてもリボイラーチュ
ーブの重合物付着による閉塞を防止できることを見出
し、本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the inside of a reboiler tube of a distillation column for distilling and separating acetic acid and the like from a reaction product liquid obtained by an acetoxylation reaction. It has been found that by setting the liquid flow rate to a certain value or more, it is possible to prevent clogging of the reboiler tube due to adhesion of a polymer even in long-term operation, and completed the present invention.
【０００６】本発明によれば、貴金属触媒の存在下に、
ブタジエン、酢酸及び酸素を反応させてジアセトキシブ
テンを生成させ、生成したジアセトキシブテンを含む反
応生成液を蒸留塔で蒸留して、酢酸を含む軽沸成分を塔
頂から留出させ、塔底からジアセトキシブテンを含む成
分を抜出すに際し、蒸留塔として塔底液を加熱するため
のシェル−チューブ式の多管式熱交換器を有するものを
用い、且つ塔底液を熱交換器のチューブ入口において
０．７ｍ／秒以上の流速で熱交換器を通過させることに
より、熱交換器の重合物付着による閉塞を回避して長時
間に亘り蒸留を行うことができる。以下、本発明につい
て詳細に説明する。According to the present invention, in the presence of a noble metal catalyst,
Butadiene, acetic acid and oxygen are reacted to form diacetoxybutene, and the reaction product solution containing diacetoxybutene is distilled in a distillation column to distill light boiling components containing acetic acid from the top of the column. In extracting a component containing diacetoxybutene from the above, using a distillation column having a shell-and-tube type multi-tube heat exchanger for heating the bottom liquid, and using the bottom liquid as a tube of a heat exchanger By allowing the heat exchanger to pass through the heat exchanger at a flow rate of 0.7 m / sec or more, it is possible to perform distillation for a long time while avoiding clogging of the heat exchanger due to adhesion of the polymer. Hereinafter, the present invention will be described in detail.
【０００７】[0007]
【発明の実施の形態】本発明の方法においては、アセト
キシ化反応生成液より酢酸を分離する蒸留塔において、
塔底液のリボイラーチューブ入口における流速を０．７
ｍ／秒以上とすることの他は、従来公知の、ブタジエ
ン、酢酸及び酸素を反応させてジアセトキシブテンを得
る方法が適宜採用される。DETAILED DESCRIPTION OF THE INVENTION In the method of the present invention, a distillation column for separating acetic acid from an acetoxylation reaction product is provided.
The flow rate of the bottom liquid at the inlet of the reboiler tube is 0.7
In addition to the m / sec or higher, a conventionally known method of reacting butadiene, acetic acid and oxygen to obtain diacetoxybutene is appropriately employed.
【０００８】アセトキシ化反応は、ブタジエン、酢酸、
及び分子状酸素を、貴金属触媒、特にパラジウム系触媒
の存在下、反応させる公知の方法により行われる。パラ
ジウム触媒としては、パラジウム金属又はその塩（例え
ば、塩化パラジウム、硝酸パラジウム、酢酸パラジウム
等の無機又は有機酸塩）を単独で用いることができる。
またパラジウム金属又はその塩を助触媒としてのビスマ
ス、セレン、アンチモン、テルル、銅等の金属又はその
塩（例えば、酸化ビスマス、セレン酸、酸化テルル、塩
化アンチモン、塩化銅等）とを組み合わせて用いること
もできる。これらの触媒成分は、シリカ、アルミナ、活
性炭等の担体に担持させて用いることが好ましい。通常
はパラジウム化合物及び助触媒成分の化合物を溶解した
溶液を担体に含浸させることにより触媒成分を担体に担
持させ、次いでこの担体上の触媒成分を水素やメタノー
ル等で還元することにより調製した触媒を用いる。担持
触媒中の触媒成分の量は、通常、金属換算でパラジウム
が０．１〜２０重量％であり、助触媒成分が０．０１〜
３０重量％の範囲で選定される。The acetoxylation reaction comprises butadiene, acetic acid,
And molecular oxygen in the presence of a noble metal catalyst, especially a palladium-based catalyst, by a known method of reacting. As the palladium catalyst, palladium metal or a salt thereof (for example, an inorganic or organic acid salt such as palladium chloride, palladium nitrate, and palladium acetate) can be used alone.
Further, a palladium metal or a salt thereof is used in combination with a metal such as bismuth, selenium, antimony, tellurium, or copper or a salt thereof (for example, bismuth oxide, selenic acid, tellurium oxide, antimony chloride, copper chloride, or the like) as a promoter. You can also. These catalyst components are preferably used by being supported on a carrier such as silica, alumina and activated carbon. Usually, a catalyst prepared by impregnating a carrier with a solution in which a compound of a palladium compound and a cocatalyst component is dissolved is supported on the carrier, and then the catalyst component on the carrier is reduced with hydrogen, methanol, or the like. Used. The amount of the catalyst component in the supported catalyst is generally 0.1 to 20% by weight of palladium in terms of metal, and 0.01 to 20% by weight of the cocatalyst component.
It is selected in the range of 30% by weight.
【０００９】アセトキシ化反応は、公知の固定床方式、
流動床方式、懸濁床方式等の任意の方法で実施され、反
応は４０〜１８０℃、好ましくは６０〜１５０℃の温度
範囲で、常圧以上、通常、３００ｋｇ／ｃｍ2 （２９．
４ＭＰａ）以下、好ましくは３０〜１５０ｋｇ／ｃｍ2
（２．９４〜１４．７ＭＰａ）の圧力下で実施される。The acetoxylation reaction is carried out by a known fixed bed method,
The reaction is carried out by any method such as a fluidized bed system and a suspension bed system, and the reaction is carried out at a temperature in the range of 40 to 180 ° C, preferably 60 to 150 ° C, at a normal pressure or higher, usually 300 kg / cm 2 (29.
4 MPa) or less, preferably 30 to 150 kg / cm 2
(2.94 to 14.7 MPa).
【００１０】このようにして得られるアセトキシ化の反
応生成液には、未反応のブタジエン等が含まれているの
で、通常は脱ガス処理してブタジエン等を除去した後、
蒸留してジアセトキシブテンを得る。通常、第１蒸留塔
で、水、酢酸、モノアセトキシブテン等を塔頂から留去
し、その塔底液を第２蒸留塔に供給する。第２蒸留塔で
は、塔頂からジアセトキシブテンを得、ジアセトキシオ
クタジエンを含む副生高沸物を塔底から抜き出す。Since the reaction product liquid of acetoxylation thus obtained contains unreacted butadiene and the like, it is usually degassed to remove butadiene and the like.
Distillation gives diacetoxybutene. Usually, water, acetic acid, monoacetoxybutene and the like are distilled off from the top of the first distillation column, and the bottom liquid is supplied to the second distillation column. In the second distillation column, diacetoxybutene is obtained from the top of the column, and high-boiling by-products including diacetoxyoctadiene are extracted from the bottom of the column.
【００１１】第１蒸留塔は、通常、理論段数４〜１０段
で、塔頂圧力３０〜３００ｍｍＨｇ（４〜４０ｋＰ
ａ）、塔底温度１９０℃以下、還流比０〜０．１で操作
され、また、第２蒸留塔は、理論段数、通常、１０〜１
５段で、塔頂圧力２〜１００ｍｍＨｇ（０．３〜１３．
３ｋＰａ）、塔底温度１９０℃以下、還流比０〜１で操
作される。The first distillation column usually has 4 to 10 theoretical plates and a top pressure of 30 to 300 mmHg (4 to 40 kP).
a), operating at a bottom temperature of 190 ° C. or lower and a reflux ratio of 0 to 0.1, and the second distillation column has a theoretical plate number, usually 10 to 1
In 5 stages, the top pressure is 2 to 100 mmHg (0.3 to 13.
3 kPa), operating at a bottom temperature of 190 ° C. or lower and a reflux ratio of 0 to 1.
【００１２】通常、蒸留塔のリボイラー、すなわち塔底
液の加熱装置としては、加熱用の熱媒体がシェル側に供
給され、チューブ内を被加熱体である塔底液が通過する
シェル−チューブ式の多管式熱交換器が用いられる。熱
交換器を通しての塔底液の流れは、チューブ内での加熱
により発生する比重差に基づく自然循環によるのが一般
的である。蒸留塔底の液粘度が高い場合等には、希に薄
膜蒸発器のような加熱方式が採用されることもある。ア
セトキシ化反応で得られるジアセトキシブテンは沸点が
２３０℃（１０１ｋＰａ）付近であり、粘度も約２．０
ＭＰａ・秒（５０℃）であるので、第１蒸留塔のリボイ
ラーを設計する際には、ジアセトキシブテンが二重結合
を持つため、温度上昇による重合を防止する以外は、特
段の配慮が必要であるとは考えられなかった。しかしな
がら、前記の蒸留条件で、塔底温度を１９０℃以下に保
ち運転を継続したところ、予想外にも、リボイラーチュ
ーブの閉塞が起こり、３０００乃至４０００時間以上の
運転の継続は不可能であった。リボイラーチューブの閉
塞を防止するために、重合防止剤例えばハイドロキノン
等の添加、或いは付着防止剤の添加等を検討したが、有
効な添加剤は見い出せなかった。Usually, a reboiler of a distillation column, that is, a device for heating a bottom liquid, is a shell-tube type in which a heating medium for heating is supplied to the shell side, and the bottom liquid as an object to be heated passes through the tube. Is used. The flow of the bottom liquid through the heat exchanger is generally caused by natural circulation based on a difference in specific gravity generated by heating in the tube. When the liquid viscosity at the bottom of the distillation column is high, a heating method such as a thin film evaporator may be rarely adopted. Diacetoxybutene obtained by the acetoxylation reaction has a boiling point of around 230 ° C. (101 kPa) and a viscosity of about 2.0.
Since the pressure is MPa · sec (50 ° C), special consideration must be taken when designing the reboiler for the first distillation column, except that diacetoxybutene has a double bond. Was not considered to be. However, when the operation was continued while maintaining the bottom temperature at 190 ° C. or lower under the above-mentioned distillation conditions, the reboiler tube was unexpectedly clogged, and it was impossible to continue the operation for 3000 to 4000 hours or more. . In order to prevent the clogging of the reboiler tube, the addition of a polymerization inhibitor such as hydroquinone or the addition of an adhesion inhibitor was examined, but no effective additive was found.
【００１３】ところが、熱交換器のチューブを通過する
塔底液の流速が大きくなると、チューブへの重合物の付
着が減少することが見出された。通常はチューブ入口で
の液速が０．７ｍ／秒以上となると重合物の付着は著し
く減少する。一般に流速が大きいほど重合物の付着は減
少するが、流速を大きくするとチューブ内での圧力損失
が増加し、熱交換器を通して塔底液を循環させるために
多量のエネルギーを必要とする。また、流速が過大とな
るとチューブが振動して熱交換器が破損する危険があ
る。従って熱交換器を通過する塔底液の流速は、チュー
ブ入口で５．０ｍ／秒以下が好ましく、これより流速を
大きくすることは有利ではない。塔底液の最も好ましい
流速は、チューブ入口で１．０〜４．０ｍ／秒である。
塔底液をこのような流速で熱交換器を通過させるには、
蒸留塔の塔底から熱交換器までの塔底液の流路にポンプ
を設置し、このポンプにより所定の流速となるように塔
底液を熱交換器に供給するのが最も簡便である。本発明
方法によれば、熱交換器を通過する塔底液の流速をチュ
ーブ入口で０．７ｍ／秒以上、特に１．０〜４．０秒と
することにより、第１蒸留塔を約１年間に亘り連続運転
することができる。However, it has been found that as the flow rate of the bottom liquid passing through the tubes of the heat exchanger increases, the adhesion of the polymer to the tubes decreases. Usually, when the liquid velocity at the tube inlet is 0.7 m / sec or more, the adhesion of the polymer is remarkably reduced. In general, the higher the flow rate, the lower the adhesion of the polymer. However, if the flow rate is increased, the pressure loss in the tube increases, and a large amount of energy is required to circulate the bottom liquid through the heat exchanger. If the flow velocity is too high, the tube may vibrate and the heat exchanger may be damaged. Therefore, the flow rate of the bottom liquid passing through the heat exchanger is preferably 5.0 m / sec or less at the inlet of the tube, and it is not advantageous to increase the flow rate more than this. The most preferred flow rate of the bottom liquid is 1.0 to 4.0 m / sec at the tube inlet.
To pass the bottom liquid through the heat exchanger at such a flow rate,
It is most simple to install a pump in the flow path of the bottom liquid from the bottom of the distillation column to the heat exchanger, and to supply the bottom liquid to the heat exchanger at a predetermined flow rate by the pump. According to the method of the present invention, the flow rate of the bottom liquid passing through the heat exchanger is set at 0.7 m / sec or more, particularly 1.0 to 4.0 seconds at the tube inlet, so that the first distillation column is reduced to about 1 It can be operated continuously over the years.
【００１４】第１蒸留塔の塔頂から回収される水及び酢
酸を主成分とする留分は、酢酸精製工程に送られ、精製
された上でアセトキシ化反応に再使用される。塔底液
は、第２蒸留塔に送られ、先に開示された方法に従い塔
頂からジアセトキシブテンを取出す。このジアセトキシ
ブテンは水素化されたのち加水分解され、１，４−ブタ
ンジオールとされる。The fraction mainly composed of water and acetic acid collected from the top of the first distillation column is sent to an acetic acid purification step, purified, and reused in the acetoxylation reaction. The bottom liquid is sent to the second distillation column, and diacetoxybutene is removed from the top according to the method disclosed above. This diacetoxybutene is hydrogenated and then hydrolyzed to give 1,4-butanediol.
【００１５】[0015]
【実施例】以下、本発明を実施例、比較例を挙げ、更に
具体的に説明するが、本発明は、その要旨を超えない限
り実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples unless it exceeds the gist thereof.
【００１６】実施例１ アセトキシ化反応器に、ブタジエン１７０重量部／ｈ
ｒ、酢酸３０００重量部／ｈｒ、及び酸素５３０重量部
／ｈｒを供給し、パラジウム３重量％及びテルル０．６
重量％を活性炭に担持した触媒の存在下、９ＭＰａ、１
００℃で反応させた。反応器から抜出した液は脱ガス処
理して、ジアセトキシブテン１４．２重量％を含む反応
生成液を得た。該反応生成液を３１００重量部／ｈｒで
第１蒸留塔に供給し、蒸留して酢酸を留出させた。蒸留
塔としては理論段数で１０段の充填物が充填されている
充填塔を用い、塔頂から数えて８段目に反応液をフィー
ドした。蒸留塔は塔頂圧力を１３．３ｋＰａ（１００ｍ
ｍＨｇ）、還流比を０．１、塔底温度を１５０℃で運転
し、塔底液は蒸留塔底部とリボイラーとの間に設置した
ポンプにより、リボイラーチューブの入口で１．５ｍ／
秒になるようにリボイラーを経て循環した。水及び酢酸
の大部分を塔頂より留去し、ジアセトキシブテン８４．
５重量％、及びジアセトキシオクタジエン３．２重量％
を含む塔底液を５８０重量部／ｈｒで塔底から抜出し
た。この条件で運転を１年間（８０００時間）継続して
実施した後、リボイラーを開放しチューブを点検したと
ころ、多数あるチューブの約２％が閉塞していた。運転
開始した時点でのリボイラーの総括伝熱係数は７８０ｋ
ｃａｌ／ｈｒ・ｍ2 ・℃であった。Example 1 170 parts by weight of butadiene / h was placed in an acetoxylation reactor.
r, acetic acid 3000 parts by weight / hr, and oxygen 530 parts by weight / hr, palladium 3% by weight and tellurium 0.6
9MPa, 1MPa, 1%
The reaction was performed at 00 ° C. The liquid discharged from the reactor was degassed to obtain a reaction product liquid containing 14.2% by weight of diacetoxybutene. The reaction product solution was supplied to the first distillation column at 3100 parts by weight / hr, and distilled to distill acetic acid. As the distillation column, a packed column filled with 10 packed packings was used, and the reaction solution was fed to the eighth plate counted from the top of the column. The distillation column has a top pressure of 13.3 kPa (100 m
mHg), the reflux ratio was 0.1, the bottom temperature was 150 ° C., and the bottom liquid was 1.5 m / m at the inlet of the reboiler tube by a pump installed between the bottom of the distillation column and the reboiler.
Circulated through the reboiler in seconds. Most of water and acetic acid were distilled off from the top of the column, and diacetoxybutene was added.
5% by weight and 3.2% by weight of diacetoxyoctadiene
Was withdrawn from the bottom at 580 parts by weight / hr. After the operation was continued for one year (8000 hours) under these conditions, the reboiler was opened and the tubes were inspected. As a result, about 2% of many tubes were closed. The overall heat transfer coefficient of the reboiler at the start of operation is 780k
cal / hr · m 2 · ° C.
【００１７】比較例１ ポンプを用いずに自然循環により塔底液がボイラーを通
過するようにした以外は、実施例と同じ操作条件により
運転を行った。リボイラーは、この操作条件下ではチュ
ーブ入口の流速が０．３ｍ／秒となるように設計されて
いる。運転開始後、２０００時間付近よりリボイラーの
シェル側における蒸気圧力が上昇し、３０００時間で運
転が出来なくなった。リボイラーを開放し点検したとこ
ろ、チューブ総数の約４０％が重合物で閉塞していた。
運転開始した時点におけるリボイラーの総括伝熱係数は
３８０ｋｃａｌ／ｈｒ・ｍ2 ・℃であった。Comparative Example 1 The operation was carried out under the same operating conditions as in the example, except that the bottom liquid passed through the boiler by natural circulation without using a pump. The reboiler is designed such that the flow rate at the tube inlet is 0.3 m / sec under these operating conditions. After the start of the operation, the steam pressure on the shell side of the reboiler increased from around 2000 hours, and the operation became impossible in 3000 hours. When the reboiler was opened and inspected, it was found that about 40% of the total number of tubes was blocked by the polymer.
The overall heat transfer coefficient of the reboiler at the start of the operation was 380 kcal / hr · m 2 · ° C.
【００１８】比較例２ リボイラーチューブ入口での液流速が０．５ｍ／秒にな
るようにポンプにより塔底液をリボイラーに供給した以
外は、実施例１と同様にして蒸留塔の運転を行った。運
転開始後、３０００時間付近よりリボイラーシェル側の
蒸気圧力が上昇し、４０００時間で運転が出来なくなっ
た。リボイラーを開放し点検したところ、チューブ総数
の約４０％が重合物で閉塞していた。運転開始した時点
におけるリボイラーの総括伝熱係数は４５０ｋｃａｌ／
ｈｒ・ｍ2 ・℃であった。Comparative Example 2 The distillation column was operated in the same manner as in Example 1 except that the bottom liquid was supplied to the reboiler by a pump so that the liquid flow rate at the inlet of the reboiler tube was 0.5 m / sec. . After the start of the operation, the steam pressure on the reboiler shell side increased from around 3000 hours, and the operation became impossible in 4000 hours. When the reboiler was opened and inspected, it was found that about 40% of the total number of tubes was blocked by the polymer. The total heat transfer coefficient of the reboiler at the start of operation was 450 kcal /
hr · m 2 · ° C.
【００１９】[0019]
【発明の効果】本発明によれば、貴金属触媒を用いてブ
タジエンからジアセトキシブテンを生成するアセトキシ
化反応生成液からの酢酸分離を、蒸留塔のリボイラーの
チューブの閉塞なしに、長期間安定的に運転を行うこと
ができる。According to the present invention, the separation of acetic acid from the acetoxylation reaction solution for producing diacetoxybutene from butadiene using a noble metal catalyst can be performed for a long period of time without clogging the tube of the reboiler of the distillation column. Driving can be performed.
Claims (6)
酸及び酸素を反応させてジアセトキシブテンを生成さ
せ、生成したジアセトキシブテンを含む反応生成液を蒸
留塔で蒸留して、酢酸を含む軽沸成分を塔頂から留出さ
せ、塔底からジアセトキシブテンを含む成分を抜出すジ
アセトキシブテンの製造方法において、蒸留塔として塔
底液を加熱するためのシェル−チューブ式の多管式熱交
換器を有するものを用い、且つこの熱交換器のチューブ
入口において０．７ｍ／秒以上となる流速で塔底液が熱
交換器を通過するようにすることを特徴とする方法。1. A reaction product containing diacetoxybutene produced by reacting butadiene, acetic acid and oxygen in the presence of a noble metal catalyst, and distilling the reaction product containing diacetoxybutene in a distillation column to obtain a light solution containing acetic acid. In a method for producing diacetoxybutene in which a boiling component is distilled off from the top of the column and a component containing diacetoxybutene is extracted from the bottom of the column, a shell-and-tube multi-tube heat for heating the bottom liquid as a distillation column is used. A method comprising using an exchanger having an exchanger, and allowing the bottom liquid to pass through the heat exchanger at a flow rate of 0.7 m / sec or more at a tube inlet of the heat exchanger.
〜４．０ｍ／秒となる流速で塔底液が熱交換器を通過す
るようにすることを特徴とする請求項１記載の方法。2. The method according to claim 1, wherein the heat exchanger has a tube inlet of 1.0.
The method according to claim 1, wherein the bottom liquid is passed through the heat exchanger at a flow rate of ~ 4.0 m / sec.
り行うことを特徴とする請求項１又は２に記載の方法。3. The method according to claim 1, wherein the supply of the bottom liquid to the heat exchanger is performed by a pump.
貴金属を含む触媒の存在下に、ブタジエン、酢酸及び酸
素を反応させて得た反応液を脱ガス処理したものである
ことを特徴とする請求項１ないし３のいずれかに記載の
方法。4. A reaction product liquid to be subjected to distillation in a distillation column,
The method according to any one of claims 1 to 3, wherein a reaction solution obtained by reacting butadiene, acetic acid and oxygen in the presence of a catalyst containing a noble metal is degassed.
ビスマス、セレン、アンチモン、テルル及び銅からなる
群から選ばれた少くとも一つを担持したものであること
を特徴とする請求項１ないし４のいずれかに記載の方
法。5. The precious metal catalyst according to claim 1, wherein the noble metal catalyst is formed by supporting palladium and at least one selected from the group consisting of bismuth, selenium, antimony, tellurium and copper on a carrier. The method according to any of the above.
下に維持することを特徴とする請求項１ないし５のいず
れかに記載の方法。6. The method according to claim 1, wherein the liquid temperature at the bottom of the distillation column is maintained at 190 ° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05789298A JP4107706B2 (en) | 1997-04-16 | 1998-03-10 | Method for producing diacetoxybutene |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-98726 | 1997-04-16 | ||
| JP9872697 | 1997-04-16 | ||
| JP05789298A JP4107706B2 (en) | 1997-04-16 | 1998-03-10 | Method for producing diacetoxybutene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH111454A true JPH111454A (en) | 1999-01-06 |
| JP4107706B2 JP4107706B2 (en) | 2008-06-25 |
Family
ID=26398981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05789298A Expired - Fee Related JP4107706B2 (en) | 1997-04-16 | 1998-03-10 | Method for producing diacetoxybutene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4107706B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016143783A1 (en) * | 2015-03-09 | 2016-09-15 | 三菱化学株式会社 | Process for producing conjugated diene |
-
1998
- 1998-03-10 JP JP05789298A patent/JP4107706B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016143783A1 (en) * | 2015-03-09 | 2016-09-15 | 三菱化学株式会社 | Process for producing conjugated diene |
| JP2016172721A (en) * | 2015-03-09 | 2016-09-29 | 三菱化学株式会社 | Method for producing conjugated diene |
| KR20170128271A (en) * | 2015-03-09 | 2017-11-22 | 미쯔비시 케미컬 주식회사 | Method for producing conjugated diene |
| US10370309B2 (en) | 2015-03-09 | 2019-08-06 | Mitsubishi Chemical Corporation | Method for producing conjugated diene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4107706B2 (en) | 2008-06-25 |
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