JPH0335301B2 - - Google Patents
Info
- Publication number
- JPH0335301B2 JPH0335301B2 JP60117399A JP11739985A JPH0335301B2 JP H0335301 B2 JPH0335301 B2 JP H0335301B2 JP 60117399 A JP60117399 A JP 60117399A JP 11739985 A JP11739985 A JP 11739985A JP H0335301 B2 JPH0335301 B2 JP H0335301B2
- Authority
- JP
- Japan
- Prior art keywords
- tank
- temperature
- cooling
- refrigerant
- expansion valve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000126 substance Substances 0.000 claims description 48
- 238000001816 cooling Methods 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000003507 refrigerant Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000007791 liquid phase Substances 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 10
- 238000005057 refrigeration Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- 239000003112 inhibitor Substances 0.000 description 8
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 4
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- JCRIDWXIBSEOEG-UHFFFAOYSA-N 2,6-dinitrophenol Chemical compound OC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O JCRIDWXIBSEOEG-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 nitrosamine compound Chemical class 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、スチレンモノマー、α−メチルスチ
レンモノマー、アクリルニトリルモノマー等の重
合しやすい常温液体である重合性物質の貯蔵方法
に係り、特にタンク内での前記重合性物質の重合
反応によるポリマーの発生を防ぎ、品質の低下を
回避する重合性物質の貯蔵方法の改良に関するも
のである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for storing polymerizable substances that are room temperature liquids that easily polymerize, such as styrene monomer, α-methylstyrene monomer, acrylonitrile monomer, etc. The present invention relates to an improvement in a method for storing a polymerizable substance that prevents the generation of polymer due to a polymerization reaction of the polymerizable substance in a container and avoids deterioration of quality.
［背景技術とその問題点］
従来、スチレンモノマー、α−メチルスチレン
モノマー、アクリルニトリルモノマー等の重合し
やすい常温液体である重合性物質をタンクに貯蔵
するために各種の方法が考えられてきた。例え
ば、タンク内の重合性物質の液相部分での重合反
応を防止するためには、重合防止剤の添加、反応
を抑えるための冷却といつた手段が一般的であ
る。[Background Art and Problems Therein] Conventionally, various methods have been devised for storing polymerizable substances that are room temperature liquids that easily polymerize, such as styrene monomers, α-methylstyrene monomers, and acrylonitrile monomers, in tanks. For example, in order to prevent a polymerization reaction in the liquid phase portion of a polymerizable substance in a tank, it is common to use such means as adding a polymerization inhibitor and cooling to suppress the reaction.
重合防止剤としては、パラターシヤリーブチル
カテコール（TBC）や硫黄が一般的であつたが、
今日ではより優れたニトロソアミン化合物（特公
昭52−39016）や、２・４ジニトロフエノールと
２・６ジニトロフエノールの混合物（特公昭53−
17583）が知られている。 Paratertiary butylcatechol (TBC) and sulfur were commonly used as polymerization inhibitors, but
Today, better nitrosamine compounds (Japanese Patent Publication No. 52-39016) and mixtures of 2,4-dinitrophenol and 2,6-dinitrophenol (Japanese Patent Publication No. 53-39016) are available.
17583) is known.
一方、冷却の方法としては、タンク外面に水を
散布する方法、タンク内の液体の一部を抜き出し
て冷却した後タンクに戻す方法などが行なわれて
いた。 On the other hand, methods of cooling include spraying water on the outer surface of the tank, or extracting a portion of the liquid inside the tank, cooling it, and then returning it to the tank.
しかしながら、これらの方法が効果的なのはタ
ンク内の液相部分の重合性物質に限られ、液面よ
り上の部分に気相として存在する重合性物質には
その効果が及ばない。つまり、気相部分の重合性
物質は、タンク内上部の気相部分に対応する壁面
の温度の影響を受けるため、冷却の効果が及ばな
いこと、さらに重合防止剤として用いられる添加
物の沸点は、一般に重合性物質の沸点よりも高い
ため、蒸発するのは専ら重合性物質だけというこ
とになる。従つて、外気温が低下した場合、気相
の重合性物質は前記壁面近くのものから冷却され
て壁面に凝縮するが、これらの凝縮した液滴には
重合防止剤が含まれておらず、液滴内の重合性物
質は数日内に重合反応を始め、ポリマーとなる。
このときポリマーは重力により下方に成長するた
め天板内面でポリマーを含んだ液滴となつて貯蔵
液中に落下したり、あるいはつらら状に成長し、
やがて自重で剥離し落下して貯蔵液中に混入す
る。また側壁面のポリマーは側壁面に沿つて下方
へ成長し、ついには液面まで達して貯蔵液中に溶
解する。特に、重合性物質が連続的にタンク内に
供給されている状態で使用量が大幅に減少した
り、あるいは追加貯蔵されて液面が上昇すること
により、壁面に成長しつつあるポリマーが液中に
浸され溶解した場合、液中のポリマー濃度が一時
的に増大することもあり、いずれの場合も、ポリ
マーが貯蔵液中に混入し、不純物となるという問
題が生じる。すなわち、貯蔵タンク内で生成した
ポリマーの分子量が、製品化の工程で生成される
ポリマーの分子量より大きい場合など、製品中の
これらの分子量の異なるポリマーの割合が増加す
ると、製品としての物性が微妙に変化し、品質が
低下する。 However, these methods are effective only for polymerizable substances in the liquid phase portion of the tank, and are not effective for polymerizable substances that exist in the vapor phase above the liquid level. In other words, the polymerizable substance in the gas phase part is affected by the temperature of the wall surface corresponding to the gas phase part at the top of the tank, so the cooling effect is not affected, and the boiling point of the additive used as a polymerization inhibitor is , which is generally higher than the boiling point of the polymerizable substance, means that only the polymerizable substance evaporates. Therefore, when the outside temperature decreases, the polymerizable substance in the gas phase is cooled from those near the wall surface and condenses on the wall surface, but these condensed droplets do not contain a polymerization inhibitor; The polymerizable substance within the droplet begins a polymerization reaction within a few days and becomes a polymer.
At this time, the polymer grows downward due to gravity, so it forms droplets containing the polymer on the inner surface of the top plate and falls into the storage liquid, or it grows in the form of icicles.
Eventually, it peels off under its own weight, falls down, and gets mixed into the stored liquid. Further, the polymer on the side wall grows downward along the side wall, eventually reaching the liquid level and being dissolved in the storage liquid. In particular, if the amount used is significantly reduced when the polymerizable substance is continuously supplied into the tank, or if the liquid level rises due to additional storage, the polymer that is growing on the wall surface will be submerged in the liquid. When the liquid is immersed in and dissolved, the concentration of the polymer in the liquid may temporarily increase, and in either case, the problem arises that the polymer mixes into the stored liquid and becomes an impurity. In other words, if the molecular weight of the polymer produced in the storage tank is larger than the molecular weight of the polymer produced in the product manufacturing process, and the proportion of polymers with different molecular weights in the product increases, the physical properties of the product may become unstable. and the quality deteriorates.
一般に、重合性物質を市販する場合のポリマー
含有量は、１〜10ppm程度と規制されており、従
来、前記ポリマーの混入により重合性物質として
の商品価値を失うことを避けるため、タンク内壁
面の清掃や重合性物質の再処理を行なう一方、タ
ンク内壁面でのポリマー生成を防止する方法が研
究されていた。 In general, the polymer content of commercially available polymerizable substances is regulated at about 1 to 10 ppm, and conventionally, in order to avoid losing the commercial value of the polymerizable substance due to contamination with the polymer, the inner wall surface of the tank was While cleaning and reprocessing polymerizable substances were carried out, research was being conducted on methods to prevent polymer formation on the inner walls of the tank.
たとえば、従来の重合防止剤の添加と液相部分
の重合性物質の冷却に加え、この重合防止剤を含
んだ重合性物質を汲みあげてタンク上部の天板に
噴霧し、壁面を洗浄して凝縮を防止するととも
に、天板を冷却することで積極的に天板付近の気
相の重合性物質を液化して回収するという方法
（特開昭58−42601）が知られている。この方法に
よれば、タンク内壁面での重合性物質の凝縮はか
なり防げるが、噴霧を一様にするのが困難といつ
た設置に関わる問題とともに、噴霧口が詰る、あ
るいは複雑な配管の隙間に重合性物質が溜る、と
いつた問題に対しては、タンク内部の配管だけに
対応が困難であつた。 For example, in addition to the conventional addition of a polymerization inhibitor and cooling of the polymerizable substance in the liquid phase, this polymerizable substance containing the polymerization inhibitor is pumped up and sprayed onto the top plate at the top of the tank, and the wall surface is washed. A method is known (Japanese Unexamined Patent Publication No. 42601/1983) in which condensation is prevented and polymerizable substances in the gas phase near the top plate are actively liquefied and recovered by cooling the top plate. This method can significantly prevent condensation of polymerizable substances on the inner wall of the tank, but it also poses installation-related problems such as difficulty in spraying uniformly, as well as clogging of the spray nozzle and gaps in complicated piping. It was difficult to deal with problems such as polymerizable substances accumulating inside the tank, which was limited to the piping inside the tank.
その他に、タンク内に窒素のような不活性ガス
を送りこみ、気相の重合性物質の分圧を下げるこ
とにより蒸発を制限したり、タンク内壁面にコー
テイングを施し、凝縮する際の液滴の核になりや
すい突起を減らすことにより凝縮を抑制する方法
があるが、いずれも決定的なものではなく、他の
方法と併用されるにすぎない。 Other methods include introducing an inert gas such as nitrogen into the tank to reduce the partial pressure of the polymerizable substance in the gas phase to limit evaporation, and coating the inner wall of the tank to prevent droplets from condensing. There are methods to suppress condensation by reducing the protrusions that tend to become nuclei, but none of them are definitive and can only be used in conjunction with other methods.
［発明の目的］
本発明の目的は、重合性物質の貯蔵に際して、
タンク内の液相の重合性物質の重合反応を防ぐと
ともに、液面からの蒸発を抑えることができ、ま
た気相の重合性物質のタンク内上部の気相部分に
対応する壁面での凝縮による液滴内での重合反応
を抑えることができて、ポリマーの発生を防ぎ、
品質の低下を回避することを容易かつ効率よく行
える重合性物質の貯蔵方法を提供することにあ
る。[Object of the invention] The object of the present invention is to
In addition to preventing the polymerization reaction of the polymerizable substance in the liquid phase in the tank, it also suppresses evaporation from the liquid surface. It is possible to suppress the polymerization reaction within the droplets, preventing the generation of polymers,
It is an object of the present invention to provide a method for storing polymerizable substances that can easily and efficiently avoid deterioration in quality.
［問題点を解決するための手段および作用］
本発明は、貯蔵タンク内の重合性物質のうち、
液相部分を冷却することにより重合性物質の重合
反応および蒸発を抑えて、タンク内上部の気相部
分に対応する壁面を加熱することにより重合性物
質の前記壁面での凝縮を抑えており、重合性物質
の貯蔵における問題点であつた重合の発生による
品質の低下を回避する。この際、液相部分の冷却
と気相部分の壁面の加熱とを冷凍サイクルにより
一元化し、機械構成の簡素化および熱効率の向上
を図るとともに、冷凍サイクルの制御を膨張弁の
開度調整により行うものとし、その開度調整にあ
たつて、前記加熱部の温度と前記タンク内の液相
部分温度との温度差を予め設定しておいた値と比
較して膨張弁の開度を求め、前記液相部分温度を
予め設定しておいた値と比較して膨張弁の開度を
求め、これらの開度のうち大きいほうの開度に従
い前記膨張弁を調節するものとし、これにより前
記冷却と加熱とを一元化しても各々による前記重
合の発生防止を確実に行えるようにしようとする
ものである。[Means and effects for solving the problems] The present invention provides that among the polymerizable substances in the storage tank,
By cooling the liquid phase part, the polymerization reaction and evaporation of the polymerizable substance are suppressed, and by heating the wall surface corresponding to the gas phase part in the upper part of the tank, condensation of the polymerizable substance on the wall surface is suppressed, This avoids deterioration in quality due to the occurrence of polymerization, which was a problem when storing polymerizable substances. At this time, cooling of the liquid phase part and heating of the wall surface of the gas phase part are unified by the refrigeration cycle, simplifying the mechanical configuration and improving thermal efficiency, and controlling the refrigeration cycle by adjusting the opening of the expansion valve. In adjusting the opening degree, the opening degree of the expansion valve is determined by comparing the temperature difference between the temperature of the heating part and the temperature of the liquid phase part in the tank with a preset value, The degree of opening of the expansion valve is determined by comparing the temperature of the liquid phase portion with a preset value, and the degree of opening of the expansion valve is adjusted according to the larger of these degrees of opening, whereby the cooling Even if the heating and heating are integrated, it is possible to reliably prevent the occurrence of the polymerization caused by each of them.
［実施例］
以下に本発明の重合性物質の貯蔵方法による実
施例を図面に基づいて説明する。[Example] Examples of the method for storing a polymerizable substance of the present invention will be described below based on the drawings.
第１図は、本発明の重合性物質の貯蔵方法によ
る貯蔵タンクの装置を示す概略図である。 FIG. 1 is a schematic diagram showing a storage tank apparatus according to the method for storing polymerizable substances of the present invention.
図において、タンク１は重合性物質であるスチ
レンモノマーに、重合防止剤としてパラターシヤ
リーブチルカテコール（TBC）を添加した液体
を貯蔵している。このタンク１のコーンルーフ型
天板１Ａの外側には、加熱部としての加熱用配管
２が設けられており、また天板温度を検出するた
めの温度センサ３が取り付けてある。さらに、天
板１Ａ及び側壁面１Ｂの内面はコーテイングによ
り平滑化されており、他の物質が付着しにくいよ
うになつている。 In the figure, tank 1 stores a liquid obtained by adding paratertiary butylcatechol (TBC) as a polymerization inhibitor to styrene monomer, which is a polymerizable substance. A heating pipe 2 as a heating section is provided on the outside of the corn roof type top plate 1A of the tank 1, and a temperature sensor 3 for detecting the temperature of the top plate is attached. Further, the inner surfaces of the top plate 1A and the side wall surfaces 1B are smoothed by coating to prevent other substances from adhering to them.
一方、タンク１内の底部内側には、冷却部とし
ての冷却用配管４がコイル状に設けてあり、また
液体温度を検出するための温度センサ５が取り付
けてある。さらに吸入管６Ａおよび吐出管６Ｂを
介して撹拌ポンプ６が接続され、この吐出管６Ｂ
からの噴流によりタンク１内の液体を常に撹拌
し、温度分布が一様になるようにして冷却効果を
高めている。これらの配管等の取り付け部分は、
二重管構造としてタンク側壁面１Ｂの耐久性に配
慮してある。 On the other hand, inside the bottom of the tank 1, a cooling pipe 4 serving as a cooling section is provided in a coil shape, and a temperature sensor 5 for detecting the liquid temperature is attached. Furthermore, a stirring pump 6 is connected via a suction pipe 6A and a discharge pipe 6B, and this discharge pipe 6B
The liquid in the tank 1 is constantly agitated by the jet stream from the tank 1, so that the temperature distribution is uniform and the cooling effect is enhanced. The installation parts of these piping etc.
The durability of the tank side wall surface 1B is considered as a double pipe structure.
前記の加熱用配管２及び冷却用配管４には冷媒
としてフレオン−22（Ｒ−22）が送り込まれるが、
この冷媒の動きを追つて他の部分を説明する。 Freon-22 (R-22) is fed into the heating pipe 2 and the cooling pipe 4 as a refrigerant.
The other parts will be explained by following the movement of this refrigerant.
前記冷却用配管４の出口側すなわち図中上端側
は、熱交換機１５を介して圧縮機７が接続され、
この圧縮機７は、吸入側圧力センサ８及びインバ
ータ方式による回転数制御装置９により吸入側圧
力がほぼ一定、例えば0.5〜1.0Kg／cm2となるよう
に制御される図示しないモータにより駆動され、
冷媒を圧縮し、吐出側圧力10〜12Kg／cm2、温度70
〜80℃で送り出す。 A compressor 7 is connected to the outlet side of the cooling pipe 4, that is, the upper end side in the figure, via a heat exchanger 15,
The compressor 7 is driven by a motor (not shown) that is controlled by a suction side pressure sensor 8 and an inverter-based rotation speed control device 9 so that the suction side pressure is approximately constant, for example, 0.5 to 1.0 kg/cm 2 .
Compress the refrigerant, discharge side pressure 10-12Kg/cm 2 , temperature 70
Deliver at ~80℃.
送り出された冷媒は三方弁１０を通過し、加熱
部配管２の上端側に送られ、この加熱部配管２を
通り天板１Ａに放熱する。この際、温度センサ３
により検出された温度が規定値より高い場合は、
天板１Ａの保護のため制御装置１１により三方弁
１０が切り換えられ、冷媒はバイパス１２を通る
ため加熱部配管２には冷媒は通らず、加熱は行な
われないようにされ、天板の温度はそれ以上上昇
しないことになる。 The sent-out refrigerant passes through the three-way valve 10, is sent to the upper end side of the heating section piping 2, passes through the heating section piping 2, and radiates heat to the top plate 1A. At this time, temperature sensor 3
If the temperature detected by is higher than the specified value,
The three-way valve 10 is switched by the control device 11 to protect the top plate 1A, and since the refrigerant passes through the bypass 12, the refrigerant does not pass through the heating section piping 2, so that heating is not performed, and the temperature of the top plate is It will not rise any further.
加熱部配管２あるいはバイパス１２を通過した
冷媒は熱交換器１３に入るが、熱交換を行なうも
う一方の配管１４には海水、地下水等の冷却液が
流通し、これにより冷媒はある程度冷却され、さ
らに熱交換器１５に入つて、冷却用配管４からの
冷媒により冷却される。一方、冷却用配管４内の
冷媒は加熱され、完全に気化するようにされ、液
相のまま圧縮機７に導入されて圧縮機７を損傷す
ることがないようにされている。 The refrigerant that has passed through the heating section piping 2 or the bypass 12 enters the heat exchanger 13, but a cooling fluid such as seawater or ground water flows through the other piping 14 where heat exchange is performed, and the refrigerant is cooled to some extent by this. Furthermore, it enters the heat exchanger 15 and is cooled by the refrigerant from the cooling pipe 4. On the other hand, the refrigerant in the cooling pipe 4 is heated and completely vaporized so as not to be introduced into the compressor 7 in a liquid phase and damage the compressor 7.
二つの熱交換機１３，１５により冷却された冷
媒は、膨張弁１６を経て断熱膨張して気化し、冷
却部配管４において気化熱を吸収し、タンク底部
の重合性物質を冷却するが、この膨張弁１６とし
ては脈動防止のためヒステリシスの大きなものを
使用し、さらに制御装置１７によるオーバーライ
ド制御により開度を調節される機構をもつ。 The refrigerant cooled by the two heat exchangers 13 and 15 passes through the expansion valve 16, expands adiabatically and vaporizes, absorbs the heat of vaporization in the cooling section piping 4, and cools the polymerizable substance at the bottom of the tank. As the valve 16, a valve with large hysteresis is used to prevent pulsation, and furthermore, it has a mechanism whose opening degree is adjusted by override control by a control device 17.
第２図に、前記オーバーライド制御による膨張
弁１６の弁開度の調節の流れを示す。 FIG. 2 shows the flow of adjusting the valve opening of the expansion valve 16 by the override control.
図において、天板温度を検出するための温度セ
ンサ３による温度Ｔ１、タンク１内の液体温度を
検出するための温度センサ５による温度Ｔ２を入
力として、制御装置１７は、まず演算器１７Ａで
温度差（T1−T2）を計算し、調節器１７Ｂによ
り前記温度差（T1−T2）と規定値Tdを比較し
て弁開度Ａ１を求める。一方、調節器１７Ｃによ
り前記温度Ｔ２と規定値Tcを比較して弁開度Ａ
２を求め、さらに比較器（ハイセレクト）１７Ｄ
において弁開度Ａ１，Ａ２のうち大きいものを選
択し、その値に従つて膨張弁１６の開度を、冷却
用配管４での冷却能力が増加する方向に操作す
る。このとき、前記規定値Tdは天板温度とタン
ク１内の液体温度の温度差の目標値であり、10℃
以上が望ましく、また前記規定値Tcはタンク１
内の液体温度の目標値であり、重合性物質の重合
反応を抑制するためには20℃以下、できれば10℃
以下にすることが望ましい。 In the figure, the control device 17 first uses the arithmetic unit 17A to calculate the temperature by inputting the temperature T1 detected by the temperature sensor 3 for detecting the temperature of the top plate and the temperature T2 detected by the temperature sensor 5 for detecting the temperature of the liquid in the tank 1. The temperature difference (T1-T2) is calculated, and the temperature difference (T1-T2) is compared with the specified value Td by the regulator 17B to determine the valve opening degree A1. On the other hand, the regulator 17C compares the temperature T2 with the specified value Tc and determines the valve opening degree A.
Find 2 and then comparator (high select) 17D
The larger one of the valve openings A1 and A2 is selected, and the opening of the expansion valve 16 is operated in a direction that increases the cooling capacity of the cooling pipe 4 according to the selected value. At this time, the specified value Td is the target value of the temperature difference between the top plate temperature and the liquid temperature in the tank 1, and is 10°C.
The above is desirable, and the specified value Tc is
The target value for the liquid temperature in
It is desirable to do the following.
再び冷媒の流れを追うと、冷却用配管４を出た
冷媒は熱交換器１５に入り、熱交換器１３からの
冷媒を冷却した後、圧縮機７に戻り、以下前述の
サイクルを形成する。 Following the flow of the refrigerant again, the refrigerant that has exited the cooling pipe 4 enters the heat exchanger 15, cools the refrigerant from the heat exchanger 13, and then returns to the compressor 7, forming the cycle described above.
第３図は、熱交換器１５を示す概略図である。 FIG. 3 is a schematic diagram showing the heat exchanger 15.
図において、加熱用配管２を出て熱交換器１３
を経由した冷媒は、入口１５Ａから入り冷却さ
れ、出口１５Ｂから出て膨張弁１６に至る。一
方、冷却用配管４からの冷媒は、入口１５Ｃから
入り吸熱して、出口１５Ｄから出て圧縮機７に至
る。このとき、冷却用配管４を出た冷媒はほとん
どが気相であるが、液相であるものも混つてお
り、これがそのまま圧縮機７に送り込まれた場
合、圧縮器７のクランクケース内のオイルが冷え
すぎたり、最悪の場合、液圧縮により圧縮機７が
破損することもあるため、図に示すように入口１
５Ｃの前に立ち上りを設け、入口１５Ｃが出口１
５Ｄより低い位置になるように接続し、液相のま
ま通過するのを止める。 In the figure, the heat exchanger 13 exits the heating pipe 2.
The refrigerant that has passed through enters through the inlet 15A and is cooled, and exits through the outlet 15B and reaches the expansion valve 16. On the other hand, the refrigerant from the cooling pipe 4 enters through the inlet 15C, absorbs heat, and exits through the outlet 15D to reach the compressor 7. At this time, most of the refrigerant that exits the cooling pipe 4 is in the gas phase, but there is also some liquid phase mixed in, and if this is sent to the compressor 7 as it is, the oil in the crankcase of the compressor 7 If the compressor 7 becomes too cold, or in the worst case, the compressor 7 may be damaged due to liquid compression,
There is a rise in front of 5C, and the entrance 15C is the exit 1.
Connect it at a position lower than 5D to stop it from passing through in the liquid phase.
本実施例の装置においては、タンク１内の重合
性物質の気相部分に冷却用配管４を設けて、液相
部分の温度を低く抑えることにより、重合反応を
抑制するとともに液面からの蒸発を抑え、かつタ
ンク天板１Ａを加熱する加熱用配管２を設けて気
相部分を加熱することにより、タンク１内壁面で
の気相の重合性物質の凝縮を防止し、かつタンク
１内に貯蔵する重合性物質の重合反応を確実に防
止できるため、品質の低下を回避することが容易
にできる。 In the apparatus of this embodiment, a cooling pipe 4 is provided in the gas phase portion of the polymerizable substance in the tank 1 to keep the temperature of the liquid phase low, thereby suppressing the polymerization reaction and preventing evaporation from the liquid surface. By heating the gas phase portion by providing heating piping 2 that heats the tank top plate 1A, condensation of the polymerizable substance in the gas phase on the inner wall surface of the tank 1 is prevented, and Since polymerization reactions of stored polymerizable substances can be reliably prevented, deterioration in quality can be easily avoided.
前記加熱および冷却は、冷媒を用いた冷凍サイ
クルにより実現されているから、コンパクトな装
置とすることができ、かつ冷凍サイクルの加熱お
よび冷却の両方を有効に利用しているからエネル
ギーコストを節減できる。また、これらのサイク
ルは温度センサ３，５と制御装置１１，１７によ
り自動化されているから、設定に従い最適の状態
に制御することができる。 Since the heating and cooling are realized by a refrigeration cycle using a refrigerant, the device can be made compact, and since both the heating and cooling of the refrigeration cycle are effectively used, energy costs can be reduced. . Further, since these cycles are automated by the temperature sensors 3 and 5 and the control devices 11 and 17, they can be controlled to the optimum state according to the settings.
制御においては、天板温度Ｔ１と液体温度Ｔ２
との温度差（T1−T2）と規定値Tdを比較して
求めた弁開度Ａ１と、液体温度Ｔ２と規定値Tc
を比較して求めた弁開度Ａ２のうち大きいものを
比較器（ハイセレクト）１７Ｄにおいて選択し、
その値に従つて膨張弁１６の開度を操作すること
により、タンク１内の液相部分を常に充分低い温
度に保つことができ、重合反応を抑制するととも
に液面からの蒸発を抑えることができる。さらに
三方弁１０及びバイパス１２による過熱防止のた
めのインターロツク機構を設けたことで、加熱用
配管２が過熱して天板１Ａ及び他の装置への障害
や、タンク１内の液相部分にまで熱の影響が及ぶ
のを防ぐことができる。 In the control, the top plate temperature T1 and the liquid temperature T2
Valve opening degree A1 obtained by comparing the temperature difference (T1 - T2) with the specified value Td, the liquid temperature T2 and the specified value Tc
The comparator (high select) 17D selects the larger one among the valve opening degrees A2 obtained by comparing the
By controlling the opening degree of the expansion valve 16 according to this value, the liquid phase portion in the tank 1 can always be kept at a sufficiently low temperature, suppressing the polymerization reaction and suppressing evaporation from the liquid surface. can. Furthermore, by providing an interlock mechanism to prevent overheating using the three-way valve 10 and the bypass 12, the heating pipe 2 may overheat and damage the top plate 1A and other devices, or the liquid phase portion within the tank 1 may be damaged. It can prevent the effects of heat from reaching up to
これらの制御は全て電気的に処理されているこ
とから、制御系を一箇所に集めることで遠隔操作
による集中管理も可能となる。さらに、冷媒の圧
縮にはインバータ制御の圧縮機７を用いてエネル
ギー効率を高め、液相部分を冷却する冷却部をタ
ンク１内に設けて直接冷却としているから、この
点においてもエネルギーコストを節減できる。ま
た、液相部分を撹拌する撹拌ポンプ６を設けたこ
とで、重合性物質の液相部分の温度分布を一定に
することができ、さらに入荷時には移送されてき
た重合性物質の冷却時間を短縮することができる
とともに、出荷時には移送管内へ送り出された重
合性物質の温度をタンク内と同様な低い温度で送
り出すことができて、移送管内での重合反応を抑
えるという効果もある。 Since all of these controls are processed electrically, central management via remote control is also possible by centralizing the control systems in one place. Furthermore, an inverter-controlled compressor 7 is used to compress the refrigerant to improve energy efficiency, and a cooling section for cooling the liquid phase is provided in the tank 1 for direct cooling, reducing energy costs in this respect as well. can. In addition, by providing a stirring pump 6 that stirs the liquid phase part, it is possible to keep the temperature distribution of the liquid phase part of the polymerizable substance constant, and furthermore, the cooling time of the polymerizable substance transferred at the time of arrival can be shortened. In addition, the temperature of the polymerizable substance sent into the transfer pipe during shipping can be sent out at a low temperature similar to that in the tank, which has the effect of suppressing the polymerization reaction within the transfer pipe.
なお、前記実施例においては、コーンルーフ型
タンク１に貯蔵する例を示したが、ドーム型、あ
るいは平板状の天板をもつタンクにも応用可能で
あり、タンク１上部の天板１Ａに設けた加熱用配
管２は、天板１Ａに限らず側壁面１Ｂの上部の気
相部分に対応する部分にまで拡張して設けてもよ
い。さらに、圧縮機７を駆動するモータの制御方
法はインバータによる回転数制御にかぎらず、ア
ンロード制御等でもよい。 In the above embodiment, an example of storage in a cone-roof type tank 1 was shown, but it is also applicable to a tank with a dome-shaped or flat top plate. The heating piping 2 may be provided not only in the top plate 1A but also in a portion corresponding to the upper gaseous phase portion of the side wall surface 1B. Furthermore, the method of controlling the motor that drives the compressor 7 is not limited to rotation speed control using an inverter, but may also be unload control.
さらに、貯蔵する重合性物質としては、スチレ
ンモノマーに限らず、たとえばα−メチルスチレ
ンモノマー、アクリルニトリルモノマー等でもよ
く、冷媒としてはフレオン−22の他、フレオン−
12等を用いてもよく、重合防止剤としてパラター
シヤリブチルカテコール（TBC）を添加したが、
これは硫黄、あるいは一層良好な結果を得られる
ニトロソアミン化合物、２・４ジニトロフエノー
ルと２・６ジニトロフエノールの混合物でもよ
い。 Furthermore, the polymerizable substance to be stored is not limited to styrene monomer, but may also be, for example, α-methylstyrene monomer, acrylonitrile monomer, etc., and the refrigerant may be Freon-22 or Freon-22.
12 or the like may be used, and paratertiary butylcatechol (TBC) was added as a polymerization inhibitor, but
This may be sulfur or, with better results, a nitrosamine compound, a mixture of 2.4 and 2.6 dinitrophenol.
［発明の効果］
上記のように、本発明の重合性物質の貯蔵方法
によれば、タンク内の重合性物質の重合反応を防
ぐとともに、液面からの蒸発を抑え、また気相の
重合性物質のタンク内での凝縮による液滴内での
重合反応を抑えることにより、ポリマーの発生を
防ぎ、品質の低下を回避することを容易かつ効率
よく行なうことができるという効果がある。[Effects of the Invention] As described above, according to the method for storing a polymerizable substance of the present invention, the polymerization reaction of the polymerizable substance in the tank is prevented, evaporation from the liquid surface is suppressed, and the polymerizability of the gas phase is reduced. By suppressing the polymerization reaction within the droplets due to condensation of the substance within the tank, it is possible to prevent the generation of polymers and to avoid deterioration in quality easily and efficiently.
第１図は本発明の方法を実施する貯蔵タンクの
装置の一例を示す概略図、第２図は第１図におけ
る膨張弁の制御の流れを示す図、第３図は第１図
の一方の熱交換器を示す概略構成図である。
１……タンク、１Ａ……天板、２……冷却用配
管、３，５……温度センサ、４……冷却用配管、
７……圧縮器、１１，１７……制御装置、１３，
１５……熱交換器、１６……膨張弁。
FIG. 1 is a schematic diagram showing an example of a storage tank device for carrying out the method of the present invention, FIG. 2 is a diagram showing the flow of control of the expansion valve in FIG. 1, and FIG. FIG. 2 is a schematic configuration diagram showing a heat exchanger. 1... Tank, 1A... Top plate, 2... Cooling piping, 3, 5... Temperature sensor, 4... Cooling piping,
7... Compressor, 11, 17... Control device, 13,
15... Heat exchanger, 16... Expansion valve.
Claims (1)
合性物質の貯蔵方法であつて、 前記タンク内に収納された重合性物質の液相部
分を冷却するための冷却部と、前記タンク内上部
の気相部分に対応する壁面を加熱するための加熱
部と、前記冷却部と加熱部との間に冷媒を循環さ
せて加熱部で放熱しかつ冷却部で吸熱する冷凍サ
イクルとを設け、前記冷凍サイクルの膨張弁を開
度調節可能としておき、 前記加熱部の温度と前記タンク内の液相部分温
度との温度差を予め設定しておいた値と比較して
膨張弁の開度を求め、前記液相部分温度を予め設
定しておいた値と比較して膨張弁の開度を求め、
これらの開度のうち大きいほうの開度に従い前記
膨張弁を調節することを特徴とする重合性物質の
貯蔵方法。 ２ 特許請求の範囲第１項において、前記加熱部
の温度が予め設定しておいた値より高い場合、冷
媒の流路を切換えて加熱部への冷媒導通を遮断す
ることを特徴とする重合性物質の貯蔵方法。 ３ 特許請求の範囲第１項または第２項におい
て、前記加熱部で放熱した冷媒を熱交換器に導通
し、さらに冷却してから膨張弁で断熱膨張させる
ことを特徴とする重合性物質の貯蔵方法。[Scope of Claims] 1. A method for storing a polymerizable substance in a storage tank, comprising: a cooling unit for cooling a liquid phase portion of the polymerizable substance stored in the tank; , a heating section for heating a wall surface corresponding to the gas phase portion in the upper part of the tank, and a refrigeration cycle in which a refrigerant is circulated between the cooling section and the heating section to radiate heat in the heating section and absorb heat in the cooling section. The opening of the expansion valve of the refrigeration cycle is adjustable, and the temperature difference between the temperature of the heating section and the temperature of the liquid phase portion in the tank is compared with a preset value, and the opening of the expansion valve of the refrigeration cycle is adjusted. Find the opening degree of the expansion valve by comparing the liquid phase temperature with a preset value,
A method for storing a polymeric substance, characterized in that the expansion valve is adjusted according to the larger of these opening degrees. 2. According to claim 1, the polymerizable method is characterized in that when the temperature of the heating section is higher than a preset value, the flow path of the refrigerant is switched to cut off the refrigerant conduction to the heating section. How to store substances. 3. Storage of a polymerizable substance according to claim 1 or 2, characterized in that the refrigerant radiated by the heating section is passed through a heat exchanger, further cooled, and then adiabatically expanded by an expansion valve. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11739985A JPS61275232A (en) | 1985-05-30 | 1985-05-30 | Storage of polymerizable substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11739985A JPS61275232A (en) | 1985-05-30 | 1985-05-30 | Storage of polymerizable substance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61275232A JPS61275232A (en) | 1986-12-05 |
| JPH0335301B2 true JPH0335301B2 (en) | 1991-05-27 |
Family
ID=14710685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11739985A Granted JPS61275232A (en) | 1985-05-30 | 1985-05-30 | Storage of polymerizable substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61275232A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6615914B1 (en) * | 1999-06-02 | 2003-09-09 | Li Young | Programmable, heatable, coolable reaction vessel utilizing phase change refrigeration |
| JP5085164B2 (en) * | 2007-03-09 | 2012-11-28 | ダイヤニトリックス株式会社 | Acrylamide aqueous solution storage tank |
| JP6070221B2 (en) * | 2013-01-29 | 2017-02-01 | 三菱化学株式会社 | Storage tank for easily polymerizable compounds |
| JP6237563B2 (en) * | 2014-10-09 | 2017-11-29 | 三菱ケミカル株式会社 | Storage tank equipment and storage method for easily polymerizable compounds |
| JP6281623B2 (en) * | 2016-11-07 | 2018-02-21 | 三菱ケミカル株式会社 | Storage method for easily polymerizable compounds |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6048938A (en) * | 1983-08-29 | 1985-03-16 | Idemitsu Petrochem Co Ltd | Apparatus for storing thermally polymerizable monomer |
-
1985
- 1985-05-30 JP JP11739985A patent/JPS61275232A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6048938A (en) * | 1983-08-29 | 1985-03-16 | Idemitsu Petrochem Co Ltd | Apparatus for storing thermally polymerizable monomer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61275232A (en) | 1986-12-05 |
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