JP4845173B2 - Method and apparatus for adiabatic cooling crystallization of organic compounds - Google Patents

Method and apparatus for adiabatic cooling crystallization of organic compounds Download PDF

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JP4845173B2
JP4845173B2 JP2005100174A JP2005100174A JP4845173B2 JP 4845173 B2 JP4845173 B2 JP 4845173B2 JP 2005100174 A JP2005100174 A JP 2005100174A JP 2005100174 A JP2005100174 A JP 2005100174A JP 4845173 B2 JP4845173 B2 JP 4845173B2
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敬三 竹上
浩司 三輪
究 石井
順司 若山
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Tsukishima Kikai Co Ltd
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Description

本発明は、有機化合物の断熱冷却式晶析方法及び装置に関する。特に、パラキシレンの結晶体を得るに適した方法及び装置に係るものである。   The present invention relates to an adiabatic cooling crystallization method and apparatus for organic compounds. In particular, the present invention relates to a method and apparatus suitable for obtaining paraxylene crystals.

ある種の異性体混合物の分離・精製は、混合物を構成する成分の沸点が近接しているために、蒸留操作では困難である。しかし、分子構造の相違により融点は大きく相違する場合が多いために、晶析操作による分離が有効であることが多い。   Separation and purification of a certain isomer mixture is difficult by distillation operation because the boiling points of the components constituting the mixture are close to each other. However, since melting points often differ greatly due to differences in molecular structure, separation by crystallization operation is often effective.

共晶２成分系や共晶多成分系に第３成分として溶剤（抽剤、付加剤）を加えた抽出晶析や付加化合物晶析があるが、溶剤の回収に難がある。   There are extraction crystallization and addition compound crystallization in which a solvent (extractant, additive) is added as a third component to the eutectic two-component system or the eutectic multi-component system, but it is difficult to recover the solvent.

その点、冷媒として、液化ガス成分を使用する場合には、その回収が容易であるので有効な方法である。   In this regard, when a liquefied gas component is used as the refrigerant, it is an effective method because it can be easily recovered.

本発明者は、石油化学の工業プロセスにおける典型的なｐ−キシレン製造における原料である混合キシレン（ｍ−キシレン＋ｏ−キシレン＋エチルベンゼン＋ｐ−キシレン系）や異性化反応後の混合キシレン（ｍ−キシレン＋ｏ−キシレン＋ｐ−キシレン系）などの共晶多成分系に冷媒として、プロパン（またはプロピレン、エチレン、炭酸ガス、アンモニアなど）を使用して晶析操作を行うことが有効であることを知見した。   The inventor of the present invention uses mixed xylene (m-xylene + o-xylene + ethylbenzene + p-xylene system), which is a raw material in typical p-xylene production in petrochemical industrial processes, and mixed xylene (m-xylene) after isomerization reaction. + O-xylene + p-xylene system) and other eutectic multicomponent systems were found to be effective to perform crystallization operation using propane (or propylene, ethylene, carbon dioxide, ammonia, etc.) as a refrigerant. .

この場合、ジャケット式晶析槽で晶析操作を行うことも可能ではあるものの、前記の共晶多成分系におけるｐ−キシレンは−３０℃〜−６０℃程度に冷却して晶析する必要があり、このために、晶析槽を冷却面掻取り機構付きとし、ジャケットからの冷媒をコンプレッサーで圧縮し、たとえば２０気圧の高圧下で凝縮させ、これをジャケットに循環させる冷媒系が必要となる。   In this case, although it is possible to perform the crystallization operation in a jacket type crystallization tank, the p-xylene in the eutectic multicomponent system needs to be cooled to about -30 ° C to -60 ° C for crystallization. For this reason, a refrigeration system is required in which the crystallization tank is equipped with a cooling surface scraping mechanism, the refrigerant from the jacket is compressed by a compressor, condensed, for example, under a high pressure of 20 atm, and circulated through the jacket. .

これでは、コンプレッサーの動力費が嵩むだけでなく、晶析槽を複雑で度々のメンテナンスが必要な冷却面掻取り機構を装備させなければならないので、設備コスト及びメンテナンスコストが嵩む。   This not only increases the power cost of the compressor but also increases the equipment cost and maintenance cost because the crystallization tank must be equipped with a cooling surface scraping mechanism that is complicated and requires frequent maintenance.

そこで、ヒートポンプを利用する形態も考えられるが（特許文献１）、ヒートポンプを構成する装置コストと必ずしも見合うシステムとは言い難い。
特開平４―３２７５４２号公報 Then, although the form using a heat pump is also considered (patent document 1), it is hard to say that it is a system which always corresponds to the device cost which constitutes a heat pump.
JP-A-4-327542

したがって、本発明の主たる課題は、運転費（メンテナンス費も含む）及び設備費を低減できる有機化合物の断熱冷却式晶析方法及び装置を提供することにある。   Accordingly, a main object of the present invention is to provide an adiabatic cooling crystallization method and apparatus for organic compounds that can reduce operating costs (including maintenance costs) and equipment costs.

他の課題は、ｐ−キシレンの晶析に適した方法及び装置を提供することにある。   Another object is to provide a method and apparatus suitable for crystallization of p-xylene.

上記課題を解決した本発明は次記のとおりである。
＜請求項１項記載の発明＞
結晶槽においてプロパンを含む対象のパラキシレンを含む混合キシレンに対して、プロパンの断熱冷却、蒸発操作を行い、
この操作により生成した結晶スラリーは前記結晶槽から抜き出し、
蒸発したプロパンベーパーは圧縮機により加圧し、吸収凝縮器に導き、
前記結晶槽の操作圧力を常圧付近または高くとも４気圧とし、かつ、前記圧縮機による加圧を前記結晶槽の操作圧力以下とし、
前記吸収凝縮器において、前記パラキシレンを含む混合キシレンと加圧された前記プロパンベーパーとを接触させながら冷却水を通水した冷却管で冷却して前記プロパンベーパーの凝縮を図り、吸収凝縮液を生成し、この吸収凝縮液を前記結晶槽に導くとともに、
前記凝縮液を前記結晶槽に導く前に設置した蒸発缶において、あらかじめ所要量の前記プロパンの断熱冷却、蒸発操作を行うことで、次の結晶槽における急激な断熱冷却を防ぎ、結晶槽内全体の結晶を含む母液を下部から上部へ良く循環させて略均一な過飽和状態とし、
前記蒸発缶における蒸発ベーパーは前記圧縮機により前記結晶槽の操作圧力以上に加圧して、前記結晶槽からの蒸発ベーパーと共に前記吸収凝縮器に導き、
前記結晶槽において精製した結晶スラリーからパラキシレン結晶を得る、ことを特徴とする有機化合物の断熱冷却式晶析方法。 The present invention that has solved the above problems is as follows.
<Invention of Claim 1>
Perform adiabatic cooling and evaporation of propane for mixed xylene containing paraxylene, which contains propane in the crystallization tank,
The crystal slurry generated by this operation is extracted from the crystal tank,
The evaporated propane vapor is pressurized by a compressor and led to an absorption condenser,
The operation pressure of the crystallization tank is close to normal pressure or at most 4 atmospheres, and the pressurization by the compressor is less than or equal to the operation pressure of the crystallization tank,
In the absorption condenser, the mixed xylene containing para-xylene and the pressurized propane vapor are brought into contact with each other and cooled by a cooling pipe through which cooling water is passed to condense the propane vapor, and the absorption condensate is obtained. Producing and leading this absorption condensate to the crystallization vessel,
In the evaporator installed before introducing the condensate into the crystallization tank, adiabatic cooling and evaporation operation of the required amount of the propane in advance is performed to prevent rapid adiabatic cooling in the next crystallization tank and The mother liquor containing crystals of
The evaporation vapor in the evaporator is pressurized by the compressor above the operating pressure of the crystallization tank and led to the absorption condenser together with the evaporation vapor from the crystallization tank,
An adiabatic cooling crystallization method for an organic compound, characterized in that para-xylene crystals are obtained from a crystal slurry purified in the crystallization tank .

（作用効果）
結晶槽において冷媒を含む対象の有機化合物の混合溶液に対して、冷媒の断熱冷却、蒸発操作を行うと、実質的には冷媒液成分だけの蒸発に伴い結晶化熱が奪い取られ、結晶が析出する。蒸発ベーパーは圧縮機により前記結晶槽の操作圧力以上に加圧し、吸収凝縮器に導き凝縮を図る。蒸発ベーパーを圧縮機により結晶槽の操作圧力以上に加圧する理由は、一般の冷凍サイクルのように凝縮のための温度差を圧縮機により加圧により確保するためである。吸収凝縮器においては、蒸気圧が低い有機化合物の混合溶液と接触するので、沸点上昇が生じ、吸収、凝縮できる温度が高まる。したがって、必要な加圧の度合いが小さくて足り、凝縮に必要な外部からの投入エネルギーが小さいもので足りる。 (Function and effect)
When the refrigerant is subjected to adiabatic cooling and evaporation of the mixed solution of the target organic compound containing the refrigerant in the crystallization tank, the crystallization heat is substantially taken away by evaporation of only the refrigerant liquid component, and crystals are deposited. To do. The evaporation vapor is pressurized by the compressor to a pressure higher than the operating pressure of the crystal tank and led to an absorption condenser for condensation. The reason why the evaporation vapor is pressurized to a pressure higher than the operation pressure of the crystallization tank by the compressor is to secure a temperature difference for condensation by pressurization by the compressor as in a general refrigeration cycle. In the absorption condenser, since it comes into contact with a mixed solution of an organic compound having a low vapor pressure, the boiling point rises and the temperature at which absorption and condensation can be increased. Therefore, it is sufficient that the degree of pressurization required is small and the input energy required for condensation is small.

吸収凝縮器での凝縮液は前記結晶槽に導くことで、連続的に晶析操作が可能である。ｐ−キシレンの晶析を例に採ると、冷媒としてプロパンを使用し、結晶槽では、たとえば常圧であり、吸収凝縮器では圧縮機による加圧によりたとえば８気圧程度である。
結晶槽の操作圧力（蒸発圧力）としては、結晶槽などに要求される耐圧性や生成結晶の分離方法、装置を考えた場合、常圧付近で操作するのが望ましく、高くとも４気圧とするのが望ましい。 The condensate in the absorption condenser can be continuously crystallized by introducing it into the crystal tank. Taking crystallization of p-xylene as an example, propane is used as a refrigerant, and in a crystallization tank, for example, normal pressure, and in an absorption condenser, for example, about 8 atm due to pressurization by a compressor.
As for the operation pressure (evaporation pressure) of the crystal tank, it is desirable to operate near normal pressure, considering the pressure resistance required for the crystal tank and the separation method and apparatus of the produced crystal, and at most 4 atm. Is desirable.

結晶槽で生成した結晶スラリーは抜き出し、固液分離手段により結晶分と母液とに分離し、結晶分はそのまま、必要により精製手段により精製し純度を高めて、製品化する。   The crystal slurry generated in the crystallization tank is extracted and separated into a crystal component and a mother liquor by solid-liquid separation means, and the crystal component is purified as it is by a purification means if necessary to be commercialized.

かかる操作によれば、結晶槽を耐圧容器とすることなく晶析操作が可能である。そして、最低限には圧縮機と吸収凝縮器とで足りるので、先行技術のような高価なヒートポンプ設備構成とする必要がないことも相俟って、システム全体及び運転コストの点で経済的である。   According to such an operation, a crystallization operation can be performed without using the crystallization tank as a pressure vessel. In addition, since the compressor and the absorption condenser are at a minimum, it is not necessary to use an expensive heat pump equipment configuration as in the prior art, so that it is economical in terms of the entire system and operating costs. is there.

他方、本発明では、凝縮液を結晶槽に導く前に設置した蒸発缶において、あらかじめ所要量の前記冷媒の断熱冷却、蒸発操作を行い、蒸発缶における蒸発ベーパーは圧縮機により結晶槽の操作圧力以上に加圧して、結晶槽からの蒸発ベーパーと共に吸収凝縮器に導くものである。   On the other hand, in the present invention, in the evaporator installed before the condensate is led to the crystallization tank, the required amount of the refrigerant is adiabatically cooled and evaporated in advance. The pressure is applied to the absorption condenser together with the evaporation vapor from the crystal tank.

前述の構成では、圧縮機により加圧された吸収凝縮液が結晶槽に導かれることになる。そこで、この吸収凝縮器での凝縮液を直接結晶槽へ導くと、結晶槽に導入した時点で、大きな圧力低下によって激しい発泡と同時に晶析が直ちに生じ、大きな結晶を得難い。晶析分離プロセスに於いては、製造した結晶粒の大きさが最後の製品の高純度生成において、大きなメリットを生む。この現象は、吸収凝縮器での凝縮液の温度と結晶が生じる温度との温度差、吸収凝縮器での凝縮液中の冷媒濃度と結晶が生じる結晶槽中における冷媒濃度との濃度差も影響していることが知見されている。   In the above-described configuration, the absorption condensate pressurized by the compressor is guided to the crystallization tank. Therefore, when the condensate in this absorption condenser is introduced directly into the crystallization tank, when it is introduced into the crystallization tank, crystallization immediately occurs simultaneously with severe foaming due to a large pressure drop, making it difficult to obtain large crystals. In the crystallization separation process, the size of the produced crystal grains has a great merit in producing the final product with high purity. This phenomenon is also affected by the temperature difference between the temperature of the condensate in the absorption condenser and the temperature at which crystals form, and the difference in concentration between the refrigerant in the condensate at the absorption condenser and the refrigerant concentration in the crystal tank in which crystals form. It has been found that

結晶槽中では、結晶槽内全体の結晶を含む母液が、可能な限り均一な過飽和の状態にあり、下部から上部に良く循環されているのが望ましい。したがって、圧縮機により加圧された凝縮液が直接、結晶槽に導かれ、直ちに蒸発が起こると供給液だけが激しく冷却される現象が生じるので、これをできるだけ少なくし、既に結晶槽に内在する母液と速やかに混合することが大きな結晶を得るために望ましい。そこで、前記凝縮液を前記結晶槽に導く前に、蒸発缶においてあらかじめ所要量の前記冷媒の断熱冷却、蒸発操作を行うことが、大きな結晶を得る上で望ましく、上記の阻害要因（圧力差、温度差、冷媒濃度差）を排除できる。この方法は、先行（断熱自己）蒸発（プレフラッシュ）とも言うべき技術である。また、かかる方法によれば、予め蒸発缶において、冷媒の断熱冷却、蒸発操作を行うので、結晶槽での蒸発の負荷を減らすことができ、装置をコンパクトに設計でき、設備費の低減に繋がるとともに、結晶缶内における急激な蒸発による圧力変動を緩衝する作用をもたらし、システムの制御を容易ならしめる機能を果たす。   In the crystallization tank, it is desirable that the mother liquor containing the entire crystal in the crystallization tank is as uniformly supersaturated as possible and is circulated well from the lower part to the upper part. Therefore, the condensate pressurized by the compressor is directly guided to the crystal tank, and if evaporation occurs immediately, only the supply liquid is cooled violently, so this is reduced as much as possible and is already in the crystal tank. Prompt mixing with the mother liquor is desirable to obtain large crystals. Therefore, it is desirable to perform adiabatic cooling and evaporation operation of the required amount of the refrigerant in advance in an evaporator before introducing the condensate into the crystallization tank, in order to obtain a large crystal. Temperature difference and refrigerant concentration difference) can be eliminated. This method is a technique that should be referred to as prior (adiabatic self) evaporation (pre-flush). Also, according to this method, since the refrigerant is adiabatically cooled and evaporated in advance in the evaporator, the evaporation load in the crystallization tank can be reduced, the apparatus can be designed compactly, and the equipment cost can be reduced. At the same time, it acts to buffer pressure fluctuations caused by rapid evaporation in the crystal can, thereby facilitating control of the system.

＜請求項２項記載の発明＞
前記結晶槽から抜き出した結晶スラリーを固液分離し、分離された母液を前記吸収凝縮器に返送する請求項１記載の有機化合物の断熱冷却式晶析方法。 <Invention of Claim 2>
The adiabatic cooling crystallization method for an organic compound according to claim 1, wherein the crystal slurry extracted from the crystallization tank is subjected to solid-liquid separation, and the separated mother liquor is returned to the absorption condenser.

（作用効果）
吸収凝縮器では、有機化合物の混合溶液を供給して加圧蒸発ベーパーとの接触を図るほか、前記結晶槽から抜き出した結晶スラリーを固液分離し、分離された母液を前記吸収凝縮器に返送することで、加圧蒸発ベーパーとの接触を図ることができる。いずれの形態を採るかは、対象の有機化合物の種別や目的の有機化合物の混合溶液中での濃度、操作条件などにより選択できる。ここで、固液分離のための設備や工程に限定はないが、たとえば遠心分離機、ろ過機、溶融精製塔、ピストン式ないしはスクリュー式の洗浄塔などを挙げることができる。 (Function and effect)
In the absorption condenser, a mixed solution of organic compounds is supplied to make contact with the pressurized evaporation vapor, and the crystal slurry extracted from the crystallization tank is subjected to solid-liquid separation, and the separated mother liquor is returned to the absorption condenser. By doing so, contact with the pressure evaporation vapor can be achieved. Which form is adopted can be selected depending on the type of the target organic compound, the concentration of the target organic compound in the mixed solution, the operating conditions, and the like. Here, the facilities and processes for solid-liquid separation are not limited, and examples thereof include a centrifugal separator, a filter, a melt purification tower, a piston type or screw type washing tower, and the like.

＜請求項３項記載の発明＞
前記吸収凝縮器から結晶槽に導く吸収凝縮液の冷媒濃度が１〜７０％とする請求項１記載の有機化合物の断熱冷却式晶析方法。 <Invention of Claim 3 >
The adiabatic cooling crystallization method of an organic compound according to claim 1, wherein the refrigerant concentration of the absorption condensate led from the absorption condenser to the crystallization tank is 1 to 70%.

（作用効果）
吸収凝縮液の冷媒濃度が濃くなると結晶化点が下がり蒸気圧も下がる。吸収凝縮液の冷媒濃度が薄くなると、分圧の関係で蒸気圧が下がる。したがって、蒸気圧の最高点が存在する。吸収凝縮液の冷媒濃度が１〜７０％であれば、蒸気圧の最高点付近での操作が可能である。 (Function and effect)
As the refrigerant concentration in the absorption condensate increases, the crystallization point decreases and the vapor pressure also decreases. When the refrigerant concentration of the absorption condensate becomes thin, the vapor pressure decreases due to the partial pressure. Therefore, there is a maximum point of vapor pressure. If the refrigerant concentration of the absorption condensate is 1 to 70%, operation near the highest point of the vapor pressure is possible.

以上の作用効果な欄で記載した効果をまとめれば、冷却晶出設備において、避けられない、冷却面に析出する結晶を掻き取る装置を設備することなく、冷却（冷凍）でき、かつ、その冷却（冷凍）のための用役エネルギーの必要量を低減でき、もって運転費及び設備費を低減できる。さらに、ｐ−キシレンの晶析に適したものとなる。   Summarizing the effects described in the above operational effect column, cooling (freezing) can be performed without installing an apparatus for scraping off crystals deposited on the cooling surface, which is inevitable in the cooling crystallization facility, and the cooling. The required amount of utility energy for (freezing) can be reduced, thereby reducing operating costs and equipment costs. Furthermore, it becomes suitable for crystallization of p-xylene.

また、吸収凝縮器と前記結晶槽との間に設置した蒸発缶において、あらかじめ所要量の冷媒の断熱冷却、蒸発操作を行い、蒸発缶における蒸発ベーパーは圧縮機により結晶槽の操作圧力以上に加圧して、結晶槽からの蒸発ベーパーと共に吸収凝縮器に導く。その結果、結晶槽での蒸発の負荷を減らすことができるとともに、大きな結晶を得ることができる。   In addition, the evaporator installed between the absorption condenser and the crystallization tank is subjected to adiabatic cooling and evaporation of the required amount of refrigerant in advance, and the evaporation vapor in the evaporator is pressurized by the compressor above the operating pressure of the crystallization tank. And lead to the absorption condenser together with the evaporated vapor from the crystallizer. As a result, it is possible to reduce the evaporation load in the crystal tank and to obtain a large crystal.

以下本発明の実施形態を挙げてさらに詳説する。
＜第１の実施の形態＞
図１は、基本的な実施の形態を示したもので、吸収凝縮器１０、結晶槽２０、圧縮機３０及び固液分離手段４０を有する。 Hereinafter, the present invention will be described in further detail with reference to embodiments.
<First Embodiment>
FIG. 1 shows a basic embodiment, which includes an absorption condenser 10, a crystal tank 20, a compressor 30, and a solid-liquid separation means 40.

冷媒を含む対象の有機化合物の混合溶液１（晶析操作の対象液。たとえば、ｐ−キシレン及びその異性体を含む共晶多成分系混合物の液）が吸収凝縮器１０に導かれ、ここで冷媒ベーパー（たとえばプロパン）を吸収して凝縮させ、均質な冷媒混合液とする。   A mixed solution 1 of a target organic compound containing a refrigerant (a target liquid for crystallization operation, for example, a liquid of a eutectic multicomponent mixture containing p-xylene and its isomer) is led to an absorption condenser 10, where Refrigerant vapor (for example, propane) is absorbed and condensed to form a homogeneous refrigerant mixture.

この吸収凝縮器１０からの均質な冷媒混合液は、管路６１Ａにより蒸発缶５０に導く。この蒸発缶５０において、あらかじめ所要量の冷媒の断熱冷却、蒸発操作を行う。   The homogeneous refrigerant mixture from the absorption condenser 10 is guided to the evaporator 50 by the pipe 61A. In this evaporator 50, adiabatic cooling and evaporation operation of a required amount of refrigerant is performed in advance.

蒸発缶５０からの冷媒混合液は、管路６１を通して結晶槽２０に導入し、結晶槽２０において冷媒を含む凝縮液に対して、冷媒の断熱冷却、蒸発操作を行う。   The refrigerant mixed liquid from the evaporator 50 is introduced into the crystallization tank 20 through the pipe 61, and the refrigerant is subjected to adiabatic cooling and evaporation of the condensate containing the refrigerant in the crystallization tank 20.

この操作により生成した結晶スラリーは結晶槽２０からポンプ６２により抜き出し、遠心分離機や液体サイクロンなどの固液分離手段４０により結晶分流れＣｒと母液流れＭｏとに分離する。   The crystal slurry generated by this operation is extracted from the crystal tank 20 by a pump 62 and separated into a crystal fraction stream Cr and a mother liquor stream Mo by a solid-liquid separation means 40 such as a centrifugal separator or a liquid cyclone.

結晶槽２０での蒸発ベーパーは管路６３を通し、圧縮機３０により前記結晶槽２０の操作圧力以上に加圧し、吸収凝縮器１０に導く。前記の蒸発缶５０における蒸発ベーパーについても、管路６１Ｂを通し、圧縮機３０により前記結晶槽２０の操作圧力以上に加圧し、吸収凝縮器１０に導く。 The evaporation vapor in the crystallization tank 20 passes through the pipe line 63, is pressurized to a pressure higher than the operating pressure of the crystallization tank 20 by the compressor 30, and is led to the absorption condenser 10. The evaporation vapor in the evaporator 50 is also pressurized through the pipe 61B to a pressure higher than the operating pressure of the crystallization tank 20 by the compressor 30 and led to the absorption condenser 10.

吸収凝縮器１０において、前記有機化合物の混合溶液（混合液１）と加圧された前記蒸発ベーパーとを接触させながら、冷却媒体２（たとえば冷水塔冷却水、冷凍機のブラインなど）のもっている冷熱により冷却して吸収凝縮を図り、この吸収凝縮液を蒸発缶５０を通して前記結晶槽２０に導くのである。   The absorption condenser 10 has a cooling medium 2 (for example, cooling water tower cooling water, refrigerator brine, etc.) while bringing the mixed solution of organic compounds (mixed liquid 1) and the pressurized vaporized vapor into contact with each other. Cooling by cold heat is performed for absorption condensation, and this absorption condensate is guided to the crystal tank 20 through the evaporator 50.

結晶槽２０において冷媒液成分を含む対象の有機化合物混合液に対して、冷媒液成分の断熱冷却、蒸発操作を行うと、冷媒液成分の蒸発に伴い結晶化熱が奪い取られ、結晶が析出する。蒸発ベーパーは圧縮機３０により前記結晶槽２０の操作圧力以上に加圧し、吸収凝縮器１０に導き吸収凝縮を図る。   When the adiabatic cooling and evaporating operation of the refrigerant liquid component is performed on the target organic compound mixed liquid containing the refrigerant liquid component in the crystallization tank 20, the heat of crystallization is taken away with the evaporation of the refrigerant liquid component, and crystals are deposited. . The evaporating vapor is pressurized by the compressor 30 to a pressure higher than the operating pressure of the crystal tank 20 and led to the absorption condenser 10 for absorption condensation.

圧縮機（加圧機）３０を設けて蒸発ベーパーの加圧を行うのは、結晶槽２０の運転温度よりはるかに高温で冷媒を再凝縮させるための、結晶槽２０と吸収凝縮器１０との温度差を、圧縮機（加圧機）３０により加圧することにより確保するものである。ｐ−キシレンの晶析を例に採ると、冷媒としてプロパンを使用し、結晶槽２０では、たとえば常圧であり、吸収凝縮器１０では、圧縮機３０による加圧により、たとえば８気圧程度である。   The reason why the compressor (pressurizer) 30 is provided to pressurize the evaporation vapor is that the temperatures of the crystal tank 20 and the absorption condenser 10 for recondensing the refrigerant at a temperature much higher than the operating temperature of the crystal tank 20. The difference is secured by pressurizing with a compressor (pressurizer) 30. Taking crystallization of p-xylene as an example, propane is used as a refrigerant, the crystallization tank 20 is, for example, normal pressure, and the absorption condenser 10 is, for example, about 8 atm due to pressurization by the compressor 30. .

吸収凝縮器１０においては、沸点の高い有機化合物の溶解液と接触するので、沸点上昇が生じ、吸収凝縮できる温度が高まる。したがって、吸収凝縮に必要な外部からの投入エネルギーが小さいもので足りる。   Since the absorption condenser 10 is in contact with a solution of an organic compound having a high boiling point, the boiling point rises and the temperature at which absorption and condensation can be increased. Therefore, a small amount of external input energy necessary for absorption condensation is sufficient.

結晶槽２０で生成した結晶スラリーは抜き出し、固液分離手段により結晶分流れＣｒと母液流れＭｏとにより分離し、結晶分流れＣｒはそのまま、必要により後述のように、精製手段や洗浄手段により精製し純度を高めて、製品化する。   The crystal slurry produced in the crystallization tank 20 is extracted and separated by the crystal fraction stream Cr and the mother liquor stream Mo by solid-liquid separation means, and the crystal fraction stream Cr is purified as it is, if necessary, by purification means and washing means as described later. The product is then commercialized with increased purity.

かかる操作によれば、結晶槽２０を耐高圧容器とすることなく晶析操作が可能である。そして、最低限には結晶槽２０と圧縮機３０と吸収凝縮器１０とで足りるので、先行技術のような高価なヒートポンプ設備構成とする必要がないことも相俟って、システム全体及び運転コストの点で経済的である。   According to this operation, the crystallization operation can be performed without using the crystallization tank 20 as a high pressure resistant container. Since the crystal tank 20, the compressor 30, and the absorption condenser 10 are sufficient at the minimum, it is not necessary to have an expensive heat pump equipment configuration as in the prior art. Is economical in terms of

＜第２の実施の形態＞
図２は第２の実施の形態を示したもので、結晶槽２０から抜き出した結晶スラリーを固液分離手段４０により固液分離し、分離された母液流れＭｏを管路６４を通して吸収凝縮器１０に返送するものである。固液分離手段４０での濾液に溶存した状態で系外へ排出された分の冷媒は後段の蒸留塔による回収や、メークアップとして圧縮機３０のサクション部に供給することができる（図１も参照）。
当初の有機化合物の混合溶液１は、直接結晶槽２０に供給するようにしてもよい。 <Second Embodiment>
FIG. 2 shows a second embodiment, in which the crystal slurry extracted from the crystallization tank 20 is solid-liquid separated by the solid-liquid separation means 40, and the separated mother liquor stream Mo is passed through the pipe 64 to the absorption condenser 10. To be returned to. The refrigerant discharged from the system in a state dissolved in the filtrate in the solid-liquid separation means 40 can be supplied to the suction section of the compressor 30 as a recovery by a subsequent distillation tower or as a make-up (FIG. 1 also). reference).
The original organic compound mixed solution 1 may be directly supplied to the crystallization tank 20.

＜晶析法の説明＞
ベンゼン―シクロヘキサン系の例によって、晶析法の説明を行う。
化学工業での一般的な製造では、シクロヘキサンはベンゼンを水素化して生成される。
Ｃ6Ｈ6 ＋３Ｈ2 → Ｃ6Ｈ12
この水素化反応に際して、副反応により次のような不純物が生成される。
メチルシクロペンタン
ｎ−ヘキサン
ｎ−ペンタン
メチルシクロヘキサン
さらに、原料ベンゼン中に含まれるトルエン、パラフィン類が含まれてくる。 <Description of crystallization method>
The crystallization method will be explained using an example of the benzene-cyclohexane system.
In a common production in the chemical industry, cyclohexane is produced by hydrogenating benzene.
C 6 H 6 + 3H 2 → C 6 H 12
In this hydrogenation reaction, the following impurities are generated by side reactions.
Methylcyclopentane n-hexane n-pentane methylcyclohexane Furthermore, toluene and paraffin contained in the raw material benzene are included.

こうした場合に、高純度シクロヘキサンを得る上で最も難しい点は、未反応のベンゼンが含まれた場合に、蒸留では分離することがほとんど不可能になることである。ベンゼンの常圧での沸点は８０．７５℃で、シクロヘキサンの沸点は８０．１６℃である。その差は、僅かに０．５９℃しかない。さらに、５４％付近に最低共沸点（７７．６２℃）がある。   In such a case, the most difficult point in obtaining high-purity cyclohexane is that when unreacted benzene is contained, it is almost impossible to separate by distillation. The boiling point of benzene at normal pressure is 80.75 ° C., and the boiling point of cyclohexane is 80.16 ° C. The difference is only 0.59 ° C. Furthermore, there is a minimum azeotropic point (77.62 ° C.) in the vicinity of 54%.

これに対し、図３に示す、プロパン−ベンゼン−シクロヘキサン系の共晶組成における固液平衡図から判るように、高純度シクロヘキサンを得ようとした場合、晶析して分離精製する方法が採れる。そして、一緒に含まれる少量のメチルシクロペンタンなどの不純物も同時に除去できることになる。   On the other hand, as can be seen from the solid-liquid equilibrium diagram in the propane-benzene-cyclohexane eutectic composition shown in FIG. 3, when obtaining high-purity cyclohexane, a method of crystallization and separation and purification can be employed. And a small amount of impurities such as methylcyclopentane contained together can be removed at the same time.

すなわち、相図上では、シクロヘキサンとベンゼンの２成分系の固液平衡線が求まる。この時、微量不純物の含有は僅かに、結晶化点カーブを下げるだけで、実質上の大きな差はない。ここでシクロヘキサンリッチの混合原料を冷却しシクロヘキサンを晶出しようとした場合、左側の固液線にぶつかり晶出を開始する。次に、プロパン断熱冷却法では、供給液とプロパンを混合し、放圧して冷却を開始すると、プロパンを添加した３成分系の固液平衡線（プロパンを抜いた組成として表示してあるが）にぶつかり、それに沿って共晶点近くまで冷却するとシクロヘキサンの結晶が晶出し、この結晶を母液と分離する。   That is, on the phase diagram, a solid-liquid equilibrium line of a binary system of cyclohexane and benzene is obtained. At this time, the inclusion of a trace amount of impurities is only slightly lowered the crystallization point curve, and there is no substantial difference. Here, when the cyclohexane-rich mixed raw material is cooled to crystallize cyclohexane, it hits the solid-liquid line on the left side and starts crystallization. Next, in the propane adiabatic cooling method, when the supply liquid and propane are mixed, the pressure is released, and cooling is started, the ternary solid-liquid equilibrium line to which propane is added (although indicated as a composition with propane removed) When hitting and cooling to near the eutectic point, cyclohexane crystals crystallize and separate from the mother liquor.

かかる操作を本発明に係る設備構成下で、連続的に行うものである。ベンゼンの結晶と分離された母液は脱プロパンを行い、原料と混合しフィードバックさせるのである。なお、ベンゼンとシクロヘキサンの混合液系は、全濃度範囲において共晶系である。ベンゼンの純品の結晶化点は、５．５℃で、シクロヘキサンの結晶化点は、５．７℃である。   Such an operation is continuously performed under the equipment configuration according to the present invention. The mother liquor separated from the benzene crystals is depropanated, mixed with the raw material, and fed back. The mixed liquid system of benzene and cyclohexane is a eutectic system in the entire concentration range. The pure benzene has a crystallization point of 5.5 ° C, and cyclohexane has a crystallization point of 5.7 ° C.

この原理説明から、プロパン−ベンゼン−シクロヘキサン系の共晶組成物からシクロヘキサン結晶を得ることができることは明らかであろう。そして、その分離に際し、本発明法によれば、安価な晶析プロセスとなることも明らかであろう。   From this explanation of the principle, it will be clear that cyclohexane crystals can be obtained from a eutectic composition of the propane-benzene-cyclohexane system. In the separation, it will be apparent that the method of the present invention is an inexpensive crystallization process.

＜他の説明＞
上記例は、結晶槽が１基である例であるが、複数の結晶槽を備えるもの構成も本発明は対象とする。複数の結晶槽を備える設備では、前段の結晶槽での結晶スラリーを後段の結晶槽に導いてさらなる結晶化を図るものである。 <Other explanation>
The above example is an example in which there is one crystallization tank, but the present invention is also directed to a configuration including a plurality of crystallization tanks. In the equipment provided with a plurality of crystal tanks, the crystal slurry in the preceding crystal tank is guided to the subsequent crystal tank to further crystallize.

この形態において、圧縮機は各段の結晶槽に付設する場合より、一台の加圧機を設けて、各段の結晶槽からの蒸発ベーパーを圧縮機に導き、加圧して上で最終段の結晶槽に付設された吸収凝縮に導く構成が望ましい。また、蒸発缶は、少なくとも最初の結晶槽に設けるのが望ましい。もちろん、蒸発缶をそれぞれ各結晶槽に付設することもできる。   In this embodiment, the compressor is provided with a single presser than the case where it is attached to the crystal tank of each stage, and the evaporation vapor from the crystal tank of each stage is guided to the compressor and pressurized, and then the final stage. A structure that leads to absorption condensation attached to the crystal tank is desirable. Further, it is desirable to provide the evaporator in at least the first crystal tank. Of course, each evaporator can be attached to each crystal tank.

以下、本発明の効果を実施例を示して明らかにする。
（実施例１）
実施例は、図２に示したプロセスにて晶析を行ったものであり、結晶槽として竪型晶出機２０（直径３００ｍｍ×高さ１．５ｍ、スラリーのホールドアップ容量２５リットル）を、吸収凝縮器１０は水平管式のものを、固液分離装置として遠心分離機４０を用いた。 Hereinafter, effects of the present invention will be clarified by showing examples.
Example 1
In the examples, crystallization was performed by the process shown in FIG. The absorption condenser 10 is a horizontal tube type, and a centrifuge 40 is used as a solid-liquid separator.

パラキシレン濃度８０〜９０％で常温の混合キシレン原料を吸収凝縮器１０に１５〜２５ｋｇ／ｈｒの割合で供給すると共に、結晶槽２０から圧縮機３０を通して０．２〜０．７ＭＰａに加圧されたベーパーと接触混合させながら約３０℃で凝縮させた。得られた凝縮液はプロパン濃度１０〜３０％のプロパンの混合キシレン溶液であり、これをプレフラッシュタンク（蒸発缶）５０にて１３０〜３５０ｋＰａの圧力下にてプレフラッシュさせ、液温度を０〜１５℃まで冷却した。プレフラッシュにより発生したベーパーは圧縮機３０を通して０．２〜０．７ＭＰａに加圧し、吸収凝縮器１０にて吸収液と接触混合させた。プレフラッシュ後の液は常圧下、−１０〜０℃で運転されている結晶槽２０に導き結晶化を図った。結晶槽２０から遠心分離機４０には結晶化により得られたパラキシレン結晶スラリーを供給した。その結果、４〜７Ｋｇ／ｈｒのキシレン結晶を得ることができた。プロパンの混合キシレン溶液である濾液は系外へ排出し、濾液に溶存した状態で系外へ排出された分のプロパンはメークアップとして加圧機のサクション部に供給した。濾液中のパラキシレン濃度は６０〜８０％であった。   A mixed xylene raw material having a paraxylene concentration of 80 to 90% and a normal temperature is supplied to the absorption condenser 10 at a rate of 15 to 25 kg / hr and is pressurized from the crystallization tank 20 through the compressor 30 to 0.2 to 0.7 MPa. The mixture was condensed at about 30 ° C. while being contact-mixed with the vapor. The obtained condensate is a mixed xylene solution of propane having a propane concentration of 10 to 30%. This is preflashed in a preflash tank (evaporator) 50 under a pressure of 130 to 350 kPa, and the liquid temperature is set to 0 to 0. Cooled to 15 ° C. The vapor generated by the preflash was pressurized to 0.2 to 0.7 MPa through the compressor 30 and contacted and mixed with the absorbing solution in the absorption condenser 10. The liquid after the preflash was led to a crystallization tank 20 operated at −10 to 0 ° C. under normal pressure for crystallization. The paraxylene crystal slurry obtained by crystallization was supplied from the crystal tank 20 to the centrifuge 40. As a result, 4-7 kg / hr xylene crystals could be obtained. The filtrate, which is a mixed xylene solution of propane, was discharged out of the system, and the propane that was discharged out of the system in a state dissolved in the filtrate was supplied as a make-up to the suction section of the pressurizer. The paraxylene concentration in the filtrate was 60-80%.

基本的な実施の形態のフローシートである。It is a flow sheet of a basic embodiment. 他の実施の形態のフローシートである。It is a flow sheet of other embodiments. プロパン−ベンゼン−シクロヘキサン系の共晶組成における固液平衡図である。It is a solid-liquid equilibrium diagram in the eutectic composition of a propane-benzene-cyclohexane system.

１…原液、２…冷却媒体、１０…吸収凝縮器、２０…結晶槽、３０…圧縮機、４０…固液分離手段、Ｃｒ…結晶分（流れ）、Ｍｏ…母液（流れ）。   DESCRIPTION OF SYMBOLS 1 ... Stock solution, 2 ... Cooling medium, 10 ... Absorption condenser, 20 ... Crystal tank, 30 ... Compressor, 40 ... Solid-liquid separation means, Cr ... Crystal component (flow), Mo ... Mother liquor (flow).

Claims (3)

結晶槽においてプロパンを含む対象のパラキシレンを含む混合キシレンに対して、プロパンの断熱冷却、蒸発操作を行い、
この操作により生成した結晶スラリーは前記結晶槽から抜き出し、
蒸発したプロパンベーパーは圧縮機により加圧し、吸収凝縮器に導き、
前記結晶槽の操作圧力を常圧付近または高くとも４気圧とし、かつ、前記圧縮機による加圧を前記結晶槽の操作圧力以下とし、
前記吸収凝縮器において、前記パラキシレンを含む混合キシレンと加圧された前記プロパンベーパーとを接触させながら冷却水を通水した冷却管で冷却して前記プロパンベーパーの凝縮を図り、吸収凝縮液を生成し、この吸収凝縮液を前記結晶槽に導くとともに、
前記凝縮液を前記結晶槽に導く前に設置した蒸発缶において、あらかじめ所要量の前記プロパンの断熱冷却、蒸発操作を行うことで、次の結晶槽における急激な断熱冷却を防ぎ、結晶槽内全体の結晶を含む母液を下部から上部へ良く循環させて略均一な過飽和状態とし、
前記蒸発缶における蒸発ベーパーは前記圧縮機により前記結晶槽の操作圧力以上に加圧して、前記結晶槽からの蒸発ベーパーと共に前記吸収凝縮器に導き、
前記結晶槽において精製した結晶スラリーからパラキシレン結晶を得る、ことを特徴とする有機化合物の断熱冷却式晶析方法。 Perform adiabatic cooling and evaporation of propane for mixed xylene containing paraxylene, which contains propane in the crystallization tank,
The crystal slurry generated by this operation is extracted from the crystal tank,
The evaporated propane vapor is pressurized by a compressor and led to an absorption condenser,
The operation pressure of the crystallization tank is close to normal pressure or at most 4 atmospheres, and the pressurization by the compressor is less than or equal to the operation pressure of the crystallization tank,
In the absorption condenser, the mixed xylene containing para-xylene and the pressurized propane vapor are brought into contact with each other and cooled by a cooling pipe through which cooling water is passed to condense the propane vapor, and the absorption condensate is obtained. Producing and leading this absorption condensate to the crystallization vessel,
In the evaporator installed before introducing the condensate into the crystallization tank, adiabatic cooling and evaporation operation of the required amount of the propane in advance is performed to prevent rapid adiabatic cooling in the next crystallization tank and The mother liquor containing crystals of
The evaporation vapor in the evaporator is pressurized by the compressor above the operating pressure of the crystallization tank and led to the absorption condenser together with the evaporation vapor from the crystallization tank,
An adiabatic cooling crystallization method for an organic compound, characterized in that para-xylene crystals are obtained from a crystal slurry purified in the crystallization tank . 前記結晶槽から抜き出した結晶スラリーを固液分離し、分離された母液を前記吸収凝縮器に返送する請求項１記載の有機化合物の断熱冷却式晶析方法。   The adiabatic cooling crystallization method for an organic compound according to claim 1, wherein the crystal slurry extracted from the crystallization tank is subjected to solid-liquid separation, and the separated mother liquor is returned to the absorption condenser. 前記吸収凝縮器からの吸収凝縮液の冷媒濃度が１〜７０％とする請求項１記載の有機化合物の断熱冷却式晶析方法。   The adiabatic cooling crystallization method of an organic compound according to claim 1, wherein the refrigerant concentration of the absorption condensate from the absorption condenser is 1 to 70%.
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