JP4517678B2 - Method for producing purified bisphenol A - Google Patents
Method for producing purified bisphenol A Download PDFInfo
- Publication number
- JP4517678B2 JP4517678B2 JP2004058331A JP2004058331A JP4517678B2 JP 4517678 B2 JP4517678 B2 JP 4517678B2 JP 2004058331 A JP2004058331 A JP 2004058331A JP 2004058331 A JP2004058331 A JP 2004058331A JP 4517678 B2 JP4517678 B2 JP 4517678B2
- Authority
- JP
- Japan
- Prior art keywords
- adduct
- phenol
- crystallization
- bisphenol
- tank
- 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims description 102
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 93
- 230000008025 crystallization Effects 0.000 claims description 93
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 61
- 239000007788 liquid Substances 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 description 19
- 239000002904 solvent Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- PBEHQFUSQJKBAS-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;phenol Chemical compound OC1=CC=CC=C1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 PBEHQFUSQJKBAS-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、精製ビスフェノールＡの製造方法に関し、詳しくは、色相に優れ且つ着色を生じ難い精製ビスフェノ−ルＡの工業的に有利な製造方法に関する。 The present invention relates to a method for producing purified bisphenol A, and more particularly, to an industrially advantageous method for producing purified bisphenol A which is excellent in hue and hardly causes coloration.
ビスフェノールＡは、酸触媒の存在下にアセトンとフェノールとを縮合反応させて製造される。そして、精製ビスフェノールＡは、ビスフェノールＡ含有晶析原料からビスフェノールＡとフェノールの付加物（アダクト体）を回収し且つ精製するための晶析工程、アダクト体からフェノールを除去する脱フェノール工程とを順次に包含してなるプロセスで製造される。 Bisphenol A is produced by a condensation reaction of acetone and phenol in the presence of an acid catalyst. And refinement | purification bisphenol A is a crystallization process for collect | recovering and refine | purifying the adduct (adduct body) of bisphenol A and a phenol from a bisphenol A containing crystallization raw material, and a dephenol process which removes phenol from an adduct body in order. Manufactured by a process comprising.
上記の晶析工程としては、一層精製された付加物を回収するため、晶析を複数回行う方法が提案されている（例えば特許文献１参照）。
ところで、ビスフェノールＡ含有晶析原料から晶析により回収されたアダクト体を再度晶析する場合、フェノール溶媒が使用され、その際のビスフェノールＡの濃度においてアダクト体の全体が溶解する温度（例えば８２℃）以上に加熱してアダクト体を溶解した後に冷却して晶析されるが、この際の加熱および冷却に要するユーティリテイーは無視できず、その軽減は、精製ビスフェノ−ルＡの工業的製造においては重要である。 By the way, when recrystallizing an adduct body recovered by crystallization from a bisphenol A-containing crystallization raw material, a phenol solvent is used, and the temperature at which the entire adduct body dissolves at the concentration of bisphenol A (for example, 82 ° C.). ) The adduct body is melted by heating and then cooled and crystallized. However, the utility required for heating and cooling at this time cannot be ignored, and the reduction is achieved in the industrial production of purified bisphenol A. Is important.
本発明は、上記実情に鑑みなされたものであり、その目的は、晶析工程のユーティリテイーの節減が図られる様に改良された精製ビスフェノ−ルＡの工業的に有利な製造方法を提供することにある。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an industrially advantageous method for producing purified bisphenol A which is improved so as to reduce the utility of the crystallization process. There is.
本発明者らは、鋭意検討を重ねた結果、ビスフェノールＡ含有晶析原料から晶析により回収されたアダクト体の再度の晶析による高純度化は、付加物の全量を晶析しなくとも一部の晶析によっても十分に達成されるとの知見を得、本発明の完成に到った。 As a result of intensive studies, the inventors of the present invention have achieved high purity by recrystallization of an adduct recovered from a bisphenol A-containing crystallization raw material without recrystallization of the entire adduct. As a result, the inventors have obtained the knowledge that it can be sufficiently achieved by crystallization of some parts, and have completed the present invention.
本発明は、ビスフェノールＡ含有晶析原料を冷却してビスフェノールＡとフェノールの付加物を析出させ、析出した付加物をフェノールに溶解させた後に得られたフェノール溶液を冷却してビスフェノールＡとフェノールの付加物を析出させ、析出した付加物と母液とを分離し、回収した付加物からフェノールを除去する精製ビスフェノールＡの製造方法において、析出した付加物をフェノールに溶解させるに際し、当該付加物の５〜７０重量％相当量を溶解し、未溶解の付加物を含有するフェノール溶液を冷却することを特徴とする精製ビスフェノールＡの製造方法に関する。 In the present invention, the bisphenol A-containing crystallization raw material is cooled to precipitate an adduct of bisphenol A and phenol, and the phenol solution obtained after dissolving the precipitated adduct in phenol is cooled to cool the bisphenol A and phenol. In the method for producing purified bisphenol A, in which an adduct is precipitated, the precipitated adduct and the mother liquor are separated, and phenol is removed from the recovered adduct, the dissolved adduct is dissolved in phenol. The present invention relates to a method for producing purified bisphenol A, which comprises dissolving an amount corresponding to ˜70% by weight and cooling a phenol solution containing an undissolved adduct .
また、本発明は、ビスフェノールＡ含有晶析原料を冷却してビスフェノールＡとフェノールの付加物を析出させる第１晶析工程、第１晶析工程で析出した付加物と母液とを分離する第１固液分離工程、第１固液分離工程で回収した付加物をフェノールに溶解させた後に得られたフェノール溶液を冷却してビスフェノールＡとフェノールの付加物を析出させる第２晶析工程、第２晶析工程で析出した付加物と母液とを分離する第２固液分離工程、第２固液分離工程で回収した付加物からフェノールを除去する脱フェノール工程とを順次に包含して成り、第２晶析工程において、第２晶析工程に供する付加物の５〜７０重量％相当量を溶解して未溶解の付加物を含有するフェノール溶液を晶析することを特徴とする精製ビスフェノールＡの製造方法に関する。 The present invention also provides a first crystallization step in which the bisphenol A-containing crystallization raw material is cooled to precipitate an adduct of bisphenol A and phenol, and the adduct precipitated in the first crystallization step is separated from the mother liquor. A second crystallization step in which a phenol solution obtained after dissolving the adduct recovered in the solid-liquid separation step and the first solid-liquid separation step in phenol is cooled to precipitate an adduct of bisphenol A and phenol; A second solid-liquid separation step for separating the adduct precipitated in the crystallization step and the mother liquor, and a dephenolization step for removing phenol from the adduct collected in the second solid-liquid separation step. A purified bisphenol A characterized by crystallization of a phenol solution containing an undissolved adduct by dissolving 5 to 70% by weight of the adduct subjected to the second crystallization step in the second crystallization step. Manufacturing method On.
本発明によれば、晶析工程のユーティリテイーの節減が図られる様に改良された精製ビスフェノ−ルＡの工業的に有利な製造方法が提供される。 INDUSTRIAL APPLICABILITY According to the present invention, there is provided an industrially advantageous method for producing purified bisphenol A which is improved so as to reduce the utility of the crystallization process.
以下、本発明を詳細に説明する。本発明は、第１晶析工程、第１固液分離工程、第２晶析工程、第２固液分離工程、脱フェノール工程を順次に包含して成る。 Hereinafter, the present invention will be described in detail. The present invention includes a first crystallization step, a first solid-liquid separation step, a second crystallization step, a second solid-liquid separation step, and a dephenolization step in order.
第１晶析工程および第２晶析工程で使用される晶析装置としては、各種の晶析装置が適宜選択して使用される。その一例としては、内部冷却式晶析槽、外部循環式冷却機構を備えた晶析槽（外部冷却式晶析槽）、蒸発冷却式晶析槽などが挙げられる。外部冷却式晶析槽は、晶析槽とその外部に配置された冷却器とを循環路で連結して成り、冷却器としては多管式冷却器が好適に使用される。そして、上記の何れの方式の場合も、例えば複数基の晶析槽を直列に配置し、第２段目以降の晶析温度を第１段目の晶析温度より低く設定し、第１晶析工程を複数段階で行うことも出来る。 As a crystallization apparatus used in the first crystallization process and the second crystallization process, various crystallization apparatuses are appropriately selected and used. Examples thereof include an internal cooling crystallization tank, a crystallization tank (external cooling crystallization tank) equipped with an external circulation cooling mechanism, and an evaporative cooling crystallization tank. The externally cooled crystallization tank is formed by connecting a crystallization tank and a cooler arranged outside thereof by a circulation path, and a multitubular cooler is preferably used as the cooler. In any of the above methods, for example, a plurality of crystallization tanks are arranged in series, the crystallization temperature after the second stage is set lower than the crystallization temperature of the first stage, and the first crystal The analysis process can be performed in a plurality of stages.
また、第１固液分離工程および第２固液分離工程で使用される固液分離装置としては、特に限定されないが、例えば真空濾過器が好適に使用される。 Further, the solid-liquid separation device used in the first solid-liquid separation step and the second solid-liquid separation step is not particularly limited, but, for example, a vacuum filter is preferably used.
ビスフェノールＡ含有晶析原料は、酸触媒の存在下にアセトンとフェノールとを縮合反応させてビスフェノールＡを得る反応工程から得られる。上記の縮合反応は、従来公知の方法に従って行うことが出来る。酸触媒としては、強酸性陽イオン交換樹脂が好適に使用される。アセトン１モルとフェノール２モルとが縮合してビスフェノールＡ１モルと水１モルが生成するため、フェノールは化学量論的に過剰量が使用される。フェノール／アセトン（モル比）は、通常３〜３０、好ましくは５〜２０である。反応温度は、通常３０〜１００℃、好ましくは４５〜８５℃であり、反応圧力は、通常、常圧から０．５ＭＰａ（ゲージ）である。 The bisphenol A-containing crystallization raw material is obtained from a reaction step in which acetone and phenol are subjected to a condensation reaction in the presence of an acid catalyst to obtain bisphenol A. Said condensation reaction can be performed in accordance with a conventionally well-known method. As the acid catalyst, a strongly acidic cation exchange resin is preferably used. Since 1 mol of acetone and 2 mol of phenol are condensed to form 1 mol of bisphenol A and 1 mol of water, the stoichiometric excess of phenol is used. The phenol / acetone (molar ratio) is usually 3 to 30, preferably 5 to 20. The reaction temperature is usually 30 to 100 ° C., preferably 45 to 85 ° C., and the reaction pressure is usually from normal pressure to 0.5 MPa (gauge).
通常、反応工程の直後には蒸留工程が設けられる。減圧蒸留により、塔頂から未反応アセトンが水および少量のフェノールと共に除去される。減圧蒸留の条件は、圧力５０〜３００ｍｍＨｇ、温度７０〜１３０℃である。蒸留塔の塔底から得られるビスフェノールＡ含有晶析原料の場合、ビスフェノールＡの濃度は、通常１８〜５０重量％、好ましくは２２〜３０重量であり、残部がフェノール及び／又は水である。ビスフェノールＡ含有晶析原料は、通常６０〜１２０℃の温度で以下の晶析工程に供給される。 Usually, a distillation step is provided immediately after the reaction step. Unreacted acetone is removed together with water and a small amount of phenol from the top of the column by distillation under reduced pressure. The conditions for vacuum distillation are a pressure of 50 to 300 mmHg and a temperature of 70 to 130 ° C. In the case of the bisphenol A-containing crystallization raw material obtained from the bottom of the distillation column, the concentration of bisphenol A is usually 18 to 50% by weight, preferably 22 to 30%, and the balance is phenol and / or water. The bisphenol A-containing crystallization raw material is usually supplied to the following crystallization step at a temperature of 60 to 120 ° C.
第１晶析工程においては、ビスフェノールＡ含有晶析原料を冷却してビスフェノールＡとフェノールの付加物を析出させる。第１段目の晶析温度（冷却温度）は、通常７０〜５５℃、好ましくは６５〜６０℃、第２段目の晶析温度は、通常５５〜４７℃、好ましくは５３〜５０℃、第１段目と第２段目の晶析温度の差は、通常５〜２３℃、好ましくは１０〜１５℃とされる。 In the first crystallization step, the bisphenol A-containing crystallization raw material is cooled to precipitate an adduct of bisphenol A and phenol. The first stage crystallization temperature (cooling temperature) is usually 70 to 55 ° C., preferably 65 to 60 ° C., and the second stage crystallization temperature is usually 55 to 47 ° C., preferably 53 to 50 ° C. The difference between the crystallization temperatures of the first stage and the second stage is usually 5 to 23 ° C, preferably 10 to 15 ° C.
第１固液分離工程においては、第１晶析工程で析出したアダクト体と母液とを分離する。 In the first solid-liquid separation step, the adduct body deposited in the first crystallization step and the mother liquor are separated.
第２晶析工程においては、第１固液分離工程で回収したアダクト体をフェノールに溶解させた後に冷却してビスフェノールＡとフェノールの付加物を析出させる。 In the second crystallization step, the adduct body recovered in the first solid-liquid separation step is dissolved in phenol and then cooled to precipitate an adduct of bisphenol A and phenol.
アダクト体の溶解に使用する溶媒フェノールは、少量のビスフェノールＡを含有していてもよい。例えば、後述するフェノール洗浄に使用したビスフェノールＡ含有フェノール（フェノール洗浄廃液）等は好適に利用することが出来る。ビスフェノールＡの含有量が多くなると、融点が上昇して溶解温度が高くなるため、ビスフェノールＡの含有量は、通常２０重量％以下とされる。溶媒（フェノール又はビスフェノールＡ含有フェノール）の使用量は、特に制限されないが、通常、第２晶析工程に供するアダクト体に対し、通常１〜３重量倍、好ましくは１〜１．５重量倍とされる。溶媒の使用量が余りに多い場合は、溶媒の加熱に必要なユーティリテイーが増加して不経済である。アダクト体の溶解は、晶析槽とは別個に設けられた溶解槽で行われる。 The solvent phenol used for dissolving the adduct body may contain a small amount of bisphenol A. For example, bisphenol A-containing phenol (phenol washing waste liquid) used for phenol washing described later can be suitably used. When the content of bisphenol A increases, the melting point increases and the melting temperature increases, so the content of bisphenol A is usually 20% by weight or less. The amount of the solvent (phenol or phenol containing bisphenol A) is not particularly limited, but is usually 1 to 3 times by weight, preferably 1 to 1.5 times by weight with respect to the adduct body to be subjected to the second crystallization step. Is done. When the amount of the solvent used is too large, the utility required for heating the solvent increases, which is uneconomical. The melting of the adduct body is performed in a dissolution tank provided separately from the crystallization tank.
本発明は、第２晶析工程に供するアダクト体の５〜７０重量％相当量を溶解して晶析することを特徴とする。すなわち、本発明者らの知見によれば、第１晶析工程でビスフェノールＡ含有晶析原料から晶析して得られたアダクト体（結晶）に残存する不純物は、表面側に集中して存在しているため、アダクト体の再晶析（溶解および冷却）は、表面から或る一定範囲までについて部分的に行えば、十分な高純度化が達成される。 The present invention is characterized in that crystallization is performed by dissolving an amount corresponding to 5 to 70% by weight of the adduct body used in the second crystallization step. That is, according to the knowledge of the present inventors, impurities remaining in the adduct body (crystal) obtained by crystallization from the bisphenol A-containing crystallization raw material in the first crystallization step are concentrated on the surface side. Therefore, if the recrystallization (dissolution and cooling) of the adduct body is partially performed from the surface to a certain range, sufficiently high purity can be achieved.
アダクト体の５〜７０重量％相当量とは、アダクト体の全体に対する局部としての量を意味するのではなく、各結晶粒子が表面から次第に溶解するとした際のその合計溶解量を意味する。部分溶解させるアダクト体の割合が５重量％未満の場合は、再晶析による高純度化の効果が十分ではなく、７０重量％を超える場合は、溶解のための加熱やその後に後に行う晶析のための冷却に必要なユーティリテイーが増加して不経済である。部分溶解させるアダクト体の割合は、好ましくは２０〜６０重量％である。 The amount corresponding to 5 to 70% by weight of the adduct body does not mean a local amount with respect to the entire adduct body, but means a total dissolution amount when each crystal particle is gradually dissolved from the surface. When the proportion of the adduct body to be partially dissolved is less than 5% by weight, the effect of purification by recrystallization is not sufficient, and when it exceeds 70% by weight, crystallization is performed after heating for dissolution or later. Due to the increased utility required for cooling, it is uneconomical. The ratio of the adduct body to be partially dissolved is preferably 20 to 60% by weight.
アダクト体の表面からの部分溶解は、溶解槽において一定の温度に維持された溶媒中へのアダクト体の浸漬時間（滞留時間）を調節することによって制御することが出来る。そして、溶媒の温度およびアダクト体の滞留時間は、適宜選択されるが、溶媒の温度は、通常５０〜９０℃、好ましくは５５〜７０℃、アダクト体の滞留時間は、通常１０分以下、好ましくは２〜５分とされる。溶媒の温度とアダクト体の滞留時間によってアダクト体の表面から溶解する量が決定されるため、予め求められたこれらの関係からアダクト体の表面からの部分溶解量を決定することが出来る。 Partial dissolution from the surface of the adduct body can be controlled by adjusting the immersion time (residence time) of the adduct body in a solvent maintained at a constant temperature in the dissolution tank. The temperature of the solvent and the residence time of the adduct body are appropriately selected. The temperature of the solvent is usually 50 to 90 ° C., preferably 55 to 70 ° C., and the residence time of the adduct body is usually 10 minutes or less, preferably Is 2 to 5 minutes. Since the amount of dissolution from the surface of the adduct body is determined by the temperature of the solvent and the residence time of the adduct body, the partial dissolution amount from the surface of the adduct body can be determined from these relationships determined in advance.
第２晶析工程における晶析操作は、前述の第１晶析工程と同様の条件を採用することが出来る。そして、第２固液分離工程においては、第２晶析工程で析出したアダクト体と母液とを分離する。 The crystallization operation in the second crystallization step can employ the same conditions as in the first crystallization step. In the second solid-liquid separation step, the adduct body and mother liquor precipitated in the second crystallization step are separated.
本発明においては、第２固液分離工程の直後に第２固液分離工程で回収したアダクト体の洗浄工程と脱溶媒工程を設けるのが好ましい。具体的には、洗浄槽に溶媒として純粋フェノールの溶融液を仕込み、この中でアダクト体を洗浄した後に付着した溶媒を除去する。フェノールの使用量は、特に制限されないが、アダクト体に対し、通常１〜４重量倍、好ましくは２〜３重量倍とされる。そして、フェノールの温度は、第２晶析工程における２段目の晶析温度と同様の温度とされる。各結晶粒子の表面から溶解させて洗浄を行う。この場合、溶解量は、通常５〜７０重量％、好ましくは２０〜６０重量％とされる。斯かる溶解量は、洗浄槽内のアダクト体の滞留時間によって制御される。脱溶媒工程は例えば遠心分離機を使用して行うことが出来る。 In this invention, it is preferable to provide the washing | cleaning process and desolvation process of the adduct body collect | recovered at the 2nd solid-liquid separation process immediately after the 2nd solid-liquid separation process. Specifically, a pure phenol melt is charged as a solvent in the washing tank, and the adhering body is washed therein, and then the adhering solvent is removed. The amount of phenol used is not particularly limited, but is usually 1 to 4 times, preferably 2 to 3 times the weight of the adduct body. The phenol temperature is set to the same temperature as the second crystallization temperature in the second crystallization step. Cleaning is performed by dissolving from the surface of each crystal particle. In this case, the dissolution amount is usually 5 to 70% by weight, preferably 20 to 60% by weight. The amount of dissolution is controlled by the residence time of the adduct body in the cleaning tank. The solvent removal step can be performed using, for example, a centrifuge.
脱フェノール工程においては、第２固液分離工程（又はその後の洗浄工程）で回収したアダクト体からフェノールを除去する。脱フェノール工程は、従来の装置および条件を使用して行うことが出来る。 In the dephenol process, phenol is removed from the adduct body recovered in the second solid-liquid separation process (or the subsequent washing process). The dephenolization step can be performed using conventional equipment and conditions.
以下、本発明を実施例により更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.
実施例１
ビスフェノールＡ含有晶析原料としては、反応工程と蒸留工程を経て回収された表１に記載の混合物を使用し、図１のフローシートに示す晶析プロセスを使用して精製ビスフェノールＡの製造を行った。晶析装置は外部冷却式晶析槽にて構成した。
Example 1
As the bisphenol A-containing crystallization raw material, the mixture shown in Table 1 recovered through the reaction step and the distillation step is used, and purified bisphenol A is produced using the crystallization process shown in the flow sheet of FIG. It was. The crystallizer was composed of an externally cooled crystallizer.
先ず、直列に配置された晶析槽（１）と晶析槽（２）にライン（Ｌ１）から晶析原料を供給して第１晶析工程を行った。この際、晶析原料の供給速度は５２重量部／分、晶析原料の温度は８０℃、晶析槽（１）内のスラリー温度は６０℃、晶析槽（２）内のスラリー温度は５０℃、晶析槽（１）と晶析槽（２）における滞留時間は各々２４０分に設定した。 First, the first crystallization step was performed by supplying the crystallization raw material from the line (L1) to the crystallization tank (1) and the crystallization tank (2) arranged in series. At this time, the supply rate of the crystallization raw material was 52 parts by weight / minute, the temperature of the crystallization raw material was 80 ° C., the slurry temperature in the crystallization tank (1) was 60 ° C., and the slurry temperature in the crystallization tank (2) was The residence time in the crystallization tank (1) and the crystallization tank (2) was set at 240 ° C. for 50 minutes.
次いで、晶析槽（２）で析出したアダクト体と母液とを真空濾過器（３）で分離し、ライン（Ｌ９）から後述のタンク（１２）内のフェノールを供給してアダクト体を洗浄した。アダクト体の供給速度は１２重量部／分、温度は５０℃に設定した。洗浄用フェノール（組成：ビスフェノールＡ；９重量％、フェノール；９１重量％、微量不純物）の供給速度は１２重量部／分、温度は５５℃に設定した。ライン（Ｌ２）からアダクト体を溶解槽（４）に供給し、ライン（Ｌ５）から母液と洗浄廃液をタンク（１１）に供給した。タンク（１１）内の液はライン（Ｌ６）から反応工程に供給した。 Subsequently, the adduct body and mother liquor deposited in the crystallization tank (2) were separated by a vacuum filter (3), and phenol in the tank (12) described later was supplied from the line (L9) to wash the adduct body. . The supply rate of the adduct body was set to 12 parts by weight / minute, and the temperature was set to 50 ° C. The feed rate of cleaning phenol (composition: bisphenol A; 9% by weight, phenol; 91% by weight, trace impurities) was set to 12 parts by weight / minute, and the temperature was set to 55 ° C. The adduct body was supplied to the dissolution tank (4) from the line (L2), and the mother liquor and the cleaning waste liquid were supplied to the tank (11) from the line (L5). The liquid in the tank (11) was supplied to the reaction process from the line (L6).
次いで、ライン（Ｌ１０）から溶解槽（４）に後述のタンク（１２）内のフェノールを供給してアダクト体をの表面を溶解した。溶媒用フェノールの供給速度は３１重量部／分とした。溶解槽（４）内はスラリー状態であり、スラリー中のアダクト体の濃度は１５重量％、スラリー温度は７０℃、スラリーの滞留時間は５分とした。上記の温度と滞留時間では溶解槽の溶媒中のアダクト体の４２重量％相当量が表面から溶解する。 Next, phenol in the tank (12) described later was supplied from the line (L10) to the dissolution tank (4) to dissolve the surface of the adduct body. The supply rate of the solvent phenol was 31 parts by weight / minute. The inside of the dissolution tank (4) was in a slurry state, the concentration of the adduct body in the slurry was 15% by weight, the slurry temperature was 70 ° C., and the slurry residence time was 5 minutes. At the above temperature and residence time, an amount equivalent to 42% by weight of the adduct body in the solvent of the dissolution tank is dissolved from the surface.
次いで、直列に配置された晶析槽（５）と晶析槽（６）にライン（Ｌ２）からアダクト体のフェノールスラリーを供給して第２晶析工程を行った。この際、スラリーの供給速度は５２重量部／分、晶析槽（５）内のスラリー温度は６０℃、晶析槽（６）内のスラリーの温度は５０℃、晶析槽（１）と晶析槽（２）における滞留時間は各々２４０分に設定した。 Then, the phenol slurry of the adduct body was supplied from the line (L2) to the crystallization tank (5) and the crystallization tank (6) arranged in series, and the 2nd crystallization process was performed. At this time, the slurry supply rate was 52 parts by weight / minute, the slurry temperature in the crystallization tank (5) was 60 ° C., the temperature of the slurry in the crystallization tank (6) was 50 ° C., and the crystallization tank (1) Each residence time in the crystallization tank (2) was set to 240 minutes.
次いで、晶析槽（６）で析出したアダクト体と母液とを真空濾過器（７）で分離し、ライン（Ｌ１２）から後述のタンク（１３）内のフェノールを供給してアダクト体を洗浄した。アダクト体の供給速度は１２重量部／分、温度は５０℃に設定した。洗浄用フェノール（組成：ビスフェノールＡ；９重量％、フェノール；９１重量％、微量不純物）の供給速度は１２重量部／分、温度は５５℃に設定した。ライン（Ｌ３）からアダクト体を結晶洗浄槽（８）に供給し、ライン（Ｌ７）から母液と洗浄廃液をタンク（１２）に供給した。 Subsequently, the adduct body and mother liquor deposited in the crystallization tank (6) were separated by a vacuum filter (7), and phenol in the tank (13) described later was supplied from the line (L12) to wash the adduct body. . The supply rate of the adduct body was set to 12 parts by weight / minute, and the temperature was set to 50 ° C. The feed rate of cleaning phenol (composition: bisphenol A; 9% by weight, phenol; 91% by weight, trace impurities) was set to 12 parts by weight / minute, and the temperature was set to 55 ° C. The adduct body was supplied to the crystal washing tank (8) from the line (L3), and the mother liquor and the washing waste liquid were supplied to the tank (12) from the line (L7).
タンク（１２）内の液は、前述の通り、アダクト体の洗浄液としてライン（Ｌ９）から真空濾過器（３）に供給され、アダクト体の溶媒としてライン（Ｌ１０）から溶解槽（４）に供給されるが、残余の液は、ライン（Ｌ８）から反応工程に供給した。 As described above, the liquid in the tank (12) is supplied from the line (L9) to the vacuum filter (3) as the cleaning liquid for the adduct body, and is supplied from the line (L10) to the dissolution tank (4) as the solvent for the adduct body. However, the remaining liquid was supplied to the reaction process from the line (L8).
次いで、図示しないラインから結晶洗浄槽（８）に高純度フェノールを供給してアダクト体を洗浄した。具体的には、５０℃の高純度フェノールでアダクト体結晶の表面から結晶の１０重量％相当量を溶解した。 Subsequently, the high purity phenol was supplied to the crystal washing tank (8) from a line (not shown) to wash the adduct body. Specifically, an amount corresponding to 10% by weight of the crystal was dissolved from the surface of the adduct crystal with high-purity phenol at 50 ° C.
次いで、遠心分離器（９）に結晶洗浄槽（８）内のアダクト体を供給して遠心分離処理を行った。その後、ライン（Ｌ４）から回収したアダクト体をタンク（１０）に排出させ、ライン（Ｌ１１）から回収したフェノールをタンク（１３）に供給した。そして、従来の装置および条件を使用して脱フェノール工程を行い、アダクト体から精製ビスフェノールＡを得た。 Subsequently, the adduct body in the crystal washing tank (8) was supplied to the centrifugal separator (9) to perform a centrifugal separation process. Thereafter, the adduct body recovered from the line (L4) was discharged to the tank (10), and the phenol recovered from the line (L11) was supplied to the tank (13). And the dephenol process was performed using the conventional apparatus and conditions, and the refinement | purification bisphenol A was obtained from the adduct body.
上記の結晶洗浄槽（８）に供給した洗浄前のアダクト体中の不純物量の測定結果は表２に示す通りであった。 Table 2 shows the measurement results of the amount of impurities in the adduct body before washing supplied to the crystal washing tank (8).
比較例１：
実施例１において、溶解槽（４）内における液温度を８０℃に変更し、溶解槽（４）内のアダクト体を完全なフェノール溶液状態とした以外は、実施例１と同一条件で精製ビスフェノールＡを得た。結晶洗浄槽（８）に供給した洗浄前のアダクト体中の不純物量の測定結果は表２に示す通りであった。
Comparative Example 1:
In Example 1, purified bisphenol was used under the same conditions as in Example 1 except that the liquid temperature in the dissolution tank (4) was changed to 80 ° C. and the adduct body in the dissolution tank (4) was in a complete phenol solution state. A was obtained. Table 2 shows the measurement results of the amount of impurities in the adduct body before being supplied to the crystal washing tank (8).
表２に示す結果から明らかな様に、実施例１と比較例１とでは精製ビスフェノールＡ中の不純物量は大差がないが、第２晶析工程に供するアダクト体を部分溶解する実施例１の場合は、第２晶析工程に供するアダクト体を全部溶解する比較例１に比し、溶解および晶析のためのユーティリティーが３０％程度節減される。 As is apparent from the results shown in Table 2, the amount of impurities in purified bisphenol A is not significantly different between Example 1 and Comparative Example 1, but the adduct body used in the second crystallization step is partially dissolved. In this case, the utility for dissolution and crystallization is reduced by about 30%, as compared with Comparative Example 1 in which all adduct bodies used in the second crystallization step are dissolved.
１、２：晶析槽
３：固液分離装置
４：溶解槽
５、６：晶析槽
７：固液分離装置
８：洗浄槽
９：固液分離装置
１０〜１３：タンク
DESCRIPTION OF SYMBOLS 1, 2: Crystallization tank 3: Solid-liquid separation apparatus 4: Dissolution tank 5, 6: Crystallization tank 7: Solid-liquid separation apparatus 8: Washing tank 9: Solid-liquid separation apparatus 10-13: Tank
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004058331A JP4517678B2 (en) | 2004-03-03 | 2004-03-03 | Method for producing purified bisphenol A |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004058331A JP4517678B2 (en) | 2004-03-03 | 2004-03-03 | Method for producing purified bisphenol A |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005247726A JP2005247726A (en) | 2005-09-15 |
| JP4517678B2 true JP4517678B2 (en) | 2010-08-04 |
Family
ID=35028565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004058331A Expired - Lifetime JP4517678B2 (en) | 2004-03-03 | 2004-03-03 | Method for producing purified bisphenol A |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4517678B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH029832A (en) * | 1988-02-19 | 1990-01-12 | Mitsui Toatsu Chem Inc | Washing and recovery of solid |
| JPH05117190A (en) * | 1991-10-25 | 1993-05-14 | Chiyoda Corp | Production of bisphenol a-phenol crystalline adduct slurry |
-
2004
- 2004-03-03 JP JP2004058331A patent/JP4517678B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH029832A (en) * | 1988-02-19 | 1990-01-12 | Mitsui Toatsu Chem Inc | Washing and recovery of solid |
| JPH05117190A (en) * | 1991-10-25 | 1993-05-14 | Chiyoda Corp | Production of bisphenol a-phenol crystalline adduct slurry |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005247726A (en) | 2005-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5265094B2 (en) | Method for producing high purity bisphenol A | |
| WO2019220003A1 (en) | Method for recovering lithium hydroxide | |
| JPH0324028A (en) | Refining of aromatic compounds | |
| US20120330006A1 (en) | Method of manufacturing epsilon-caprolactam | |
| US4382916A (en) | Method of preparing hydrochloric acid and high purity ferrous sulfate hydrate crystals from hydrochloric acid waste pickle liquor | |
| JP2018533595A (en) | Method of purifying alkanesulfonic acid | |
| JPH01146839A (en) | Production of high-purity 2,2-bis(4-hydroxyphenyl)propane | |
| JPH029832A (en) | Washing and recovery of solid | |
| CN102633293B (en) | Method for refining multistage circulation evaporation-free copper sulfate | |
| JP4517678B2 (en) | Method for producing purified bisphenol A | |
| WO2013129405A1 (en) | Method for manufacturing refined methionine | |
| JP4398674B2 (en) | Method for producing bisphenol A | |
| JP4309648B2 (en) | High purity aluminum chloride manufacturing method and high purity aluminum chloride manufacturing apparatus | |
| KR101223384B1 (en) | Apparatus and method for manufacturing lithium hexafluoro phosphate | |
| JPS61106535A (en) | Recovery of benzoic acid | |
| JP2683762B2 (en) | Method for producing bisphenol A / phenol crystal adduct having good hue | |
| JP2005232134A (en) | Method for producing bisphenol-a | |
| JPH0361605B2 (en) | ||
| JPS62275018A (en) | Method for recovering valuable metal and acid from acidic waste liquor | |
| JP3882859B2 (en) | Method for producing hydrated hydrazine | |
| JP4228049B2 (en) | Alkaline waste liquid recycling method in aluminum processing factory | |
| JP3784331B2 (en) | Method for purifying gold-containing gallium and method for collecting gold from gallium containing gold | |
| JP2001031419A (en) | Purification of copper sulfate | |
| US1009864A (en) | Process of producing verdigris. | |
| CN116947789A (en) | Refining and impurity removing method for ranitidine alkali |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061207 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100118 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100202 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100331 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100427 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100510 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130528 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4517678 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140528 Year of fee payment: 4 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |