WO2001094014A1 - Procede de preparation de lit fixe de resine acide echangeuse de cations - Google Patents

Procede de preparation de lit fixe de resine acide echangeuse de cations Download PDF

Info

Publication number
WO2001094014A1
WO2001094014A1 PCT/JP2001/004779 JP0104779W WO0194014A1 WO 2001094014 A1 WO2001094014 A1 WO 2001094014A1 JP 0104779 W JP0104779 W JP 0104779W WO 0194014 A1 WO0194014 A1 WO 0194014A1
Authority
WO
WIPO (PCT)
Prior art keywords
fixed bed
exchange resin
acid
preparing
cation exchange
Prior art date
Application number
PCT/JP2001/004779
Other languages
English (en)
Japanese (ja)
Inventor
Tetsuya Saruwatari
Masahiro Iwahara
Original Assignee
Idemitsu Petrochemical Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Idemitsu Petrochemical Co., Ltd. filed Critical Idemitsu Petrochemical Co., Ltd.
Publication of WO2001094014A1 publication Critical patent/WO2001094014A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
    • B01J49/06—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing cationic exchangers

Definitions

  • the present invention relates to a method for preparing a fixed bed of an acidic cation exchange resin. More specifically, the present invention relates to a method for preparing a fixed bed of an acid cation exchange resin which is partially neutralized with good uniformity over the entire fixed bed of an acidic cation exchange resin packed in a reactor.
  • the acidic cation exchange resin fixed bed is useful for continuous production of bisphenols.
  • Bisphenols especially 2,2-bis (4-hydroxyphenyl) alkanes used as raw materials for producing plastics such as polycarbonate resins and polyarylate resins or epoxy resins, for example 2,2-bis (4 -Hydroxyfu / propane (hereinafter abbreviated as bisphenol A) is produced by the reaction of phenols with carbonyl compounds. In carrying out the reaction between these phenols and a carbon compound, it is well known to use a fixed bed of an acidic cation exchange resin as a catalyst.
  • UK Patent 1,53,9,463 discloses that after contacting the fixed bed with an amount of mercaptoamine that neutralizes 2 to 25 ° / 0 of the sulfonate groups of the sulfonic acid cation exchange resin. Further, a method for producing a fixed bed of a sulfonic acid cation exchange resin in which an acid solution is brought into contact with the fixed bed to uniformly distribute the sulfonic acid groups neutralized with mercaptoamine in the fixed bed has been proposed. I have. However, in this method, hydrochloric acid or sulfuric acid There is a problem of equipment corrosion due to the use of strong acids. Also, Japanese Patent Application Laid-Open No.
  • Hei 8-49061 proposes a method of using an aromatic sulfonic acid and a nitrogen-containing sulfur compound when preparing a fixed bed of an acidic cation exchange resin.
  • an aromatic sulfonic acid and a nitrogen-containing sulfur compound when preparing a fixed bed of an acidic cation exchange resin.
  • the equipment is corroded because aromatic sulfonates are used as the acid.
  • 21-mercaptoethylamine is used as the neutralizing agent
  • the acidic cation exchange resin packed in the reactor is used.
  • the neutralization ratio in each part of the fixed fat bed becomes uneven. Disclosure of the invention
  • An object of the present invention is to provide a method for preparing a fixed bed of an acidic cation exchange resin which is partially neutralized with good uniformity over the entirety of an acidic cation exchange resin charged in a reactor.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, when preparing a fixed bed of an acidic cation exchange resin, after forming a fixed bed by filling an acidic cation exchange resin in a reactor.
  • the above object can be achieved by introducing an aqueous solution in which an acid, a nitrogen-containing sulfur compound, a ketone or an aldehyde is dissolved into the reactor and circulating it before starting the synthesis reaction of the bisphenols. This led to the completion of the present invention based on this finding.
  • an aqueous solution in which an acid, a nitrogen-containing sulfur compound, and a ketone or aldehyde are dissolved is formed by filling an acid cation exchange resin in a reactor to form a fixed bed.
  • a method for preparing a fixed bed comprising a partially neutralized acidic cation exchange resin, wherein the fixed bed is introduced into the reactor, passed through the fixed bed, and the effluent passed through the fixed bed is circulated. is there.
  • a second aspect of the present invention is a fixed bed comprising the partially neutralized acidic cation exchange resin prepared as described above.
  • the fixed bed is prepared in a reactor before the reaction of the carbonyl compound with the phenol compound, and the fixed bed is continuously treated with the carbonyl compound and the phenol compound.
  • a continuous process for producing bisphenols. BEST MODE FOR CARRYING OUT THE INVENTION
  • a fixed bed is formed by filling an acidic cation exchange resin in a reactor, an aqueous solution in which an acid, a nitrogen-containing sulfur compound, and a ketone or an aldehyde are dissolved is brought into contact with the fixed bed. By doing so, the acidic cation exchange resin is partially neutralized.
  • the fixed bed made of the acidic cation exchange resin partially neutralized in this way is suitable as a catalyst for producing bisphenols from a carbol compound and phenols, and the carbonyl compounds include acetone and methyl.
  • the carbonyl compounds include acetone and methyl.
  • ketones such as ethyl ketone, methyl isobutyl ketone, methyl 1-n-propyl ketone, methyl phenyl ketone, acetophene, benzophenone and cyclohexanone
  • aldehydes such as formalin, acetaldehyde and benzaldehyde.
  • phenols include phenols having a structure having no substituent at the para-position to the hydroxyl group on the benzene ring, for example, phenol, o-cresolone, m-cresolone, o-tert-butyl / lefenole, o—Feninole phenol, m—Feninole phenol, 2,6-xylenole, 3,5-xylenole, 2,6-di-tert-butynolephenole, 3,5-di-tert- Phenol phenols such as butyl phenol, and phenol phenols; o-chlorophenol, m-clophenol, 2,6-dichlorophenol, 2,6-dibromophenol And halogenated phenols.
  • phenols having a structure having no substituent at the para-position to the hydroxyl group on the benzene ring for example, phenol, o-cresolone, m-cresolone,
  • Bisphenols produced from these carbohydrate compounds and phenols are basically bisphenols having a chemical structure in which two hydroxyphenyl groups are bonded via a carbon atom. , Bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphene-methane, bis (4-hydroxyphenyl) phenol, methane, bis (3-methynoleic 4-hydroxyphenyl) methane, Bis (3,5_dimethinole-1-hydroxyphene) Methane, Bis (3,5_dihydroxyphenol) Methane, Bis (3-chloro-4-hydroxyphene) Methane, Bis (3-funoleol 4-hydroxydrenophene) methane, Bis (2-tert-butyltinole-4-hydroxyphene) Phenolemethane, Bis (hydroxyphenyl) methanes such as methane (2-hydroxyphenyl) methane, 2-hydroxyphenyl methane, 4-hydroxyphenyl methane, and bis
  • the acid cation exchange resin used as a catalyst in the reaction of these phenol compounds with phenol compounds is preferably a sulfonic acid resin.
  • a styrenedibutylbenzene copolymer, a perfluoroethylene copolymer, a phenol-formaldehyde polymer, or the like can be used.
  • a styrene dibutylbenzene copolymer system is preferably used.
  • the acidic cation exchange resin examples include a sulfonated styrene-divinylolebenzene copolymer, a sulfonated perfluoroethylene copolymer, and a sulfonated phenol formaldehyde resin obtained by sulfonating the above-described base resin.
  • the acidic cation exchange resin may be of a gel type or a porous type. Further, those having a relatively low degree of crosslinking of 2 to 8% are preferred.
  • the acidic cation exchange resin is charged to the reactor to form a fixed bed. After forming the fixed resin bed and before starting the above bisphenol synthesis reaction, introduce and circulate an aqueous solution in which acid, nitrogen-containing sulfur compound, and ketones or aldehydes are dissolved in the reactor. With this, the acidic cation exchange resin is partially neutralized with the nitrogen-containing sulfur compound uniformly throughout the resin fixed bed. In this case, it is preferable to neutralize 2 to 50%, preferably 5 to 30% of the sulfonic acid groups bonded to the acidic cation exchange resin with a nitrogen-containing sulfur compound.
  • the acid examples include benzene sulfonic acid, NO. It may be an aromatic sulfonic acid such as rat toluenesulfonic acid or xylene sulfonic acid, or may be an alkylsulfonic acid such as methanesulfonic acid or ethanesulfonic acid.
  • organic acids Power ⁇ Inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid may be used.
  • Preferred acids are paratoluenesulfonic acid and phosphoric acid. These acids are preferably used in the form of an aqueous solution, and the concentration thereof is usually desirably 0.1 to 500 mmol / l. If the concentration is less than 0.1 mmol / l, sufficient effects may not be obtained.If the concentration exceeds 500 mmol / l, it may be uneconomical. The possibility of causing corrosion of the device is increased.
  • nitrogen-containing sulfur compound examples include, for example, mercaptoalkylamines such as 2-mercaptoethylamine and 3-mercaptobutylamine, aminoaminophenols such as 1,4-aminothiophenol, 3-mercapto Examples thereof include mercaptoalkylpyridines such as methylpyridine, 3-mercaptoethylpyridine, and 3-mercaptoethylpyridine. Among these compounds, mercaptoalkylamines are particularly preferred.
  • the concentration of the aqueous solution of the nitrogen-containing sulfur compound is preferably from 1 to 10% by mass.
  • ketones used together with the acid and the nitrogen-containing sulfur compound include acetone, methyl ethyl ketone, getyl ketone, and methyl isobutyl ketone. Of these, acetone is particularly preferred.
  • the amount of ketones used is desirably in the range of 0.1 to 5 mol per 1 mol of the nitrogen-containing sulfur compound. This is because if the amount of ketones is less than 0.1 mol, the effect may not be sufficiently obtained, and if it exceeds 5 mol, ketones may be heavier. .
  • aldehydes may be used instead of ketones. As the aldehydes, formalin, acetoaldehyde, and benzaldehyde are preferably used.
  • the amount of the aldehyde used is preferably in the range of 0.1 to 5 mol per 1 mol of the nitrogen-containing sulfur compound as in the case of the ketone.
  • the neutralization of the acidic cation exchange resin fixed bed filled in the reactor is carried out by introducing an aqueous solution containing all acids, nitrogen-containing sulfur compounds and ketones or aldehydes into the reactor and circulating it.
  • an aqueous solution of an acid is introduced into the reactor first, and is passed through the fixed resin bed at least once, and the nitrogen-containing sulfur compound and the ketones or aldehydes are directly added to the effluent after passing through the fixed resin bed.
  • these aqueous solutions may be mixed, and the resulting aqueous solution may be introduced into the reactor and circulated.
  • the aqueous solution for the neutralization treatment is used until the neutralization rate of the acidic cation exchange resin reaches a desired value.
  • it is circulated until acid groups such as sulfonic acid groups are neutralized by 2 to 50%, and then passed through a resin fixed bed.
  • the flow rate of the aqueous solution for neutralization treatment, the amount of the aqueous solution for neutralization treatment, and the neutralization treatment time are appropriately selected so as to achieve a desired neutralization rate.
  • the flow rate is 0.1 to 1 Om LZ hr / mL resin
  • the amount used is 0.5 to 10 L per mole of acidic group
  • the neutralization time is 20 to 200 hours. It is.
  • the neutralization temperature may be room temperature or may be heated to a temperature range of 30 to 100 ° C.
  • the higher the neutralization temperature the higher the reaction speed, which can shorten the reaction time. If the temperature exceeds 1S100 ° C, the possibility of acid corrosion of the equipment increases, and the sulfone group of the acidic cation exchange resin increases. Is not preferred, since the desorption of the compound increases.
  • the acidic cation exchange resin fixed bed of the present invention prepared as described above is used for continuous production of bisphenols after washing with water as necessary.
  • the continuous production of bisphenols is well known and will not be described in detail here.
  • a fixed bed of the acid cation exchange resin in which the above-mentioned carbonyl compound and phenols are placed in a reactor is 0.1.
  • 110 L 'catalyst is performed by passing at a space velocity of 1 L 1 ⁇ 1 hour 1 .
  • the molar ratio between the carbyl compound and the phenols is 0.5: 10 to 2:10, and the reaction temperature is 60 to L 0 ° C.
  • a glass column having an inner diameter of 25 mm and a length of 20 cm was used as a reactor.
  • a water-swelled sulfonic acid type cation exchange resin (Mitsubishi Chemical Corporation, Diao SK—100 mm) was filled with 100 milliliters to form a resin fixed bed. Then, at room temperature, 100 milliliters of a 1% by mass aqueous solution of paratoluenesulfonic acid was introduced into the reactor, and allowed to flow through the fixed resin bed.
  • Example 1 was repeated except that acetone was not used. Table 1 shows the results.
  • the acidic cation exchange resin packed in the reactor can be partially neutralized uniformly with good uniformity.
  • the acidic cation exchange resin fixed bed prepared by the method of the present invention is suitable as a catalyst for producing bisphenols from a raw material containing a carbyl compound and phenols.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un lit fixe préparé par enveloppement d'un réacteur au moyen d'une résine acide échangeuse de cations, d'où la formation d'un lit fixe, et par mise en contact du lit fixe résultant avec une solution aqueuse dans laquelle sont dissous un acide, un composé sulfuré azoté ainsi qu'une cétone ou un aldéhyde, ce qui permet de neutraliser partiellement ladite résine acide échangeuse de cations. Lors d'un traitement avec cette solution aqueuse, laquelle contient une cétone ou un aldéhyde en plus d'un acide et d'un composé sulfuré azoté, la résine acide échangeuse de cations est partiellement neutralisée de façon uniforme sur l'ensemble du lit fixe. En faisant réagir un composé carbonylé avec un phénol en présence du lit fixe ainsi préparé, on peut obtenir un bisphénol à teneur en sous-produit réduite de manière continue.
PCT/JP2001/004779 2000-06-07 2001-06-06 Procede de preparation de lit fixe de resine acide echangeuse de cations WO2001094014A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000-169877 2000-06-07
JP2000169877A JP2001348350A (ja) 2000-06-07 2000-06-07 ビスフェノール類製造用酸性陽イオン交換樹脂固定床の調製方法

Publications (1)

Publication Number Publication Date
WO2001094014A1 true WO2001094014A1 (fr) 2001-12-13

Family

ID=18672669

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2001/004779 WO2001094014A1 (fr) 2000-06-07 2001-06-06 Procede de preparation de lit fixe de resine acide echangeuse de cations

Country Status (2)

Country Link
JP (1) JP2001348350A (fr)
WO (1) WO2001094014A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8932976B2 (en) 2007-06-14 2015-01-13 Dow Global Technologies Llc Preparation of catalyst for bisphenols production

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4298438B2 (ja) * 2003-09-01 2009-07-22 出光興産株式会社 ビスフェノールａ製造用変性触媒の調製方法
JP2005074353A (ja) * 2003-09-02 2005-03-24 Idemitsu Kosan Co Ltd ビスフェノールａ製造用変性触媒の調製方法
JP4452058B2 (ja) * 2003-11-04 2010-04-21 出光興産株式会社 ビスフェノールａ製造用変性触媒の調製方法
JP4452119B2 (ja) * 2004-04-26 2010-04-21 出光興産株式会社 ビスフェノール類製造用触媒の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1539463A (en) * 1976-07-26 1979-01-31 Shell Int Research Preparation of a fixed bed catalyst
JPH06296871A (ja) * 1993-04-20 1994-10-25 Chiyoda Corp 反応器に対するビスフェノールａ製造用触媒の充填方法
JPH0840961A (ja) * 1994-08-02 1996-02-13 Nippon Steel Chem Co Ltd 酸性陽イオン交換樹脂固定床の調製方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1539463A (en) * 1976-07-26 1979-01-31 Shell Int Research Preparation of a fixed bed catalyst
JPH06296871A (ja) * 1993-04-20 1994-10-25 Chiyoda Corp 反応器に対するビスフェノールａ製造用触媒の充填方法
JPH0840961A (ja) * 1994-08-02 1996-02-13 Nippon Steel Chem Co Ltd 酸性陽イオン交換樹脂固定床の調製方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8932976B2 (en) 2007-06-14 2015-01-13 Dow Global Technologies Llc Preparation of catalyst for bisphenols production

Also Published As

Publication number Publication date
JP2001348350A (ja) 2001-12-18

Similar Documents

Publication Publication Date Title
JP3446060B2 (ja) ビスフエノール類の製造法
JPH0217144A (ja) ビスフエノールの製造方法
JPH0840963A (ja) ビスフェノールの製造法
WO2014101374A1 (fr) Procédé de production de crésol
JP4050053B2 (ja) ビスフェノール類製造用触媒及び該触媒を用いるビスフェノール類の製造方法
KR101418765B1 (ko) 강산 양이온 교환 수지
WO2001094014A1 (fr) Procede de preparation de lit fixe de resine acide echangeuse de cations
US5491268A (en) Process for removal of acidic compounds from phenol process streams
JP4213467B2 (ja) ビスフェノール製造用アミン修飾触媒
WO2001074488A1 (fr) Procede pour l'elaboration de lit fixe de resine echangeuse de cation acide destine a la production de bisphenols
EP1672005A4 (fr) Procede de production de bisphenol a
RU2373994C2 (ru) Катализатор для получения бисфенолов
JPS593455B2 (ja) ４，４′−ジヒドロキシ−３，３′，５，５′−テトラアルキル−ジフエニルアルカンの製造方法
JP4790601B2 (ja) クメンヒドロペルオキシドからビスフェノールａを製造するための統合プロセス
JP3770634B2 (ja) ビスフェノールａの製造方法
RU2620086C2 (ru) Способ преобразования побочных продуктов в процессе синтеза бисфенола a
RU2339608C2 (ru) Совмещенный способ получения дифенола а из гидропероксида кумена
TW202017891A (zh) 來自雙酚製造之殘餘物流的處理
KR100878062B1 (ko) 비스페놀의 제조에 사용되는 촉매의 재생 방법
WO2001074489A1 (fr) Preparation d'un lit fixe de resine acide echangeuse de cations destine a la production de bisphenols
WO2000053315A1 (fr) Procede de preparation d'un catalyseur destine a etre utilise pour produire du bisphenol
JP2004508929A (ja) 強酸性陽イオン交換樹脂の製造方法
TW202237264A (zh) 觸媒系統和製造雙酚ａ的方法
JPH10216532A (ja) 強酸性陽イオン交換樹脂およびこれを用いるビスフェノ−ル誘導体の製造方法
TW202132245A (zh) 在羥丙酮存在下製備雙酚ａ（ｂｐａ）之方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): BR CN ID IN KR SG US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase