JPS6126771B2 - - Google Patents
Info
- Publication number
- JPS6126771B2 JPS6126771B2 JP53063389A JP6338978A JPS6126771B2 JP S6126771 B2 JPS6126771 B2 JP S6126771B2 JP 53063389 A JP53063389 A JP 53063389A JP 6338978 A JP6338978 A JP 6338978A JP S6126771 B2 JPS6126771 B2 JP S6126771B2
- Authority
- JP
- Japan
- Prior art keywords
- slurry
- tank
- esterification reaction
- batch
- pump
- 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
Links
- 239000002002 slurry Substances 0.000 claims description 241
- 238000005886 esterification reaction Methods 0.000 claims description 84
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 70
- 239000007788 liquid Substances 0.000 claims description 58
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- 238000003860 storage Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 230000032050 esterification Effects 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 241000270295 Serpentes Species 0.000 claims description 9
- 238000005259 measurement Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001088022 Malpolon monspessulanus Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002716 delivery method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- HDBOOJCPFYJMBJ-UHFFFAOYSA-M hydroxy(oxo)tin Chemical compound O[Sn]=O HDBOOJCPFYJMBJ-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid esters
- C07C69/82—Terephthalic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
- Treatment Of Sludge (AREA)
Description
【発明の詳細な説明】
本発明は主としてテレフタル酸とエチレングリ
コールとからビス−β−ヒドロキシエチルテレフ
タレートおよび／またはその低重合体を主体とし
てなる物質を得る直接エステル化法の改良に関す
るものである。更に詳しくは、テレフタル酸とエ
チレングリコールのスラリの製造、スラリの貯
蔵、スラリの製造帯域とエステル化反応槽帯域間
のスラリの輸送、スラリの複数のエステル化反応
槽への供給、および回分式エステル化反応で構成
された新規なトータルシステムに関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention mainly relates to an improvement in the direct esterification method for obtaining a substance mainly consisting of bis-β-hydroxyethyl terephthalate and/or its low polymer from terephthalic acid and ethylene glycol. More specifically, the production of slurries of terephthalic acid and ethylene glycol, storage of slurries, transportation of slurries between slurry production zones and esterification reactor zones, feeding of slurries to multiple esterification reactors, and batch esterification. It concerns a new total system composed of chemical reactions.
テレフタル酸（以下TPAという）とエチレン
グリコール（以下EGという）とから、エステル
化反応によつてビス−β−ヒドロキシエチルテレ
フタレートおよび／またはその低重合体（以下
BHTという）を得、次いでそれを重縮合反応し
てポリエチレンテレフタレート（以下PETとい
う）を得る直接重合法はよく知られている。 Bis-β-hydroxyethyl terephthalate and/or its low polymer (hereinafter referred to as EG) is produced from terephthalic acid (hereinafter referred to as TPA) and ethylene glycol (hereinafter referred to as EG) through an esterification reaction.
The direct polymerization method of obtaining polyethylene terephthalate (hereinafter referred to as PET) by polycondensation reaction is well known.
また直接エステル化法は、テレフタル酸ジメチ
ルエステルから出発するエステル交換法よりも経
済的により有利な方法であることもよく知られて
いる。更に直接重合法は連続式または回分式が知
られているが、近年は連続式についての提案が多
くなされている。 It is also well known that the direct esterification process is economically more advantageous than the transesterification process starting from dimethyl terephthalate. Further, direct polymerization methods are known to be of a continuous type or a batch type, but in recent years, many proposals have been made for a continuous type.
しかしながら連続式直接重合法は少量多品種生
産の目的のためには機能的でないこと、および反
応器内のゲル化物、異物等の生成が完全には防止
できず、このようなゲル化物、異物等がポリマ内
に混入される等の欠点があり、必ずしも連続式直
重法が有利であるということはない。 However, the continuous direct polymerization method is not functional for the purpose of low-volume, high-mix production, and cannot completely prevent the formation of gelled substances, foreign substances, etc. in the reactor. Continuous direct loading method is not necessarily advantageous since it has drawbacks such as the fact that it is mixed into the polymer.
このため改良した直重法として、特開昭51−
91993号公報および特開昭52−147694号公報に記
載されている方法のように、TPAとEGとを連続
エステル化方法を用いて反応させBHTを得、次
いでこのBHTを多数の回分式重縮合反応槽に分
配して、各種の用途に見合つた多様なポリエステ
ルを得る方法がある。 For this reason, as an improved direct loading method, JP-A-51-
BHT is obtained by reacting TPA and EG using a continuous esterification method, as described in JP-A-91993 and JP-A-52-147694, and then this BHT is subjected to multiple batch polycondensation processes. There is a method of distributing the polyester into a reaction tank to obtain a variety of polyesters suitable for various uses.
しかしながらこのような方法でも、さらに多品
種化生産を行う要求には不満足な点がある。すな
わちエステル化反応帯域でなければ改良のできな
い品種には不向きであり、例えばTPAとEG以外
の第３成分の共重合反応も重縮合反応帯域よりは
エステル化反応帯域の方がより有利である。更に
上記の公開公報では、BHTの貯蔵、送液等につ
いては何ら記載されてないが、少なくとも200℃
以上の融点をもつBHTを、高温に保持したまま
貯蔵し多数の回分式重縮合反応槽へ送液すること
は、熱量的にも、着色およびジエチレングリコー
ル含量増加等の品質面においても不利な点がある
ことは否めない。特に長距離輸送には不利であ
る。 However, even this method is unsatisfactory in meeting the demand for more diverse production. In other words, it is not suitable for varieties that cannot be improved without the esterification reaction zone, and for example, the esterification reaction zone is more advantageous than the polycondensation reaction zone for the copolymerization reaction of a third component other than TPA and EG. Furthermore, the above publication does not mention anything about BHT storage, liquid delivery, etc., but at least 200℃
Storing BHT, which has a melting point above, at a high temperature and sending it to multiple batch polycondensation reactors has disadvantages in terms of calorific value and quality, such as coloration and increased diethylene glycol content. There is no denying that. This is especially disadvantageous for long-distance transportation.
本発明者らは多数の回分式エステル化反応槽へ
TPAとEGとからなるスラリを送液し反応を行う
ため、スラリをエステル化反応帯域とは別の帯域
で製造し、これをエステル化反応帯域へ長距離送
液し、各々の回分式エステル化反応槽へ仕込んで
各種用途に見合つた品種のポリエステルを製造す
る方法を提供することを目的として、かかる直重
法のシステムを種々検討し、最も有利と思われる
システムを鋭意検討した結果本発明に到達したも
のである。 The present inventors used a large number of batch-type esterification reactors.
In order to transport and react a slurry consisting of TPA and EG, the slurry is produced in a zone separate from the esterification reaction zone, and is transported over a long distance to the esterification reaction zone for each batch-type esterification. With the aim of providing a method for producing polyester of a variety suitable for various uses by charging it into a reaction tank, we have studied various systems of the direct loading method, and as a result of intensive study of the system that seems to be the most advantageous, we have developed the present invention. It has been reached.
すなわち、本発明は、
(A) TPAとEGとからなるスラリの製造帯域にお
いて、EG／TPAモル比0.80以上1.70以下の範
囲内で設定モル比となるようにスラリ量及びモ
ル比を制御して、TPAとEGとのスラリを得、
これをスラリ貯槽に貯え、
(B) 該スラリ貯槽に貯えたスラリを、貯槽下に設
けたスラリ送液用ポンプを用いて、エステル化
反応帯域に存在するスラリ供給槽へスラリを送
液し、
(C) 該スラリ供給槽へ貯えたスラリを、スラリ供
給槽下に設けた第１次供給用スラリポンプを用
いて第１次スラリ供給回路へ送液し、
(D) 該第１次スラリ供給回路から分岐しエステル
化反応槽へ直結した複数の第２次スラリ供給回
路に第２次スラリ供給ポンプを設け、該スラリ
ポンプを用いてスラリを連続的に回分式エステ
ル化反応槽へ仕込み、エステル化反応を行うこ
とを特徴とする回分式エステル化方法である。 That is, the present invention provides: (A) In the production zone of the slurry consisting of TPA and EG, the slurry amount and molar ratio are controlled so that the EG/TPA molar ratio is within the range of 0.80 to 1.70. , obtain a slurry with TPA and EG,
storing this in a slurry storage tank; (B) sending the slurry stored in the slurry storage tank to a slurry supply tank present in the esterification reaction zone using a slurry feeding pump provided below the storage tank; (C) Sending the slurry stored in the slurry supply tank to the primary slurry supply circuit using a slurry pump for primary supply provided below the slurry supply tank, (D) Supplying the primary slurry. A plurality of secondary slurry supply circuits branched from the circuit and directly connected to the esterification reaction tank are provided with secondary slurry supply pumps, and the slurry is continuously fed into the batch type esterification reaction tank using the slurry pump, and the esterification This is a batch esterification method characterized by carrying out a chemical reaction.
本発明の第１段階は、EG／TPAモル比0.80以
上1.70以下の範囲内のスラリを、設定モル比とな
るように連続的に制御して得、これをスラリ貯槽
に貯えることにある。 The first step of the present invention is to obtain a slurry having an EG/TPA molar ratio of 0.80 to 1.70 by continuously controlling the slurry to a set molar ratio, and store this in a slurry storage tank.
EG／TPAモル比を0.80以上1.70以下の範囲に
限定したことは、スラリの流動性および送液性を
向上させ、かつエステル化反応性を良好に保たせ
るために必要なことである。またより好ましいモ
ル比は1.05以上1.50以下の範囲である。 Limiting the EG/TPA molar ratio to a range of 0.80 or more and 1.70 or less is necessary to improve the fluidity and feedability of the slurry and to maintain good esterification reactivity. Further, a more preferable molar ratio is in the range of 1.05 or more and 1.50 or less.
EG／TPAモル比が0.80未満では、スラリが流
動しにくく、送液性が悪化し、取り扱い性が悪く
なり好ましくない。 If the EG/TPA molar ratio is less than 0.80, the slurry will be difficult to flow, the liquid transferability will be poor, and the handling property will be poor, which is not preferable.
EG／TPAモル比が1.70をこえる範囲では、ス
ラリの流動化現象は好ましい方向にあるが、一方
スラリ中のTPAの沈降現象が激しくなり、やは
り取り扱い性は悪化する傾向にあると同時に、エ
ステル化反応にとつて余剰のEGが多くなり、反
応性、品質等が悪化する傾向にあつて好ましくな
い。 In a range where the EG/TPA molar ratio exceeds 1.70, the fluidization phenomenon of the slurry is favorable, but on the other hand, the sedimentation phenomenon of TPA in the slurry becomes severe, and the handling properties tend to deteriorate as well.At the same time, the esterification This is not preferable because it increases the amount of excess EG for the reaction and tends to deteriorate reactivity, quality, etc.
EG／TPAモル比を0.80以上1.70以下の範囲に
設定したスラリは、設定したモル比の変化巾が少
なく、一定したモル比となるように制御すること
が必要である。モル比の変化巾は0.80以上1.70以
下の範囲内において、好ましくはあらかじめ設定
したモル比の±0.05以下であるが、更に好ましく
は±0.02以下である。このように精度の高い一定
モル比の管理下であるとスラリの製造送液、反応
面にとつて操作が安定し、品質の変化の少ない
BHTを得ることができる。 The slurry in which the EG/TPA molar ratio is set in the range of 0.80 or more and 1.70 or less needs to be controlled so that the set molar ratio has a small variation range and becomes a constant molar ratio. The variation width of the molar ratio is within the range of 0.80 or more and 1.70 or less, preferably ±0.05 or less of the preset molar ratio, more preferably ±0.02 or less. Controlling a fixed molar ratio with high precision in this way ensures stable operations for slurry production, liquid delivery, and reaction surfaces, with little change in quality.
You can get BHT.
一方TPAとEGとを混合したスラリは一時スラ
リ貯槽に貯え、これを反応帯域へ送液するが、こ
の送液量は常に一定であるとは限らず、複数のエ
ステル化槽の需要状態により、その送液量を適宜
変化させなければならない。もし送液量が一定で
あるならば、TPAとEGとの計量は一点制御でよ
いが送液量を適宜変化させる場合は、TPAとEG
との計量をスラリ貯槽の液量に合わせてカスケー
ド制御を行う。 On the other hand, the slurry containing TPA and EG is temporarily stored in a slurry storage tank and sent to the reaction zone, but the amount of liquid sent is not always constant and depends on the demand status of multiple esterification tanks. The amount of liquid fed must be changed as appropriate. If the amount of liquid fed is constant, the measurement of TPA and EG can be controlled at one point, but if the amount of liquid fed is changed appropriately, TPA and EG
Cascade control is performed by matching the amount of liquid with the amount of liquid in the slurry storage tank.
これを第１図を用いて説明する。 This will be explained using FIG.
第１図は本発明の第１段階の好ましい実施態様
を示したものである。 FIG. 1 shows a preferred embodiment of the first stage of the invention.
TPAは回路Ａからホツパー１に導入する。ホ
ツパー１に貯えられたTPAはロータリーバルブ
２を通過させて無端ベルト式計量機３に導入され
計量された後、混練機４に送り込まれる。TPA
計量機は無端ベルト式のほか容積式または電磁振
動式等の他の計量機であつてもよい。 TPA is introduced into hopper 1 from circuit A. The TPA stored in the hopper 1 passes through a rotary valve 2, is introduced into an endless belt type weighing machine 3, is weighed, and is then fed into a kneading machine 4. TPA
The weighing machine may be an endless belt type, or may be a volumetric type or an electromagnetic vibration type.
EGは回路Ｂよりポンプ５を用いて流量計６に
導き、続いてコントロールバルブ７を通過させて
混練機４に送り込む。混練機４でTPAとEGを混
合してスラリを得、これをスラリ貯槽８に貯え
る。スラリ貯槽８に貯えられたスラリは貯槽下の
スラリポンプ９を用いて、エステル化反応帯域に
送液される。このスラリ送液量は、エステル化反
応帯域におけるスラリ需要量に応じてポンプ９の
回転数を適宜増減し、送液量を制御する。従つて
スラリ貯槽の液面計１０によりスラリ貯槽８の液
面を測定し、設定液面の範囲を保つようにスラリ
製造量をカスケード制御する。このカスケード制
御方法は、スラリ貯槽８の液面を測定し、この信
号をTPA重合コントローラWRC１１に与え、
TPA計量機３の速度およびロータリーバルブ２
の回転速度を調整してTPA重量を制御する。ス
ラリ貯槽８の液面は公知の液面計を用いて測定し
てもよいし、ロードセルを用いて液量を測定して
もよい。 EG is guided from circuit B to a flow meter 6 using a pump 5, and then passed through a control valve 7 and sent to a kneader 4. TPA and EG are mixed in a kneader 4 to obtain a slurry, which is stored in a slurry storage tank 8. The slurry stored in the slurry storage tank 8 is sent to the esterification reaction zone using a slurry pump 9 below the storage tank. The amount of slurry to be fed is controlled by appropriately increasing or decreasing the rotational speed of the pump 9 according to the amount of slurry demanded in the esterification reaction zone. Therefore, the liquid level of the slurry storage tank 8 is measured by the liquid level gauge 10 of the slurry storage tank, and the slurry production amount is controlled in cascade so as to maintain the set liquid level range. This cascade control method measures the liquid level of the slurry storage tank 8, gives this signal to the TPA polymerization controller WRC11,
TPA weighing machine 3 speed and rotary valve 2
Control the TPA weight by adjusting the rotation speed. The liquid level in the slurry storage tank 8 may be measured using a known liquid level gauge, or the liquid level may be measured using a load cell.
TPA重量コントローラWRC１１はTPA重量を
制御すると同時に、重量測定信号をモル比演算器
MRC１２に与え、モル比演算器MRC１２では
TPA重量に見合いかつ設定モル比に見合つたEG
量を演算し、この値をEG流量コントローラFRC
１３に与え、EG流量コントローラFRC１３はこ
の値に見合つたEGを計量するようにコントロー
ルバルブ７の開度を調整して、EGを制御する。
モル比演算器MRC１２は次の式により瞬時的に
EG量を演算する。 The TPA weight controller WRC11 controls the TPA weight and at the same time converts the weight measurement signal into a molar ratio calculator.
In the molar ratio calculator MRC12,
EG commensurate with TPA weight and set molar ratio
Calculate the amount and send this value to the EG flow controller FRC.
13, and the EG flow rate controller FRC13 controls the EG by adjusting the opening degree of the control valve 7 so as to measure EG corresponding to this value.
The molar ratio calculator MRC12 instantaneously calculates
Calculate the EG amount.
EG量＝Ｗ／１６６×Ｍ×62 （ただしEG量単位：Kg Ｗ：TPA重量（Kg） Ｍ：設定モル比） EGの通過量は流量計６でカウントする。 EG amount = W/166 x M x 62 (However, EG amount unit: Kg W: TPA weight (Kg) M: set molar ratio) The amount passing through the EG is counted by a flowmeter 6.
流量計は通常容積式であるので、EGの温度に
応じた比重を勘案してEG重量を求めねばならな
い。 Since the flowmeter is usually a positive displacement type, the weight of the EG must be determined by taking into account the specific gravity depending on the temperature of the EG.
また、上記のカスケード制御方法においては
TPAから先に制御を行つたが、EG側から先に制
御してもよい。 In addition, in the above cascade control method,
Although the TPA was controlled first, the EG side may be controlled first.
本発明の第２段階は、スラリ貯槽に貯えたスラ
リを、貯槽下に設けた送液用スラリポンプを用い
てエステル化反応帯域に供給するためのスラリ供
給槽へスラリを送液するにある。この送液にあた
つて更に好ましい方法は、スラリ貯槽とスラリ供
給槽との中間に、中間スラリ槽および中間スラリ
槽下に設けた送液用スラリポンプからなるユニツ
トを設けて送液する方法である。この方法により
スラリ製造帯域とエステル化反応帯域とを別の帯
域に設け、スラリを長距離送液することができ
る。 The second step of the present invention consists in transporting the slurry stored in the slurry storage tank to the slurry supply tank for supplying to the esterification reaction zone using a slurry pump for transport provided below the storage tank. A more preferable method for this liquid feeding is to provide a unit between the slurry storage tank and the slurry supply tank, which consists of an intermediate slurry tank and a slurry pump for liquid feeding installed under the intermediate slurry tank, to transport the liquid. be. With this method, the slurry production zone and the esterification reaction zone are provided in separate zones, and the slurry can be transported over long distances.
またスラリを長距離送液するにあたつての送液
量制御は、中間スラリ槽および／またはスラリ供
給槽の液量を測定し、設定液面を保つように当該
槽下に設けたスラリポンプおよび／または当該槽
より以前の槽の下に設けたスラリポンプの回転数
を制御して行う。 In addition, when sending slurry over long distances, the amount of liquid sent is controlled by measuring the amount of liquid in the intermediate slurry tank and/or slurry supply tank, and using a slurry pump installed below the tank to maintain the set liquid level. and/or by controlling the rotational speed of a slurry pump provided below the tank before the tank.
これを第２図を用いて説明する。第２図は本発
明の第２段階、第３段階および第４段階の好まし
い実施態様を図示したものである。まず第２段階
について説明すると、矢印Ｃより導入され、スラ
リ貯槽８に貯えられたスラリは、スラリポンプ９
を用い送液回路３１を通して中間スラリ槽３３に
送液される。 This will be explained using FIG. FIG. 2 illustrates a preferred embodiment of the second, third and fourth stages of the present invention. First, to explain the second stage, the slurry introduced from the arrow C and stored in the slurry storage tank 8 is pumped into the slurry pump 9.
The liquid is sent to the intermediate slurry tank 33 through the liquid sending circuit 31 using a liquid pump.
中間スラリ槽３３に一時貯えられたスラリは、
スラリポンプ３４を用い送液回路３２を通してス
ラリ供給槽４１に送液される。 The slurry temporarily stored in the intermediate slurry tank 33 is
The slurry pump 34 is used to send the liquid to the slurry supply tank 41 through the liquid sending circuit 32.
なお中間スラリ槽および中間スラリ槽下に設け
たスラリポンプからなるユニツトは多数あつても
よい。このような送液方法では、長距離輸送が可
能なため、各スラリ槽間の距離は、60ｍ以上とす
ることもでき、スラリ製造帯域からエステル化反
応帯域までの距離は100ｍ以上、更に条件を選ぶ
ならば１Km以上としてもさしつかえない。 Note that there may be a large number of units each consisting of an intermediate slurry tank and a slurry pump provided below the intermediate slurry tank. With such a liquid delivery method, long-distance transportation is possible, so the distance between each slurry tank can be 60 m or more, and the distance from the slurry production zone to the esterification reaction zone can be 100 m or more. If you have a choice, you can go for more than 1km.
また、スラリ製造帯域とエステル化反応帯域
は、別の階に設けることも、別の建物に設けるこ
とも可能である。 Additionally, the slurry production zone and the esterification reaction zone can be located on separate floors or in separate buildings.
また各スラリ槽下のスラリポンプは複数個設
け、故障の場合に備えた方がより好ましい。また
各スラリ槽下に設けた複数のスラリポンプを用い
て、複数のスラリ送液回路を送液させてもよく、
スラリ製造帯域を１個所とし、複数のエステル化
反応帯域に送液してもよい。この場合スラリ貯槽
８は１個にし、スラリ供給槽４１は複数個設ける
ことになる。 Further, it is more preferable to provide a plurality of slurry pumps under each slurry tank in case of failure. Alternatively, a plurality of slurry pumps provided under each slurry tank may be used to send liquid through a plurality of slurry liquid feeding circuits.
One slurry production zone may be used, and the slurry may be sent to a plurality of esterification reaction zones. In this case, one slurry storage tank 8 will be provided, and a plurality of slurry supply tanks 41 will be provided.
上記した第２図のスラリ送液システムにおいて
のスラリ送液制御は、中間スラリ槽３３において
は中間スラリ槽３３の液面を液面計３５によつて
測定し、この液面に応じて中間スラリ槽３３下に
設けたスラリポンプ３４の回転数を制御して行
い、スラリ供給槽４１においては液面を液面計４
４によつて測定し、この液量に応じて、スラリ製
造帯域のスラリ貯槽８の下に設けたスラリポンプ
９の回転数を制御して行う。もちろん各スラリ槽
の液面コントロールは、当該槽下に設けたスラリ
ポンプの回転数および／または当該槽より以前の
槽下に設けたスラリポンプの回転数を制御して行
うので、液面計４４のコントロール信号をポンプ
３４に、液面計３５のコントロール信号をポンプ
９に与えてもよい。 The slurry feeding control in the slurry feeding system shown in FIG. This is done by controlling the rotation speed of the slurry pump 34 provided below the tank 33, and the liquid level in the slurry supply tank 41 is measured using a level gauge 4.
4, and the rotational speed of the slurry pump 9 provided below the slurry storage tank 8 in the slurry production zone is controlled in accordance with this liquid amount. Of course, the liquid level in each slurry tank is controlled by controlling the rotation speed of the slurry pump installed under the tank and/or the rotation speed of the slurry pump installed under the tank before the current tank. The control signal of the liquid level gauge 35 may be applied to the pump 34 and the control signal of the liquid level gauge 35 may be applied to the pump 9.
スラリを貯える槽８，３３，４１および／また
は送液する回路３１，３２は、冬期スラリが冷却
されない程度の温度に温度調整するのが好まし
く、また逆に80℃以上となるとスラリは異常に粘
度が上るので、80℃以上とならないように温度調
整するのが好ましい。 It is preferable to adjust the temperature of the tanks 8, 33, 41 that store the slurry and/or the circuits 31, 32 that feed the liquid to a temperature that does not cool the slurry in the winter, and conversely, if the temperature exceeds 80°C, the slurry will have an abnormally viscous viscosity. It is preferable to adjust the temperature so that it does not exceed 80°C.
またスラリを貯える槽８，３３，４１では、槽
下のスラリ循環用スラリポンプを用いて、スラリ
を循環させ、スラリを槽に戻し、スラリを常に流
動させてもよい。 Further, in the tanks 8, 33, and 41 for storing slurry, a slurry pump for circulating slurry under the tank may be used to circulate the slurry and return the slurry to the tank, so that the slurry is constantly flowing.
本発明の第３段階は、エステル化反応帯域に存
在するスラリ供給槽に貯えたスラリを、スラリ供
給槽下に設けた第１次供給用スラリポンプを用い
て第１次スラリ供給回路へ送液するにある。 In the third step of the present invention, the slurry stored in the slurry supply tank existing in the esterification reaction zone is sent to the first slurry supply circuit using the first supply slurry pump provided below the slurry supply tank. There is something to do.
これを第２図を用いて説明するならば、スラリ
供給槽４１に貯えたスラリを、第１次供給用スラ
リポンプ４２を用いて第１次スラリ供給回路４５
へ送液するにある。第１次スラリ供給回路４５で
送液されるスラリ量は、複数のエステル化反応槽
で瞬時に必要とする量の1.2倍〜10倍程度でよ
い。また第１次スラリ供給回路４５の送液スラリ
量はスラリポンプ４２の回転数をコントロールし
て決める。 To explain this using FIG. 2, the slurry stored in the slurry supply tank 41 is transferred to the primary slurry supply circuit 45 using the primary supply slurry pump 42.
To send liquid to. The amount of slurry fed in the first slurry supply circuit 45 may be approximately 1.2 times to 10 times the amount instantly required by the plurality of esterification reaction tanks. Further, the amount of slurry sent to the primary slurry supply circuit 45 is determined by controlling the rotation speed of the slurry pump 42.
第１次スラリ供給回路４５へ送液したスラリ
は、１部はエステル化反応槽へ仕込まれるが、余
剰分は循環させてスラリ供給槽４１に戻してもよ
く、あるいは他の槽へ送液してもよい。 A portion of the slurry sent to the primary slurry supply circuit 45 is charged into the esterification reaction tank, but the surplus may be circulated and returned to the slurry supply tank 41, or may be sent to another tank. It's okay.
またスラリ供給槽４１に貯えたスラリは、更に
分岐して他のエステル化反応帯域に存在するスラ
リ供給槽へ送液してもよい。 Further, the slurry stored in the slurry supply tank 41 may be further branched and sent to a slurry supply tank existing in another esterification reaction zone.
本発明の第４段階は、第１スラリ供給回路から
複数のエステル化反応槽へ直結した各々の第２次
スラリ供給回路に第２次スラリ供給ポンプを設
け、該スラリポンプを用いてスラリを連続的に複
数の回分式エステル化反応槽へ仕込み、反応を行
うにある。 The fourth step of the present invention is to provide a secondary slurry supply pump in each secondary slurry supply circuit directly connected from the first slurry supply circuit to the plurality of esterification reactors, and use the slurry pump to continuously supply the slurry. The method is to charge it into multiple batch-type esterification reactors and carry out the reaction.
これを第２図を用いて説明するならば、第１次
スラリ供給回路４５から分岐しエステル化反応槽
５０，５０′，……、へ直結した複数の第２次ス
ラリ供給回路５４，５４′，……、に第２次スラ
リ供給ポンプ４７，４７′，……、を設け、この
第２次スラリ供給ポンプ４７，４７′，……、を
用いてスラリを連続的に回分式エステル化反応槽
５０，５０′，……、へ仕込み、反応を行う。な
お第１次スラリ供給回路４５から第２次スラリ供
給回路５４，５４′，……、への分岐部にはボー
ル弁等の弁４６，４６′，……、を設けた方が好
ましいが、弁を設けなくてもよい。また第２次ス
ラリ供給回路５４，５４′，……、のエステル化
反応槽５０，５０′，……、への供給部もボール
弁等の弁（図示せず）を設けた方が好ましい。さ
らに、エステル化反応槽５０，５０′，……、へ
の供給部は加熱によりスラリが閉塞しやすいの
で、水を用いて冷却するのが好ましい。 To explain this using FIG. 2, a plurality of secondary slurry supply circuits 54, 54' are branched from the primary slurry supply circuit 45 and directly connected to the esterification reaction vessels 50, 50', . , ..., are provided with secondary slurry supply pumps 47, 47', ..., and the slurry is continuously subjected to a batch esterification reaction using the secondary slurry supply pumps 47, 47', .... The reactants are charged into tanks 50, 50', . . . and reacted. Note that it is preferable to provide valves 46, 46', . . . such as ball valves at the branch portions from the primary slurry supply circuit 45 to the secondary slurry supply circuits 54, 54', . It is not necessary to provide a valve. Further, it is preferable that the supply portions of the secondary slurry supply circuits 54, 54', . . . to the esterification reaction vessels 50, 50', . Furthermore, since slurry is likely to clog the supply section to the esterification reaction vessels 50, 50', . . . due to heating, it is preferable to cool the supply section using water.
エステル化反応槽５０，５０′，……、へのス
ラリの供給量はスラリポンプ４７，４７′，…
…、の総回転数によつて管理してもよいし、また
はエステル化反応槽に液面計４９，４９′，…
…、を設けこれによつて管理してもよい。スラリ
のエステル化反応槽５０，５０′，……、への供
給時間は１回分の反応当り、２時間〜５時間がよ
い。すなわち１回分の反応では、スラリは２時間
〜５時間かけて供給し、供給が終了すると第２次
スラリ供給ポンプ４７，４７′，……、は停止
し、また反応が終了するまでの規定時間と、反応
が終了したBHTを移行弁５１，５１′，……、を
開いて規定量重合反応槽（図示せず）へ移行させ
る時間、第２次スラリ供給ポンプ４７，４７′，
……、は停止したままにしておく。従つて反応開
始はスラリ供給開始した点にあり、以降規定時間
スラリを連続して供給する。 The amount of slurry supplied to the esterification reaction tanks 50, 50', . . . is determined by the slurry pumps 47, 47', .
It may be controlled by the total number of revolutions of the esterification reaction tank, or the liquid level gauges 49, 49',...
... may be provided for management. The supply time of the slurry to the esterification reaction vessels 50, 50', . . . is preferably 2 to 5 hours per reaction. In other words, in one reaction, the slurry is supplied over a period of 2 to 5 hours, and when the supply is finished, the secondary slurry supply pumps 47, 47', . , the time for opening the transfer valves 51, 51', . . . , and transferring a specified amount of the BHT after the reaction to the polymerization reaction tank (not shown), and the second slurry supply pumps 47, 47', .
..., remains stopped. Therefore, the reaction starts at the point where the slurry supply starts, and thereafter the slurry is continuously supplied for a specified period of time.
エステル化反応槽５０，５０′，……、には反
応前に予め前回分に得た生成物であるBHTを１
部残余させて存在させておく。BHTの残存量
は、反応後の全BHTの1/5〜2/3がよい。 Before the reaction, 1 liter of BHT, the product obtained in the previous batch, was added to the esterification reaction tanks 50, 50', ....
Let some parts remain and exist. The amount of BHT remaining is preferably 1/5 to 2/3 of the total BHT after the reaction.
エステル化反応の温度は220〜265℃がよく、特
にスラリ供給時は225℃〜255℃の温度がよい。 The temperature of the esterification reaction is preferably 220 to 265°C, particularly 225 to 255°C when slurry is supplied.
エステル化反応槽５０，５０′，……、の加熱
器はコイル、ジヤケツト、カランドリア等を用い
ることができ、加熱媒体はスチーム、ダウサム
油、SK油等が好ましい。 A coil, a jacket, a calandria, etc. can be used as the heater for the esterification reaction vessels 50, 50', . . . , and the heating medium is preferably steam, dowsam oil, SK oil, etc.
エステル化反応圧力は−0.87〜3.5Kg/cm2Gの範
囲が好ましく、さらに好ましくは−0.50〜2.5Kg/
cm2Ｇの範囲である。 The esterification reaction pressure is preferably in the range of -0.87 to 3.5Kg/ cm2G , more preferably -0.50 to 2.5Kg/cm2G.
It is in the range of cm 2 G.
特にスラリ供給中の反応圧力は大気圧を含めた
圧力から2.5Kg/cm2Gとし、スラリ供給終了後から
反応終了までは−0.50Kg/cm2Gから大気圧を含む
圧力までとするのがよい。このようにすると、エ
ステル化反応率が高反応率領域まで進行し重合反
応にとつて好ましい。なお加圧反応は不活性ガス
例えば窒素等を用いても、エステル化反応による
自発性圧力を利用してもよい。 In particular, the reaction pressure during slurry supply should be from a pressure including atmospheric pressure to 2.5Kg/cm 2 G, and from -0.50Kg/cm 2 G to a pressure including atmospheric pressure from the end of slurry supply until the end of the reaction. good. In this case, the esterification reaction rate progresses to a high reaction rate region, which is preferable for the polymerization reaction. In the pressurized reaction, an inert gas such as nitrogen may be used, or the spontaneous pressure caused by the esterification reaction may be used.
エステル化反応中の好ましいEGユニツト／
TPAユニツトモル比は1.05〜1.50であり特に好ま
しくは1.10〜1.35である。ここでEGユニツトと
は（エステル結合されたEG成分＋未反応EG成
分）を示し、TPAユニツトとは（エステル結合
されたTPA成分＋未反応TPA成分）を示す。上
記したモル比のスラリがエステル化反応槽に供給
されるならば特に反応中にモル比を調整する必要
はないが、スラリのEG／TPAモル比が1.05以下
であるならば必要量エステル化反応槽５０，５
０′，……、にEGを追添加する必要があり、スラ
リのEG／TPAモル比が1.50以上であるならば、
エステル化反応槽５０，５０′，……、の各々の
上部に設けたEGと水とを分離する精留塔（図示
せず）の塔底部よりEGを必要量抜き出す必要が
ある。なお付け加えるなら、精留塔底部より抜き
出したEGは精製を省略しそのままスラリ製造帯
域へ戻しスラリ化に用いることができる。 Preferred EG unit during esterification reaction/
The TPA unit molar ratio is 1.05 to 1.50, particularly preferably 1.10 to 1.35. Here, the EG unit refers to (ester bonded EG component + unreacted EG component), and the TPA unit refers to (ester bonded TPA component + unreacted TPA component). If the slurry with the above molar ratio is supplied to the esterification reaction tank, there is no need to adjust the molar ratio during the reaction, but if the EG/TPA molar ratio of the slurry is 1.05 or less, the required amount will be used for the esterification reaction. Tank 50,5
If it is necessary to additionally add EG to 0',..., and the EG/TPA molar ratio of the slurry is 1.50 or more,
It is necessary to extract a required amount of EG from the bottom of a rectification column (not shown) provided above each of the esterification reaction vessels 50, 50', . . . for separating EG and water. In addition, the EG extracted from the bottom of the rectification column can be returned to the slurry production zone without any purification and used for slurry production.
本発明方法では、スラリ供給中のエステル化反
応率は大部分の時間65〜90％を保持させる。エス
テル化反応率とは、−COOH基の−COO−結合へ
の転換率として表わす。 In the method of the present invention, the esterification reaction rate during slurry feeding is maintained at 65-90% most of the time. The esterification reaction rate is expressed as the conversion rate of -COOH group to -COO- bond.
本発明においてエステル化反応は反応前または
反応前〜反応中窒素等の不活性ガスを導入しつつ
行つてもよい。 In the present invention, the esterification reaction may be carried out while introducing an inert gas such as nitrogen before or during the reaction.
本発明においてはエステル化反応槽５０，５
０′，……、に少量成分を添加する回路を設けて
もよい。第２図の添加装置５２，５２′，……、
がこの添加回路の１例を示す。添加装置５２，５
２′，……、は、多数のエステル化反応槽が存在
する場合、１部のエステル化反応槽に限つて設け
てもよく、またエステル化反応槽１個に対し複数
個設けてもよい。この添加回路はホツパー形式、
混合槽形式からの回路のつなぎ込み方式であつて
もよく、他に液体や液体に近い流動性をもつ添加
物であるならば循環回路から添加回路をつなぎ込
んだ方式であつてもよい。特異な例としては、フ
イルムやボルトに入れて添加する回路であつても
よい。少量成分とは25重量％／ポリマ以下の共重
合もしくは混合される第３成分を意味する。具体
的にはイソフタル酸、アジピン酸、セバシン酸、
ドデカン２酸、５−ナトリウムスルホイソフタル
酸、トリメリツト酸、トリメシン酸、２・６−ナ
フタリンジカルボン酸、１・４−テトラメチレン
グリコール、プロピレングリコール、ペンタエリ
スリトール、ポリエチレングリコール、ポリプロ
ピレングリコール、ポリテトラメチレングリコー
ル、シクロヘキサンジメタノール等を示す。 In the present invention, the esterification reaction vessels 50, 5
A circuit for adding a small amount of components to 0', . . . may be provided. Addition devices 52, 52', . . . in FIG.
shows an example of this addition circuit. Addition device 52,5
2', . . . may be provided in only one part of the esterification reaction vessels when a large number of esterification reaction vessels are present, or may be provided in plural numbers for one esterification reaction vessel. This addition circuit is a hopper type,
It may be a method of connecting a circuit from a mixing tank type, or a method of connecting an addition circuit from a circulation circuit if the additive is a liquid or has fluidity close to that of a liquid. A specific example may be a circuit that is added in a film or bolt. By minor component is meant a third component that is copolymerized or mixed with less than 25% by weight of polymer. Specifically, isophthalic acid, adipic acid, sebacic acid,
Dodecanedioic acid, 5-sodium sulfoisophthalic acid, trimellitic acid, trimesic acid, 2,6-naphthalenedicarboxylic acid, 1,4-tetramethylene glycol, propylene glycol, pentaerythritol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, Indicates cyclohexanedimethanol etc.
また触媒としては、有機チタン化合物例えばア
ルキルオルソチタネートおよびその誘導体、三酸
化アンチモン、二酸化ゲルマニウム、有機スズ化
合物例えばモノアルキルヒドロキシチンオキサイ
ドおよびその誘導体等を示す。また少量成分とは
着色防止剤も含み、この着色防止剤としてはリン
酸、亜リン酸、リン酸エステル、亜リン酸エステ
ル、およびその誘導体等を示す。また少量成分と
は添加剤も含み、この添加剤とは、ヒンダードフ
エノール等の耐酸化防止剤、カオリナイト、シリ
カ、アルミナ、タルク、シリカ−アルミナ、酸化
チタン等の外部粒子化合物、第１、２、３、４級
アミン類等のようなDEG生成防止剤、カーボン
ブラツク、フタロシアニン系顔料等の原着剤、カ
ルシウム、カリウム、リチウム、マグネシウム、
マンガン、ストロンチウム、亜鉛等の内部粒子生
成剤、およびDEG生成防止剤、シリコーンオイ
ル等の可塑剤、ホウ酸等の増粘剤等を示す。これ
らは単一で添加しても、相互に組み合わせて添加
してもよい。 Examples of the catalyst include organic titanium compounds such as alkyl orthotitanate and its derivatives, antimony trioxide and germanium dioxide, and organic tin compounds such as monoalkyl hydroxytin oxide and its derivatives. Minor components also include anti-coloring agents, such as phosphoric acid, phosphorous acid, phosphoric acid esters, phosphorous acid esters, and derivatives thereof. Minor components also include additives, such as antioxidants such as hindered phenols, external particle compounds such as kaolinite, silica, alumina, talc, silica-alumina, titanium oxide, etc. DEG generation inhibitors such as secondary, tertiary, and quaternary amines, base dyes such as carbon black and phthalocyanine pigments, calcium, potassium, lithium, magnesium,
Indicates internal particle generators such as manganese, strontium, and zinc, DEG generation inhibitors, plasticizers such as silicone oil, and thickeners such as boric acid. These may be added singly or in combination with each other.
本発明ではスラリを送液および供給するスラリ
ポンプとしてスネークポンプを使用するのが好ま
しい。スネークポンプとは別名モーノポンプとも
いい、二条メネジのステーター内部に一条オネジ
のローターが遊星運動をすることにより形づけら
れる空隙を利用して送液させる非圧縮性のポンプ
であつて、例えば第３図で示されるものである。
すなわち、スラリを矢印Ｄ方向よりローター５８
の軸５５が貫通する密閉系のハウジング内に供給
する。 In the present invention, it is preferable to use a snake pump as a slurry pump for feeding and supplying slurry. A snake pump, also known as a monopump, is a non-compressible pump that pumps liquid by utilizing the gap formed by the planetary motion of a rotor with a single thread male thread inside a stator with a double thread female thread. This is shown in .
That is, the slurry is transferred to the rotor 58 from the direction of arrow D.
It is supplied into a closed housing through which the shaft 55 of the cylinder passes.
ローター５８はその表面に凹凸を有し、かつ駆
動源に連結してなる軸５９により回転が与えられ
る。またローター５８を内包してなるステーター
５６は内面にローター５８と同一ピツチで、かつ
空隙部５７を有するように構成されている。該空
隙部５７はローター５８の回転に伴いハウジング
部分より流出部分に向つて推進される。従つて送
液および供給されるスラリは矢印Ｄ方向から入
り、空隙部５７を移動し、矢印Ｅ方向へ向つて連
続的にかつ定量的に押し出される。 The rotor 58 has an uneven surface and is rotated by a shaft 59 connected to a drive source. Further, the stator 56 containing the rotor 58 is configured to have the same pitch as the rotor 58 and a gap 57 on its inner surface. The cavity 57 is propelled from the housing portion toward the outflow portion as the rotor 58 rotates. Therefore, the slurry to be sent and supplied enters from the direction of arrow D, moves through the cavity 57, and is continuously and quantitatively pushed out in the direction of arrow E.
なおスラリ供給側のハウジング部の軸５５には
TPAの沈降を防止するためにかき取り羽根を設
けた方が更によい。 Note that the shaft 55 of the housing part on the slurry supply side is
It is even better to provide a scraping blade to prevent TPA from settling.
スネークポンプに使用される好ましい材質はロ
ーター部が金属、ステーター部がゴムもしくは合
成樹脂であるが、必ずしもこれらに限定されるも
のではない。 Preferred materials for use in the snake pump include metal for the rotor and rubber or synthetic resin for the stator, but the materials are not necessarily limited to these.
本発明での効果を列挙すると次の通りである。 The effects of the present invention are listed below.
通常の大気温度で安定なスラリを長距離輸送
し、エステル化反応槽に供給するので、スラリ
配管の温度管理は冬期の厳寒時を除いては特別
に配慮する必要がなく、また異常滞留部等が
少々あつても製品に悪影響を与えることがな
く、取扱いが容易である。 Since the slurry, which is stable at normal atmospheric temperature, is transported over long distances and supplied to the esterification reaction tank, there is no need to take special consideration in temperature control of the slurry piping except during the severe cold of winter, and there is no need to take special measures to control the temperature of the slurry piping. Even if there is a small amount, it does not have a negative effect on the product and is easy to handle.
粉体TPAを扱う場所と反応を行う場所とが
別の帯域に置くことが可能であるため、粉体
TPAの粉塵がPETに混入することが避けら
れ、異物の少ないPETが得られる。 The place where powder TPA is handled and the place where the reaction is carried out can be placed in different zones, so powder TPA
This prevents TPA dust from entering PET, resulting in PET with fewer foreign substances.
スラリ製造帯域および送液システムは圧力容
器ではないので定期修理による操業停止が不必
要で、また洗浄するための停止も必要ない。 Since the slurry production zone and liquid delivery system are not pressure vessels, there is no need to shut down operations for periodic repairs or for cleaning.
エステル化反応槽および重縮合反応槽の定期
修理および洗浄による操業停止は一括して行う
必要がなく、本発明のシステムによれば反応は
常にどこかの槽で行われ、ポリマは常に製造で
きる。 It is not necessary to stop the operation of the esterification reaction tank and the polycondensation reaction tank due to periodic repairs and cleaning all at once, and according to the system of the present invention, the reaction is always carried out in some tank, and polymer can always be produced.
エステル化反応段階における共重合反応、内
部粒子生成反応等が容易にでき、多品種少量生
産プロセスに適し、高付加価値製品を生み出す
ことができる。 Copolymerization reactions, internal particle formation reactions, etc. in the esterification reaction stage can be easily carried out, making it suitable for high-mix, low-volume production processes, and producing high value-added products.
などの利点が挙げられる。Benefits include:
以下実施例を挙げて本発明を具体的に説明す
る。 The present invention will be specifically explained below with reference to Examples.
実施例 １
第１図、第２図および第３図に示した装置を用
いて、スラリ製造、スラリ送液、スラリ供給およ
びエステル化反応を行つた。エステル化反応槽５
０は１回分当り、EG／TPAモル比1.20のスラリ
を375.6重量部仕込める容量の大きさの槽とし、
これを５系列用いた。エステル化反応槽５０では
反応前に前回分の生成BHTおよび／またはその
共重合体の1/2を常に残存させ、この残存BHT中
にTPAとEGとからなるスラリを供給して大気圧
下235〜250℃の温度範囲で反応させた。少量成分
の添加回路５２からは第１系列ではイソフタル酸
を仕込TPAに対して8.0モル％、エステル化反応
前に添加し、第２系列ではトリメリツト酸を、仕
込TPAに対して1.0モル％反応前に添加し、第３
系列では５−ナトリウムホイソフタル酸2.0モル
％反応前に添加し、第４系列では艶消剤の酸化チ
タン微粒子のEGスラリを、仕込みTPAに対して
TiO2で0.578重量％（１回分当りのポリマ換算値
で0.5重量％／PET）エステル化反応後に添加
し、第５系列ではSiO2の微粒子のEGスラリを
TPAに対してSiO2で1.0重量％エステル化反応中
に添加した。Example 1 Using the apparatus shown in FIGS. 1, 2, and 3, slurry production, slurry feeding, slurry supply, and esterification reaction were performed. Esterification reaction tank 5
0 is a tank with a capacity that can hold 375.6 parts by weight of slurry with an EG/TPA molar ratio of 1.20 per batch,
Five series of these were used. In the esterification reaction tank 50, before the reaction, 1/2 of the BHT and/or its copolymer produced in the previous batch is always left, and a slurry consisting of TPA and EG is supplied into the remaining BHT and heated under atmospheric pressure at 235 °C. The reaction was carried out at a temperature range of ~250°C. From the small component addition circuit 52, in the first line, isophthalic acid is added at 8.0 mol% to the charged TPA before the esterification reaction, and in the second line, trimellitic acid is added at 1.0 mol% to the charged TPA before the reaction. Add to the third
In the series, 2.0 mol% of 5-sodium foisophthalic acid was added before the reaction, and in the fourth series, EG slurry of titanium oxide fine particles as a matting agent was added to the prepared TPA.
0.578% by weight of TiO 2 (0.5% by weight in terms of polymer per batch/PET) was added after the esterification reaction, and in the fifth series, EG slurry of fine particles of SiO 2 was added.
1.0% by weight of SiO2 relative to TPA was added during the esterification reaction.
各系列の品種は、第１系列がイソフタル酸共重
合による風合の異なつた衣料用フイラメントに用
いるポリマ、第２系列がトリメリツト酸共重合に
よる増粘された低い強度を示す衣料用ステープル
に用いるポリマ、第３系列が５−ナトリウムスル
ホイソフタル酸共重合による塩基性可染型衣料用
フイラメントに用いるポリマ、第４系列が汎用品
の衣料用加工糸に用いるポリマ、第５系列が表面
滑り性のすぐれたフイルムに用いるポリマとし
た。 The first series consists of polymers used for clothing filaments with different textures made by copolymerizing isophthalic acid, and the second series uses polymers used for clothing staples with increased viscosity and low strength produced by trimellitic acid copolymerization. , the third series is a polymer used for basic dyeable clothing filaments made by copolymerizing 5-sodium sulfoisophthalic acid, the fourth series is a polymer used for processed yarn for general-purpose clothing, and the fifth series is a polymer with excellent surface slipperiness. This was used as a polymer for use in film.
各系列はそれぞれ反応時間は異なり、TPAと
EGとからなるスラリの供給速度も異なるが、１
日当り全系列で9391部のスラリを使用した。一方
スラリ製造帯域では、液面計１０によつてスラリ
液面を測定し、スラリ槽８の全容量の20％〜70％
の液面高さの範囲となるように、スラリ量をカス
ケード制御して製造した。スラリ製造量は最低時
50重量部／Hr、最高時626重量部／Hrとなるよう
にカスケード制御して製造した。液面計１０の測
定値はTPA重量コントローラWRC１１に与え、
TPA計量機３の計量を制御し、同時にモル比演
算器MRC１２に液面測定信号を与え、ここで
TPAの1.20モル倍のEGを演算し、この値をEG流
量コントローラFRC１３に与えてEGを計量して
混合機４に供給した。スラリのEG／TPAモル比
は1.18〜1.22の管理巾で製造され、平均値は1.20
であつた。スラリ貯槽８に貯えられたスラリは、
スネークポンプ９を用いて中間スラリ槽３３に送
液し、続いてスネークポンプ３４を用いてスラリ
供給槽４１に送液した。 Each series has different reaction times, and TPA and
The supply speed of slurry consisting of EG also differs, but 1
9391 parts of slurry was used in all series per day. On the other hand, in the slurry production zone, the slurry liquid level is measured by the liquid level gauge 10, and the slurry liquid level is measured at 20% to 70% of the total capacity of the slurry tank 8.
The amount of slurry was controlled in cascade so that the liquid level height was within the range of . Slurry production volume is at its lowest
It was manufactured under cascade control so that the amount was 50 parts by weight/Hr and 626 parts by weight/Hr at the highest. The measured value of the liquid level gauge 10 is given to the TPA weight controller WRC11,
Controls the measurement of the TPA measuring device 3, and at the same time gives a liquid level measurement signal to the molar ratio calculator MRC12.
EG was calculated to be 1.20 mol times that of TPA, and this value was given to the EG flow rate controller FRC13 to measure and supply the EG to the mixer 4. The slurry's EG/TPA molar ratio is manufactured within a control range of 1.18 to 1.22, with an average value of 1.20.
It was hot. The slurry stored in the slurry storage tank 8 is
The snake pump 9 was used to send the liquid to the intermediate slurry tank 33, and then the snake pump 34 was used to send the liquid to the slurry supply tank 41.
各槽の最大容量は、EG／TPAモル比1.20のス
ラリで、スラリ貯槽８が600重量部、中間槽３３
が100重量部、スラリ供給槽４１が600重量部各々
貯えられるものとした。 The maximum capacity of each tank is 600 parts by weight of slurry with an EG/TPA molar ratio of 1.20 in slurry storage tank 8, and 600 parts by weight in intermediate tank 33.
It is assumed that 100 parts by weight can be stored in the slurry supply tank 41, and 600 parts by weight can be stored in the slurry supply tank 41.
またスラリ送液回路３１の長さは120ｍ、送液
回路３２の長さは80ｍとした。スネークポンプ９
および３４のスラリ送液量は、中間槽３３の液面
計３５およびスラリ供給槽４１の液面計４４の測
定値に従つて、適宜制御され、50〜626重量部／
Hrの幅で送液した。 Further, the length of the slurry liquid feeding circuit 31 was 120 m, and the length of the liquid feeding circuit 32 was 80 m. snake pump 9
The amount of slurry fed in and 34 is appropriately controlled according to the measured values of the level gauge 35 of the intermediate tank 33 and the level gauge 44 of the slurry supply tank 41, and is 50 to 626 parts by weight/
The liquid was delivered at a width of Hr.
スラリ供給槽４１に貯えられたスラリは、スネ
ークポンプ４２により600重量部／Hrの流速で第
１次スラリ供給回路４５に送られた。送液された
スラリは第１次スラリ供給回路４５を循環してス
ラリ供給槽４１に戻した。 The slurry stored in the slurry supply tank 41 was sent to the primary slurry supply circuit 45 by a snake pump 42 at a flow rate of 600 parts by weight/Hr. The fed slurry was circulated through the primary slurry supply circuit 45 and returned to the slurry supply tank 41.
第１次スラリ供給回路からは分岐した第２次ス
ラリ供給回路を設け、途中にスネークポンプ４７
を設けてエステル化反応槽５０にスラリを仕込ん
だ。 A secondary slurry supply circuit is provided that branches off from the primary slurry supply circuit, and a snake pump 47 is installed in the middle.
The slurry was charged into the esterification reaction tank 50.
各エステル化反応槽へのTPAとEGからなるス
ラリの供給時間は、第１〜第５系列によつて異な
るが、平均すると３時間であり、エステル化反応
時間は平均４時間半であつた。 The time for supplying the slurry consisting of TPA and EG to each esterification reactor differed depending on the first to fifth series, but was 3 hours on average, and the esterification reaction time was 4 and a half hours on average.
第１図は本発明の第１段階を示し、スラリを設
定されたモル比で製造する好ましい工程概略図、
第２図は本発明の第２、３、および４段階を示す
好ましい工程概略図、第３図は本発明で使用する
スネークポンプを説明するための概略図でであ
る。
３：TPA計量機、４：混練機、６：EG計量
機、８：スラリ貯槽、１２：モル比演算器、９，
３４，４２，４７，４７′：スラリポンプ、１
０，３５，４４：スラリ槽液面計、３３：スラリ
中間槽、４１：スラリ供給槽、４５：第１次スラ
リ供給回路、５４，５４′：第２次スラリ供給回
路、５０，５０′：エステル化反応槽、５２，５
２′：添加回路。
FIG. 1 shows the first step of the present invention, and is a preferred process schematic for producing slurry at a set molar ratio,
FIG. 2 is a preferred process schematic diagram showing the second, third, and fourth stages of the present invention, and FIG. 3 is a schematic diagram for explaining the snake pump used in the present invention. 3: TPA measuring machine, 4: Kneading machine, 6: EG measuring machine, 8: Slurry storage tank, 12: Molar ratio calculator, 9,
34, 42, 47, 47': Slurry pump, 1
0, 35, 44: Slurry tank level gauge, 33: Slurry intermediate tank, 41: Slurry supply tank, 45: Primary slurry supply circuit, 54, 54': Secondary slurry supply circuit, 50, 50': Esterification reaction tank, 52,5
2': Addition circuit.
Claims (1)
らなるスラリの製造帯域において、エチレング
リコール／テレフタル酸モル比0.80以上1.70以
下の範囲内で設定モル比となるように、スラリ
量及びモル比を制御して、テレフタル酸とエチ
レングリコールとのスラリを得、これをスラリ
槽に貯え Ｂ 該スラリ貯槽に貯えたスラリを、貯槽下に設
けたスラリ送液用ポンプを用いて、エステル化
反応帯域に存在するスラリ供給槽へスラリを送
液し、 Ｃ 該スラリ供給槽へ貯えたスラリを、スラリ供
給槽下に設けた第１次供給用スラリポンプを用
いて第１次スラリ供給回路へ送液し、 Ｄ 該第１次スラリ供給回路から分岐しエステル
化反応槽へ直結した複数の第２次スラリ供給ポ
ンプを設け、該スラリポンプを用いてスラリを
連続的に回分式エステル化反応槽へ仕込み、エ
ステル化反応を行うことを特徴とする回分式エ
ステル化方法。 ２ スラリ貯槽の液量を測定し、設定液量を保つ
ように、テレフタル酸とエチレングリコールの
各々の計量をカスケード制御することを特徴とす
る前記第１項記載の回分式エステル化方法。 ３ テレフタル酸とエチレングリコールとからな
るスラリの製造帯域におけるスラリ貯槽と、エス
テル化反応帯域におけるスラリ供給槽との中間
に、中間スラリ槽および中間スラリ槽下に設けた
送液用スラリポンプからなるユニツトを設けるこ
とを特徴とする前記第１項記載の回分式エステル
化方法。 ４ 中間スラリ槽および／またはスラリ供給槽の
液量を測定し、設定液面を保つように当該槽下に
設けたスラリポンプおよび／または当該槽より以
前の槽の下に設けたスラリポンプの回転数を変更
することにより制御することを特徴とする前記第
３項記載の回分式エステル化方法。 ５ テレフタル酸とエチレングリコールとからな
るスラリを送液および供給するスラリポンプとし
てスネークポンプを使用することを特徴とする前
記第１項記載の回分式エステル化方法。 ６ エステル化反応槽に、少量成分を添加する回
路を設けることを特徴とする前記第１項記載の回
分式エステル化方法。[Scope of Claims] 1A In the production zone of slurry consisting of terephthalic acid and ethylene glycol, the slurry amount and molar ratio are adjusted so that the ethylene glycol/terephthalic acid molar ratio is set within the range of 0.80 to 1.70. A slurry of terephthalic acid and ethylene glycol is obtained and stored in a slurry tank B. The slurry stored in the slurry storage tank is transferred to the esterification reaction zone using a slurry pump installed below the storage tank. C The slurry stored in the slurry supply tank is sent to the primary slurry supply circuit using a slurry pump for primary supply provided below the slurry supply tank. D. Provide a plurality of secondary slurry supply pumps branched from the first slurry supply circuit and directly connected to the esterification reaction tank, and use the slurry pumps to continuously feed slurry into the batch-type esterification reaction tank. , a batch esterification method characterized by carrying out an esterification reaction. 2. The batch esterification method according to item 1 above, characterized in that the liquid volume in the slurry storage tank is measured, and the respective measurements of terephthalic acid and ethylene glycol are controlled in cascade so as to maintain the set liquid volume. 3. A unit consisting of an intermediate slurry tank and a slurry pump for liquid feeding provided below the intermediate slurry tank, located between the slurry storage tank in the slurry production zone consisting of terephthalic acid and ethylene glycol and the slurry supply tank in the esterification reaction zone. 2. The batch esterification method according to item 1, further comprising: 4 Measure the liquid level in the intermediate slurry tank and/or slurry supply tank, and rotate the slurry pump installed under the tank and/or the slurry pump installed under the tank before the tank to maintain the set liquid level. 4. The batch esterification method according to item 3, characterized in that control is carried out by changing the number of esterifications. 5. The batch esterification method according to item 1, wherein a snake pump is used as the slurry pump for feeding and supplying the slurry consisting of terephthalic acid and ethylene glycol. 6. The batch-type esterification method according to item 1 above, characterized in that the esterification reaction tank is provided with a circuit for adding small amounts of components.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6338978A JPS54157535A (en) | 1978-05-29 | 1978-05-29 | Batchwise esterification process |
| DE19792921478 DE2921478A1 (en) | 1978-05-29 | 1979-05-26 | APPROACH PROCESS FOR THE DIRECT ESTERIFICATION OF TEREPHTHALIC ACID WITH AETHYLENE GLYCOL |
| FR7913519A FR2427324A1 (en) | 1978-05-29 | 1979-05-28 | Batch direct esterification of terephthalic acid with ethylene glycol - using slurry pumped from remote storage vessel to esterification reactors |
| IT68139/79A IT1120975B (en) | 1978-05-29 | 1979-05-28 | DISCONTINUOUS PROCEDURE FOR THE DIRECT ESTERIFICATION OF TEREPHTHALIC ACID WITH ETHYLENE GLYCOL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6338978A JPS54157535A (en) | 1978-05-29 | 1978-05-29 | Batchwise esterification process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54157535A JPS54157535A (en) | 1979-12-12 |
| JPS6126771B2 true JPS6126771B2 (en) | 1986-06-21 |
Family
ID=13227886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6338978A Granted JPS54157535A (en) | 1978-05-29 | 1978-05-29 | Batchwise esterification process |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS54157535A (en) |
| DE (1) | DE2921478A1 (en) |
| FR (1) | FR2427324A1 (en) |
| IT (1) | IT1120975B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5479242A (en) * | 1977-12-05 | 1979-06-25 | Teijin Ltd | Method of esterification |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1000045A (en) * | 1961-04-17 | 1965-08-04 | Toyo Rayon Co Ltd | Method of testing terephthalic acid to be converted into polyethylene terephthalate |
| US3590072A (en) * | 1966-11-18 | 1971-06-29 | Monsanto Co | Method for direct esterification of terephthalic acid with ethylene glycol |
| FR1545012A (en) * | 1966-11-18 | 1968-11-08 | Monsanto Co | Process for the direct esterification of terephthalic acid with ethylene glycol and product obtained by this process |
-
1978
- 1978-05-29 JP JP6338978A patent/JPS54157535A/en active Granted
-
1979
- 1979-05-26 DE DE19792921478 patent/DE2921478A1/en active Granted
- 1979-05-28 IT IT68139/79A patent/IT1120975B/en active
- 1979-05-28 FR FR7913519A patent/FR2427324A1/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5479242A (en) * | 1977-12-05 | 1979-06-25 | Teijin Ltd | Method of esterification |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2921478A1 (en) | 1979-12-13 |
| JPS54157535A (en) | 1979-12-12 |
| IT1120975B (en) | 1986-03-26 |
| IT7968139A0 (en) | 1979-05-28 |
| FR2427324B1 (en) | 1984-05-11 |
| FR2427324A1 (en) | 1979-12-28 |
| DE2921478C2 (en) | 1989-08-03 |
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