JP2008308500A - Method for producing high purity butyl acetate - Google Patents
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- JP2008308500A JP2008308500A JP2008159836A JP2008159836A JP2008308500A JP 2008308500 A JP2008308500 A JP 2008308500A JP 2008159836 A JP2008159836 A JP 2008159836A JP 2008159836 A JP2008159836 A JP 2008159836A JP 2008308500 A JP2008308500 A JP 2008308500A
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 title claims abstract description 83
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 174
- 238000004821 distillation Methods 0.000 claims abstract description 58
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- 238000009835 boiling Methods 0.000 claims description 65
- 239000000126 substance Substances 0.000 abstract description 64
- 150000002500 ions Chemical class 0.000 abstract description 16
- 238000004587 chromatography analysis Methods 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 52
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 25
- 238000000034 method Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- LMEDOLJKVASKTP-UHFFFAOYSA-N dibutyl sulfate Chemical compound CCCCOS(=O)(=O)OCCCC LMEDOLJKVASKTP-UHFFFAOYSA-N 0.000 description 16
- ZTHQBROSBNNGPU-UHFFFAOYSA-N Butyl hydrogen sulfate Chemical compound CCCCOS(O)(=O)=O ZTHQBROSBNNGPU-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 13
- 150000008051 alkyl sulfates Chemical class 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000000066 reactive distillation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
【課題】イオンクロマトグラフ分析により検出される硫酸由来物質及び硫酸の合計濃度が著しく低く、且つ、経時変化による硫酸の増加が少ない高純度酢酸ブチルの製造方法を提供すること。
【解決手段】本発明に係る高純度酢酸ブチルの製造方法は、硫酸触媒の存在下、酢酸とｎ−ブタノールから酢酸ブチルを合成し、脱低沸蒸留後、脱高沸蒸留することにより酢酸ブチルを製造する際、脱高沸物蒸留塔の塔頂圧力を５０〜７００ｍｍＨｇ、塔頂温度を４０〜１２０℃、塔底温度を７０〜１３０℃にコントロールすることを特徴とする。
【選択図】図１The present invention provides a method for producing high-purity butyl acetate in which the total concentration of sulfuric acid-derived substances and sulfuric acid detected by ion chromatographic analysis is extremely low, and the increase in sulfuric acid due to aging is small.
A method for producing high purity butyl acetate according to the present invention comprises synthesizing butyl acetate from acetic acid and n-butanol in the presence of a sulfuric acid catalyst. Is produced by controlling the column top pressure of the deboiling distillation column from 50 to 700 mmHg, the column top temperature from 40 to 120 ° C., and the column bottom temperature from 70 to 130 ° C.
[Selection] Figure 1
Description
本発明は、酢酸とｎ−ブタノールを原料として硫酸等の触媒の存在下に反応させ、その反応粗液から硫酸由来物質及び硫酸を分離精製することにより得られる高純度酢酸ブチルの製造方法に関する。詳しくは、イオンクロマトグラフ分析により検出される未同定の硫酸由来物質及び硫酸の合計濃度が２０ｐｐｂ以下の高純度酢酸ブチルを製造する方法に関する。 The present invention relates to a method for producing high-purity butyl acetate obtained by reacting acetic acid and n-butanol as raw materials in the presence of a catalyst such as sulfuric acid, and separating and purifying sulfuric acid-derived substances and sulfuric acid from the reaction crude liquid. Specifically, the present invention relates to a method for producing high-purity butyl acetate having a total concentration of unidentified sulfuric acid-derived substances and sulfuric acid detected by ion chromatographic analysis of 20 ppb or less.
酢酸ブチル（本発明では酢酸ｎ−ブチルを示す）は、沸点１２４〜１２５℃の無色透明、果実の芳香を持つ液体で、多くの種類の物質を溶解させる、優れた溶解性を有している。従って、その用途はニトロセルロースラッカーの溶剤の他、多くの樹脂の溶剤や、合成皮革、合成繊維、合成樹脂の製造溶媒、油脂、医薬の抽出溶剤、香水や合成香料の一成分等として広く利用されている。
従来、酢酸ブチルの製造方法としては、酢酸とｎ−ブタノールを硫酸等の酸触媒の存在下にエステル化して得られた粗酢酸ブチルを脱低沸物蒸留塔に導入して低沸物を除去し、その缶出液を脱高沸物蒸留塔に導入してその塔頂から酢酸ブチルを留出製品として得る方法『CHEM SYSTEMS’PERP-Ethyl Acetate/Buthyl Acetate 97/98S5』等が知られている。
しかしながら、この方法では、原料であるｎ−ブタノールあるいはｎ−ブタノール中に含まれるアルコール類と硫酸が反応して、硫酸の中性エステルであるジブチル硫酸のような硫酸ジアルキルＲ2ＳＯ4やイオン解離可能なモノブチル硫酸のような硫酸モノアルキルＲＨＳＯ4（両者を硫酸アルキル類という）等が生成することが知られており、これらが酢酸ブチル中に混入することになる。
近年、酢酸ブチルは電材向け溶剤としての需要を伸ばしており、フォトレジストを使用した半導体製造時にトラブルの原因となる硫酸由来物質及び硫酸の低減が望まれているが、上記の方法で得られた酢酸ブチルは、純度９９．５ｗｔ％以上、ｎ−ブタノール０．５０ｗｔ％以下、水分０．０５０ｗｔ％以下、酸分（酢酸換算）０．０１ｗｔ％以下の品質を有しているものの、上記硫酸由来物質及び硫酸の除去が不十分であり、フォトレジスト等の用途には適していない。
従来、酢酸ブチルの精製方法としては、蒸留精製による方法、蒸留精製後さらにイオン交換樹脂または活性炭処理する方法（特開昭６０−２３７０４３号公報）等が知られている。このようにして得られた酢酸ブチルは、純度９９．５％以上、エステル価４８０ｍｇ−ＫＯＨ／ｇ以上、酸価０．０５ｍｇ−ＫＯＨ／ｇ以下、硫酸着色２０以下、蒸発残分０．００５％以下、色相ＡＰＨＡ４以下、屈折率１．３９２〜１．３９６、沸点１２４〜１２５℃、初留点１２０℃以上、乾点１３０．５℃以下、比重（２０／２０℃）０．８７９〜０．８８５の品質を有するが、フォトレジスト用等には不十分である。
本発明者らは、フォトレジスト用等に使用されるべき酢酸ブチル中の上記のような硫酸由来物質及び硫酸を低減するために、脱低沸蒸留後、脱高沸蒸留し、さらにイオン交換樹脂により硫酸由来物質及び硫酸を吸着除去させる方法を先に提案（特願２００２−０３１７６０）した。しかし、この方法には処理設備の建設及び運転に費用がかかること、劣化したイオン交換樹脂の交換等の作業が必要であるといった問題があった。
Butyl acetate (showing n-butyl acetate in the present invention) is a colorless and transparent liquid having a boiling point of 124 to 125 ° C., and has a fruity fragrance, and has excellent solubility for dissolving many kinds of substances. . Therefore, in addition to nitrocellulose lacquer solvents, it is widely used as a solvent for many resins, synthetic leather, synthetic fibers, synthetic resin production solvents, fats and oils, pharmaceutical extraction solvents, and a component of perfumes and synthetic fragrances. Has been.
Conventionally, as a method for producing butyl acetate, crude butyl acetate obtained by esterification of acetic acid and n-butanol in the presence of an acid catalyst such as sulfuric acid is introduced into a low-boiling distillation column to remove low-boiling substances. In addition, there are known methods such as “CHEM SYSTEMS'PERP-Ethyl Acetate / Buthyl Acetate 97 / 98S5” that introduces the bottoms into a high boiling distillation column and obtains butyl acetate as a distillate from the top of the column. Yes.
However, in this method, n-butanol as a raw material or an alcohol contained in n-butanol reacts with sulfuric acid, and dialkyl sulfate R 2 SO 4 such as dibutyl sulfate, which is a neutral ester of sulfuric acid, or ion dissociation. It is known that monoalkyl sulfate RHSO 4 (both are referred to as alkyl sulfates) such as monobutyl sulfate which can be produced, and these are mixed in butyl acetate.
In recent years, butyl acetate has been increasingly demanded as a solvent for electrical materials, and it is desired to reduce sulfuric acid-derived substances and sulfuric acid that cause troubles in semiconductor manufacturing using photoresists. Although butyl acetate has a purity of 99.5 wt% or more, n-butanol 0.50 wt% or less, moisture 0.050 wt% or less, and acid content (acetic acid equivalent) 0.01 wt% or less, it is derived from the above sulfuric acid. Insufficient removal of substances and sulfuric acid is not suitable for applications such as photoresists.
Conventionally, as a purification method of butyl acetate, a method by distillation purification, a method of further treating with ion exchange resin or activated carbon after distillation purification (Japanese Patent Laid-Open No. 60-237043), and the like are known. The butyl acetate thus obtained has a purity of 99.5% or more, an ester value of 480 mg-KOH / g or more, an acid value of 0.05 mg-KOH / g or less, sulfuric acid coloring of 20 or less, and an evaporation residue of 0.005%. Hereinafter, hue APHA 4 or less, refractive index 1.392 to 1.396, boiling point 124 to 125 ° C., initial boiling point 120 ° C. or more, dry point 130.5 ° C. or less, specific gravity (20/20 ° C.) 0.879 to 0. Although it has a quality of 885, it is insufficient for a photoresist or the like.
In order to reduce sulfuric acid-derived substances and sulfuric acid as described above in butyl acetate to be used for photoresists and the like, the present inventors perform de-low boiling distillation, de-high boiling distillation, and further ion exchange resins. Previously proposed a method for adsorbing and removing sulfuric acid-derived substances and sulfuric acid (Japanese Patent Application No. 2002-031760). However, this method has a problem that it costs money for the construction and operation of the treatment facility, and requires work such as replacement of a deteriorated ion exchange resin.
本発明の目的は、イオンクロマトグラフ分析により検出される硫酸由来物質及び硫酸の合計濃度が著しく低く、且つ、経時変化による硫酸の増加が少ない高純度酢酸ブチルの製造方法を提供することである。 An object of the present invention is to provide a method for producing high-purity butyl acetate in which the total concentration of sulfuric acid-derived substances and sulfuric acid detected by ion chromatographic analysis is extremely low and the increase in sulfuric acid due to changes over time is small.
本発明者は、前記課題を達成するために鋭意検討した結果、精製工程の段階で硫酸アルキル類等が加熱されて硫酸由来物質となり製品酢酸ブチル中に混入すること、及びこの硫酸由来物質が除去されていない酢酸ブチルは、経時的に硫酸濃度が増加することを見出した。また、硫酸アルキル類等は酢酸ブチルより高沸物であるので脱低沸物蒸留塔の塔底液中に濃縮させ、脱低沸物蒸留塔からの酢酸ブチルを（缶出抜き取りでなく）サイドカット抜き取りとすることにより、脱高沸物蒸留塔に導入される硫酸アルキル類等を削減できること、及びこの硫酸アルキル類等の少ない酢酸ブチルを脱高沸物蒸留塔にて蒸留することにより、硫酸由来物質及び硫酸の合計濃度が２０ｐｐｂ以下の高純度酢酸ブチルを経済的に製造可能であることを見出し、本発明を完成するに至った。また、硫酸アルキル類等が含まれていても脱高沸物蒸留塔での塔内温度を低減する又は滞留時間を短縮するなどの手段で熱履歴を軽減することにより、硫酸由来物質の生成を抑制できることを見出した。特に、脱高沸物蒸留塔内の温度を低減することにより、硫酸由来物質の生成が著しく抑制され、硫酸由来物質及び硫酸の合計濃度が２０ｐｐｂ以下の高純度酢酸ブチルを経済的に製造可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that alkyl sulfates and the like are heated in the purification process to become sulfuric acid-derived substances and mixed into product butyl acetate, and this sulfuric acid-derived substances are removed. It has been found that untreated butyl acetate increases the sulfuric acid concentration over time. In addition, alkyl sulfates are higher in boiling point than butyl acetate, so they are concentrated in the bottom liquid of the low-boiling distillation column, and the butyl acetate from the low-boiling distillation column is not removed from the side. By removing the cut, it is possible to reduce alkyl sulfates and the like introduced into the dehigh-boiling distillation column, and distilling butyl acetate containing a small amount of this alkyl sulfates in the de-high-boiling distillation column, It has been found that high-purity butyl acetate having a total concentration of the derived substance and sulfuric acid of 20 ppb or less can be produced economically, and the present invention has been completed. In addition, even if alkyl sulfates are included, the production of sulfuric acid-derived substances is reduced by reducing the thermal history by means such as reducing the temperature in the high boiling distillation column or reducing the residence time. It was found that it can be suppressed. In particular, by reducing the temperature in the dehigh-boiling distillation column, the production of sulfuric acid-derived substances is remarkably suppressed, and high-purity butyl acetate having a total concentration of sulfuric acid-derived substances and sulfuric acid of 20 ppb or less can be produced economically. As a result, the present invention has been completed.
すなわち、本発明は、「硫酸触媒の存在下、酢酸とｎ−ブタノールから酢酸ブチルを合成し、脱低沸蒸留後、脱高沸蒸留することにより酢酸ブチルを製造する際、脱高沸物蒸留塔の塔頂圧力を５０〜７００ｍｍＨｇ、塔頂温度を４０〜１２０℃、塔底温度を７０〜１３０℃にコントロールすることを特徴とする高純度酢酸ブチルの製造方法」である。 That is, the present invention describes the following: “In the presence of sulfuric acid catalyst, butyl acetate is synthesized from acetic acid and n-butanol, and after delow-boiling distillation, de-high-boiling distillation to produce butyl acetate. A method for producing high-purity butyl acetate, characterized in that the tower top pressure is 50 to 700 mmHg, the tower top temperature is 40 to 120 ° C., and the tower bottom temperature is 70 to 130 ° C.
本発明によれば、イオンクロマトグラフ分析により検出される硫酸由来物質および硫酸の合計濃度が２０ｐｐｂ以下の高純度酢酸ブチルが得られた。 According to the present invention, high-purity butyl acetate having a total concentration of sulfuric acid-derived substances and sulfuric acid detected by ion chromatographic analysis of 20 ppb or less was obtained.
以下、本発明について詳細に説明する。
原料等
本発明で原料に使用される酢酸は、特に限定されるものではなく、例えば純度９９重量％以上、好ましくは純度９９．５重量％以上のものであり、工業用グレードが使用できる。
本発明で原料に使用するｎ−ブタノールは、特に限定されるものではなく、例えば純度９８重量％以上、好ましくは純度９９重量％以上のものであり、工業用グレードが使用できる。
本発明でエステル化反応に使用する触媒は硫酸である。
上記硫酸は、特に限定されるものではなく、例えば純度９６重量％以上、好ましくは純度９７重量％以上、さらに好ましくは純度９８重量％以上のものであるが、希硫酸を供給して、所定濃度範囲に脱水しながら使用することもできる。
Hereinafter, the present invention will be described in detail.
Raw material etc. The acetic acid used for a raw material by this invention is not specifically limited, For example, purity is 99 weight% or more, Preferably it is a thing of purity 99.5 weight% or more, and an industrial grade can be used.
The n-butanol used as a raw material in the present invention is not particularly limited. For example, the purity is 98% by weight or more, preferably 99% by weight or more, and an industrial grade can be used.
The catalyst used for the esterification reaction in the present invention is sulfuric acid.
The sulfuric acid is not particularly limited. For example, the purity is 96% by weight or more, preferably 97% by weight or more, and more preferably 98% by weight or more. It can also be used while dehydrating to the range.
反応工程
以下、触媒に硫酸を使用した場合を例にして本発明を説明する。エステル化方法は特に限定されるものではなく、回分式、半回分式、または連続式のいずれでも行うことができる。連続式は槽型反応器でも管型反応器でも行うことが可能である。例えば、連続式の槽型反応器で予備反応させた後、連続式の反応蒸留塔により、蒸留塔の塔頂から酢酸ブチル／ｎ−ブタノール／水の共沸混合物として、副生する水を系外に除去しながら反応させると効率よく製造できる。
反応蒸留塔から得られた酢酸ブチル粗液については、硫酸分をアルカリ中和し、水で洗浄した後、水分の除去を行う。
Reaction Step Hereinafter, the present invention will be described with reference to the case where sulfuric acid is used as a catalyst. The esterification method is not particularly limited, and can be carried out by any of batch, semi-batch, and continuous methods. The continuous type can be carried out in either a tank reactor or a tube reactor. For example, after pre-reacting in a continuous tank reactor, water produced as a by-product is converted into a butyl acetate / n-butanol / water azeotrope from the top of the distillation column by a continuous reactive distillation column. If it is made to react while removing outside, it can manufacture efficiently.
About the butyl acetate crude liquid obtained from the reactive distillation tower, the sulfuric acid content is neutralized with alkali, washed with water, and then the water is removed.
精製工程
本発明の具体例を図１に基づいて説明する。なお、図１は主要な装置の概略のみを示している。反応系（図示せず）で得られた粗反応生成物を中和水洗し、デカンターにより大部分の水及び硫酸を分離した後の酢酸ブチル、ｎ−ブタノール、水、硫酸及び微量の副生物を含む供給液は、ラインＡを経てｎ−ブタノール及び水等の低沸物を除去する目的の脱低沸物蒸留塔１−１に供給される。
なお、図１において、点線は従来（たとえば、前記特願２００２−０３１７６０等）行われていた方法における脱低沸物蒸留塔から缶出され、脱高沸物蒸留塔１−２へ供給される、主として酢酸ブチル及び高沸点物からなる混合物の供給ラインＣである。
脱低沸物蒸留塔１−１は気液の交流多段接触機構を備えるものであれば特にその形式に制約条件は無いが、通常は設備の簡便性から塔形式の装置が選ばれる。塔の充填物はラシヒリング、インターロックサドル、ポールリング、カスケードミニリング、ネットリング等の不規則充填物、或いはメラパック、スルーザーパック、フレキシパック等の規則充填物、或いはシーブトレイ、フレキシトレイ、バルブトレイ、キャップトレイ等の棚段等から幅広く１種或いは２種以上の組合せにおいて自由に選択でき、かつこれら内容物の材質も金属、プラスチック、磁製等制限されない。
脱低沸物蒸留塔１−１は通常、常圧、塔頂温度１０５〜１１５℃、塔底温度１３０〜１４０℃、還流比５〜１５で運転される。
塔頂部からは酢酸ブチルの一部、ｎ−ブタノール、水及び副生物が留出する。
塔底部からは酢酸ブチルの他に、反応系から持ち込まれる微量の硫酸、モノブチル硫酸、ジブチル硫酸等の硫酸アルキル類、希には硫酸由来物質及び副生物が缶出する。なお、本発明では、硫酸由来物質とは、未同定の物質であり、イオンクロマトグラフ分析により硫酸の直前に検出され、経時的に減少し、代わりに硫酸が増加する原因物質を指す。
脱高沸物蒸留塔は気液の交流多段接触機構を備えるものであれば特にその形式に制約条件は無いが、通常は設備の簡便性から塔形式の装置が選ばれる。塔の充填物はラシヒリング、インターロックサドル、ポールリング、カスケードミニリング、ネットリング等の不規則充填物、或いはメラパック、スルーザーパック、フレキシパック等の規則充填物、或いはシーブトレイ、フレキシトレイ、バルブトレイ、キャップトレイ等の棚段等から幅広く１種或いは２種以上の組合せにおいて自由に選択でき、かつこれら充填物の材質も金属、プラスチック、磁製等制限されない。
脱高沸物蒸留塔は通常、常圧条件下では、脱高沸物蒸留塔の塔頂及び塔底温度はそれぞれ１２４〜１３０℃、１３０〜１３５℃である。
この範囲内で脱高沸物蒸留塔内の温度が変動しても、製品の品質などには特に影響は現れない（理論上は、より低温なほど熱履歴が軽減されるので、硫酸由来物質の発生量は減少することも考えられる）。
還流比は通常０．１〜１．０の範囲内で特に制限されないが、還流比を高くすると製品酸価が若干高くなる傾向がある。反対に低くすると、プロピオン酸ブチルなどの（比較的低分子量の）高沸点物が塔の上方にまで移動し、製品酢酸ブチルに混入するようになる。
Purification Step A specific example of the present invention will be described with reference to FIG. FIG. 1 shows only the outline of the main apparatus. The crude reaction product obtained in the reaction system (not shown) is washed with neutralized water, and most of the water and sulfuric acid are separated by a decanter, and then butyl acetate, n-butanol, water, sulfuric acid and a small amount of by-products are removed. The feed liquid that is contained is supplied via line A to a delow boiling product distillation column 1-1 for the purpose of removing low boiling materials such as n-butanol and water.
In FIG. 1, a dotted line is taken out from the low-boiling distillation column in the conventional method (for example, the above-mentioned Japanese Patent Application No. 2002-031760) and supplied to the high-boiling distillation column 1-2. , A feed line C for a mixture consisting mainly of butyl acetate and high boilers.
There are no particular restrictions on the type of the low-boiling distillation column 1-1 provided that it has a gas-liquid AC multistage contact mechanism, but a column-type apparatus is usually selected from the standpoint of facility simplicity. Tower packing is irregular packing such as Raschig rings, interlock saddles, pole rings, cascade mini-rings, net rings, etc. From a shelf such as a cap tray, etc., one or a combination of two or more can be freely selected, and the material of these contents is not limited to metal, plastic, magnetic, etc.
The low-boiling distillation column 1-1 is usually operated at normal pressure, a column top temperature of 105 to 115 ° C, a column bottom temperature of 130 to 140 ° C, and a reflux ratio of 5 to 15.
A part of butyl acetate, n-butanol, water and by-products are distilled from the top of the column.
In addition to butyl acetate, trace amounts of sulfuric acid such as sulfuric acid, monobutyl sulfuric acid and dibutyl sulfuric acid, and rarely sulfuric acid-derived substances and by-products are taken out from the bottom of the column. In the present invention, the sulfuric acid-derived substance is an unidentified substance, which is detected just before sulfuric acid by ion chromatographic analysis, decreases with time, and instead indicates a causative substance that increases sulfuric acid.
There are no particular restrictions on the type of the deboiling distillation column provided that it has a gas-liquid AC multistage contact mechanism, but a column-type apparatus is usually selected because of the simplicity of the equipment. Tower packing is irregular packing such as Raschig rings, interlock saddles, pole rings, cascade mini-rings, net rings, etc. In addition, it can be freely selected from one or a combination of two or more types from a shelf such as a cap tray, and the material of these fillers is not limited to metal, plastic, magnetic, etc.
In the high-boiling distillation column, normally, the top and bottom temperatures of the high-boiling distillation column are 124 to 130 ° C. and 130 to 135 ° C., respectively, under normal pressure conditions.
Even if the temperature in the deboiling distillation column fluctuates within this range, there is no particular effect on the quality of the product (theoretically, the lower the temperature, the lesser the heat history, so sulfuric acid-derived substances) It is also possible that the amount of generated will decrease).
The reflux ratio is usually not particularly limited within the range of 0.1 to 1.0, but if the reflux ratio is increased, the product acid value tends to be slightly higher. On the contrary, if it is lowered, high boiling point substances (relatively low molecular weight) such as butyl propionate will move to the top of the column and become mixed into the product butyl acetate.
本発明においては、脱低沸物蒸留塔から取り出される脱高沸物蒸留塔への供給液を、図１における点線のように塔底から抜き取る方式を採用し、塔頂圧力を５０〜７００ｍｍＨｇ、塔頂温度４０〜１２０℃、塔底温度７０〜１３３℃にコントロールする。
塔頂圧力、塔頂温度、塔底温度はどれも低くなるほど、脱高沸物蒸留塔での熱履歴が軽減されるようになるので、より好ましい。
脱高沸物蒸留塔１−２からの製品酢酸ブチルの取り出し方法は、塔頂からの取り出し、或いは塔側面からのサイドカット等いずれの方法も使用できる。その方法は特に限定されるものではないが、製品酢酸ブチルに残存する低沸成分である硫酸由来物質の量を低減することを目的とするには、サイドカットで抜き取る方がより好ましい。
塔底部からは酢酸ブチルの他に、硫酸、モノブチル硫酸、ジブチル硫酸等の硫酸アルキル類及び副生物が缶出する。
In the present invention, a method of extracting the feed liquid to the high-boiling distillation column taken out from the low-boiling distillation column from the column bottom as indicated by the dotted line in FIG. 1, and the column top pressure is 50 to 700 mmHg, The tower top temperature is controlled to 40 to 120 ° C., and the tower bottom temperature is controlled to 70 to 133 ° C.
The lower the column top pressure, the column top temperature, and the column bottom temperature are more preferable, because the thermal history in the dehydroboiling distillation column is reduced.
As a method for taking out product butyl acetate from the deboiling distillation column 1-2, any method such as taking out from the top of the column or side-cutting from the side of the column can be used. The method is not particularly limited, but in order to reduce the amount of sulfuric acid-derived substance that is a low-boiling component remaining in the product butyl acetate, it is more preferable to extract by side cut.
In addition to butyl acetate, alkyl sulfates such as sulfuric acid, monobutyl sulfuric acid and dibutyl sulfuric acid and by-products are taken out from the bottom of the column.
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例で用いられている「部」は、特別の説明がない限り「重量部」を意味する。
［評価方法］
１．分析試料の前処理：試料となる酢酸ブチルはイオンクロマトグラフ分析の妨害成分となるので、酢酸ブチルからイオン性物質（硫酸由来物質、硫酸およびモノブチル硫酸）を水抽出して、酢酸ブチルの含まれない水溶液を調製する。具体的には、試料となる酢酸ブチル５０ミリリットルとイオン交換水５０ミリリットルを分液漏斗に入れ、３分間振とう、２分間静置、分液した後、下層水をイオン交換水で洗浄した１００ミリリットルビーカーに採取し、採取した下層水が酢酸ブチルの臭いがしなくなるまで、例えば、３０℃の恒温槽内で３分間振とうした水溶液を調製する。
２．イオンクロマトグラフ分析：上記１の前処理方法により得られた水溶液をイオンクロマトグラフにて分析し、濃度既知の硫酸ナトリウムの標準液と比較することにより、硫酸由来物質の濃度を算出する。この分析での硫酸イオンSO4２−の検出限界は１ｐｐｂ以下である。硫酸由来物質の感度係数は、硫酸由来物質を６０℃、９０時間加熱処理して硫酸イオンにまで完全に変化させ、硫酸イオンの増量から求めた。本実施例では、硫酸由来物質の硫酸イオン換算濃度［ｐｐｂ］＝硫酸由来物質のピーク面積／３３３．６である。
イオンクロマトグラフ分析の条件は以下の通りである。
装置：ＤＸ−３２０（ダイオネクス製）
検出器：電気伝導度計
プレカラム：ＩｏｎＰａｃＡＧ１７（ダイオネクス製）
分離カラム：ＩｏｎＰａｃＡＳ１７（ダイオネクス製）
恒温槽温度：３０℃
溶離液：２５ミリモルＫＯＨ水溶液
溶離液流量：１．５ミリリットル／分
試料注入量：１０μリットル
３．ガスクロマトグラフ分析：蒸留塔の仕込液及び各留分をガスクロマトグラフにて分析し、濃度既知のジブチル硫酸で作成した検量線を元にして、ピーク面積から絶対検量線法にて試料中のジブチル硫酸濃度を算出する。
ガスクロマトグラフ分析の条件は以下の通りである。
装置：ＨＰ６８９０（ヒューレットパッカード製）
検出器：ＦＩＤ
カラム：ＨＰ５（６０ｍ×０．３２ｍｍ×１．０μｍ）（ヒューレットパッカード製）
昇温速度：１００℃で１０分保持→５℃／分で昇温→２３０℃で１４分保持
Ｈｅキャリア：２．４ミリリットル／分、２２．５ｐｓｉ
試料注入量：１μリットル
４．経時変化試験：脱高沸物蒸留塔の塔頂から留出した酢酸ブチルを褐色の広口瓶に入れ、気相部を窒素シールした後密栓した試料を、２５［℃］に設定した恒温槽に３ヶ月間保持し、イオンクロマトグラフ分析及びガスクロマトグラフ分析を行った。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The “part” used in the examples means “part by weight” unless otherwise specified.
[Evaluation methods]
1. Pretreatment of analytical sample: Since butyl acetate as a sample is an interference component for ion chromatographic analysis, ionic substances (sulfuric acid-derived substances, sulfuric acid and monobutyl sulfuric acid) are extracted from butyl acetate with water, and butyl acetate is contained. Prepare no aqueous solution. Specifically, 50 mL of butyl acetate as a sample and 50 mL of ion exchange water were placed in a separatory funnel, shaken for 3 minutes, allowed to stand for 2 minutes and separated, and then the lower layer water was washed with ion exchange water. The sample is collected in a milliliter beaker, and an aqueous solution shaken for 3 minutes in a thermostatic bath at 30 ° C., for example, is prepared until the collected lower layer water does not smell of butyl acetate.
2. Ion chromatographic analysis: The concentration of sulfuric acid-derived substance is calculated by analyzing the aqueous solution obtained by the above pretreatment method 1 with an ion chromatograph and comparing it with a standard solution of sodium sulfate of known concentration. The detection limit of sulfate ion SO4 2- in this analysis is 1 ppb or less. The sensitivity coefficient of the sulfuric acid-derived substance was obtained from the increase in the sulfate ion by heat-treating the sulfuric acid-derived substance at 60 ° C. for 90 hours to completely change it to sulfate ion. In this example, the sulfate ion equivalent concentration [ppb] of the sulfuric acid-derived substance = peak area of the sulfuric acid-derived substance / 333.6.
The conditions for ion chromatographic analysis are as follows.
Device: DX-320 (manufactured by Dionex)
Detector: Electric conductivity meter
Precolumn: IonPacAG17 (manufactured by Dionex)
Separation column: IonPacAS17 (Dionex)
Thermostatic bath temperature: 30 ° C
Eluent: 25 mM KOH aqueous solution Eluent flow rate: 1.5 ml / min Sample injection amount: 10 μl3. Gas chromatographic analysis: Analyzing the charged solution and each fraction of the distillation column with a gas chromatograph, and using a calibration curve created with dibutyl sulfate of known concentration, dibutyl sulfate in the sample from the peak area using the absolute calibration curve method Calculate the concentration.
The conditions for gas chromatographic analysis are as follows.
Device: HP6890 (manufactured by Hewlett-Packard)
Detector: FID
Column: HP5 (60 m × 0.32 mm × 1.0 μm) (manufactured by Hewlett Packard)
Rate of temperature rise: held at 100 ° C. for 10 minutes → heated at 5 ° C./minute→held at 230 ° C. for 14 minutes He carrier: 2.4 ml / min, 22.5 psi
Sample injection volume: 1 μl 4. Temporal change test: Put butyl acetate distilled from the top of the deboiling tower into a brown jar, seal the gas phase with nitrogen, and seal the sample in a thermostat set at 25 [° C]. The sample was held for 3 months and subjected to ion chromatography analysis and gas chromatography analysis.
［参考例１〜２、比較例１］
図１に示されるフローシートに従って本発明を説明する。原料として、酢酸１００部、ｎ−ブタノール１２４部、触媒として硫酸１．７部を槽型反応器（図示せず）に仕込んだ。槽型反応器を温度９５〜１０５℃、圧力７６０ｍｍＨｇに、１時間保持した。槽型反応器から取り出した液を反応蒸留塔（図示せず）に供給し、エステル化反応により生成する水を塔頂より共沸により除去しながら反応を完結させた。反応蒸留塔は、塔頂温度９５〜１０５℃、塔底温度１２５〜１３５℃、塔頂圧力７６０ｍｍＨｇに保持した。
ここでは、仕込み液量１００部に対して水、ｎ−ブタノール及び低沸点物が塔頂より１４部留出された。
塔底からは缶出液として、酢酸ブチル、硫酸、未反応の酢酸及び高沸点物が８６部取り出された。
反応蒸留塔の缶出液は、中和洗浄槽（図示せず）に仕込まれ、水酸化ナトリウム水溶液により、硫酸及び未反応の酢酸を中和し、高沸点物の一部を水酸化ナトリウムにより分解させた後、静置分液された。中和洗浄槽へは、缶出液１００部に対して１部の水酸化ナトリウム及び５０部の水が仕込まれた。中和洗浄槽への仕込み液全量１００部に対して、硫酸を除去された酢酸ブチル、高沸点物の残り及び水酸化ナトリウムによる分解により生じた低沸点物の一部が６６部、上層に取り出された。中和により生じた硫酸塩、酢酸塩及び水酸化ナトリウムによる分解により生じた低沸点物の一部を含む水が３４部、下層に排出された。
[Reference Examples 1-2, Comparative Example 1]
The present invention will be described with reference to the flow sheet shown in FIG. As raw materials, 100 parts of acetic acid, 124 parts of n-butanol, and 1.7 parts of sulfuric acid as a catalyst were charged into a tank reactor (not shown). The tank reactor was maintained at a temperature of 95 to 105 ° C. and a pressure of 760 mmHg for 1 hour. The liquid taken out from the tank reactor was supplied to a reactive distillation column (not shown), and the reaction was completed while removing water generated by the esterification reaction from the top of the column by azeotropic distillation. The reactive distillation column was maintained at a column top temperature of 95 to 105 ° C., a column bottom temperature of 125 to 135 ° C., and a column top pressure of 760 mmHg.
Here, 14 parts of water, n-butanol and low-boiling substances were distilled from the top of the column with respect to 100 parts of the charged liquid.
From the bottom of the tower, 86 parts of butyl acetate, sulfuric acid, unreacted acetic acid and high-boiling substances were taken out as bottoms.
The bottoms of the reactive distillation column are charged into a neutralization washing tank (not shown), neutralized with sulfuric acid and unreacted acetic acid with an aqueous sodium hydroxide solution, and a portion of the high-boiling products with sodium hydroxide. After decomposing, it was subjected to stationary separation. The neutralization washing tank was charged with 1 part of sodium hydroxide and 50 parts of water with respect to 100 parts of the bottoms. 66 parts of butyl acetate from which sulfuric acid has been removed, the remaining high-boiling substances and a part of low-boiling substances generated by decomposition with sodium hydroxide are taken out to the upper layer with respect to 100 parts of the total amount of the liquid charged into the neutralization washing tank. It was. 34 parts of water containing a part of low-boiling substances generated by decomposition with sulfate, acetate and sodium hydroxide generated by neutralization were discharged to the lower layer.
＜参考例１（気体サイドカット）＞
中和洗浄槽の上層液を分析した結果、硫酸由来物質濃度は２ｐｐｂ、硫酸イオン濃度は２６ｐｐｂ、モノブチル硫酸濃度は３６０ｐｐｂ、ジブチル硫酸濃度は７８０ｐｐｍであった。
段数４０段の多孔板塔からなる内径３０ｍｍの脱低沸物蒸留塔１−１の下から３０段目に上層液１００部を仕込み、塔内が温度１１０〜１３０℃、圧力７６０ｍｍＨｇ、還流比１０となるように保持した。
これにより、塔頂液１として低沸点物及び酢酸ブチルの一部が塔頂より５部排出された。脱低沸物蒸留塔１−１の塔底からは、塔底液１として酢酸ブチル及び硫酸アルキル類等の高沸点物が５部排出された。
脱低沸物蒸留塔１−１の下から５段目の棚からは、サイドカット気体１として酢酸ブチル及び高沸点物が９０部取り出された。
サイドカット気体１の凝縮液を分析した結果、硫酸由来物質濃度は６ｐｐｂ、硫酸イオン濃度は１２ｐｐｂ、モノブチル硫酸濃度は１ｐｐｂ以下、ジブチル硫酸濃度は７ｐｐｍであった。（表１）
段数３０段の多孔板塔からなる内径３０［ｍｍ］の脱高沸物蒸留塔１−２の下から３段目に、上記サイドカット気体１の凝縮液を１００部仕込み、塔内が温度１２４〜１３５℃、圧力７６０ｍｍＨｇ、還流比０．５となるように保持した。これにより、塔底液２として高沸点物及び酢酸ブチルの一部が塔底より５部排出された。
脱高沸物蒸留塔１−２の塔頂からは、塔頂液２として酢酸ブチルが９５部留出された。
上記方法により製造された酢酸ブチルについて、製造直後と製造３ヶ月後イオンクロマトグラフ及びガスクロマトグラフにより、硫酸等の分析を行った。結果を表２に示す。製造直後の塔頂液２を分析した結果、硫酸由来物質濃度は７ｐｐｂ、硫酸イオン濃度は２ｐｐｂ、モノブチル硫酸濃度は１ｐｐｂ以下、ジブチル硫酸濃度は１ｐｐｍ以下であった。製造３ヶ月後においても、硫酸由来物質濃度は検出限界以下であり、硫酸イオン濃度は１０ｐｐｂであった。
<Reference example 1 (gas side cut)>
As a result of analyzing the upper layer solution of the neutralization washing tank, the sulfuric acid-derived substance concentration was 2 ppb, the sulfate ion concentration was 26 ppb, the monobutyl sulfate concentration was 360 ppb, and the dibutyl sulfate concentration was 780 ppm.
100 parts of the upper layer liquid is charged to the 30th stage from the bottom of the low-boiling distillation tower 1-1 having an inner diameter of 30 mm consisting of a perforated plate tower having 40 stages, the temperature in the tower is 110 to 130 ° C., the pressure is 760 mmHg, the reflux ratio is 10 Was held to be.
Thereby, 5 parts of low boiling point substances and a part of butyl acetate were discharged from the top of the tower as the top liquid 1. From the bottom of the low-boiling distillation column 1-1, 5 parts of high-boiling substances such as butyl acetate and alkyl sulfates were discharged as the bottom liquid 1.
90 parts of butyl acetate and high-boiling substances were taken out as a side cut gas 1 from the bottom shelf at the bottom of the low-boiling distillation column 1-1.
As a result of analyzing the condensate of the side cut gas 1, the concentration of the sulfuric acid-derived substance was 6 ppb, the sulfate ion concentration was 12 ppb, the monobutyl sulfate concentration was 1 ppb or less, and the dibutyl sulfate concentration was 7 ppm. (Table 1)
100 parts of the condensate of the above-mentioned sidecut gas 1 is charged to the third stage from the bottom of the dehydroboiling distillation tower 1-2 having an inner diameter of 30 [mm] consisting of a perforated plate tower having 30 stages, and the temperature in the tower is 124. It was kept at ˜135 ° C., a pressure of 760 mmHg, and a reflux ratio of 0.5. Thereby, 5 parts of high boilers and a part of butyl acetate were discharged from the bottom of the tower bottom liquid 2.
95 parts of butyl acetate was distilled as a top liquid 2 from the top of the deboiling column 1-2.
About the butyl acetate manufactured by the said method, the sulfuric acid etc. were analyzed by the ion chromatograph and the gas chromatograph immediately after manufacture and 3 months after manufacture. The results are shown in Table 2. As a result of analyzing the top liquid 2 immediately after production, the concentration of the sulfuric acid-derived substance was 7 ppb, the sulfate ion concentration was 2 ppb, the monobutyl sulfate concentration was 1 ppb or less, and the dibutyl sulfate concentration was 1 ppm or less. Even after 3 months of production, the sulfuric acid-derived substance concentration was below the detection limit, and the sulfate ion concentration was 10 ppb.
＜参考例２（液サイドカット）＞
段数４０段の多孔板塔からなる内径３０ｍｍの脱低沸物蒸留塔１−１の下から３０段目に、参考例１記載の上層液１００部を仕込み、塔内が温度１１０〜１３０℃、圧力７６０ｍｍＨｇ、還流比１０となるように保持した。
これにより、塔頂液１として低沸点物及び酢酸ブチルの一部が塔頂より５部排出された。
脱低沸物蒸留塔１−１の塔底からは、塔底液１として酢酸ブチル及び硫酸アルキル類等の高沸点物が５部排出された。
脱低沸物蒸留塔１−１の下から５段目の棚からは、サイドカット液体１として酢酸ブチル及び高沸点物が９０部取り出された。
サイドカット液体１を分析した結果、硫酸由来物質濃度は１ｐｐｂ以下、硫酸イオン濃度は４０ｐｐｂ、モノブチル硫酸濃度は９５ｐｐｂ、ジブチル硫酸濃度は１８０ｐｐｍであった。（表１）
段数３０段の多孔板塔からなる内径３０ｍｍの脱高沸物蒸留塔１−２の下から３段目に、上記サイドカット液体１を１００部仕込み、塔内が温度１２４〜１３５℃、圧力７６０ｍｍＨｇ、還流比０．５となるように保持した。これにより、塔底液２として高沸点物及び酢酸ブチルの一部が塔底より５部排出された。
脱高沸物蒸留塔１−２の塔頂からは、塔頂液２として酢酸ブチルが９５部留出された。
上記方法により製造された酢酸ブチルについて、製造直後と製造３ヶ月後イオンクロマトグラフ及びガスクロマトグラフにより、硫酸等の分析を行った。製造直後の塔頂液２を分析した結果、硫酸由来物質濃度は８ｐｐｂ、硫酸イオン濃度は７ｐｐｂ、モノブチル硫酸濃度は１ｐｐｂ以下、ジブチル硫酸濃度は１ｐｐｍ以下であった。製造３ヶ月後においても、硫酸由来物質濃度は検出限界以下であり、硫酸イオン濃度は１５ｐｐｂであった。（表２）
<Reference Example 2 (Liquid Side Cut)>
100 parts of the upper layer liquid described in Reference Example 1 is charged to the 30th stage from the bottom of the low-boiling distillation tower 1-1 having an inner diameter of 30 mm composed of a perforated plate tower having 40 stages, and the temperature in the tower is 110 to 130 ° C. The pressure was maintained at 760 mmHg and a reflux ratio of 10.
Thereby, 5 parts of low boiling point substances and a part of butyl acetate were discharged from the top of the tower as the top liquid 1.
From the bottom of the low-boiling distillation column 1-1, 5 parts of high-boiling substances such as butyl acetate and alkyl sulfates were discharged as the bottom liquid 1.
90 parts of butyl acetate and high-boiling substances were taken out as the side cut liquid 1 from the bottom shelf at the bottom of the low-boiling distillation column 1-1.
As a result of analyzing the side cut liquid 1, the sulfuric acid-derived substance concentration was 1 ppb or less, the sulfate ion concentration was 40 ppb, the monobutyl sulfate concentration was 95 ppb, and the dibutyl sulfate concentration was 180 ppm. (Table 1)
100 parts of the above-mentioned side cut liquid 1 is charged into the third stage from the bottom of the 30 mm inner diameter dehigh boiling boiling column 1-2 consisting of a perforated plate tower having 30 stages, and the inside of the tower is at a temperature of 124 to 135 ° C. and a pressure of 760 mmHg. The reflux ratio was kept at 0.5. Thereby, 5 parts of high boilers and a part of butyl acetate were discharged from the bottom of the tower bottom liquid 2.
95 parts of butyl acetate was distilled as a top liquid 2 from the top of the deboiling column 1-2.
About the butyl acetate manufactured by the said method, the sulfuric acid etc. were analyzed by the ion chromatograph and the gas chromatograph immediately after manufacture and 3 months after manufacture. As a result of analyzing the column top liquid 2 immediately after production, the concentration of the sulfuric acid-derived substance was 8 ppb, the sulfate ion concentration was 7 ppb, the monobutyl sulfate concentration was 1 ppb or less, and the dibutyl sulfate concentration was 1 ppm or less. Even after 3 months of production, the sulfuric acid-derived substance concentration was below the detection limit, and the sulfate ion concentration was 15 ppb. (Table 2)
＜比較例１（図１のラインＣによる缶出抜き取り）＞
段数４０段の多孔板塔からなる内径３０［ｍｍ］の脱低沸物蒸留塔１−１の下から３０段目に、参考例１記載の上層液１００部を仕込み、塔内が温度１１０〜１３０［℃］、圧力７６０［ｍｍＨｇ］、還流比１０となるように保持した。
これにより、塔頂液１として低沸点物及び酢酸ブチルの一部が塔頂より５部排出された。
脱低沸物蒸留塔１−１の塔底からは、塔底液１として酢酸ブチル及び硫酸アルキル類等の高沸点物が９５部取り出された。
塔底液１を分析した結果、硫酸由来物質濃度は２４ｐｐｂ、硫酸イオン濃度は４２８ｐｐｂ、モノブチル硫酸濃度は４３５ｐｐｂ、ジブチル硫酸濃度は１２７６ｐｐｍであった。（表１）
段数３０段の多孔板塔からなる内径３０［ｍｍ］の脱高沸物蒸留塔１−２の下から３段目に、上記塔底液１を１００部仕込み、塔内が温度１２４〜１３５［℃］、圧力７６０［ｍｍＨｇ］、還流比０．５となるように保持した。
これにより、塔底液２として高沸点物及び酢酸ブチルの一部が塔底より５部排出された。
脱高沸物蒸留塔１−２の塔頂からは、塔頂液２として酢酸ブチルが９５部留出された。
上記方法により製造された酢酸ブチルについて、製造直後と製造３ヶ月後イオンクロマトグラフ及びガスクロマトグラフにより、硫酸等の分析を行った。製造直後の塔頂液２を分析した結果、硫酸由来物質濃度は４６０ｐｐｂ、硫酸イオン濃度は２７ｐｐｂ、モノブチル硫酸濃度は１ｐｐｂ以下、ジブチル硫酸濃度は１ｐｐｍ以下であった。製造３ヶ月後においては、硫酸由来物質濃度は検出限界以下となり、硫酸イオン濃度が４８３ｐｐｂに増加していた。（表２）
これら蒸留において、脱低沸物蒸留塔から取り出し、脱高沸物蒸留塔に仕込んだ酢酸ブチルの分析結果を、以下の表１に示す。
<Comparative example 1 (can extraction / drawing by line C in FIG. 1)>
100 parts of the upper layer liquid described in Reference Example 1 was charged in the 30th stage from the bottom of the delow boiling distillation tower 1-1 having an inner diameter of 30 [mm] consisting of a perforated plate tower having 40 stages. It was maintained at 130 [° C.], a pressure of 760 [mmHg], and a reflux ratio of 10.
Thereby, 5 parts of low boiling point substances and a part of butyl acetate were discharged from the top of the tower as the top liquid 1.
From the bottom of the low-boiling distillation column 1-1, 95 parts of high-boiling substances such as butyl acetate and alkyl sulfates were taken out as the bottom liquid 1.
As a result of analyzing the bottom liquid 1, the sulfuric acid-derived substance concentration was 24 ppb, the sulfate ion concentration was 428 ppb, the monobutyl sulfate concentration was 435 ppb, and the dibutyl sulfate concentration was 1276 ppm. (Table 1)
100 parts of the above-mentioned column bottom liquid 1 is charged to the third stage from the bottom of the dehydroboiling distillation tower 1-2 having an inner diameter of 30 [mm] consisting of a perforated plate tower having 30 stages, and the temperature in the tower is 124 to 135 [ [° C.], a pressure of 760 [mmHg], and a reflux ratio of 0.5.
Thereby, 5 parts of high boilers and a part of butyl acetate were discharged from the bottom of the tower bottom liquid 2.
95 parts of butyl acetate was distilled as a top liquid 2 from the top of the deboiling column 1-2.
About the butyl acetate manufactured by the said method, the sulfuric acid etc. were analyzed by the ion chromatograph and the gas chromatograph immediately after manufacture and 3 months after manufacture. As a result of analyzing the tower top liquid 2 immediately after the production, the concentration of the sulfuric acid-derived substance was 460 ppb, the sulfate ion concentration was 27 ppb, the monobutyl sulfate concentration was 1 ppb or less, and the dibutyl sulfate concentration was 1 ppm or less. After 3 months of production, the concentration of sulfuric acid-derived substance was below the detection limit, and the sulfate ion concentration was increased to 483 ppb. (Table 2)
In these distillations, the analysis results of butyl acetate taken out from the low-boiling distillation column and charged into the high-boiling distillation column are shown in Table 1 below.
＊２：検出限界は１ｐｐｂ以下である。
＊３：検出限界は１ｐｐｍ以下である。
（表２および表３において同じ。）
* 2: The detection limit is 1 ppb or less.
* 3: The detection limit is 1 ppm or less.
(The same applies to Table 2 and Table 3.)
これら蒸留において、脱高沸物蒸留塔から留出した酢酸ブチルの分析結果を、以下の表２に示す。 In these distillations, the analysis results of butyl acetate distilled from the deboiling distillation column are shown in Table 2 below.
［実施例１〜２、比較例２］
酢酸ブチルの合成については、参考例１および２と同様に仕込み、合成、中和等を行ない上層液を得た。
＜実施例１（塔底温度１００℃）＞
４０段の多孔板塔からなる内径３０ｍｍの脱低沸物蒸留塔１−１の下から３０段目に上層液１００部を仕込み、塔内が温度１１０〜１３０℃、圧力７６０ｍｍＨｇ、還流比１０となるように保持した。
これにより、塔頂液１として低沸点物及び酢酸ブチルの一部が塔頂より５部排出された。
脱低沸物蒸留塔１−１の塔底からは、塔底液１として酢酸ブチル及び硫酸アルキル類等の高沸点物が９５部取り出された。塔底液１を分析した結果、硫酸由来物質濃度は６ｐｐｂ、硫酸イオン濃度は５１３ｐｐｂ、モノブチル硫酸濃度は３１７ｐｐｂ、ジブチル硫酸濃度は９６８ｐｐｍであった。
段数３０段の多孔板塔からなる内径３０ｍｍの脱高沸物蒸留塔１−２の下から３段目に、上記塔底液１を１００部仕込み（図１のラインＣ）、塔内が温度９２〜１００℃、圧力２８０ｍｍＨｇ、還流比０．５となるように保持した。これにより、塔底液２として高沸点物及び酢酸ブチルの一部が塔底より５部排出された。
脱高沸物蒸留塔１−２の塔頂からは、塔頂液２として酢酸ブチルが９５部留出された。
上記方法により製造された酢酸ブチルについて、製造直後と製造３ヶ月後、イオンクロマトグラフ及びガスクロマトグラフにより、硫酸等の分析を行った。製造直後の塔頂液２を分析した結果、硫酸由来物質濃度は１２ｐｐｂ、硫酸イオン濃度は３ｐｐｂ、モノブチル硫酸濃度は１ｐｐｂ以下、ジブチル硫酸濃度は１ｐｐｍ以下であった。製造３ヶ月後においても、硫酸由来物質濃度は検出限界以下であり、硫酸イオン濃度は１６ｐｐｂであった。（表３）
[Examples 1 and 2, Comparative Example 2]
The synthesis of butyl acetate was carried out in the same manner as in Reference Examples 1 and 2, and synthesis, neutralization and the like were performed to obtain an upper layer liquid.
<Example 1 (column bottom temperature 100 ° C.)>
100 parts of the upper layer liquid is charged to the 30th stage from the bottom of the low-boiling distillation tower 1-1 having an inner diameter of 30 mm consisting of a 40-stage perforated plate tower, and the temperature in the tower is 110 to 130 ° C., the pressure is 760 mmHg, and the reflux ratio is 10. Held to be.
Thereby, 5 parts of low boiling point substances and a part of butyl acetate were discharged from the top of the tower as the top liquid 1.
From the bottom of the low-boiling distillation column 1-1, 95 parts of high-boiling substances such as butyl acetate and alkyl sulfates were taken out as the bottom liquid 1. As a result of analyzing the bottom liquid 1, the concentration of the sulfuric acid-derived substance was 6 ppb, the sulfate ion concentration was 513 ppb, the monobutyl sulfate concentration was 317 ppb, and the dibutyl sulfate concentration was 968 ppm.
100 parts of the above-mentioned column bottom liquid 1 (line C in FIG. 1) is charged to the third stage from the bottom of the high-boiling distillation tower 1-2 having a 30-mm inner diameter and a perforated plate tower having 30 stages. The temperature was maintained at 92 to 100 ° C., a pressure of 280 mmHg, and a reflux ratio of 0.5. Thereby, 5 parts of high boilers and a part of butyl acetate were discharged from the bottom of the tower bottom liquid 2.
95 parts of butyl acetate was distilled as a top liquid 2 from the top of the deboiling column 1-2.
About the butyl acetate manufactured by the said method, the sulfuric acid etc. were analyzed by the ion chromatograph and the gas chromatograph immediately after manufacture and 3 months after manufacture. As a result of analyzing the top liquid 2 immediately after production, the concentration of the sulfuric acid-derived substance was 12 ppb, the concentration of sulfate ions was 3 ppb, the concentration of monobutyl sulfate was 1 ppb or less, and the concentration of dibutyl sulfate was 1 ppm or less. Even after 3 months of production, the sulfuric acid-derived substance concentration was below the detection limit, and the sulfate ion concentration was 16 ppb. (Table 3)
＜実施例２（塔底温度７６℃…実験からの推算により、硫酸由来成分の発生が０になる温度）＞
段数３０段の多孔板塔からなる内径３０ｍｍの脱高沸物蒸留塔１−２の下から３段目に、実施例１記載の塔底液１を１００部仕込み（図１のラインＣ）、塔内が温度６５〜７６℃、圧力１１５ｍｍＨｇ、還流比０．５となるように保持した。これにより、塔底液２として高沸点物及び酢酸ブチルの一部が塔底より５部排出された。
脱高沸物蒸留塔１−２の塔頂からは、塔頂液２として酢酸ブチルが９５部留出された。
上記方法により製造された酢酸ブチルについて、製造直後と製造３ヶ月後、イオンクロマトグラフ及びガスクロマトグラフにより、硫酸等の分析を行った。製造直後の塔頂液２を分析した結果、硫酸由来物質濃度は１ｐｐｂ、硫酸イオン濃度は２ｐｐｂ、モノブチル硫酸濃度は１ｐｐｂ以下、ジブチル硫酸濃度は１ｐｐｍ以下であった。製造３ヶ月後においても、硫酸由来物質濃度は検出限界以下であり、硫酸イオン濃度は３ｐｐｂであった。（表３）
<Example 2 (Temperature at 76 ° C .... temperature at which generation of sulfuric acid-derived component becomes 0 by estimation from experiments)>
100 parts of the bottom liquid 1 described in Example 1 was charged to the third stage from the bottom of the dehydroboiling distillation tower 1-2 having a 30 mm inner diameter and a perforated plate tower having 30 stages (line C in FIG. 1). The inside of the tower was maintained at a temperature of 65 to 76 ° C., a pressure of 115 mmHg, and a reflux ratio of 0.5. Thereby, 5 parts of high boilers and a part of butyl acetate were discharged from the bottom of the tower bottom liquid 2.
95 parts of butyl acetate was distilled as a top liquid 2 from the top of the deboiling column 1-2.
About the butyl acetate manufactured by the said method, the sulfuric acid etc. were analyzed by the ion chromatograph and the gas chromatograph immediately after manufacture and 3 months after manufacture. As a result of analyzing the top liquid 2 immediately after production, the concentration of the sulfuric acid-derived substance was 1 ppb, the sulfate ion concentration was 2 ppb, the monobutyl sulfate concentration was 1 ppb or less, and the dibutyl sulfate concentration was 1 ppm or less. Even after 3 months of production, the sulfuric acid-derived substance concentration was below the detection limit, and the sulfate ion concentration was 3 ppb. (Table 3)
＜比較例２（従来の塔底温度（常圧）での蒸留）＞
段数３０段の多孔板塔からなる内径３０ｍｍの脱高沸物蒸留塔１−２の下から３段目に、実施例１記載の塔底液１を１００部仕込み（図１のラインＣ）、塔内が温度１２４〜１３５℃、圧力７６０ｍｍＨｇ、還流比０．５となるように保持した。これにより、塔底液２として高沸点物及び酢酸ブチルの一部が塔底より５部排出された。
脱高沸物蒸留塔１−２の塔頂からは、塔頂液２として酢酸ブチルが９５部留出された。
上記方法により製造された酢酸ブチルについて、製造直後と製造３ヶ月後、イオンクロマトグラフ及びガスクロマトグラフにより、硫酸等の分析を行った。製造直後の塔頂液２を分析した結果、硫酸由来物質濃度は３２２ｐｐｂ、硫酸イオン濃度は１７ｐｐｂ、モノブチル硫酸濃度は１ｐｐｂ以下、ジブチル硫酸濃度は１ｐｐｍ以下であった。製造３ヶ月後においては、硫酸由来物質濃度は検出限界以下となり、硫酸イオン濃度が３２５ｐｐｂに増加していた。（表３）
これら蒸留における脱高沸物蒸留塔から留出した酢酸ブチルの分析結果を、以下の表３に示す。
<Comparative Example 2 (distillation at conventional tower bottom temperature (normal pressure))>
100 parts of the bottom liquid 1 described in Example 1 was charged to the third stage from the bottom of the dehydroboiling distillation tower 1-2 having a 30 mm inner diameter and a perforated plate tower having 30 stages (line C in FIG. 1). The inside of the tower was maintained at a temperature of 124 to 135 ° C., a pressure of 760 mmHg, and a reflux ratio of 0.5. Thereby, 5 parts of high boilers and a part of butyl acetate were discharged from the bottom of the tower bottom liquid 2.
95 parts of butyl acetate was distilled as a top liquid 2 from the top of the deboiling column 1-2.
About the butyl acetate manufactured by the said method, the sulfuric acid etc. were analyzed by the ion chromatograph and the gas chromatograph immediately after manufacture and 3 months after manufacture. As a result of analyzing the tower top liquid 2 immediately after the production, the concentration of the sulfuric acid-derived substance was 322 ppb, the sulfate ion concentration was 17 ppb, the monobutyl sulfate concentration was 1 ppb or less, and the dibutyl sulfate concentration was 1 ppm or less. Three months after the production, the concentration of the sulfuric acid-derived substance was below the detection limit, and the sulfate ion concentration was increased to 325 ppb. (Table 3)
The analysis results of butyl acetate distilled from the deboiling distillation column in these distillations are shown in Table 3 below.
１−１：脱低沸物蒸留塔
１−２：脱高沸物蒸留塔
１−１−１、１−２−１：リボイラー
１−１−２、１−２−２：コンデンサー
1-1: Removal of low boiling point distillation column 1-2: Removal of high boiling point distillation column 1-1-1, 1-2-1: Reboiler 1-1-2, 1-2-2: condenser
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980115A (en) * | 2014-06-03 | 2014-08-13 | 湖南瑞源石化股份有限公司 | Method for recycling acetic acid sec-butyl ester from reaction product during preparation of acetic acid sec-butyl ester with high efficiency |
| CN109704959A (en) * | 2018-12-21 | 2019-05-03 | 江门谦信化工发展有限公司 | A kind of industrialized preparing process of electronic grade acetic acid ester solvent |
| CN110041197A (en) * | 2019-04-28 | 2019-07-23 | 青岛科技大学 | A kind of method of complete thermal coupling separation of extractive distillation ethyl acetate, alcohol and water mixture |
| US11079677B2 (en) | 2017-02-20 | 2021-08-03 | Fujifilm Corporation | Chemical liquid, chemical liquid storage body, and pattern forming method |
| US11747727B2 (en) | 2016-11-18 | 2023-09-05 | Fujifilm Corporation | Chemical liquid, chemical liquid storage body, pattern forming method, and kit |
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2008
- 2008-06-19 JP JP2008159836A patent/JP2008308500A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980115A (en) * | 2014-06-03 | 2014-08-13 | 湖南瑞源石化股份有限公司 | Method for recycling acetic acid sec-butyl ester from reaction product during preparation of acetic acid sec-butyl ester with high efficiency |
| US11747727B2 (en) | 2016-11-18 | 2023-09-05 | Fujifilm Corporation | Chemical liquid, chemical liquid storage body, pattern forming method, and kit |
| US11079677B2 (en) | 2017-02-20 | 2021-08-03 | Fujifilm Corporation | Chemical liquid, chemical liquid storage body, and pattern forming method |
| CN109704959A (en) * | 2018-12-21 | 2019-05-03 | 江门谦信化工发展有限公司 | A kind of industrialized preparing process of electronic grade acetic acid ester solvent |
| CN110041197A (en) * | 2019-04-28 | 2019-07-23 | 青岛科技大学 | A kind of method of complete thermal coupling separation of extractive distillation ethyl acetate, alcohol and water mixture |
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