JP6266453B2 - Method for purifying dimethyl sulfoxide - Google Patents
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- JP6266453B2 JP6266453B2 JP2014139616A JP2014139616A JP6266453B2 JP 6266453 B2 JP6266453 B2 JP 6266453B2 JP 2014139616 A JP2014139616 A JP 2014139616A JP 2014139616 A JP2014139616 A JP 2014139616A JP 6266453 B2 JP6266453 B2 JP 6266453B2
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 title claims description 278
- 238000000034 method Methods 0.000 title claims description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000002994 raw material Substances 0.000 claims description 36
- 239000003513 alkali Substances 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000002835 absorbance Methods 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 5
- 235000019645 odor Nutrition 0.000 description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000012535 impurity Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 13
- 238000000746 purification Methods 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000001133 acceleration Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000000686 lactone group Chemical group 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101000671819 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 36 Proteins 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 102100040109 Ubiquitin carboxyl-terminal hydrolase 36 Human genes 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- -1 water vapor activated activated carbon Chemical class 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、ジメチルスルホキシドの精製方法に関し、さらに詳しくは、米国薬局方（Ｕ．Ｓ．Ｐｈａｒｍａｃｏｐｅｉａ）の規格を満たし、かつ臭気を低減した高品質のジメチルスルホキシドを経済的かつ、収率良く精製する方法に関するものである。 The present invention relates to a method for purifying dimethyl sulfoxide. More specifically, the present invention purifies high-quality dimethyl sulfoxide that satisfies the specifications of the US Pharmacopoeia and has reduced odor economically and in high yield. It is about the method.
ジメチルスルホキシドは、医農薬中間体の反応溶剤や合成試薬、あるいは電子材料等の特殊洗浄剤等として工業的に幅広く使用されている。なかでも米国薬局方に指定されているジメチルスルホキシドは、工業品質のジメチルスルホキシド以上に高純度で、かつ臭気が少ないことが必要とされている。 Dimethyl sulfoxide is widely used industrially as a reaction solvent, a synthetic reagent for medical and agrochemical intermediates, or a special detergent for electronic materials. Among them, dimethyl sulfoxide designated by the United States Pharmacopeia is required to have higher purity and less odor than industrial dimethyl sulfoxide.
従来、ジメチルスルホキシドの精製方法としては、一般工業品質のジメチルスルホキシドに活性炭を接触させ、次いで蒸留処理を行う精製方法（例えば特許文献１参照）、一般工業品質のジメチルスルホキシドに活性炭を接触させ、次いで一部のジメチルスルホキシドを凝固させて固液分離した後、ジメチルスルホキシドを再度溶解させる精製方法（例えば特許文献２参照）、特殊な専用設備で一般工業品質のジメチルスルホキシドを凝固させて固液分離した後でジメチルスルホキシドを再度溶解させる晶析方法（例えば特許文献３参照）などが知られている。 Conventionally, as a purification method of dimethyl sulfoxide, activated carbon is brought into contact with general industrial quality dimethyl sulfoxide and then subjected to distillation treatment (see, for example, Patent Document 1), activated carbon is brought into contact with general industrial quality dimethyl sulfoxide, After solidifying a part of dimethyl sulfoxide by solid-liquid separation, a purification method (see, for example, Patent Document 2) for re-dissolving dimethyl sulfoxide, solid-liquid separation was performed by coagulating general industrial quality dimethyl sulfoxide with special dedicated equipment. A crystallization method (for example, see Patent Document 3) in which dimethyl sulfoxide is dissolved again later is known.
しかしながら、特許文献１の精製方法では、臭気を除去することができない。臭気は、米国薬局方の規格には設定されていないものの、医薬用ジメチルスルホキシドに事実上求められている重要な要求品質である。 However, the purification method of Patent Document 1 cannot remove odor. Odor is an important quality requirement for pharmaceutical dimethyl sulfoxide, although it is not set in US Pharmacopoeia standards.
特許文献２の精製方法では、ジメチルスルホキシドの晶析や溶解において専用設備が必要であり不経済である。 The purification method of Patent Document 2 is uneconomical because dedicated equipment is required for crystallization and dissolution of dimethyl sulfoxide.
特許文献３の精製方法では、ジメチルスルホキシドの融点が低いため（融点１８℃）、特殊な専用設備が必要となる上、ジメチルスルホキシドの収率が１５％と低く、工業的に不利である。 In the purification method of Patent Document 3, since the melting point of dimethyl sulfoxide is low (melting point: 18 ° C.), special dedicated equipment is required and the yield of dimethyl sulfoxide is as low as 15%, which is industrially disadvantageous.
本発明の目的は、このような問題点を解消し、米国薬局方の規格を満たし、かつ臭気を低減すると共に、加熱促進試験において、臭気増加および不明不純物の生成を抑制した高品質のジメチルスルホキシドを、経済的かつ、収率良く精製する方法を提供することにある。 The object of the present invention is to solve such problems, satisfy the standards of the United States Pharmacopeia, reduce odor, and suppress high-quality dimethyl sulfoxide, which suppresses increase in odor and generation of unknown impurities in the heating accelerated test. Is to provide a method for purifying the product economically and with good yield.
上記課題を解決する本発明のジメチルスルホキシドの精製方法は、以下のいずれかの構成からなる。
（１）原料ジメチルスルホキシド１００重量部に、水を２０重量部以上、アルカリを添加した混合液を、活性炭と接触させた後、内温１３０℃以下で蒸留することを特徴とするジメチルスルホキシドの精製方法。
（２）前記アルカリの添加量を、前記混合液中の活性炭表面に存在する酸性官能基に由来する酸のグラム当量に対し、０．６〜３．１倍に相当するグラム当量にすることを特徴とする（１）記載のジメチルスルホキシドの精製方法。
The method for purifying dimethyl sulfoxide of the present invention that solves the above problems comprises any one of the following constitutions.
(1) Purification of dimethyl sulfoxide, characterized in that a mixed solution in which 20 parts by weight of water and alkali are added to 100 parts by weight of dimethyl sulfoxide is brought into contact with activated carbon and then distilled at an internal temperature of 130 ° C. or lower. Method.
(2) The addition amount of the alkali is set to a gram equivalent equivalent to 0.6 to 3.1 times the gram equivalent of the acid derived from the acidic functional group present on the activated carbon surface in the mixed solution. The method for purifying dimethyl sulfoxide according to (1), which is characterized in that
本発明のジメチルスルホキシドの精製方法は、米国薬局方の規格項目である吸光度を改良するとともに、事実上の要求品質として求められる臭気を大幅に改良することができる。この精製方法は、原料ジメチルスルホキシドに、蒸留分離しやすい水と、アルカリを添加し、活性炭と接触させた後、蒸留するだけで、収率良く高純度のジメチルスルホキシドを取得でき、臭気の低減に加え、加熱促進試験した後でも臭気および不明不純物の生成を抑制するので、医薬用途に使用し得る高品質のジメチルスルホキシドを、経済的かつ、高い収率で得ることができる。しかも特殊な専用設備が不要であるため、経済的である。 The method for purifying dimethyl sulfoxide of the present invention can improve the absorbance, which is a standard item of the United States Pharmacopeia, and can greatly improve the odor required as a practically required quality. In this purification method, water and alkali that are easy to separate by distillation and alkali are added to the raw material dimethyl sulfoxide, and after contact with activated carbon, high-purity dimethyl sulfoxide can be obtained in high yield by simply distilling, reducing odor. In addition, since the generation of odors and unknown impurities is suppressed even after the heating acceleration test, high-quality dimethyl sulfoxide that can be used for pharmaceutical use can be obtained economically and in a high yield. In addition, it is economical because no special dedicated equipment is required.
本発明のジメチルスルホキシドの精製方法は、米国薬局方の規格を満たし、かつその臭気を低減した高品質のジメチルスルホキシドを、経済的かつ、収率良く得る精製方法である。上述した通り、一般工業品レベルのジメチルスルホキシドを通常の方法で精製したのでは、米国薬局方の規格を満たすジメチルスルホキシドが得られたとしても臭気を除去することができなかったため医薬用途に使用することは困難であった。臭気を除去するためには、特許文献２および３に記載されたように、専用設備が必要であり、精製コストが高いものであった。 The method for purifying dimethyl sulfoxide according to the present invention is a method for obtaining a high-quality dimethyl sulfoxide that satisfies the specifications of the US Pharmacopoeia and has reduced odor, economically and in a high yield. As described above, when dimethyl sulfoxide at the level of general industrial products is purified by a normal method, even if dimethyl sulfoxide satisfying the standards of the United States Pharmacopeia is obtained, the odor cannot be removed, so that it is used for pharmaceutical purposes. It was difficult. In order to remove the odor, as described in Patent Documents 2 and 3, dedicated equipment is necessary, and the purification cost is high.
ここで、米国薬局方（Ｕ．Ｓ．Ｐｈａｒｍａｃｏｐｅｉａ ＵＳＰ３６、ＮＦ３１、３２６９ページ）では品質規格のひとつに２７５ｎｍの吸光度など、また、欧州薬局方（Ｅｕｒｏｐｅａｎ Ｐｈａｒｍａｃｏｐｅｉａ ７．０）においても２７５ｎｍの吸光度などが設定されている。一般工業品と薬局方品では２７５ｎｍの吸光度の差が最も大きいため、本明細書では、薬局方規格の代表値として２７５ｎｍの吸光度でジメチルスルホキシド品質を評価する。吸光度の測定は、紫外吸光光度計を使用し、幅１ｃｍのセルを使用し、水をブランクとする。ジメチルスルホキシドは事前に窒素バブリングを３０分間実施した後１０分以内に測定する。 Here, in the US Pharmacopoeia (US Pharmacopia USP36, NF31, p. 3269), one of the quality standards is 275 nm absorbance, and in the European Pharmacopoeia (European Pharmacopia 7.0), 275 nm absorbance is also set. Has been. Since the difference in absorbance at 275 nm is the largest between a general industrial product and a pharmacopoeia product, in this specification, the dimethyl sulfoxide quality is evaluated based on the absorbance at 275 nm as a representative value of the pharmacopoeia standard. The absorbance is measured using an ultraviolet absorptiometer, using a cell having a width of 1 cm, and using water as a blank. Dimethyl sulfoxide is measured within 10 minutes after 30 minutes of prior nitrogen bubbling.
本明細書において、ジメチルスルホキシドの臭気は、悪臭防止法等の臭気判定方法として使用されている６段階臭気強度表示法を用いる。この臭気強度表示法は、においの強さを下記に示す０〜５の６段階の判定基準で評価する方法であり、この方法に基づきジメチルスルホキシドの臭気レベルを評価することができる。
臭気強度０： 無臭
臭気強度１： やっと感知できるにおい
臭気強度２： 何のにおいか判る弱いにおい
臭気強度３： 楽に感知できるにおい
臭気強度４： 強いにおい
臭気強度５： 強烈なにおい
In this specification, the odor of dimethyl sulfoxide uses the 6-step odor intensity display method used as an odor determination method such as the malodor prevention method. This odor intensity display method is a method for evaluating the odor intensity by the following 6-step criteria of 0 to 5, and the odor level of dimethyl sulfoxide can be evaluated based on this method.
Odor intensity 0: Odorless Odor intensity 1: A smell that can be finally detected Odor intensity 2: A weak smell that can be detected by any smell Odor intensity 3: A smell that can be easily detected Odor intensity 4: Strong smell Odor intensity 5: Intense smell
ジメチルスルホキシドのにおいの嗅ぎ方としては、３０ｍＬサンプル瓶にジメチルスルホキシドを１５ｍＬ入れ、室温下でサンプル瓶に鼻を近づけ、同じサンプルをパネラー３人以上で嗅ぎ、全員の判定値のうち多数の値をサンプルの臭気強度とする。 To smell dimethyl sulfoxide, put 15 mL of dimethyl sulfoxide into a 30 mL sample bottle, bring the nose close to the sample bottle at room temperature, sniff the same sample with more than 3 panelists, The odor intensity of the sample.
本発明のジメチルスルホキシドの精製方法が処理対象にするジメチルスルホキシド（以下、「原料ジメチルスルホキシド」という。）としては、その原料、製造方法および生産国を制限するものではないが、好ましくは一般工業品レベルのジメチルスルホキシドであるとよい。また原料ジメチルスルホキシドの純度は、特に制限されるものではないが、好ましくは９９重量％以上、より好ましくは９９．９〜１００．０重量％であるとよい。このような純度の原料ジメチルスルホキシドを使用することにより、不純物の含有量が少なく米国薬局方の規格を満たし、かつ臭気がない高品質のジメチルスルホキシドを得ることができる。なお本明細書において、ジメチルスルホキシドの純度は、米国薬局方（ＵＳＰ３６−ＮＦ３１、３２６９ページ）に基づく方法でガスクロマトグラフにより測定するものとする。なお原料ジメチルスルホキシドには、ジメチルスルホキシドと蒸留で分離可能であれば、ジメチルスルホキシド以外の化合物を含んでいてもよい。 The dimethyl sulfoxide (hereinafter referred to as “raw dimethyl sulfoxide”) to be treated by the method for purifying dimethyl sulfoxide of the present invention is not limited to its raw material, production method and country of production, but is preferably a general industrial product. A level of dimethyl sulfoxide is preferred. The purity of the raw material dimethyl sulfoxide is not particularly limited, but is preferably 99% by weight or more, more preferably 99.9 to 100.0% by weight. By using the raw material dimethyl sulfoxide having such a purity, it is possible to obtain a high-quality dimethyl sulfoxide having a low impurity content and satisfying the standards of the US Pharmacopoeia and having no odor. In the present specification, the purity of dimethyl sulfoxide is measured by gas chromatography using a method based on the United States Pharmacopeia (USP36-NF31, page 3269). The raw material dimethyl sulfoxide may contain a compound other than dimethyl sulfoxide as long as it can be separated from dimethyl sulfoxide by distillation.
本発明のジメチルスルホキシドの精製方法は、原料ジメチルスルホキシド１００重量部に水を２０重量部以上、およびアルカリを添加した混合液を調製し、得られた混合液を活性炭と接触させる。原料ジメチルスルホキシドを、水およびアルカリの存在下で活性炭と接触させることにより、原料ジメチルスルホキシド中の微量不純物を活性炭に吸着させることができ、活性炭の表面に存在するカルボキシ基、ラクトン基やフェノール性ヒドロキシ基によるジメチルスルホキシドの劣化を抑制することができる。 In the method for purifying dimethyl sulfoxide of the present invention, a mixed solution is prepared by adding 20 parts by weight of water and alkali to 100 parts by weight of raw material dimethyl sulfoxide, and the obtained mixed solution is brought into contact with activated carbon. By contacting the raw material dimethyl sulfoxide with activated carbon in the presence of water and alkali, trace amounts of impurities in the raw material dimethyl sulfoxide can be adsorbed on the activated carbon, and carboxy groups, lactone groups and phenolic hydroxy groups present on the surface of the activated carbon. Degradation of dimethyl sulfoxide by a group can be suppressed.
本発明の精製方法において、水が存在することにより、原料ジメチルスルホキシド中に微量含まれる不純物を除去しやすくなり、とりわけ臭気を大幅に低減することができる。原料ジメチルスルホキシドに水を添加しない場合や、水以外の溶媒を添加した場合には、ジメチルスルホキシドの吸光度を小さくすることおよび臭気を低減することができない。 In the purification method of the present invention, the presence of water makes it easy to remove impurities contained in trace amounts in the raw material dimethyl sulfoxide, and in particular, the odor can be greatly reduced. When water is not added to the raw material dimethyl sulfoxide or when a solvent other than water is added, the absorbance of dimethyl sulfoxide cannot be reduced and the odor cannot be reduced.
原料ジメチルスルホキシドに添加する水としては、一般的に入手可能な水であれば良く、例えば水道水、工業用水、純水、スチーム凝縮水、蒸留水、イオン交換水、超純水等を例示することができる。 The water added to the raw material dimethyl sulfoxide may be water that is generally available. Examples thereof include tap water, industrial water, pure water, steam condensed water, distilled water, ion-exchanged water, and ultrapure water. be able to.
原料ジメチルスルホキシドへの水の混合量は、原料ジメチルスルホキシド１００重量部に対し２０重量部以上、好ましくは２５重量部以上にする。水の混合量が、２０重量部より少ないと臭気改善効果を十分に得ることができない。水の混合量の上限は、生産効率の観点から好ましくは５００重量部くらいにすることができる。水の混合量は、好ましくは２０〜５００重量部、より好ましくは２０〜３００重量部、さらに好ましくは２５〜２００重量部、とりわけ好ましくは２５〜１００重量部にするとよい。 The amount of water mixed with the raw material dimethyl sulfoxide is 20 parts by weight or more, preferably 25 parts by weight or more with respect to 100 parts by weight of the raw material dimethyl sulfoxide. If the amount of water mixed is less than 20 parts by weight, the effect of improving odor cannot be obtained sufficiently. The upper limit of the mixing amount of water is preferably about 500 parts by weight from the viewpoint of production efficiency. The mixing amount of water is preferably 20 to 500 parts by weight, more preferably 20 to 300 parts by weight, further preferably 25 to 200 parts by weight, and particularly preferably 25 to 100 parts by weight.
上述したように、原料ジメチルスルホキシドを水の存在下、活性炭と接触させた後、蒸留することにより得られたジメチルスルホキシドは、米国薬局方の規格を満たし、かつ臭気が低減されている。しかし、医農薬中間体の反応溶剤や合成試薬として加熱処理が施されると、楽に感知できる臭気が発生したり、不明不純物が生成したりすることがある。本発明の精製方法では、アルカリを添加することにより、活性炭の表面に存在するカルボキシ基、ラクトン基やフェノール性ヒドロキシ基などに代表される酸性官能基よるジメチルスルホキシドの劣化を抑制することができる。アルカリを添加しない場合やアルカリの代わりに酸を添加した場合は、ジメチルスルホキシドを加熱促進試験したとき、ジメチルスルホキシドの臭気の増加および不明不純物の生成を抑制することができない。 As described above, the dimethyl sulfoxide obtained by bringing the raw material dimethyl sulfoxide into contact with activated carbon in the presence of water and then distilling it meets the specifications of the United States Pharmacopoeia and has a reduced odor. However, when heat treatment is performed as a reaction solvent or synthetic reagent for intermediates for pharmaceuticals and agricultural chemicals, an easily perceivable odor may be generated or unknown impurities may be generated. In the purification method of the present invention, by adding an alkali, it is possible to suppress deterioration of dimethyl sulfoxide due to an acidic functional group represented by a carboxy group, a lactone group, a phenolic hydroxy group and the like present on the surface of activated carbon. When an alkali is not added or when an acid is added instead of an alkali, an increase in the odor of dimethyl sulfoxide and generation of unknown impurities cannot be suppressed when dimethyl sulfoxide is subjected to a heating acceleration test.
原料ジメチルスルホキシドに添加するアルカリとしては、アルカリ金属およびアルカリ土類金属の水酸化物、炭酸塩、重炭酸塩がよく、例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を例示することができ、なかでも水酸化ナトリウム、水酸化カリウムが好ましい。 The alkali added to the raw material dimethyl sulfoxide is preferably an alkali metal or alkaline earth metal hydroxide, carbonate or bicarbonate, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, Examples thereof include potassium hydrogen carbonate, and sodium hydroxide and potassium hydroxide are preferable.
原料ジメチルスルホキシドへのアルカリの添加量は、原料ジメチルスルホキシドに接触させる活性炭の表面に存在する酸性官能基に由来する酸の量、すなわち混合液中の活性炭表面に存在する酸性官能基に起因する酸量（グラム当量）に対して、０．６〜３．１倍に相当するグラム当量、好ましくは１．０〜２．０倍に相当するグラム当量にする。また、混合液中の活性炭表面に存在する酸性官能基に起因する酸量（グラム当量）は、活性炭表面に存在する酸性官能基の濃度および活性炭の添加量から求めることができる。 The amount of alkali added to the raw material dimethyl sulfoxide is the amount of acid derived from the acidic functional group present on the surface of the activated carbon to be contacted with the raw material dimethyl sulfoxide, that is, the acid attributed to the acidic functional group present on the activated carbon surface in the mixture. A gram equivalent corresponding to 0.6 to 3.1 times, preferably a gram equivalent corresponding to 1.0 to 2.0 times the amount (gram equivalent). Moreover, the acid amount (gram equivalent) resulting from the acidic functional group present on the activated carbon surface in the mixed solution can be determined from the concentration of the acidic functional group present on the activated carbon surface and the added amount of activated carbon.
活性炭表面に存在する酸性官能基の濃度の定量方法は一般によく知られている。具体的には、活性炭を１ｇ測り採り、０．１グラム当量／Ｌ水酸化ナトリウムを５０ｍＬ加えて４８時間恒温槽にて振とうする。振とう後、ろ過したろ液に未反応のアルカリ試薬を０．１グラム当量／Ｌ塩酸で滴定してアルカリ消費量を算出することにより、活性炭１ｇ当たりの表面に存在する酸性官能基の量（グラム当量／ｇ）を求めることができる。 Methods for determining the concentration of acidic functional groups present on the surface of activated carbon are generally well known. Specifically, 1 g of activated carbon is measured, 50 mL of 0.1 gram equivalent / L sodium hydroxide is added, and shaken in a thermostatic bath for 48 hours. After shaking, the amount of acidic functional groups present on the surface per 1 g of activated carbon is calculated by titrating an unreacted alkali reagent with 0.1 gram equivalent / L hydrochloric acid to the filtrate filtered to calculate the amount of alkali consumption ( Gram equivalent / g).
本発明において、使用する活性炭は、特に制限されるものではなく、粉末炭、粒状炭、繊維状炭のいずれでも良い。好ましくは粉末活性炭がよい。また活性炭の賦活方法は、主に薬品賦活法と水蒸気賦活法の２種類があり、好ましくは水蒸気賦活した活性炭がよい。薬品賦活した活性炭は、賦活時の薬品等がわずかに残存しており、薬品等の影響で満足な精製効果が得られない虞がある。 In the present invention, the activated carbon to be used is not particularly limited, and may be powdered coal, granular coal, or fibrous coal. Powdered activated carbon is preferable. There are mainly two types of activated carbon activation methods, a chemical activation method and a water vapor activation method, preferably water vapor activated activated carbon. The activated carbon activated by the chemical has a slight amount of chemical remaining at the time of activation, and there is a possibility that a satisfactory purification effect cannot be obtained due to the influence of the chemical or the like.
原料ジメチルスルホキシドに接触させる活性炭の量は、原料ジメチルスルホキシド１００重量部に対し、好ましくは０．１重量部以上、より好ましくは０．５重量部以上であるとよい。活性炭の添加量が０．１重量部より少ないと蒸留して取得したジメチルスルホキシドの臭気改善効果と吸光度改善効果を十分に得ることができない。また、活性炭の添加量の上限は、好ましくは２０．０重量部、より好ましくは１０．０重量部、さらに好ましくは５．０重量部である。活性炭の添加量が２０．０重量部を超えると流動性とろ過性が悪化し、工業的に不利である。 The amount of the activated carbon brought into contact with the raw material dimethyl sulfoxide is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more with respect to 100 parts by weight of the raw material dimethyl sulfoxide. If the amount of activated carbon added is less than 0.1 parts by weight, the odor improving effect and the light absorbing improving effect of dimethyl sulfoxide obtained by distillation cannot be sufficiently obtained. Moreover, the upper limit of the addition amount of activated carbon becomes like this. Preferably it is 20.0 weight part, More preferably, it is 10.0 weight part, More preferably, it is 5.0 weight part. When the addition amount of activated carbon exceeds 20.0 parts by weight, fluidity and filterability are deteriorated, which is industrially disadvantageous.
原料ジメチルスルホキシドを水およびアルカリを含む混合液を、活性炭と接触させる方法は、通常用いられる方法で行うことができる。活性炭の全量を原料ジメチルスルホキシド、水およびアルカリの混合液に一度に添加してもよいし、逐次、分割して添加してもよい。また混合液を適宜攪拌しながら活性炭を添加してもよい。さらに原料ジメチルスルホキシドに水およびアルカリを添加し混合液を調製した後、直ちに活性炭を添加してもよいし、時間をおいてから活性炭を添加してもよい。また、原料ジメチルスルホキシドに、水、アルカリおよび活性炭を同時に添加してもよいし、水に原料ジメチルスルホキシド、アルカリおよび活性炭を同時に添加してもよい。また、活性炭を充填したカラムに原料ジメチルスルホキシド、水およびアルカリの混合液を通液してもよい。 The method of bringing the raw material dimethyl sulfoxide into contact with activated carbon in a mixed solution containing water and alkali can be performed by a commonly used method. The total amount of the activated carbon may be added to the raw material dimethyl sulfoxide, water and alkali mixed solution at once, or may be added in divided portions sequentially. Moreover, you may add activated carbon, stirring a liquid mixture suitably. Furthermore, activated carbon may be added immediately after adding water and alkali to raw material dimethyl sulfoxide to prepare a mixed solution, or activated carbon may be added after a period of time. Further, water, alkali and activated carbon may be added simultaneously to the raw material dimethyl sulfoxide, or the raw material dimethyl sulfoxide, alkali and activated carbon may be added simultaneously to the water. Further, a mixed liquid of raw material dimethyl sulfoxide, water and alkali may be passed through a column filled with activated carbon.
原料ジメチルスルホキシド、水およびアルカリの混合液と活性炭を接触させる温度は、特に制限されるものではないが、好ましくは８０℃以下、より好ましくは０〜４０℃にするとよい。８０℃より高い温度で接触させると活性炭への不純物吸着能力が低下し、吸光度および臭気の改善効果が低下する。０℃よりも低い温度で接触させる場合には、原料ジメチルスルホキシド、水およびアルカリを含む混合液を調製した後、混合液を冷却する必要があるため、経済的に非効率である。 The temperature at which the mixed solution of raw material dimethyl sulfoxide, water and alkali and activated carbon is not particularly limited, but is preferably 80 ° C. or less, more preferably 0 to 40 ° C. When contact is made at a temperature higher than 80 ° C., the ability to adsorb impurities on the activated carbon decreases, and the effect of improving absorbance and odor decreases. When contacting at a temperature lower than 0 ° C., it is economically inefficient because it is necessary to cool the mixed solution after preparing the mixed solution containing the raw material dimethyl sulfoxide, water and alkali.
また原料ジメチルスルホキシド、水およびアルカリの混合液を、活性炭と接触させる時間は、特に制限されるものではないが、好ましくは１０分以上、より好ましくは３０分以上であるとよい。このような時間で原料ジメチルスルホキシドを活性炭と接触させることにより、臭気改善効果および吸光度改善効果を確実に得ることができる。また、原料ジメチルスルホキシド、水およびアルカリの混合液に活性炭を含ませて攪拌することにより、原料ジメチルスルホキシドを活性炭に効率的に接触させることができる。 The time for bringing the mixed solution of the raw material dimethyl sulfoxide, water and alkali into contact with the activated carbon is not particularly limited, but is preferably 10 minutes or more, more preferably 30 minutes or more. By bringing the raw material dimethyl sulfoxide into contact with the activated carbon for such a time, an odor improving effect and an absorbance improving effect can be reliably obtained. Moreover, the raw material dimethyl sulfoxide can be efficiently brought into contact with the activated carbon by mixing and stirring the raw material dimethyl sulfoxide, water and alkali in a mixed solution.
本発明では、原料ジメチルスルホキシドを水およびアルカリの存在下で、活性炭と接触させた工程の後、活性炭を固液分離し、ジメチルスルホキシド、水およびアルカリを含む混合液を蒸留することにより、水およびアルカリを除去してジメチルスルホキシドを精製することができる。 In the present invention, after the step of bringing the raw material dimethyl sulfoxide into contact with activated carbon in the presence of water and alkali, the activated carbon is subjected to solid-liquid separation, and the mixed solution containing dimethyl sulfoxide, water and alkali is distilled, thereby allowing water and The dimethyl sulfoxide can be purified by removing the alkali.
活性炭の固液分離は、通常行われる方法を用いることができ、例えば加圧ろ過、減圧ろ過、デカンテーション、遠心分離等を例示することができ、なかでも加圧ろ過が好ましい。ろ過に用いるフィルターは、活性炭を分離することができるものであれば特に制限されることはない。 For the solid-liquid separation of the activated carbon, a commonly performed method can be used. For example, pressure filtration, vacuum filtration, decantation, centrifugation and the like can be exemplified, and pressure filtration is particularly preferable. The filter used for filtration is not particularly limited as long as it can separate activated carbon.
本発明において、固液分離されたジメチルスルホキシド、水およびアルカリを含む混合液の蒸留としては、例えば高圧蒸留、低圧蒸留、減圧蒸留、分子蒸留、単蒸留、精留、連続蒸留、回分蒸留等を例示することができ、なかでも減圧での精留が好ましい。 In the present invention, the distillation of the mixed liquid containing dimethyl sulfoxide, water and alkali separated in solid and liquid includes, for example, high pressure distillation, low pressure distillation, vacuum distillation, molecular distillation, simple distillation, rectification, continuous distillation, batch distillation and the like. Among them, rectification under reduced pressure is preferable.
本発明において、ジメチルスルホキシド、水およびアルカリを含む混合液を蒸留する際の内温は、１３０℃以下、好ましくは１１０℃以下である。内温１３０℃以下で蒸留することにより、ジメチルスルホキシドが分解するのを抑制し、かつ分解に起因する臭気の発生を防ぐことができる。 In this invention, the internal temperature at the time of distilling the liquid mixture containing a dimethylsulfoxide, water, and an alkali is 130 degrees C or less, Preferably it is 110 degrees C or less. By distilling at an internal temperature of 130 ° C. or lower, decomposition of dimethyl sulfoxide can be suppressed, and generation of odor due to decomposition can be prevented.
また、ジメチルスルホキシドを減圧で蒸留するときの圧力は、好ましくは１４．２ｋＰａ以下、より好ましくは６．７ｋＰａ以下である。減圧して蒸留することにより、ジメチルスルホキシドの分解を抑制し、臭気の増加を抑制することができる。 Moreover, the pressure when distilling dimethyl sulfoxide under reduced pressure is preferably 14.2 kPa or less, more preferably 6.7 kPa or less. By distilling under reduced pressure, decomposition of dimethyl sulfoxide can be suppressed and increase in odor can be suppressed.
以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
本実施例において、精製処理によって得られたジメチルスルホキシド（以下、「精製ジメチルスルホキシド」という。）、加熱促進試験によって得られたジメチルスルホキシド（以下、「加熱ジメチルスルホキシド」という。）の吸光度、臭気強度および不純物分析は、以下の方法で測定した。 In this example, the absorbance and odor intensity of dimethyl sulfoxide obtained by purification treatment (hereinafter referred to as “purified dimethyl sulfoxide”) and dimethyl sulfoxide obtained by heating acceleration test (hereinafter referred to as “heated dimethyl sulfoxide”). And the impurity analysis was measured by the following method.
（精製ジメチルスルホキシドの吸光度の測定方法）
ジメチルスルホキシドを事前に窒素バブリングを３０分間実施し、その後１０分以内に、紫外吸光光度計（島津社製ＵＶ−１８００）を使用し、以下の条件で２７５ｎｍの吸光度を測定した。
分析装置 ：紫外吸光光度計
セル ：石英、幅１ｃｍ
ブランク ：水
(Measurement method of absorbance of purified dimethyl sulfoxide)
Nitrogen bubbling of dimethyl sulfoxide was performed in advance for 30 minutes, and then within 10 minutes, an ultraviolet absorptiometer (UV-1800 manufactured by Shimadzu Corporation) was used, and absorbance at 275 nm was measured under the following conditions.
Analyzer: UV absorption photometer Cell: Quartz, width 1cm
Blank: Water
（精製および加熱ジメチルスルホキシドの不純物分析）
以下の条件のガスクロマトグラフ（Ａｇｉｌｅｎｔ社製７８９０Ａ）により分析を行い、保持時間４．３分に検出した不明不純物を測定した。
分析装置 ：ＧＣ
キャリアガス ：ヘリウム （カラム流量２．０ｍＬ／分）
分析カラム ：ＲＥＳＴＥＫ社製Ｓｔａｂｉｌｗａｘ （３０ｍ×０．３２ｍｍ×
０．５μｍ）
カラム温度 ：３５℃（３分）→（７℃／分）→１３０℃（１０分）→（７℃／分）
→１６０℃→（１５℃／分）→２５０℃（８分）
注入口温度 ：２００℃
注入量 ：１μＬ
検出器 ：ＦＩＤ
検出器温度 ：２７０℃
(Impurity analysis of purified and heated dimethyl sulfoxide)
Analysis was performed by a gas chromatograph (Agilent 7890A) under the following conditions, and the unknown impurities detected at a retention time of 4.3 minutes were measured.
Analyzer: GC
Carrier gas: Helium (column flow rate 2.0 mL / min)
Analysis column: Stabilwax (30 m × 0.32 mm × manufactured by RESTEK)
0.5μm)
Column temperature: 35 ° C. (3 minutes) → (7 ° C./minute)→130° C. (10 minutes) → (7 ° C./minute)
→ 160 ℃ → (15 ℃ / min) → 250 ℃ (8 minutes)
Inlet temperature: 200 ° C
Injection volume: 1 μL
Detector: FID
Detector temperature: 270 ° C
（精製および加熱ジメチルスルホキシドの臭気強度の測定方法）
ジメチルスルホキシドの臭気を、下記に示す６段階の臭気強度表示法に基づき３人のパネラーが官能評価した。３０ｍＬサンプル瓶に、精製ジメチルスルホキシドまたは加熱ジメチルスルホキシドを１５ｍＬ入れサンプルとした。パネラー３人が同じサンプルの臭気を、室温下でサンプル瓶に鼻を近づけて嗅ぎ、下記に示す０〜５の６段階の基準で判定し、３人の判定値のうち多数の値をサンプルの臭気強度とした。
臭気強度０： 無臭
臭気強度１： やっと感知できるにおい
臭気強度２： 何のにおいか判る弱いにおい
臭気強度３： 楽に感知できるにおい
臭気強度４： 強いにおい
臭気強度５： 強烈なにおい
(Measurement method of odor intensity of purified and heated dimethyl sulfoxide)
The odor of dimethyl sulfoxide was sensorially evaluated by three panelists based on the following six-step odor intensity display method. 15 mL of purified dimethyl sulfoxide or heated dimethyl sulfoxide was placed in a 30 mL sample bottle to make a sample. Three panelists sniff the odor of the same sample with the nose close to the sample bottle at room temperature, and judged on the basis of 6 levels of 0 to 5 shown below. Odor intensity was set.
Odor intensity 0: Odorless Odor intensity 1: A smell that can be finally detected Odor intensity 2: A weak smell that can be detected by any smell Odor intensity 3: A smell that can be easily detected Odor intensity 4: Strong smell Odor intensity 5: Intense smell
（精製ジメチルスルホキシドの加熱促進試験）
本発明において、精製ジメチルスルホキシドを使用して加熱促進試験を行い、得られた加熱ジメチルスルホキシドについて、不純物分析および臭気強度を測定した。加熱促進試験は１００℃で、２４時間後、４８時間後および７２時間後の加熱ジメチルスルホキシドの臭気強度、並びに７２時間後の加熱ジメチルスルホキシドの不純物分析を測定した。
(Heating acceleration test of purified dimethyl sulfoxide)
In the present invention, a heating acceleration test was performed using purified dimethyl sulfoxide, and impurity analysis and odor intensity were measured for the obtained heated dimethyl sulfoxide. In the heating acceleration test, the odor intensity of heated dimethyl sulfoxide after 24 hours, 48 hours and 72 hours, and impurity analysis of heated dimethyl sulfoxide after 72 hours were measured at 100 ° C.
（実施例１）
１１０ｍＬサンプル瓶に純度９９．９重量％の一般工業品質のジメチルスルホキシド（臭気強度が３）５０ｇに、イオン交換水を５０ｇ（１００重量部／ジメチルスルホキシド１００重量部）、水酸化ナトリウムを０．０１ｇ（０．０２重量部／ジメチルスルホキシド１００重量部、０．０００２５グラム当量、活性炭表面に存在する酸性官能基に由来する酸のグラム当量に対し１．０４倍に相当するグラム当量）添加して混合液を調製し、この混合液に粉末活性炭（日本エンバイロケミカルズ社製、表面に存在する酸性官能基の酸濃度が０．０００４８グラム当量／ｇ）０．５ｇ（１．０重量部／ジメチルスルホキシド１００重量部、表面に存在する酸性官能基が０．０００２４グラム当量）を仕込み、室温下で１時間撹拌した。その後０．４５μｍのフィルターに通液し活性炭を除去した。得られたろ液を、２００ｍＬ丸底フラスコに移し、丸底フラスコの口にラシヒリング（長さ５ｍｍ、内径３ｍｍ、外径５ｍｍ）を１０ｃｍ充填した直径３ｃｍ、高さ１５ｃｍの精留管を設置し、６．７ｋＰａで減圧蒸留した。丸底フラスコの内温４５℃から加熱を開始し、温度が１０７℃に到達した時点で受器を交換し、４０ｇの精製ジメチルスルホキシドを得た。得られた精製ジメチルスルホキシドの臭気強度は１であった。また不明不純物は検出されなかった。
Example 1
In a 110 mL sample bottle, 50 g of general industrial quality dimethyl sulfoxide (odor intensity 3) with a purity of 99.9 wt%, 50 g of ion-exchanged water (100 parts by weight / 100 parts by weight of dimethyl sulfoxide), 0.01 g of sodium hydroxide (0.02 parts by weight / 100 parts by weight of dimethyl sulfoxide, 0.00025 gram equivalent, gram equivalent equivalent to 1.04 times the gram equivalent of the acid derived from the acidic functional group present on the activated carbon surface) 0.5 g (1.0 part by weight / dimethyl sulfoxide 100, powder activated carbon (manufactured by Nippon Enviro Chemicals Co., Ltd., acid concentration of acidic functional group present on the surface is 0.00048 gram equivalent / g) was prepared. Parts by weight, and the acidic functional group present on the surface was 0.00024 gram equivalent), and the mixture was stirred at room temperature for 1 hour. Thereafter, the solution was passed through a 0.45 μm filter to remove the activated carbon. The obtained filtrate was transferred to a 200 mL round bottom flask, and a rectifying tube having a diameter of 3 cm and a height of 15 cm in which a Raschig ring (length 5 mm, inner diameter 3 mm, outer diameter 5 mm) was filled 10 cm in the mouth of the round bottom flask was installed. Distilled under reduced pressure at 6.7 kPa. Heating was started from the internal temperature of 45 ° C. of the round bottom flask, and when the temperature reached 107 ° C., the receiver was exchanged to obtain 40 g of purified dimethyl sulfoxide. The purified dimethyl sulfoxide obtained had an odor intensity of 1. Unknown impurities were not detected.
次いで精製ジメチルスルホキシドを使用して１００℃で加熱促進試験を行なった。得られた加熱ジメチルスルホキシド（２４時間、４８時間および７２時間後の加熱ジメチルスルホキシド）の臭気強度は１であった。また７２時間後の加熱ジメチルスルホキシドに不明不純物は検出されなかった。これらの結果を表１、３にまとめて示す。なお表１に記載の「添加物の添加量」の単位は、混合液中の活性炭表面に存在する酸性官能基に由来する酸の量に対するグラム当量、および原料ジメチルスルホキシド（ＤＭＳＯ）１００重量部に対する重量部を併記した。また、表中のＮＤは１ｐｐｍ以下であることを意味する。 Next, a heating acceleration test was conducted at 100 ° C. using purified dimethyl sulfoxide. The odor intensity of the obtained heated dimethyl sulfoxide (heated dimethyl sulfoxide after 24, 48 and 72 hours) was 1. Further, no unknown impurities were detected in the heated dimethyl sulfoxide after 72 hours. These results are summarized in Tables 1 and 3. The unit of “addition amount of additive” described in Table 1 is based on the gram equivalent with respect to the amount of acid derived from the acidic functional group present on the activated carbon surface in the mixed solution, and 100 parts by weight of raw material dimethyl sulfoxide (DMSO). The parts by weight are also shown. Moreover, ND in a table | surface means that it is 1 ppm or less.
（実施例２〜３）
水酸化ナトリウムの添加量を表１に記載するように変更したことを除き、実施例１と同様の精製操作、加熱促進試験を行った。得られた精製および加熱ジメチルスルホキシドの品質を、表１に記載する。
(Examples 2-3)
A purification operation and a heating acceleration test were performed in the same manner as in Example 1 except that the amount of sodium hydroxide added was changed as described in Table 1. The quality of the purified and heated dimethyl sulfoxide obtained is listed in Table 1.
（実施例４〜７）
実施例１において、添加するアルカリの種類を、水酸化カリウム、炭酸ナトリウム、炭酸カリウムおよび炭酸水素ナトリウムに変更したことを除き、実施例１と同様の精製操作、加熱促進試験を行った。得られた精製および加熱ジメチルスルホキシドの品質を、表１に記載する。
(Examples 4 to 7)
In Example 1, the same purification operation and heating acceleration test as in Example 1 were performed except that the type of alkali to be added was changed to potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate. The quality of the purified and heated dimethyl sulfoxide obtained is listed in Table 1.
（実施例８〜１０、比較例１〜２）
実施例１において、イオン交換水の添加量を変更したことを除き、実施例１と同様の操作を行った。得られたジメチルスルホキシドの品質は表１、２、３に記載の通りであった。
(Examples 8-10, Comparative Examples 1-2)
In Example 1, operation similar to Example 1 was performed except having changed the addition amount of ion-exchange water. The quality of the obtained dimethyl sulfoxide was as shown in Tables 1, 2, and 3.
（実施例１１）
実施例１において、水酸化ナトリウムの添加量を０．００５ｇ（０．０１重量部／ジメチルスルホキシド１００重量部）に、粉末活性炭の仕込み量を０．２５ｇ（０．５重量部／ジメチルスルホキシド１００重量部）に変更したことを除き、実施例１と同様の操作を行った。得られたジメチルスルホキシドの品質は表２に記載の通りであった。
(Example 11)
In Example 1, the addition amount of sodium hydroxide was 0.005 g (0.01 parts by weight / 100 parts by weight of dimethyl sulfoxide), and the charged amount of powdered activated carbon was 0.25 g (0.5 parts by weight / 100 parts by weight of dimethyl sulfoxide). The same operation as in Example 1 was performed except that the change was made to (part). The quality of the obtained dimethyl sulfoxide was as shown in Table 2.
（比較例３）
実施例１において、水酸化ナトリウムを添加しなかったことを除き、実施例１と同様の操作を行った。得られたジメチルスルホキシドの品質は表２、３に記載の通りであった。比較例３で得られた精製ジメチルスルホキシドは、臭気強度は１で、不明不純物は検出されなかった。しかし、７２時間後の加熱ジメチルスルホキシドは、臭気強度が３に悪化し、不明不純物が検出された。
(Comparative Example 3)
In Example 1, the same operation as in Example 1 was performed, except that sodium hydroxide was not added. The quality of the obtained dimethyl sulfoxide was as shown in Tables 2 and 3. The purified dimethyl sulfoxide obtained in Comparative Example 3 had an odor intensity of 1 and no unknown impurities were detected. However, the heated dimethyl sulfoxide after 72 hours had an odor intensity deteriorated to 3, and an unknown impurity was detected.
（比較例４）
実施例１において、アルカリの代わりに安息香酸を添加したことを除き、実施例１と同様の操作を行った。得られたジメチルスルホキシドの品質は表２、３の通りである。
(Comparative Example 4)
In Example 1, the same operation as in Example 1 was performed except that benzoic acid was added instead of alkali. The quality of the obtained dimethyl sulfoxide is as shown in Tables 2 and 3.
（比較例５）
実施例１において、丸底フラスコの内温４５℃から加熱を開始し、温度を１３５℃に到達させた減圧蒸留を行ったことを除き、実施例１と同様の操作を行った。得られたジメチルスルホキシドの品質は表２、３の通りである。
(Comparative Example 5)
In Example 1, the same operation as in Example 1 was performed except that heating was started from the internal temperature of 45 ° C. of the round bottom flask and vacuum distillation was performed at which the temperature reached 135 ° C. The quality of the obtained dimethyl sulfoxide is as shown in Tables 2 and 3.
（比較例６）
実施例１において、粉末活性炭の代わりにモレキュラーシーブ０．５ｇ（１．０重量部／ジメチルスルホキシド１００重量部）を添加したことを除き、実施例１と同様の操作を行った。得られたジメチルスルホキシドの品質は表２、３の通りである。
(Comparative Example 6)
In Example 1, the same operation as in Example 1 was performed, except that 0.5 g of molecular sieve (1.0 part by weight / 100 parts by weight of dimethyl sulfoxide) was added instead of powdered activated carbon. The quality of the obtained dimethyl sulfoxide is as shown in Tables 2 and 3.
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