JP7421096B2 - Trimethylamine purification method - Google Patents
Trimethylamine purification method Download PDFInfo
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- JP7421096B2 JP7421096B2 JP2020068456A JP2020068456A JP7421096B2 JP 7421096 B2 JP7421096 B2 JP 7421096B2 JP 2020068456 A JP2020068456 A JP 2020068456A JP 2020068456 A JP2020068456 A JP 2020068456A JP 7421096 B2 JP7421096 B2 JP 7421096B2
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 title claims description 152
- 238000000034 method Methods 0.000 title claims description 44
- 238000000746 purification Methods 0.000 title claims description 20
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 106
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 70
- 229910021536 Zeolite Inorganic materials 0.000 claims description 67
- 239000010457 zeolite Substances 0.000 claims description 67
- 239000011148 porous material Substances 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 13
- 239000012535 impurity Substances 0.000 description 10
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Of Gases By Adsorption (AREA)
Description
本開示は、ゼオライトを用いてジメチルアミンを除去するトリメチルアミンの精製方法に関する。 The present disclosure relates to a method for purifying trimethylamine using zeolite to remove dimethylamine.
有機アミンの１つであるトリメチルアミンの粗体中には、不純物として１０００体積ｐｐｍ程度のジメチルアミンが含まれていることがある。トリメチルアミンとジメチルアミンは蒸気圧が近く、共沸となるため、蒸留ではジメチルアミンの濃度を４００～５００体積ｐｐｍ程度までしか低減することができない。 Crude trimethylamine, which is one of the organic amines, may contain about 1000 volume ppm of dimethylamine as an impurity. Since trimethylamine and dimethylamine have close vapor pressures and are azeotropic, distillation can only reduce the concentration of dimethylamine to about 400 to 500 ppm by volume.
近年、有機アミンの粗体中に含まれる不純物を除去する方法として、合成ゼオライトを用いる方法が提案されている。
特許文献１では、平均直径が０．３ｎｍ又は０．４ｎｍの細孔を有する合成ゼオライトを用いて、モノメチルアミンに含まれる低沸点不純物を除去する精製装置が開示されている。除去する低沸点不純物としては、水素、酸素、窒素、一酸化炭素、二酸化炭素及びメタンが挙げられている。更に特許文献１では、平均直径が０．５ｎｍの細孔を有する合成ゼオライトを用いて、水分及び炭化水素を吸着することが開示されている。
In recent years, a method using synthetic zeolite has been proposed as a method for removing impurities contained in crude organic amines.
Patent Document 1 discloses a purification device that uses synthetic zeolite having pores with an average diameter of 0.3 nm or 0.4 nm to remove low-boiling impurities contained in monomethylamine. Low boiling impurities to be removed include hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide and methane. Further, Patent Document 1 discloses that a synthetic zeolite having pores with an average diameter of 0.5 nm is used to adsorb moisture and hydrocarbons.
特許文献２では、３Ａ又は４Ａのゼオライトを用いてトリメチルアミン含有ガス中の水及びアンモニアを除去し、５Ａのゼオライトを用いてモノメチルアミン及び窒素を除去する、トリメチルアミンの精製方法が開示されている。 Patent Document 2 discloses a method for purifying trimethylamine in which water and ammonia in a trimethylamine-containing gas are removed using a 3A or 4A zeolite, and monomethylamine and nitrogen are removed using a 5A zeolite.
しかしながら、これまでは、不純物としてジメチルアミンを含むトリメチルアミン中のジメチルアミンを４００体積ｐｐｍ以下に低減する方法はなかった。なお特許文献２では、合成ゼオライトを用いてモノメチルアミンを除去する方法が開示されているが、合成ゼオライトを用いてジメチルアミンが除去されることは記載されておらず、従って、ジメチルアミンが除去されることはこれまで知られていない。 However, until now, there has been no method for reducing dimethylamine in trimethylamine containing dimethylamine as an impurity to 400 volume ppm or less. Note that Patent Document 2 discloses a method for removing monomethylamine using a synthetic zeolite, but does not describe that dimethylamine is removed using a synthetic zeolite. This has not been known until now.
本開示は、上記課題に鑑み、粗トリメチルアミン中のジメチルアミン濃度を低減させる新規な方法を提供することを目的とする。 In view of the above problems, the present disclosure aims to provide a novel method for reducing the dimethylamine concentration in crude trimethylamine.
本発明者らは、鋭意検討の結果、ジメチルアミンを含む粗トリメチルアミンを直径０．２～０．６ｎｍの細孔を有するゼオライトに接触させることにより、ジメチルアミン濃度を低減させることができることを見出し、本開示を完成させるに至った。 As a result of extensive studies, the present inventors have discovered that the dimethylamine concentration can be reduced by bringing crude trimethylamine containing dimethylamine into contact with zeolite having pores with a diameter of 0.2 to 0.6 nm. We have now completed this disclosure.
具体的には、本開示のトリメチルアミンの精製方法は、少なくともジメチルアミンを含む粗トリメチルアミンを直径０．２～０．６ｎｍの細孔を有するゼオライトに接触させ、上記粗トリメチルアミン中のジメチルアミン濃度を上記ゼオライト接触前よりも低減させることを特徴とする。
本開示のトリメチルアミンの精製方法によれば、蒸留のようにエネルギーを消費する必要がなく、粗トリメチルアミン中のジメチルアミンを除去することができる。
Specifically, the trimethylamine purification method of the present disclosure involves contacting crude trimethylamine containing at least dimethylamine with a zeolite having pores with a diameter of 0.2 to 0.6 nm, and adjusting the dimethylamine concentration in the crude trimethylamine to the above level. It is characterized by being lower than before contact with zeolite.
According to the trimethylamine purification method of the present disclosure, dimethylamine in crude trimethylamine can be removed without consuming energy unlike distillation.
本開示のトリメチルアミンの精製方法により、蒸留のようにエネルギーを消費することなく粗トリメチルアミン中のジメチルアミンを除去することができ、半導体製造工程においても使用することが可能な、極めて純度が高いトリメチルアミンを供給することができる。 The trimethylamine purification method of the present disclosure can remove dimethylamine from crude trimethylamine without consuming energy like distillation, producing extremely pure trimethylamine that can be used in semiconductor manufacturing processes. can be supplied.
以下、本開示について詳細に説明するが、以下に記載する構成要件の説明は本開示の実施形態の一例であり、これらの具体的内容に限定はされない。その要旨の範囲内で種々変形して実施することができる。 Hereinafter, the present disclosure will be described in detail, but the explanation of the constituent elements described below is an example of an embodiment of the present disclosure, and the present disclosure is not limited to these specific contents. Various modifications can be made within the scope of the gist.
本開示のトリメチルアミンの精製方法は、少なくともジメチルアミンを含む粗トリメチルアミンを直径０．２～０．６ｎｍの細孔を有するゼオライトに接触させ、上記粗トリメチルアミン中のジメチルアミン濃度を上記ゼオライト接触前よりも低減させることを特徴とする。 The method for purifying trimethylamine of the present disclosure includes contacting crude trimethylamine containing at least dimethylamine with a zeolite having pores with a diameter of 0.2 to 0.6 nm, and increasing the dimethylamine concentration in the crude trimethylamine to a level higher than that before contact with the zeolite. It is characterized by reducing
本開示の精製方法で用いるゼオライトは、モレキュラーシーブ（分子篩）とも呼ばれる結晶性アルミノケイ酸塩であり、合成ゼオライト、人工ゼオライト、天然ゼオライトに分類される。本開示の精製方法においては、直径０．２～０．６ｎｍ、又は、直径３～５Åの細孔を有するゼオライトであれば、合成ゼオライト、人工ゼオライト、天然ゼオライトのいずれも用い得るが、純度が高い合成ゼオライトを用いることが好ましい。ゼオライトの細孔の直径が０．２ｎｍ未満であるか、０．６ｎｍを超えると、粗トリメチルアミン中のジメチルアミン濃度の低減効果が小さくなる。 The zeolite used in the purification method of the present disclosure is a crystalline aluminosilicate also called a molecular sieve, and is classified into synthetic zeolite, artificial zeolite, and natural zeolite. In the purification method of the present disclosure, synthetic zeolite, artificial zeolite, and natural zeolite can be used as long as they have pores with a diameter of 0.2 to 0.6 nm or 3 to 5 Å, but purity Preference is given to using highly synthetic zeolites. When the diameter of the pores of the zeolite is less than 0.2 nm or more than 0.6 nm, the effect of reducing the dimethylamine concentration in crude trimethylamine becomes small.
直径０．２～０．６ｎｍの細孔を有する合成ゼオライトとしては、３Ａ型、４Ａ型又は５Ａ型の合成ゼオライトが好適である。なお、３Ａ型、４Ａ型又は５Ａ型の合成ゼオライトにおける「Ａ」とは、Å（オングストローム）のことを表す。
３Ａ型の合成ゼオライトは、細孔径が０．３ｎｍであり、直径が０．３ｎｍまでの分子を通過させることができる。４Ａ型の合成ゼオライトの細孔径は０．３５ｎｍであるが、通常の操作温度において、空洞内に入ってくる分子の伸縮と運動エネルギーのため、直径０．４ｎｍまでの分子を通過させることができる。また、５Ａ型の合成ゼオライトについても、それの細孔径は０．４２ｎｍであるが、同様の理由により、直径が０．５ｎｍまでの分子を通過させることができる。
ここで、３Ａ型、４Ａ型又は５Ａ型の合成ゼオライトの、通過できる分子の直径（吸着口径）の範囲を以下、明記する。
３Ａ型 ０．３ｎｍ以下
４Ａ型 ０．３ｎｍを超えて、０．４ｎｍ以下
５Ａ型 ０．４ｎｍを超えて、０．５ｎｍ以下
As the synthetic zeolite having pores with a diameter of 0.2 to 0.6 nm, 3A type, 4A type or 5A type synthetic zeolite is suitable. In addition, "A" in the 3A type, 4A type, or 5A type synthetic zeolite represents Å (angstrom).
Type 3A synthetic zeolite has a pore diameter of 0.3 nm and can pass molecules up to 0.3 nm in diameter. The pore diameter of type 4A synthetic zeolite is 0.35 nm, but at normal operating temperatures, molecules with a diameter of up to 0.4 nm can pass through due to the stretching and kinetic energy of the molecules entering the cavity. . Furthermore, although the pore diameter of type 5A synthetic zeolite is 0.42 nm, molecules with a diameter of up to 0.5 nm can pass through it for the same reason.
Here, the range of the diameter (adsorption aperture) of molecules that can pass through synthetic zeolite of type 3A, type 4A, or type 5A is specified below.
3A type: 0.3 nm or less 4A type: More than 0.3 nm, 0.4 nm or less 5A type: More than 0.4 nm, 0.5 nm or less
３Ａ型、４Ａ型、５Ａ型の合成ゼオライトとしては、具体的には、ユニオン昭和社製のモレキュラーシーブ３Ａ、モレキュラーシーブ４Ａ、モレキュラーシーブ５Ａ；富士フイルム和光純薬社製のモレキュラーシーブス３Ａ、モレキュラーシーブス４Ａ、モレキュラーシーブス５Ａ等を用い得る。
本開示の精製方法で用いるゼオライトの形状は特に限定されず、ビーズ状、ペレット状、パウダー状等のいずれでもよいが、ビーズ状、ペレット状のものが化学工業プラントで用い易く好ましい。
Specifically, the synthetic zeolites of type 3A, type 4A, and type 5A include Molecular Sieve 3A, Molecular Sieve 4A, and Molecular Sieve 5A manufactured by Union Showa Co., Ltd.; Molecular Sieve 3A and Molecular Sieve manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. 4A, molecular sieves 5A, etc. may be used.
The shape of the zeolite used in the purification method of the present disclosure is not particularly limited, and may be bead-like, pellet-like, powder-like, etc., but bead-like and pellet-like are preferred because they are easy to use in chemical industrial plants.
本開示の精製方法で用いるゼオライトは、購入したものをそのまま用いることもできるが、使用する前に乾燥させることが好ましい。乾燥条件としては、１ｋＰａ以下、１５０℃以上で３０分以上が好ましく、１ｋＰａ以下、１５０～２００℃、３０～６０分がより好ましい。 The purchased zeolite used in the purification method of the present disclosure can be used as is, but it is preferable to dry it before use. The drying conditions are preferably 1 kPa or less, 150° C. or more for 30 minutes or more, and more preferably 1 kPa or less, 150 to 200° C., and 30 to 60 minutes.
粗トリメチルアミンをゼオライトに接触させる方法は特に限定されず、粗トリメチルアミンを貯留する容器等にゼオライトを添加して放置する方法（静置法）、ゼオライトをカラムや充填塔等に充填し、粗トリメチルアミンをカラムや充填塔に流通させてゼオライトに流通接触させる方法（カラム法）等が挙げられる。ジメチルアミンを除去する効果が高いこと、短時間で精製が行える点でカラム法が好ましい。しかしながら、粗トリメチルアミン中のジメチルアミンの濃度が高い場合は、カラム法を行う前に静置法を行い、ジメチルアミンの濃度を一定まで低減してからカラム法を行う等、静置法とカラム法とを組み合わせて行うこともできる。 The method of bringing crude trimethylamine into contact with zeolite is not particularly limited, and there are methods such as adding zeolite to a container for storing crude trimethylamine and leaving it there (standing method), filling zeolite into a column or packed tower, etc., and bringing crude trimethylamine into contact with the zeolite. Examples include a method of flowing through a column or a packed tower and bringing it into contact with zeolite (column method). A column method is preferred because it is highly effective in removing dimethylamine and purification can be performed in a short time. However, if the concentration of dimethylamine in the crude trimethylamine is high, the static method and column method can be used, such as performing the static method before the column method and reducing the concentration of dimethylamine to a certain level before performing the column method. It can also be done in combination.
粗トリメチルアミンをゼオライトに流通接触させる温度及び圧力条件は、２０～３０℃、大気圧以上が好ましい。圧力条件は、１５０～２００ｋＰａがより好ましい。
粗トリメチルアミンをゼオライトに流通接触させる時間は、５０～２００秒が好ましい。５０秒未満であると、ジメチルアミンが十分除去されない場合がある。一方、２００秒を超えて流通接触させても、ジメチルアミンを除去する効果が上がらない場合がある。粗トリメチルアミンをゼオライトに流通接触させる時間は、１００～１５０秒がより好ましい。
The temperature and pressure conditions for flowing and contacting crude trimethylamine with zeolite are preferably 20 to 30°C and atmospheric pressure or higher. The pressure condition is more preferably 150 to 200 kPa.
The time period for which the crude trimethylamine is brought into contact with the zeolite by flowing is preferably 50 to 200 seconds. If the time is less than 50 seconds, dimethylamine may not be sufficiently removed. On the other hand, even if the flow contact is carried out for more than 200 seconds, the effect of removing dimethylamine may not be improved. The time period for which the crude trimethylamine is brought into contact with the zeolite in a flowing manner is more preferably 100 to 150 seconds.
本開示の精製方法において、好ましい態様は、気体状態の粗トリメチルアミンを、２０～３０℃、大気圧以上の条件下で、ゼオライトに１００秒以上流通接触させることである。 In the purification method of the present disclosure, a preferred embodiment is to bring crude trimethylamine in a gaseous state into contact with zeolite in a flow for 100 seconds or more under conditions of 20 to 30°C and atmospheric pressure or higher.
粗トリメチルアミンをゼオライトに流通接触させる場合、粗トリメチルアミンの線速度は、０．００１～０．１ｍ／ｓｅｃが好ましい。より好ましくは０．０１～０．１ｍ／ｓｅｃである。 When crude trimethylamine is brought into contact with zeolite in a flowing manner, the linear velocity of crude trimethylamine is preferably 0.001 to 0.1 m/sec. More preferably, it is 0.01 to 0.1 m/sec.
本開示の精製方法で精製する対象となる粗トリメチルアミンは、少なくともジメチルアミンを不純物として含むトリメチルアミンである。粗トリメチルアミンは、トリメチルアミンを従来公知の方法（例えば、特開昭５８－０４９３４０号公報に記載の方法等）で合成して得られたものであってもよいし、購入したものであってもよく、入手方法は特に限定されない。粗トリメチルアミンは、ジメチルアミン以外の他の不純物を含んでいてもよく、他の不純物としては、モノメチルアミン、水素、酸素、窒素、一酸化炭素、二酸化炭素、メタン、アンモニア、水等が挙げられる。 The crude trimethylamine to be purified by the purification method of the present disclosure is trimethylamine containing at least dimethylamine as an impurity. Crude trimethylamine may be obtained by synthesizing trimethylamine by a conventionally known method (for example, the method described in JP-A-58-049340), or may be purchased. , the method of acquisition is not particularly limited. Crude trimethylamine may contain impurities other than dimethylamine, and other impurities include monomethylamine, hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide, methane, ammonia, water, and the like.
粗トリメチルアミンは、トリメチルアミンを９８重量％含むことが好ましく、９９重量％以上含むことがより好ましく、９９．９重量％以上含むことが更に好ましい。
粗トリメチルアミン中のジメチルアミンの濃度は、５００～１５００体積ｐｐｍが好ましい。粗トリメチルアミン中のジメチルアミンの濃度が上記の値より大きい場合、本開示の精製方法で処理する前に蒸留等の方法を用いてジメチルアミンを除去しておくか、又は、上記の静置法とカラム法とを組み合わせて行うことが考えられる。
The crude trimethylamine preferably contains 98% by weight of trimethylamine, more preferably 99% by weight or more, and even more preferably 99.9% by weight or more.
The concentration of dimethylamine in the crude trimethylamine is preferably 500 to 1500 ppm by volume. If the concentration of dimethylamine in crude trimethylamine is higher than the above value, the dimethylamine should be removed using a method such as distillation before being treated with the purification method of the present disclosure, or the above-mentioned standing method and It is conceivable to perform this in combination with a column method.
粗トリメチルアミン中のジメチルアミンは不安定で、気相中の濃度は安定しない。
好ましい態様において、本開示の精製方法で精製する粗トリメチルアミンは液体でも気体でもよいが、常温常圧で精製が行えることから気体が好ましい。
Dimethylamine in crude trimethylamine is unstable and its concentration in the gas phase is not stable.
In a preferred embodiment, the crude trimethylamine purified by the purification method of the present disclosure may be a liquid or a gas, but a gas is preferable since the purification can be performed at normal temperature and pressure.
本開示の精製方法では、粗トリメチルアミン中のジメチルアミン濃度を４００体積ｐｐｍ以下に低減することが好ましい。より好ましくは３００体積ｐｐｍ以下である。本開示の精製方法を用いれば、上述のような純度が高いトリメチルアミンを得ることができる。このような純度が高いトリメチルアミンは、シリコン酸化物のドライエッチング等の用途に好適に用いられる。 In the purification method of the present disclosure, it is preferable to reduce the dimethylamine concentration in crude trimethylamine to 400 volume ppm or less. More preferably, it is 300 volume ppm or less. By using the purification method of the present disclosure, trimethylamine with high purity as described above can be obtained. Trimethylamine with such high purity is suitably used for applications such as dry etching of silicon oxide.
以下、本開示の実施形態をより具体的に開示した実施例を示す。なお、本開示はこれらの実施例のみに限定されるものではない。なお、実施例で用いたモレキュラーシーブ３Ａ、４Ａ及び５Ａは、それぞれ３Ａ型、４Ａ型又は５Ａ型の合成ゼオライトに対応する。 Examples that more specifically disclose the embodiments of the present disclosure will be shown below. Note that the present disclosure is not limited to these examples. Note that the molecular sieves 3A, 4A, and 5A used in the examples correspond to 3A type, 4A type, or 5A type synthetic zeolite, respectively.
（粗トリメチルアミン）
本実施例で用いる粗トリメチルアミンは、従来の製造方法を参考に合成した。当該トリメチルアミンには、不純物として、気相にジメチルアミン５００～２０００体積ｐｐｍ、水分１００～１０００体積ｐｐｍを含んでいた。不純物濃度は、ガスクロマトグラフ分析装置（ＧＣ－２０１４、株式会社島津製作所製、検出器：ＦＩＤ）で分析した。
(crude trimethylamine)
Crude trimethylamine used in this example was synthesized with reference to a conventional production method. The trimethylamine contained 500 to 2000 volume ppm of dimethylamine and 100 to 1000 volume ppm of water in the gas phase as impurities. The impurity concentration was analyzed using a gas chromatograph analyzer (GC-2014, manufactured by Shimadzu Corporation, detector: FID).
［実施例１］
直径１０．６ｍｍ、長さ０．１ｍの充填塔１本に、ゼオライトとしてモレキュラーシーブ３Ａ（細孔径０．３ｎｍ、ユニオン昭和社製）を充填し、減圧条件、１５０℃で３０分間乾燥させたのち、粗トリメチルアミンを線速度０．０２ｍ／ｓｅｃで流通させ（ゼオライトへの接触時間５秒）、充填塔出口からトリメチルアミンを捕集してジメチルアミン濃度を分析した。結果を表１に示す。
[Example 1]
One packed column with a diameter of 10.6 mm and a length of 0.1 m was filled with Molecular Sieve 3A (pore diameter 0.3 nm, manufactured by Union Showa Co., Ltd.) as zeolite, and dried at 150°C for 30 minutes under reduced pressure conditions. Crude trimethylamine was passed through at a linear velocity of 0.02 m/sec (contact time to zeolite was 5 seconds), trimethylamine was collected from the outlet of the packed column, and the dimethylamine concentration was analyzed. The results are shown in Table 1.
［実施例２］
充填塔の長さを１ｍに変更した以外は、実施例１と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間５０秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Example 2]
Crude trimethylamine was passed through in the same manner as in Example 1 except that the length of the packed column was changed to 1 m (contact time to zeolite was 50 seconds), and the dimethylamine concentration was analyzed. The results are shown in Table 1.
［実施例３］
充填塔の本数を２本に変更した以外は、実施例２と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間１００秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Example 3]
Crude trimethylamine was passed in the same manner as in Example 2 except that the number of packed columns was changed to two (contact time to zeolite was 100 seconds), and the dimethylamine concentration was analyzed. The results are shown in Table 1.
［実施例４］
充填塔の本数を３本に変更した以外は、実施例２と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間１５０秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Example 4]
Crude trimethylamine was passed in the same manner as in Example 2 except that the number of packed columns was changed to three (contact time to zeolite was 150 seconds), and the dimethylamine concentration was analyzed. The results are shown in Table 1.
［実施例５］
ゼオライトをモレキュラーシーブ４Ａ（細孔径０．３５ｎｍ、ユニオン昭和社製）に変更した以外は、実施例１と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間５秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Example 5]
Crude trimethylamine was passed in the same manner as in Example 1, except that the zeolite was changed to Molecular Sieve 4A (pore size 0.35 nm, manufactured by Union Showa Co., Ltd.) (contact time to zeolite was 5 seconds), and dimethylamine concentration was analyzed. . The results are shown in Table 1.
［実施例６］
充填塔の長さを１ｍに変更した以外は、実施例５と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間５０秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Example 6]
Crude trimethylamine was passed through in the same manner as in Example 5, except that the length of the packed column was changed to 1 m (contact time to zeolite was 50 seconds), and the dimethylamine concentration was analyzed. The results are shown in Table 1.
［実施例７］
充填塔の本数を２本に変更した以外は、実施例６と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間１００秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Example 7]
Crude trimethylamine was passed in the same manner as in Example 6 except that the number of packed columns was changed to two (contact time to zeolite was 100 seconds), and the dimethylamine concentration was analyzed. The results are shown in Table 1.
［実施例８］
充填塔の本数を３本に変更した以外は、実施例６と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間１５０秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Example 8]
Crude trimethylamine was passed through in the same manner as in Example 6, except that the number of packed columns was changed to three (contact time to zeolite: 150 seconds), and dimethylamine concentration was analyzed. The results are shown in Table 1.
［実施例９］
ゼオライトをモレキュラーシーブ５Ａ（細孔径０．４２ｎｍ、ユニオン昭和社製）に変更した以外は、実施例１と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間５秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Example 9]
Crude trimethylamine was passed through in the same manner as in Example 1 (contact time to zeolite was 5 seconds), except that the zeolite was changed to Molecular Sieve 5A (pore size 0.42 nm, manufactured by Union Showa Co., Ltd.), and the dimethylamine concentration was analyzed. . The results are shown in Table 1.
［実施例１０］
充填塔の長さを１ｍに変更した以外は、実施例９と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間５０秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Example 10]
Crude trimethylamine was passed through in the same manner as in Example 9 except that the length of the packed column was changed to 1 m (contact time to zeolite was 50 seconds), and the dimethylamine concentration was analyzed. The results are shown in Table 1.
［実施例１１］
充填塔の本数を２本に変更した以外は、実施例１０と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間１００秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Example 11]
Crude trimethylamine was passed through in the same manner as in Example 10 (contact time to zeolite was 100 seconds), except that the number of packed columns was changed to two, and the dimethylamine concentration was analyzed. The results are shown in Table 1.
［実施例１２］
充填塔の本数を３本に変更した以外は、実施例１０と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間１５０秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Example 12]
Crude trimethylamine was passed through in the same manner as in Example 10, except that the number of packed columns was changed to three (contact time to zeolite: 150 seconds), and dimethylamine concentration was analyzed. The results are shown in Table 1.
［比較例１］
充填塔にゼオライトを充填しなかった以外は、実施例1と同様に粗トリメチルアミンを流通させ、ジメチルアミン濃度を分析した。結果を表１に示す。
[Comparative example 1]
Crude trimethylamine was passed through in the same manner as in Example 1, except that the packed tower was not filled with zeolite, and the dimethylamine concentration was analyzed. The results are shown in Table 1.
［比較例２］
ゼオライトをモレキュラーシーブ１３Ｘ（細孔径１．０ｎｍ、ユニオン昭和社製）に変更した以外は、実施例１と同様に粗トリメチルアミンを流通させ（ゼオライトへの接触時間５秒）、ジメチルアミン濃度を分析した。結果を表１に示す。
[Comparative example 2]
Crude trimethylamine was passed through in the same manner as in Example 1 (contact time to zeolite was 5 seconds), except that the zeolite was changed to Molecular Sieve 13X (pore diameter 1.0 nm, manufactured by Union Showa Co., Ltd.), and the dimethylamine concentration was analyzed. . The results are shown in Table 1.
［比較例３］
粗トリメチルアミンを、理論段数２０段で全還流を７２時間行った後、還流比２００で塔頂部より仕込み量の３０重量％のトリメチルアミンをパージし、液相のトリメチルアミン中のジメチルアミン濃度を分析した。結果を表１に示す。
[Comparative example 3]
After the crude trimethylamine was completely refluxed for 72 hours using 20 theoretical plates, 30% by weight of trimethylamine was purged from the top of the column at a reflux ratio of 200, and the concentration of dimethylamine in the liquid phase of trimethylamine was analyzed. The results are shown in Table 1.
表１の結果から明らかなように、実施例１～１２では、充填剤を使用しなかった比較例１と比べて、精製後のジメチルアミンの濃度が著しく低くなった。ゼオライトとの接触時間が５０秒以上の実施例２～４、６～８、１０～１２では、蒸留を行った比較例３よりもジメチルアミン濃度が低くなった。なお、ゼオライトとの接触時間が１００秒以上の実施例３～４、７～８、１１～１２では、比較例３と比べてジメチルアミン濃度が半分以下となった。ゼオライトとしてモレキュラーシーブ１３Ｘを用いた比較例２では、充填剤を使用しなかった比較例１と比べてジメチルアミンの濃度がほとんど変わらなかった。 As is clear from the results in Table 1, in Examples 1 to 12, the concentration of dimethylamine after purification was significantly lower than in Comparative Example 1 in which no filler was used. In Examples 2 to 4, 6 to 8, and 10 to 12, in which the contact time with zeolite was 50 seconds or more, the dimethylamine concentration was lower than in Comparative Example 3, in which distillation was performed. In addition, in Examples 3 to 4, 7 to 8, and 11 to 12, in which the contact time with zeolite was 100 seconds or more, the dimethylamine concentration was less than half that of Comparative Example 3. In Comparative Example 2 in which Molecular Sieve 13X was used as the zeolite, the concentration of dimethylamine was almost unchanged compared to Comparative Example 1 in which no filler was used.
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