JP2021165239A - Method for purifying trimethylamine - Google Patents
Method for purifying trimethylamine Download PDFInfo
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- JP2021165239A JP2021165239A JP2020068456A JP2020068456A JP2021165239A JP 2021165239 A JP2021165239 A JP 2021165239A JP 2020068456 A JP2020068456 A JP 2020068456A JP 2020068456 A JP2020068456 A JP 2020068456A JP 2021165239 A JP2021165239 A JP 2021165239A
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- trimethylamine
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- dimethylamine
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 238000000034 method Methods 0.000 title claims abstract description 48
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000010457 zeolite Substances 0.000 claims abstract description 71
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 68
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims description 14
- 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
- 238000011049 filling Methods 0.000 description 10
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 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
- 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
- 238000010992 reflux Methods 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
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying 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
- 238000012856 packing 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)
Abstract
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, which removes dimethylamine using zeolite.
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。 The crude product of trimethylamine, which is one of the organic amines, may contain about 1000 volume ppm of dimethylamine as an impurity. Since trimethylamine and dimethylamine have similar vapor pressures and are azeotropic, the concentration of dimethylamine can be reduced only to about 400 to 500 by volume ppm by distillation.
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 a crude organic amine.
Patent Document 1 discloses a purification apparatus for removing low boiling point impurities contained in monomethylamine by using a synthetic zeolite having pores having an average diameter of 0.3 nm or 0.4 nm. Examples of low boiling point 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 having an average diameter of 0.5 nm is used to adsorb water 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, which removes water and ammonia in a trimethylamine-containing gas using a 3A or 4A zeolite, and removes monomethylamine and nitrogen 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 parts by volume or less. Note that Patent Document 2 discloses a method for removing monomethylamine using synthetic zeolite, but does not describe that dimethylamine is removed using synthetic zeolite, and therefore dimethylamine is removed. It has never been known.
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, it is an object of the present disclosure to provide a novel method for reducing the concentration of dimethylamine 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 diligent studies, the present inventors have found that the dimethylamine concentration can be reduced by contacting crude trimethylamine containing dimethylamine with a zeolite having pores having a diameter of 0.2 to 0.6 nm. This disclosure has been completed.
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, in the method for purifying trimethylamine of the present disclosure, crude trimethylamine containing at least dimethylamine is brought into contact with a zeolite having pores having a diameter of 0.2 to 0.6 nm, and the concentration of dimethylamine in the crude trimethylamine is adjusted as described above. It is characterized in that the amount is reduced as compared with that before the zeolite contact.
According to the method for purifying trimethylamine of the present disclosure, it is possible to remove dimethylamine in crude trimethylamine without consuming energy as in 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。 According to the method for purifying trimethylamine of the present disclosure, dimethylamine in crude trimethylamine can be removed without consuming energy as in distillation, and an extremely high-purity trimethylamine that can be used in a semiconductor manufacturing process can be obtained. 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 description of the constituent requirements described below is an example of the embodiments of the present disclosure, and the specific contents thereof are not limited. It can be modified in various ways 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。 In the method for purifying trimethylamine of the present disclosure, crude trimethylamine containing at least dimethylamine is brought into contact with a zeolite having pores having a diameter of 0.2 to 0.6 nm, and the concentration of dimethylamine in the crude trimethylamine is 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。 Zeolites used in the purification method of the present disclosure are crystalline aluminosilicates, also called molecular sieves, and are classified into synthetic zeolites, artificial zeolites, and natural zeolites. In the purification method of the present disclosure, any of synthetic zeolite, artificial zeolite, and natural zeolite can be used as long as it is a zeolite having pores having a diameter of 0.2 to 0.6 nm or a diameter of 3 to 5 Å, but the purity is high. It is preferable to use a high synthetic zeolite. When the diameter of the pores of the zeolite is less than 0.2 nm or exceeds 0.6 nm, the effect of reducing the concentration of dimethylamine 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 having a diameter of 0.2 to 0.6 nm, 3A type, 4A type or 5A type synthetic zeolite is suitable. In addition, "A" in 3A type, 4A type or 5A type synthetic zeolite represents Å (angstrom).
The 3A type synthetic zeolite has a pore diameter of 0.3 nm and can pass molecules up to a diameter of 0.3 nm. The pore size of 4A type synthetic zeolite is 0.35 nm, but at normal operating temperature, molecules up to 0.4 nm in diameter can pass through due to the expansion and contraction and kinetic energy of the molecules entering the cavity. .. Further, the pore diameter of the 5A type synthetic zeolite is 0.42 nm, but for the same reason, molecules having a diameter of up to 0.5 nm can be passed through.
Here, the range of the diameter (adsorption diameter) of the molecules that can pass through the synthetic zeolite of 3A type, 4A type or 5A type will be specified below.
3A type 0.3nm or less 4A type more than 0.3nm, 0.4nm or less 5A type more than 0.4nm, 0.5nm 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。
Specific examples of the 3A, 4A, and 5A synthetic zeolites are Molecular Sieves 3A, Molecular Sieves 4A, and Molecular Sieves 5A manufactured by Union Showa; Molecular Sieves 3A and Molecular Sieves manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. 4A, molecular sieves 5A and the like can be used.
The shape of the zeolite used in the purification method of the present disclosure is not particularly limited and may be bead-shaped, pellet-shaped, powder-shaped or the like, but bead-shaped or pellet-shaped one is preferable because it is easy to use in a chemical industry plant.
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。 As the zeolite used in the purification method of the present disclosure, the purchased zeolite can be used as it is, but it is preferable to dry it before use. The drying conditions are preferably 1 kPa or less, 150 ° C. or higher for 30 minutes or longer, and more preferably 1 kPa or lower, 150 to 200 ° C., 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 the crude trimethylamine into contact with the zeolite is not particularly limited, and a method of adding the zeolite to a container or the like for storing the crude trimethylamine and leaving it to stand (standing method), or a method of filling the column or a packed bed with the zeolite to prepare the crude trimethylamine. Examples thereof include a method of circulating the zeolite through a column or a packed bed and bringing it into contact with the zeolite (column method). The column method is preferable because it has a high effect of removing dimethylamine and can be purified in a short time. However, when the concentration of dimethylamine in the crude trimethylamine is high, the static method and the column method are performed, for example, the static method is performed before the column method, the concentration of dimethylamine is reduced to a certain level, and then the column method is performed. It can also be done in combination with.
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 under which the crude trimethylamine is brought into flow contact with the zeolite are preferably 20 to 30 ° C. and above atmospheric pressure. The pressure condition is more preferably 150 to 200 kPa.
The time for the crude trimethylamine to be in circulation contact with the zeolite is preferably 50 to 200 seconds. If it is less than 50 seconds, dimethylamine may not be sufficiently removed. On the other hand, the effect of removing dimethylamine may not be improved even if the distribution contact is performed for more than 200 seconds. The time for the crude trimethylamine to be in circulation contact with the zeolite 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 the crude trimethylamine in a gaseous state into flow contact with the zeolite for 100 seconds or longer under the 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 flow contact with zeolite, 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. The 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 acquisition method is not particularly limited. Crude trimethylamine may contain impurities other than dimethylamine, and examples of 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 further preferably 99.9% by weight or more.
The concentration of dimethylamine in the crude trimethylamine is preferably 500 to 1500 parts by volume ppm. If the concentration of dimethylamine in the crude trimethylamine is greater than the above value, the dimethylamine may be removed by a method such as distillation before treatment by the purification method of the present disclosure, or the above-mentioned standing method and the above-mentioned standing method may be used. It is conceivable to perform it in combination with the 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 because it can be purified 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 concentration of dimethylamine in crude trimethylamine to 400 parts by volume or less. More preferably, it is 300 volume ppm or less. By using the purification method of the present disclosure, trimethylamine having high purity as described above can be obtained. Such high-purity trimethylamine 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。 Hereinafter, examples in which the embodiments of the present disclosure are disclosed more specifically will be shown. The present disclosure is not limited to these examples. 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)
The crude trimethylamine used in this example was synthesized with reference to a conventional production method. The trimethylamine contained 500 to 2000 parts by volume of dimethylamine and 100 to 1000 parts by volume of water in the gas phase as impurities. The impurity concentration was analyzed by 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 having 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) as zeolite, and dried under reduced pressure conditions at 150 ° C. for 30 minutes. , Crude trimethylamine was circulated at a linear velocity of 0.02 m / sec (contact time with zeolite for 5 seconds), and trimethylamine was collected from the outlet of the packing column to analyze the dimethylamine concentration. 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 circulated (contact time with zeolite for 50 seconds) in the same manner as in Example 1 except that the length of the filling column was changed to 1 m, 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 circulated (contact time with zeolite for 100 seconds) in the same manner as in Example 2 except that the number of filling towers was changed to 2, 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 circulated (contact time with zeolite for 150 seconds) in the same manner as in Example 2 except that the number of filling towers was changed to 3, 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 circulated (contact time with zeolite for 5 seconds) and the dimethylamine concentration was analyzed in the same manner as in Example 1 except that the zeolite was changed to molecular sieve 4A (pore diameter 0.35 nm, manufactured by Union Showa). .. 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 circulated (contact time with zeolite for 50 seconds) in the same manner as in Example 5 except that the length of the filling column was changed to 1 m, 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 circulated (contact time with zeolite for 100 seconds) in the same manner as in Example 6 except that the number of filling towers was changed to 2, 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 circulated (contact time with zeolite for 150 seconds) in the same manner as in Example 6 except that the number of filling towers was changed to 3, and the 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 circulated (contact time with zeolite for 5 seconds) and the dimethylamine concentration was analyzed in the same manner as in Example 1 except that the zeolite was changed to molecular sieve 5A (pore diameter 0.42 nm, manufactured by Union Showa). .. 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 circulated (contact time with zeolite for 50 seconds) in the same manner as in Example 9 except that the length of the filling column was changed to 1 m, 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 circulated (contact time with zeolite for 100 seconds) in the same manner as in Example 10 except that the number of filling towers was changed to 2, 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 circulated (contact time with zeolite for 150 seconds) in the same manner as in Example 10 except that the number of filling towers was changed to 3, and the 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 circulated in the same manner as in Example 1 except that the packed bed 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 circulated (contact time with zeolite for 5 seconds) and the dimethylamine concentration was analyzed in the same manner as in Example 1 except that the zeolite was changed to molecular sieve 13X (pore diameter 1.0 nm, manufactured by Union Showa). .. 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 total reflux of crude trimethylamine was carried out in 20 theoretical plates for 72 hours, 30% by weight of the charged amount 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 that 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 the zeolite was 50 seconds or more, the dimethylamine concentration was lower than that in Comparative Example 3 in which distillation was performed. 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 the same as that in Comparative Example 1 in which no filler was used.
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