JP4313513B2 - NMR cell for supercritical fluid measurement - Google Patents
NMR cell for supercritical fluid measurement Download PDFInfo
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- JP4313513B2 JP4313513B2 JP2000372394A JP2000372394A JP4313513B2 JP 4313513 B2 JP4313513 B2 JP 4313513B2 JP 2000372394 A JP2000372394 A JP 2000372394A JP 2000372394 A JP2000372394 A JP 2000372394A JP 4313513 B2 JP4313513 B2 JP 4313513B2
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- cell
- supercritical fluid
- nmr
- capillary
- inner plug
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Description
【０００１】
【産業上の利用分野】
本発明は、対流防止のための中栓を入れて超臨界状態流体のＮＭＲ測定に使用する超臨界流体測定用ＮＭＲセルに関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
図２は中栓を入れた従来の超臨界流体測定用ＮＭＲセルの構成例を示す図である。超臨界状態は、高圧・高温状態で実現できる。超臨界状態流体では、圧力・温度の条件により物性が非常に変化するが、一般に粘性が低くなるため、超臨界状態流体に若干の温度勾配があっても対流が生じやすい。そのためＮＭＲの観測において、分解能が乱れてしまう。
【０００３】
そこで、図２に示すように対流を抑えるべくＮＭＲサンプル用の耐圧セル３に中栓４を入れ、超臨界状態流体６のサンプル量を制限することにより、測定サンプル系内の温度勾配を小さくして対流が生じるのをできるだけ抑制していた。しかしながら、分解能を調整するモニターとして重水素化溶媒をしばし使用する必要がある。また、Ｓ／Ｎの悪い試料の観測においては、ＮＭＲロックの必要性も出てくる。
【０００４】
しかし、従来の超臨界流体測定用ＮＭＲセル３では、図２に示すように対流止めの中栓４と分解能モニターおよびＮＭＲロック用として重水素化溶媒を封入したキャピラリ５とはそれぞれが独立していた。そのため、超臨界状態流体６に若干の対流が生じると、キャピラリ５が動き分解能調整に支障をきたすという問題があった。またＮＭＲロックをかけてもキャピラリ５が動くため、ＮＭＲスペクトルを安定に保つことが困難であった。
【０００５】
また、サンプルを交換するためには耐圧セル３を取り外さなければならないため、サンプル交換後に耐圧セル３をセットしなおすと、キャピラリ５の挿入位置が変わり、分解能の再現性が全くないなどの問題も含んでいた。
【０００６】
【課題を解決するための手段】
本発明は、上記課題を解決するものであって、キャピラリを固定して保持し分解能の向上、ＮＭＲロックの安定化を図るものである。
【０００７】
そのために本発明は、超臨界状態流体のＮＭＲ測定に使用する超臨界流体測定用ＮＭＲセルであって、超臨界状態流体のサンプル量を制限し対流を抑制するための中栓と重水素化溶媒を封入したキャピラリとを一体化してセル内に入れたことを特徴とするものである。
【０００８】
【発明の実施の形態】
以下、本発明の実施の形態を図面を参照しつつ説明する。図１は本発明に係る超臨界流体測定用ＮＭＲセルの実施の形態を示す図であり、１はパイプ、２はセルホルダ、３は耐圧セル、４は中栓、５はキャピラリ、６は超臨界状態流体を示す。
【０００９】
図１において、パイプ１は、ステンレス製のパイプであり、高圧発生器を有する加圧器を耐圧セル３に接続している。セルホルダ２は、チタン合金製の非磁性高耐圧のホルダ兼圧力媒体接続部となっている。耐圧セル３は、サファイヤやジルコニアなどのセラミックで作られた高耐圧セルである。中栓４は、水晶やパイレックスガラス、その他のガラス、石英などで作られ、超臨界状態流体６のサンプル量を制限することにより温度勾配を小さくして対流を防ぐために耐圧セル３の中に入れられるものである。キャピラリ５は、中栓４と同一材料で作られ、分解能調整用モニタとＮＭＲロック用の重水素化溶媒を封入したものである。中栓４とキャピラリ５の関係は、両者が一体となってつながっていてもよいし、中栓４に重水素化溶媒を封入したキャピラリ５を取り付ける方式であってもよい。超臨界状態流体６は、中栓４によりサンプル量を制限して耐圧セル３の底近傍にキャピラリ５と共に収容される。
【００１０】
上記のように本発明に係る超臨界流体測定用ＮＭＲセルは、パイプ１、セルホルダ２、耐圧セル３、中栓４、キャピラリ５からなり、温度可変可能なＮＭＲプローブに挿入して適当な圧力と温度をかけることにより、超臨界状態流体を作りＮＭＲで観測する。そのため超臨界流体測定用ＮＭＲセルは、セルホルダ２の上部からステンレス製パイプ１を介して接続された圧力発生器により、媒体を通して任意の圧力に加圧される。
【００１１】
任意の圧力に加圧されたセルは、必要な温度まで加温可能なプローブを備えたＮＭＲ観測装置の検出部に上部から挿入されて、適当な温度に加温されてセル内に超臨界状態流体が作られる。このとき、中栓４は、セル内のサンプル量を制限することにより、サンプル全体の温度勾配（温度差）による対流を抑える役割をする。分解能モニタとＮＭＲロックのための重水素化溶媒を封入したキャピラリ５は、この中栓４と一体化されている。
【００１２】
従来の図２に示す超臨界流体測定用ＮＭＲセルのようにそれぞれが独立した中栓４とキャピラリ５とを内部に入れると、キャピラリ５は超臨界状態流体の対流があるとその対流によって動いてしまう。そのため、分解能の調整に支障をきたし、かつＮＭＲのロックが安定しない。
【００１３】
しかし、図１に示す本発明に係る超臨界流体測定用ＮＭＲセルのようにキャピラリ５と中栓４とを一体化することにより、キャピラリ５の微動を押さえると同時に、ＮＭＲロックの安定性を向上させることができる。また、キャピラリ５は、中栓４と一体化しているため再現性良く常にセルの中心に設定され、分解能調整の再現性も良くなる。
【００１４】
なお、本発明は、上記実施の形態に限定されるものではなく、種々の変形が可能である。例えば上記実施の形態では、キャピラリ一体型中栓が水晶やパイレックスガラスで作られているが、耐圧セルの磁化率と同じ磁化率に合わせたガラスを用いることも可能であり、このことにより更なる分解能の向上を必要とする場合に対応が可能となる。
【００１５】
【発明の効果】
以上の説明から明らかなように、本発明によれば、超臨界状態流体のＮＭＲ測定に使用する超臨界流体測定用ＮＭＲセルであって、超臨界状態流体のサンプル量を制限し対流を抑制するための中栓と重水素化溶媒を封入したキャピラリとを一体化してセル内に入れたので、中栓にキャピラリを固定して保持することができ、耐圧セル内に中栓を入れたときにキャピラリが動かなくなり、分解能を向上させ、ＮＭＲロックの安定化を図ることができる。さらには、キャピラリ挿入の再現性が良くなるので、サンプル設定毎の分解能の再現性が良くなり、分解能調整も容易になる。
【図面の簡単な説明】
【図１】 本発明に係る超臨界流体測定用ＮＭＲセルの実施の形態を示す図である。
【図２】 中栓を入れた従来の超臨界流体測定用ＮＭＲセルの構成例を示す図である。
【符号の説明】
１…パイプ、２…セルホルダ、３…耐圧セル、４…中栓、５…キャピラリ、６…超臨界状態流体[0001]
[Industrial application fields]
The present invention relates to an NMR cell for measuring a supercritical fluid that is used for NMR measurement of a supercritical fluid by inserting an inner plug for preventing convection.
[0002]
[Prior art and problems to be solved by the invention]
FIG. 2 is a diagram showing a configuration example of a conventional supercritical fluid measurement NMR cell with an inner plug inserted therein. The supercritical state can be realized at high pressure and high temperature. In the supercritical fluid, the physical properties vary greatly depending on the pressure and temperature conditions. However, since the viscosity is generally low, convection is likely to occur even if the supercritical fluid has a slight temperature gradient. Therefore, the resolution is disturbed in the NMR observation.
[0003]
Therefore, as shown in FIG. 2, the temperature gradient in the measurement sample system is reduced by inserting the inner plug 4 in the pressure cell 3 for NMR samples to limit convection and limiting the sample amount of the supercritical fluid 6. Therefore, the occurrence of convection was suppressed as much as possible. However, it is often necessary to use a deuterated solvent as a monitor for adjusting the resolution. In addition, in the observation of a sample having a poor S / N, the necessity of NMR lock comes out.
[0004]
However, in the conventional NMR cell 3 for supercritical fluid measurement, as shown in FIG. 2, the convection stopper 4 and the capillary 5 enclosing a deuterated solvent for resolution monitoring and NMR lock are independent of each other. It was. For this reason, when a slight convection occurs in the supercritical fluid 6, there is a problem that the capillary 5 moves and hinders the resolution adjustment. Further, since the capillary 5 moves even when the NMR lock is applied, it is difficult to keep the NMR spectrum stable.
[0005]
In addition, since the pressure cell 3 must be removed in order to replace the sample, if the pressure cell 3 is reset after the sample is replaced, the insertion position of the capillary 5 changes and there is no reproducibility of the resolution at all. Included.
[0006]
[Means for Solving the Problems]
The present invention solves the above-described problems and aims to improve the resolution and stabilize the NMR lock by fixing and holding the capillary.
[0007]
Therefore, the present invention is an NMR cell for supercritical fluid measurement used for NMR measurement of supercritical fluid, and includes a plug and a deuterated solvent for limiting the sample amount of supercritical fluid and suppressing convection. The capillaries encapsulating the are integrated into the cell.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 shows an embodiment of an NMR cell for supercritical fluid measurement according to the present invention. 1 is a pipe, 2 is a cell holder, 3 is a pressure cell, 4 is a plug, 5 is a capillary, and 6 is supercritical. Indicates the state fluid.
[0009]
In FIG. 1, a pipe 1 is a stainless steel pipe, and a pressurizer having a high pressure generator is connected to a pressure cell 3. The cell holder 2 is a non-magnetic high pressure resistant holder and pressure medium connecting portion made of titanium alloy. The pressure cell 3 is a high voltage cell made of ceramic such as sapphire or zirconia. The plug 4 is made of quartz, Pyrex glass, other glass, quartz, etc., and is placed in the pressure cell 3 to limit the sample amount of the supercritical fluid 6 to reduce the temperature gradient and prevent convection. It is The capillary 5 is made of the same material as the inner plug 4 and encloses a resolution adjusting monitor and a deuterated solvent for NMR lock. The relationship between the inner plug 4 and the capillary 5 may be such that they are connected together, or a system in which a capillary 5 in which a deuterated solvent is sealed is attached to the inner plug 4 may be used. The supercritical fluid 6 is accommodated together with the capillary 5 in the vicinity of the bottom of the pressure cell 3 while limiting the amount of sample by the inner plug 4.
[0010]
As described above, the NMR cell for supercritical fluid measurement according to the present invention comprises the pipe 1, the cell holder 2, the pressure cell 3, the inner plug 4, and the capillary 5. A supercritical fluid is created by applying temperature and observed by NMR. Therefore, the NMR cell for supercritical fluid measurement is pressurized to an arbitrary pressure through the medium by a pressure generator connected via the stainless steel pipe 1 from the upper part of the cell holder 2.
[0011]
A cell pressurized to an arbitrary pressure is inserted from the top into the detection unit of an NMR observation device equipped with a probe that can be heated to the required temperature, and is heated to an appropriate temperature and supercritical in the cell. A fluid is created. At this time, the inner plug 4 serves to suppress convection due to a temperature gradient (temperature difference) of the entire sample by limiting the amount of sample in the cell. A capillary 5 enclosing a resolution monitor and a deuterated solvent for NMR lock is integrated with the inner plug 4.
[0012]
When the internal plug 4 and the capillary 5 that are independent from each other are inserted into the inside as in the conventional NMR cell for measuring the supercritical fluid shown in FIG. End up. Therefore, the resolution adjustment is hindered and the NMR lock is not stable.
[0013]
However, by integrating the capillary 5 and the inner plug 4 as in the NMR cell for supercritical fluid measurement according to the present invention shown in FIG. 1, the capillary movement is suppressed and at the same time the stability of the NMR lock is improved. Can be made. Further, since the capillary 5 is integrated with the inner plug 4, it is always set at the center of the cell with good reproducibility, and the reproducibility of resolution adjustment is improved.
[0014]
In addition, this invention is not limited to the said embodiment, A various deformation | transformation is possible. For example, in the above-described embodiment, the capillary-integrated inner plug is made of quartz or Pyrex glass, but it is also possible to use glass matched to the same magnetic susceptibility as that of the pressure-resistant cell. It is possible to cope with the case where the resolution needs to be improved.
[0015]
【The invention's effect】
As is apparent from the above description, according to the present invention, a supercritical fluid measurement NMR cell used for NMR measurement of a supercritical fluid, which limits the sample amount of the supercritical fluid and suppresses convection. The inner plug and the capillary filled with the deuterated solvent are integrated into the cell, so that the capillary can be fixed and held in the inner plug, and when the inner plug is inserted into the pressure cell Capillaries can be stopped, resolution can be improved, and NMR lock can be stabilized. Furthermore, since the reproducibility of the capillary insertion is improved, the reproducibility of the resolution for each sample setting is improved and the resolution can be easily adjusted.
[Brief description of the drawings]
FIG. 1 is a diagram showing an embodiment of an NMR cell for supercritical fluid measurement according to the present invention.
FIG. 2 is a diagram showing a configuration example of a conventional supercritical fluid measurement NMR cell with an inner plug inserted therein.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Pipe, 2 ... Cell holder, 3 ... Pressure-resistant cell, 4 ... Inner plug, 5 ... Capillary, 6 ... Supercritical fluid
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000372394A JP4313513B2 (en) | 2000-12-07 | 2000-12-07 | NMR cell for supercritical fluid measurement |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000372394A JP4313513B2 (en) | 2000-12-07 | 2000-12-07 | NMR cell for supercritical fluid measurement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002174673A JP2002174673A (en) | 2002-06-21 |
| JP4313513B2 true JP4313513B2 (en) | 2009-08-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000372394A Expired - Fee Related JP4313513B2 (en) | 2000-12-07 | 2000-12-07 | NMR cell for supercritical fluid measurement |
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| Country | Link |
|---|---|
| JP (1) | JP4313513B2 (en) |
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- 2000-12-07 JP JP2000372394A patent/JP4313513B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JP2002174673A (en) | 2002-06-21 |
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