JP4859714B2 - Gas hydrate concentration measuring device - Google Patents

Gas hydrate concentration measuring device Download PDF

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JP4859714B2
JP4859714B2 JP2007062113A JP2007062113A JP4859714B2 JP 4859714 B2 JP4859714 B2 JP 4859714B2 JP 2007062113 A JP2007062113 A JP 2007062113A JP 2007062113 A JP2007062113 A JP 2007062113A JP 4859714 B2 JP4859714 B2 JP 4859714B2
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gas hydrate
valve
water
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新井　　敬
徹 岩崎
英教 守屋
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Mitsui Engineering and Shipbuilding Co Ltd
Mitsui E&S Holdings Co Ltd
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Mitsui E&S Holdings Co Ltd
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Description

本発明は、ガスハイドレート濃度の測定方法及び測定装置に関する。   The present invention relates to a method and an apparatus for measuring a gas hydrate concentration.

近年、天然ガスやメタンなどの安全かつ経済的な輸送・貯蔵手段として、それら原料ガスの固体状の水和物であるガスハイドレートを用いる方法が注目されている。   In recent years, a method using gas hydrate, which is a solid hydrate of these raw material gases, has attracted attention as a safe and economical means for transporting and storing natural gas and methane.

このガスハイドレートは一般に高圧・低温下（例えば、５．４ＭＰａ・５℃）で生成され、その生成方法としては、原料水中に原料ガスを気泡として吹き込みながら撹拌するいわゆる「気液撹拌方式」（例えば、特許文献１を参照）が代表的なものとして知られている。   This gas hydrate is generally produced under high pressure and low temperature (for example, 5.4 MPa · 5 ° C.), and as its production method, a so-called “gas-liquid agitation method” in which the raw material gas is blown into the raw material water as bubbles is stirred. For example, see Patent Document 1).

ガスハイドレート事業の商業化を図る上からは、ガスハイドレート生成装置により一定の濃度のガスハイドレートを生成する必要があるが、生成されるガスハイドレートは多量の水の中に浮遊してスラリー状となっているため、ガスハイドレート濃度を直接測定することは一般に困難である。   In order to commercialize the gas hydrate business, it is necessary to generate a gas hydrate with a certain concentration using a gas hydrate generator, but the generated gas hydrate is suspended in a large amount of water. Since it is in the form of a slurry, it is generally difficult to directly measure the gas hydrate concentration.

現状のガスハイドレート濃度の測定方法の一例を以下に説明する。   An example of the current method for measuring the gas hydrate concentration will be described below.

この測定方法においては、図５に示すように、あらかじめ内部をガスハイドレートの生成圧力よりも低い圧力（例えば、３．５ＭＰａ）に保持したサンプリング容器３０を用いる。まず、サンプリング容器３０をガスハイドレート生成容器３１に、エアロックを構成する２つのボール弁３２、３３を介して接続する。そして、これらのボール弁３２、３３を同時に開くことにより、２つの容器間の差圧を利用してサンプリング容器３０内にガスハイドレートと付着水からなる液状試料と未反応の原料ガスを導入する。所定の量を導入した後にボール弁３２、３３を閉じ、その中間部でサンプリング容器３０を生成容器３１から切り離す。切り離し後のサンプリング容器３０を大気圧下でガスハイドレートが分解しにくい温度（約−２０℃）まで冷却して液状試料を凍結させてから、ガス抜き弁３４を開いて未反応の原料ガスを外部へ放出する。ガスを放出した後に、サンプリング容器３０の総重量と風袋重量から液状試料の重量Ｗｓを求める。最後に、サンプリング容器３０をガスハイドレートの生成温度以上まで加熱してガスハイドレートを原料ガスと原料水に分解した後に、サンプリング容器３０内の残留水を取り出してその重量Ｗｗを測定する。 In this measurement method, as shown in FIG. 5, a sampling container 30 is used in which the interior is previously maintained at a pressure lower than the gas hydrate generation pressure (for example, 3.5 MPa). First, the sampling container 30 is connected to the gas hydrate generation container 31 via two ball valves 32 and 33 constituting an air lock. By opening these ball valves 32 and 33 simultaneously, a liquid sample composed of gas hydrate and adhering water and an unreacted source gas are introduced into the sampling container 30 by utilizing the differential pressure between the two containers. . After the predetermined amount is introduced, the ball valves 32 and 33 are closed, and the sampling container 30 is separated from the production container 31 at an intermediate portion thereof. After the separation, the sampling container 30 is cooled to a temperature (about −20 ° C.) at which the gas hydrate is not easily decomposed at atmospheric pressure to freeze the liquid sample, and then the gas release valve 34 is opened to remove the unreacted source gas. Release to the outside. After releasing the gas, obtains the weight W s of the liquid sample from the total weight and the tare weight of the sampling vessel 30. Finally, the sampling vessel 30 is heated to a gas hydrate production temperature or higher to decompose the gas hydrate into raw material gas and raw water, and then the residual water in the sampling vessel 30 is taken out and its weight Ww is measured.

このようにして測定した液状試料の重量Ｗｓと残留水（付着水＋原料水）の重量Ｗｗから、ガスハイドレートを生成していた原料ガスの重量Ｗｇを求める。
Ｗｇ＝Ｗｓ−Ｗｗ ---（１） From the weight W s of the liquid sample thus measured and the weight W w of the residual water (attached water + raw material water), the weight W g of the raw material gas that has generated the gas hydrate is obtained.
W g = W s −W w --- (1)

ガスハイドレートの重量Ｗｈは、水和数をｎとすると以下のようになる。
Ｗｈ＝Ｗｇ×（１＋ｎ×Ｍｗ／Ｍｇ） ---（２) The weight W h of the gas hydrate is as follows when the hydration number is n.
W h = W g × (1 + n × M w / M g ) --- (2)

ここで、Ｍｗ及びＭｇは、それぞれ原料ガス及び原料水の分子量を表す。 Here, M w and M g each represent molecular weight of the raw material gas and the raw water.

従って、ガスハイドレート濃度αｈ（重量％）は、次のように求められる。
αｈ＝Ｗｈ／Ｗｓ×１００ ---（３） Accordingly, the gas hydrate concentration α h (% by weight) is obtained as follows.
α h = W h / W s × 100 --- (3)

しかし、このようなガスハイドレート濃度の測定方法では、サンプリング容器を−２０℃まで冷却して液状試料を凍結させる必要があるため、測定に費用と時間がかかり効率が悪いという問題があった。
特開２０００−３０２７０１号公報 However, in such a gas hydrate concentration measurement method, it is necessary to cool the sampling container to −20 ° C. to freeze the liquid sample, and thus there is a problem that the measurement is expensive and time consuming and the efficiency is poor.
JP 2000-302701 A

本発明の目的は、ガスハイドレート濃度を効率よく測定することができる測定方法及びその装置を提供することにある。   The objective of this invention is providing the measuring method and its apparatus which can measure a gas hydrate density | concentration efficiently.

上記の目的を達成するための本発明は、原料ガス及び原料水から生成されるガスハイドレートと付着水とからなる液状試料中のガスハイドレート濃度の測定装置であって、前記液状試料が流れる管路（３）に入口弁（１０）及び出口弁（１１）を両端にそれぞれ有するバイパス管（４）を介して接続する測定容器（５）と、前記測定容器（５）の外側に設置された加熱ヒーター（６）と、前記測定容器（５）に外部へ向けて順に接続する排気弁（１２）、差圧弁（７）、ガス流量計（８）及びガスクロマトグラフィ（１４）と、前記排気弁（１２）と差圧弁（７）との間に接続する圧力計（１３）と、前記測定容器（５）に接続する排水弁（９）と、を備え、前記入口弁（１０）及び出口弁（１１）を開弁して前記測定容器（５）内に前記液状試料を通過させた後に、前記出口弁（１１）及び入口弁（１０）を順に閉弁して前記測定容器（５）内に前記液状試料を貯留させ、前記加熱ヒーター（６）で前記測定容器（５）内を前記ガスハイドレートの平衡温度以上に加熱して前記ガスハイドレートを前記原料ガスと前記原料水とに分解し、前記排気弁（１２）を開弁して前記測定容器（５）内が貯留時の圧力に維持されるように前記圧力計（１３）を確認しつつ前記差圧弁（７）を開弁して前記原料ガスの体積Ｖ g を前記ガス流量計（８）で測定するとともに、前記原料ガスの組成を前記ガスクロマトグラフィ（１４）で分析し、前記排水弁（９）を開弁して前記測定容器（５）内に残留する前記原料水及び付着水を抜き出してその重量をＷ w を測定し、前記原料ガスの体積Ｖ g を前記ガスクロマトグラフィ（１４）の組成分析結果を基に前記原料ガスの重量Ｗ g に変換し、Ｗ s ＝Ｗ g ＋Ｗ w 、Ｗ h ＝Ｗ g ×（１＋ｎ×Ｍ w ／Ｍ g ）及びα h ＝Ｗ h ／Ｗ s ×１００からなる３つの式を用いてガスハイドレート濃度α h を算出することを特徴とするガスハイドレート濃度の測定装置である。なお、Ｗ s は液状試料の重量、Ｗ h はガスハイドレートの重量、Ｍ w は原料ガスの分子量、Ｍ g は原料水の分子量及びｎはガスハイドレートの水和数を示す。 The present invention for achieving the above object, there is provided a measuring apparatus for a gas hydrate concentration in the liquid sample of the material gas and the raw water or et gas hydrate produced and deposited water, the liquid sample A measuring container (5) connected to a flowing pipe line (3) via a bypass pipe (4) having an inlet valve (10) and an outlet valve (11) at both ends, respectively, and installed outside the measuring container (5) The heated heater (6), the exhaust valve (12), the differential pressure valve (7), the gas flow meter (8), and the gas chromatography (14) connected in order to the outside of the measurement container (5), A pressure gauge (13) connected between the exhaust valve (12) and the differential pressure valve (7), and a drain valve (9) connected to the measurement container (5), the inlet valve (10) and The outlet valve (11) is opened and the liquid is put into the measuring container (5). After passing the sample, the outlet valve (11) and the inlet valve (10) are sequentially closed to store the liquid sample in the measurement container (5), and the measurement container is heated by the heater (6). (5) The inside is heated above the equilibrium temperature of the gas hydrate to decompose the gas hydrate into the raw material gas and the raw water, and the exhaust valve (12) is opened to open the measuring vessel (5 ) Opening the differential pressure valve (7) while checking the pressure gauge (13) so that the inside is maintained at the pressure at the time of storage, and the volume V g of the source gas is determined by the gas flow meter (8). While measuring, the composition of the raw material gas is analyzed by the gas chromatography (14), the drain valve (9) is opened, and the raw water and adhering water remaining in the measuring vessel (5) are extracted. the weight was measured W w, before the volume V g of the raw material gas The composition analysis results of gas chromatography (14) into the weight W g of the raw material gas based, W s = W g + W w, W h = W g × (1 + n × M w / M g) and alpha h = The gas hydrate concentration measuring apparatus is characterized in that the gas hydrate concentration α h is calculated using three equations of W h / W s × 100 . Incidentally, W s is the weight of the liquid sample, W h denotes the weight of the gas hydrate, the molecular weight M w of the raw material gas, the molecular weight and n M g raw material water hydration number of the gas hydrate.

この原料ガスとしては天然ガスを用いることが望ましい。   As this raw material gas, it is desirable to use natural gas.

この測定容器（５）は、排水弁（９）を最低部に有する下に凸のＵ字状であることが望ましい。 The measurement container (5) preferably has a downward U-shape having a drain valve (9) at the lowest part .

本発明であるガスハイドレート濃度の測定装置によれば、ガスハイドレートと付着水が流れる管路に測定容器をバイパスとして接続することにより測定容器内に液状試料を導入し、測定容器をガスハイドレートの平衡温度以上に加熱してガスハイドレートを原料ガスと原料水とに分解し、次いで測定容器外に放出された原料ガスの体積及び組成と、測定容器内に残留した原料水と付着水との重量とからガスハイドレートの濃度を求めるようにしたので、測定容器を冷却して液状試料を凍結させる必要がないため、ガスハイドレートの濃度を効率よく測定することができる。 According to the gas hydrate concentration measuring apparatus of the present invention, a liquid sample is introduced into a measurement container by connecting the measurement container as a bypass to a pipeline through which the gas hydrate and adhering water flow. The gas hydrate is heated to a temperature equal to or higher than the equilibrium temperature of the rate to decompose the gas hydrate into raw material gas and raw material water, and then the volume and composition of the raw material gas released to the outside of the measuring vessel, and the raw material water and adhering water remaining in the measuring vessel Since the gas hydrate concentration is obtained from the weight of the gas sample, there is no need to cool the measurement container and freeze the liquid sample, so that the gas hydrate concentration can be measured efficiently.

以下に、本発明の実施の形態について、図面を参照して説明する。   Embodiments of the present invention will be described below with reference to the drawings.

本発明に係るガスハイドレート濃度の測定装置は、ガスハイドレートと付着水とからなる液状試料中に含まれるガスハイドレートの濃度を測定するものである。ガスハイドレートを生成する原料ガスとしては天然ガスが例示されるが、所定の圧力及び温度でガスハイドレートを生成するものならば特に種類は問わず、天然ガスの成分であるメタン、エタン、プロパンなどの炭化水素ガス及びそれらの混合ガス、あるいは二酸化炭素、硫化水素及びそれらの混合ガスなどでもよい。また、ガスハイドレートの生成圧力及び生成温度とは、上記のそれぞれの原料ガスと水からガスハイドレートを生成する際の圧力範囲及び温度範囲をいう。この生成圧力と生成温度は、ガスハイドレートとガスと水（又は氷）が平衡状態にある三相平衡条件よりも低温・高圧側である安定領域の圧力と温度に設定する必要がある。 The gas hydrate concentration measuring apparatus according to the present invention measures the concentration of gas hydrate contained in a liquid sample composed of gas hydrate and adhering water. Natural gas is exemplified as a raw material gas for producing gas hydrate, but any kind of gas may be used as long as it produces gas hydrate at a predetermined pressure and temperature, and methane, ethane, and propane, which are components of natural gas. Or a mixed gas thereof, or carbon dioxide, hydrogen sulfide and a mixed gas thereof. Further, the gas hydrate production pressure and production temperature refer to the pressure range and temperature range in producing gas hydrate from each of the above raw material gases and water. It is necessary to set the generation pressure and the generation temperature to a pressure and temperature in a stable region at a lower temperature and a higher pressure than a three-phase equilibrium condition in which gas hydrate, gas, and water (or ice) are in an equilibrium state.

図１は、本発明の実施形態からなるガスハイドレート濃度の測定装置である。   FIG. 1 is a gas hydrate concentration measuring apparatus according to an embodiment of the present invention.

このガスハイドレート濃度の測定装置（以下、単に「測定装置」という。）１は、ガスハイドレートと付着水からなるスラリー状のガスハイドレート２が流れる管路３にバイパス管４を介して接続する測定容器５と、その測定容器５の外側に設置された加熱ヒーター６及び測定容器５に接続された差圧弁７、ガス流量計８及び排水弁９から主に構成される。測定容器５は、バイパス管４の一部として形成することもできる。バイパス管４には、上流側及び下流側に開閉手段である入口弁１０及び出口弁１１が、それぞれ設けられている。差圧弁７とガス流量計８は排気弁１２を介して測定容器５に順に接続されており、差圧弁７と排気弁１２の間には圧力計１３が設置されている。また、ガス流量計８の下流側には、ガスの組成を分析するガスクロマトグラフィ１４が接続されている。なお、温度計１５は、測定容器５の内部温度を測定するためのものである。   This gas hydrate concentration measuring device (hereinafter simply referred to as “measuring device”) 1 is connected via a bypass pipe 4 to a conduit 3 through which a slurry-like gas hydrate 2 composed of gas hydrate and adhering water flows. The measurement vessel 5 is mainly composed of a heater 6 installed outside the measurement vessel 5, a differential pressure valve 7 connected to the measurement vessel 5, a gas flow meter 8, and a drain valve 9. The measurement container 5 can also be formed as a part of the bypass pipe 4. The bypass pipe 4 is provided with an inlet valve 10 and an outlet valve 11 as opening / closing means on the upstream side and the downstream side, respectively. The differential pressure valve 7 and the gas flow meter 8 are sequentially connected to the measurement container 5 via an exhaust valve 12, and a pressure gauge 13 is installed between the differential pressure valve 7 and the exhaust valve 12. A gas chromatograph 14 for analyzing the gas composition is connected to the downstream side of the gas flow meter 8. The thermometer 15 is for measuring the internal temperature of the measurement container 5.

スラリー状のガスハイドレート２が流れる管路３としては、図２に示すような、ガスハイドレート生成装置２０の循環水ライン２１を例示することができる。このガスハイドレート生成装置２０は、耐圧容器２２内に貯留する冷水２３内に気泡として吹き出された原料ガス２４を回転する撹拌羽根２５により撹拌することで原料ガス２４を水和させてガスハイドレートを生成するものである。その生成されたガスハイドレートは、スラリー状となって耐圧容器２２の底部から送出ポンプ２５により脱水装置等の図示しない次工程へ送り出されるが、その一部は循環水ライン２１に流れ込んで熱交換器２６で反応熱が除去された後に、原料となる水２７と共に耐圧容器内へ戻されるようになっている。本発明に係る測定装置１は、この循環水ライン２１における送出ポンプ２５の下流側に設置するのが望ましい。なお、ここではいわゆる気液撹拌方式によるガスハイドレート生成装置を示しているが、いわゆる水スプレー方式（例えば、特開２０００−２６４８５２号公報を参照）によるガスハイドレート生成装置でもよい。   As the pipe line 3 through which the slurry-like gas hydrate 2 flows, a circulating water line 21 of the gas hydrate generator 20 as shown in FIG. 2 can be exemplified. The gas hydrate generator 20 hydrates the raw material gas 24 by stirring the raw material gas 24 blown out as bubbles in the cold water 23 stored in the pressure resistant vessel 22 with a rotating stirring blade 25 to gas hydrate the gas hydrate. Is generated. The generated gas hydrate is in the form of a slurry and is sent from the bottom of the pressure vessel 22 to the next process (not shown) such as a dehydrator by the delivery pump 25. A part of the gas hydrate flows into the circulating water line 21 to exchange heat. After the reaction heat is removed by the vessel 26, it is returned to the pressure vessel together with water 27 as a raw material. The measuring device 1 according to the present invention is desirably installed on the downstream side of the delivery pump 25 in the circulating water line 21. In addition, although the gas hydrate production | generation apparatus by what is called a gas-liquid stirring system is shown here, the gas hydrate production | generation apparatus by what is called a water spray system (for example, refer Unexamined-Japanese-Patent No. 2000-264852) may be used.

このような測定装置を用いたガスハイドレート濃度の測定方法を以下に説明する。   A method for measuring the gas hydrate concentration using such a measuring apparatus will be described below.

まず、入口弁１０と出口弁１１を開くことにより管路３からガスハイドレートと付着水２が測定容器５内を通過するようにバイパスさせる。なお、管路３に切替弁１６を設けて、ガスハイドレートと付着水２の全量がバイパス管４へ流れるようにしてもよい。これにより、測定容器５内はガスハイドレートの生成圧力（例えば、５．４ＭＰａ）及び生成温度（例えば、５℃）に維持されることになる。次に、出口弁１１を閉じて、測定対象となる液状試料を測定容器５内に貯留させる。一定時間経過後に入口弁１０を閉じ、加熱ヒーター６により測定容器５を容器内の圧力で決まるガスハイドレートの平衡温度以上（例えば、１０℃）に加熱してガスハイドレートを原料ガスと原料水に分解する。そして排気弁１２を開き、測定容器５内が液状試料の貯留時の圧力に維持されるように、圧力計１３を確認しつつ差圧弁７を開いて、測定容器５内の原料ガスをガス流量計８へ流して体積Ｖｇを測定すると共に、ガスクロマトグラフィ１４でガスの組成を分析する。測定容器５の内部に残留した原料水と付着水は、排水弁９を開いて測定容器５外に抜き出して重量Ｗｗを測定する。 First, the inlet valve 10 and the outlet valve 11 are opened to bypass the gas hydrate and the adhering water 2 from the pipe line 3 so as to pass through the measurement container 5. Note that a switching valve 16 may be provided in the pipe line 3 so that the entire amount of gas hydrate and adhering water 2 flows to the bypass pipe 4. Thereby, the inside of the measurement container 5 is maintained at the generation pressure (for example, 5.4 MPa) and the generation temperature (for example, 5 ° C.) of the gas hydrate. Next, the outlet valve 11 is closed, and the liquid sample to be measured is stored in the measurement container 5. After a predetermined time has elapsed, the inlet valve 10 is closed, and the measuring vessel 5 is heated by the heater 6 to a temperature equal to or higher than the equilibrium temperature of the gas hydrate determined by the pressure in the vessel (for example, 10 ° C.). Disassembled into Then, the exhaust valve 12 is opened, and the differential pressure valve 7 is opened while checking the pressure gauge 13 so that the inside of the measurement container 5 is maintained at the pressure at the time of storing the liquid sample, and the raw material gas in the measurement container 5 is supplied to the gas flow rate. The gas is flowed to a total of 8 to measure the volume V g and the gas composition is analyzed by the gas chromatography 14. The raw material water and adhering water remaining inside the measurement container 5 are opened to the outside of the measurement container 5 by opening the drain valve 9, and the weight Ww is measured.

なお、図３に示す別の実施形態のように、測定容器５の形状を下に凸のＵ字状として、その最底部に排水弁９を設けることにより、原料水と付着水を測定容器５外へ容易に抜き出すことができる。あるいは、図４に示す参考例のように、排水弁９を設ける代わりに入口弁１０と出口弁１１を二重にして、測定容器５を管路３に対して脱着可能とすることで、測定容器５の風袋重量と取り外し後の測定重量から原料水と付着水の重量Ｗｗを求めることもできる。 In addition, like another embodiment shown in FIG. 3, the shape of the measurement container 5 is made downward U-shaped, and the drainage valve 9 is provided at the bottom of the measurement container 5 so that the raw water and the adhering water are measured in the measurement container 5. Can be easily pulled out. Alternatively, as in the reference example shown in FIG. 4, instead of providing the drain valve 9, the inlet valve 10 and the outlet valve 11 are doubled so that the measurement container 5 can be attached to and detached from the pipe line 3. From the tare weight of the container 5 and the measured weight after removal, the weight Ww of raw material water and adhering water can also be obtained.

測定した原料ガスの体積Ｖｇについては、原料ガスの組成分析結果を基に重量Ｗｇに変換する。そして、原料ガスの重量Ｗｇ及び原料水と付着水の重量Ｗｗから液状試料の重量Ｗｓを以下のように求める。
Ｗｓ＝Ｗｇ＋Ｗｗ ---（４） The measured volume V g of the source gas is converted into a weight W g based on the composition analysis result of the source gas. Then, determine the weight W g and raw water of the raw material gas from the weight W w of water adhered to the weight W s of the liquid sample, as follows.
W s = W g + W w --- (4)

これから、前出の（１）〜（３）式を用いることにより、ガスハイドレート濃度αｈを求めることができる。 From this, the gas hydrate concentration α h can be obtained by using the above-described equations (1) to (3).

以上のように、本発明に係るガスハイドレート濃度の測定装置によれば、測定容器を冷却して液状試料を凍結させる必要がないため、液状試料中のガスハイドレート濃度を効率よく測定することができる。 As described above, according to the measurement apparatus for a gas hydrate concentration according to the present invention, since the measurement container does not need to be cooled to freeze the liquid sample, measuring the gas hydrate concentration in the liquid sample effectively be able to.

本発明の実施形態からなるガスハイドレート濃度の測定装置である。1 is a gas hydrate concentration measuring apparatus according to an embodiment of the present invention. 本発明に係るガスハイドレート濃度の測定装置の設置場所の一例を示す系統図である。It is a systematic diagram which shows an example of the installation place of the measuring apparatus of the gas hydrate concentration which concerns on this invention. 本発明の別の実施形態からなるガスハイドレート濃度の測定装置である。It is a measuring device of gas hydrate concentration which consists of another embodiment of the present invention. 本発明の更に別の実施形態からなるガスハイドレート濃度の測定装置である。It is a gas hydrate density | concentration measuring apparatus which consists of another embodiment of this invention. 従来のガスハイドレート濃度の測定装置である。This is a conventional gas hydrate concentration measuring apparatus.

符号の説明Explanation of symbols

１ 測定装置
２ スラリー状のガスハイドレート
３ 管路
４ バイパス管
５ 測定容器
６ 加熱ヒーター
７ 差圧弁
８ ガス流量計
９ 排水弁
１０ 入口弁
１１ 出口弁
１２ 排気弁
１３ 圧力計
１４ ガスクロマトグラフィ
１５ 温度計
１６ 切替弁
２０ ガスハイドレート生成装置
２１ 循環水ライン
２２ 耐圧容器
２３ 冷水
２４ 原料ガス
２５ 撹拌羽根
２６ 熱交換器
２７ 水 DESCRIPTION OF SYMBOLS 1 Measuring apparatus 2 Slurry gas hydrate 3 Pipe line 4 Bypass pipe 5 Measuring container 6 Heater 7 Differential pressure valve 8 Gas flow meter 9 Drain valve 10 Inlet valve 11 Outlet valve 12 Exhaust valve 13 Pressure gauge 14 Gas chromatography 15 Thermometer 16 Switching valve 20 Gas hydrate generator 21 Circulating water line 22 Pressure vessel 23 Cold water 24 Raw material gas 25 Stirring blade 26 Heat exchanger 27 Water

Claims (3)

原料ガス及び原料水から生成されるガスハイドレートと付着水とからなる液状試料中のガスハイドレート濃度の測定装置であって、
前記液状試料が流れる管路（３）に入口弁（１０）及び出口弁（１１）を両端にそれぞれ有するバイパス管（４）を介して接続する測定容器（５）と、
前記測定容器（５）の外側に設置された加熱ヒーター（６）と、
前記測定容器（５）に外部へ向けて順に接続する排気弁（１２）、差圧弁（７）、ガス流量計（８）及びガスクロマトグラフィ（１４）と、
前記排気弁（１２）と差圧弁（７）との間に接続する圧力計（１３）と、
前記測定容器（５）に接続する排水弁（９）と、を備え、
前記入口弁（１０）及び出口弁（１１）を開弁して前記測定容器（５）内に前記液状試料を通過させた後に、前記出口弁（１１）及び入口弁（１０）を順に閉弁して前記測定容器（５）内に前記液状試料を貯留させ、
前記加熱ヒーター（６）で前記測定容器（５）内を前記ガスハイドレートの平衡温度以上に加熱して前記ガスハイドレートを前記原料ガスと前記原料水とに分解し、
前記排気弁（１２）を開弁して前記測定容器（５）内が貯留時の圧力に維持されるように前記圧力計（１３）を確認しつつ前記差圧弁（７）を開弁して前記原料ガスの体積Ｖ g を前記ガス流量計（８）で測定するとともに、前記原料ガスの組成を前記ガスクロマトグラフィ（１４）で分析し、
前記排水弁（９）を開弁して前記測定容器（５）内に残留する前記原料水及び付着水を抜き出してその重量をＷ w を測定し、
前記原料ガスの体積Ｖ g を前記ガスクロマトグラフィ（１４）の組成分析結果を基に前記原料ガスの重量Ｗ g に変換し、
以下に示す（１）〜（３）式を用いてガスハイドレート濃度α h を算出することを特徴とするガスハイドレート濃度の測定装置。
Ｗ s ＝Ｗ g ＋Ｗ w ---（１）
Ｗ h ＝Ｗ g ×（１＋ｎ×Ｍ w ／Ｍ g ） ---（２）
α h ＝Ｗ h ／Ｗ s ×１００ ---（３）
但し、Ｗ s ：液状試料の重量、Ｗ h ：ガスハイドレートの重量、Ｍ w ：原料ガスの分子量、Ｍ g ：原料水の分子量、ｎ：ガスハイドレートの水和数 A measuring apparatus for a gas hydrate concentration in the liquid sample of the material gas and the raw water or et gas hydrate produced and deposited water,
A measurement vessel (5) connected to a pipe line (3) through which the liquid sample flows via a bypass pipe (4) having an inlet valve (10) and an outlet valve (11) at both ends;
A heater (6) installed outside the measurement vessel (5);
An exhaust valve (12), a differential pressure valve (7), a gas flow meter (8), and a gas chromatography (14), which are sequentially connected to the measurement container (5) toward the outside;
A pressure gauge (13) connected between the exhaust valve (12) and the differential pressure valve (7);
A drain valve (9) connected to the measurement container (5),
After the inlet valve (10) and the outlet valve (11) are opened to allow the liquid sample to pass through the measurement container (5), the outlet valve (11) and the inlet valve (10) are closed in order. And storing the liquid sample in the measurement container (5),
The inside of the measurement vessel (5) is heated above the equilibrium temperature of the gas hydrate with the heater (6) to decompose the gas hydrate into the source gas and the source water,
Open the exhaust valve (12) and open the differential pressure valve (7) while checking the pressure gauge (13) so that the inside of the measurement container (5) is maintained at the pressure during storage. While measuring the volume V g of the source gas with the gas flow meter (8), the composition of the source gas is analyzed with the gas chromatography (14),
Open the drain valve (9), extract the raw material water and adhering water remaining in the measurement container (5), measure the weight W w ,
The volume V g of the source gas is converted into the weight W g of the source gas based on the composition analysis result of the gas chromatography (14) ,
An apparatus for measuring a gas hydrate concentration, wherein the gas hydrate concentration α h is calculated using the following equations (1) to (3) .
W s = W g + W w --- (1)
W h = W g × (1 + n × M w / M g ) --- (2)
α h = W h / W s × 100 --- (3)
However, W s: weight of the liquid sample, W h: weight of gas hydrate, M w: molecular weight of the raw material gas, M g: molecular weight of the raw water, n: number hydration of gas hydrate 前記原料ガスが天然ガスである請求項１に記載のガスハイドレート濃度の測定装置。 The apparatus for measuring a gas hydrate concentration according to claim 1, wherein the source gas is natural gas. 前記測定容器（５）が、前記排水弁（９）を最低部に有する下に凸のＵ字状である請求項１又は２に記載のガスハイドレート濃度の測定装置。 The gas hydrate concentration measuring device according to claim 1 or 2 , wherein the measuring container (5) has a downwardly convex U shape having the drain valve (9) at a lowest part .
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