JP7000217B2 - Quantitative method of elemental mercury in crude oil and selection method of crude oil - Google Patents
Quantitative method of elemental mercury in crude oil and selection method of crude oil Download PDFInfo
- Publication number
- JP7000217B2 JP7000217B2 JP2018054046A JP2018054046A JP7000217B2 JP 7000217 B2 JP7000217 B2 JP 7000217B2 JP 2018054046 A JP2018054046 A JP 2018054046A JP 2018054046 A JP2018054046 A JP 2018054046A JP 7000217 B2 JP7000217 B2 JP 7000217B2
- Authority
- JP
- Japan
- Prior art keywords
- crude oil
- measurement sample
- mercury
- elemental mercury
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Description
本発明は、原油中の元素水銀の定量方法および原油の選別方法に関する。 The present invention relates to a method for quantifying elemental mercury in crude oil and a method for selecting crude oil.
石油精製プロセスにおいては、先ず原油が常圧蒸留装置で蒸留されて液化石油ガス（ＬＰＧ）、ライトナフサ（Ｌ／Ｎ）、ヘビーナフサ（Ｈ／Ｎ）等の留分を生成し、これ等の留分が、必要に応じてさらに二次的な精製処理を施された上で、各種燃料油基材や石油化学製品の原料として供給されている。 In the petroleum refining process, crude oil is first distilled by an atmospheric distillation apparatus to generate fractions such as liquefied petroleum gas (LPG), light naphtha (L / N), and heavy naphtha (H / N), and these distillates are produced. The fraction is supplied as a raw material for various petroleum oil base materials and petroleum chemical products after being further refined as necessary.
ところで、自然界においては水銀が地殻等に比較的豊富に存在しており、このために原油中にも微量の水銀が混入する場合がある（例えば、特許文献１（特表２０１４-５２４４９６号公報）参照）。
近年、原油価格の上昇に伴って多様な原油が処理されるようになっており、元素水銀の含有割合が相対的に高い原油は一般に安価で経済性に優れることから、その取扱量を増加させることが検討されている。
By the way, in the natural world, mercury is relatively abundant in the crust and the like, and for this reason, a trace amount of mercury may be mixed in the crude oil (for example, Patent Document 1 (Japanese Patent Laid-Open No. 2014-524996)). reference).
In recent years, various crude oils have been processed as the price of crude oil rises, and crude oil with a relatively high content of elemental mercury is generally cheap and economical, so the amount handled is increased. Is being considered.
一方、原油中の水銀量が増加すると、原油を常圧蒸留装置で蒸留処理して得られる、液化石油ガス（ＬＰＧ）、ライトナフサ（Ｌ／Ｎ）、ヘビーナフサ（Ｈ／Ｎ）等の石油留分中の元素水銀濃度も増加し易くなり、この元素水銀により二次的な精製処理装置（二次処理装置）に腐食等を生じ易くなる。
このため、多量の元素水銀を含む石油留分を取り扱う場合には、その取り扱い量を制限したり、上記液化石油ガス（ＬＰＧ）、ライトナフサ（Ｌ／Ｎ）、ヘビーナフサ（Ｈ／Ｎ）等の流通ラインに元素水銀除去装置を設け、活性炭等により元素水銀を除去する必要がある。
On the other hand, when the amount of mercury in crude oil increases, oil distillates such as liquefied petroleum gas (LPG), light naphtha (L / N), and heavy naphtha (H / N) obtained by distilling the crude oil with an atmospheric distillation apparatus. The concentration of elemental mercury in the fraction also tends to increase, and this elemental mercury tends to cause corrosion or the like in the secondary purification treatment device (secondary treatment device).
Therefore, when handling petroleum distillates containing a large amount of elemental mercury, the handling amount may be limited, or the above-mentioned liquefied petroleum gas (LPG), light naphtha (L / N), heavy naphtha (H / N), etc. may be handled. It is necessary to install an elemental mercury removal device on the distribution line and remove the elemental mercury with activated charcoal or the like.
上記元素水銀除去装置の処理能力の過不足を管理する上では、処理対象となる液化石油ガス（ＬＰＧ）、ライトナフサ（Ｌ／Ｎ）、ヘビーナフサ（Ｈ／Ｎ）等の石油留分中の元素水銀量を把握する必要があり、これ等石油留分中の元素水銀量を把握する上で原油中の元素水銀量を把握することが便宜である。 Elements in the petroleum distillate such as liquefied petroleum gas (LPG), light naphtha (L / N), and heavy naphtha (H / N) to be treated in order to control the excess or deficiency of the processing capacity of the elemental mercury removing device. It is necessary to grasp the amount of mercury, and it is convenient to grasp the amount of elemental mercury in crude oil in order to grasp the amount of elemental mercury in these petroleum distillates.
しかしながら、本発明者等が検討したところ、原油中の元素水銀量をガスクロマトグラフにより分析しようとすると、原油中に元素水銀とともに含有される一部の水銀化合物がガスクロマトグラフ内で熱分解して元素水銀を生じる結果、原油中に元々存在する元素水銀量が不明となってしまい、精度の高い定量分析を行い難いことが判明した。 However, as a result of studies by the present inventors, when an attempt is made to analyze the amount of elemental mercury in crude oil by a gas chromatograph, some mercury compounds contained together with elemental mercury in crude oil are thermally decomposed in the gas chromatograph and are elements. As a result of producing mercury, the amount of elemental mercury originally present in crude oil became unknown, and it was found that it was difficult to perform highly accurate quantitative analysis.
また、元素水銀は揮発性が高いことから原油中に不活性ガスを吹き込んで元素水銀を揮発除去し、揮発除去前後における原油中の全水銀量の差から元々原油中に存在していた元素水銀量を定量する方法が考えられたが、本発明者等が検討したところ、上記方法によっても必ずしも精度よく元素水銀量を定量できないことが判明した。 In addition, since elemental mercury is highly volatile, an inert gas is blown into the crude oil to volatilize and remove the elemental mercury. A method for quantifying the amount has been considered, but as a result of examination by the present inventors, it has been found that the amount of elemental mercury cannot always be quantified with high accuracy even by the above method.
従って、本発明は、原油中の元素水銀を高精度に定量する方法および原油中の元素水銀の含有量を高精度に分析して原油を選別する方法を提供することを目的とするものである。 Therefore, an object of the present invention is to provide a method for quantifying elemental mercury in crude oil with high accuracy and a method for selecting crude oil by analyzing the content of elemental mercury in crude oil with high accuracy. ..
このような状況下、本発明者等が鋭意検討したところ、原油に対して炭素数６～１０の芳香族炭化水素化合物を添加して、粘度を０．５～７．５ｍＰａ・ｓに制御した測定試料を調製し、得られた測定試料１ｍＬあたり１～２０ｍＬ／分間の割合で１５～２４０分間不活性ガスを吹き込み、前記不活性ガスの吹き込み前後における前記測定試料中の全水銀量の差から前記原油中に元々含まれていた元素水銀量を算出することにより上記技術課題を解決し得ることを見出し、本知見に基づいて本発明を完成するに至った。 Under such circumstances, as a result of diligent studies by the present inventors, an aromatic hydrocarbon compound having 6 to 10 carbon atoms was added to the crude oil to control the viscosity to 0.5 to 7.5 mPa · s. A measurement sample was prepared, and the inert gas was blown at a rate of 1 to 20 mL / min per 1 mL of the obtained measurement sample for 15 to 240 minutes. It has been found that the above technical problem can be solved by calculating the amount of elemental mercury originally contained in the crude oil, and the present invention has been completed based on this finding.
すなわち、本発明は、
（１）原油中の元素水銀を定量する方法であって、
原油に対して炭素数６～１０の芳香族炭化水素化合物を添加して、粘度を０．５～７．５ｍＰａ・ｓに制御した測定試料を調製し、
得られた測定試料１ｍＬあたり１～２０ｍＬ／分間の割合で１５～２４０分間不活性ガスを吹き込み、
前記不活性ガスの吹き込み前後における前記測定試料中の全水銀量の差から前記原油中に元々含まれていた元素水銀量を算出する
ことを特徴とする原油中の元素水銀の定量方法、
（２）前記測定試料を調製した後、不活性ガスの吹き込み前に測定試料をさらにろ過処理する上記（１）に記載の原油中の元素水銀の定量方法、
（３）原油を選別する方法であって、
原油に対して炭素数６～１０の芳香族炭化水素化合物を添加して、粘度を０．５～７．５ｍＰａ・ｓに制御した測定試料を調製し、
得られた測定試料１ｍＬあたり１～２０ｍＬ／分間の割合で１５～２４０分間不活性ガスを吹き込み、
前記不活性ガスの吹き込み前後における前記測定試料中の全水銀量の差から前記原油中に元々含まれていた元素水銀量を算出し、
前記元素水銀量の多少に基づいて原油を選別する
ことを特徴とする原油の選別方法、
（４）前記測定試料を調製した後、不活性ガスの吹き込み前に測定試料をさらにろ過処理する上記（３）に記載の原油の選別方法、を提供するものである。
That is, the present invention
(1) A method for quantifying elemental mercury in crude oil.
An aromatic hydrocarbon compound having 6 to 10 carbon atoms was added to the crude oil to prepare a measurement sample having a viscosity controlled to 0.5 to 7.5 mPa · s.
The inert gas was blown into the obtained measurement sample at a rate of 1 to 20 mL / min for 15 to 240 minutes per 1 mL.
A method for quantifying elemental mercury in crude oil, which comprises calculating the amount of elemental mercury originally contained in the crude oil from the difference in the total amount of mercury in the measurement sample before and after the injection of the inert gas.
(2) The method for quantifying elemental mercury in crude oil according to (1) above, wherein the measurement sample is further filtered after the measurement sample is prepared and before the inert gas is blown into the measurement sample.
(3) A method of sorting crude oil.
An aromatic hydrocarbon compound having 6 to 10 carbon atoms was added to the crude oil to prepare a measurement sample having a viscosity controlled to 0.5 to 7.5 mPa · s.
The inert gas was blown into the obtained measurement sample at a rate of 1 to 20 mL / min for 15 to 240 minutes per 1 mL.
The amount of elemental mercury originally contained in the crude oil was calculated from the difference in the total amount of mercury in the measurement sample before and after the injection of the inert gas.
A crude oil sorting method, which comprises sorting crude oil based on the amount of elemental mercury.
(4) The method for selecting crude oil according to (3) above, wherein the measurement sample is further filtered after the measurement sample is prepared and before the inert gas is blown into the measurement sample.
本発明によれば、原油中の元素水銀を高精度に定量する方法および原油中の元素水銀の含有量を高精度に分析して原油を選別する方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for quantifying elemental mercury in crude oil with high accuracy and a method for selecting crude oil by analyzing the content of elemental mercury in crude oil with high accuracy.
本発明に係る原油中の元素水銀の定量方法は、原油中の元素水銀を定量する方法であって、原油に対して炭素数６～１０の芳香族炭化水素化合物を添加して、粘度を０．５～７．５ｍＰａ・ｓに制御した測定試料を調製し、得られた測定試料１ｍＬあたり１～２０ｍＬ／分間の割合で１５～２４０分間不活性ガスを吹き込み、
前記不活性ガスの吹き込み前後における前記測定試料中の全水銀量の差から前記原油中に元々含まれていた元素水銀量を算出する
ことを特徴とするものである。
The method for quantifying elemental mercury in crude oil according to the present invention is a method for quantifying elemental mercury in crude oil, in which an aromatic hydrocarbon compound having 6 to 10 carbon atoms is added to the crude oil to reduce the viscosity to 0. A measurement sample controlled to 5.5 to 7.5 mPa · s was prepared, and an inert gas was blown into the obtained measurement sample at a rate of 1 to 20 mL / min for 15 to 240 minutes.
It is characterized in that the amount of elemental mercury originally contained in the crude oil is calculated from the difference in the total amount of mercury in the measurement sample before and after the injection of the inert gas.
本発明に係る原油中の元素水銀の定量方法においては、原油に対して炭素数が６～１０の芳香族炭化水素化合物を添加する。
芳香族炭化水素化合物の炭素数は、６～９が好ましく、７～８がより好ましい。
In the method for quantifying elemental mercury in crude oil according to the present invention, an aromatic hydrocarbon compound having 6 to 10 carbon atoms is added to the crude oil.
The number of carbon atoms of the aromatic hydrocarbon compound is preferably 6 to 9, and more preferably 7 to 8.
芳香族炭化水素化合物として、具体的には、トルエン、キシレン、エチルベンゼン、トリメチルベンゼン、テトラメチルベンゼン、ジエチルベンゼン等から選ばれる一種以上を挙げることができる。 Specific examples of the aromatic hydrocarbon compound include one or more selected from toluene, xylene, ethylbenzene, trimethylbenzene, tetramethylbenzene, diethylbenzene and the like.
原油に対し、芳香族炭化水素化合物に代えて例えば飽和炭化水素化合物を添加した場合には、アスファルテン分が析出し易くなり、後述する不活性ガスを吹き込んだ際に不活性ガスが十分に拡散し難くなる。
一方、原油に対して芳香族炭化水素化合物を添加することにより、原油中に不活性ガスが好適に拡散し易くなる結果、元素水銀を効果的に除去することができる。
When, for example, a saturated hydrocarbon compound is added to the crude oil instead of the aromatic hydrocarbon compound, the asphaltene component tends to precipitate, and the inert gas sufficiently diffuses when the inert gas described later is blown into the crude oil. It becomes difficult.
On the other hand, by adding the aromatic hydrocarbon compound to the crude oil, the inert gas can be suitably diffused into the crude oil, and as a result, the elemental mercury can be effectively removed.
原油に対する芳香族炭化水素化合物の添加量は、得られる測定試料の粘度が、０．５～７．５ｍＰａ・ｓとなる量であり、０．６～４ｍＰａ・ｓとなる量であることが好ましく、１～３ｍＰａ・ｓとなる量であることがより好ましい。 The amount of the aromatic hydrocarbon compound added to the crude oil is such that the viscosity of the obtained measurement sample is 0.5 to 7.5 mPa · s, and preferably 0.6 to 4 mPa · s. It is more preferable that the amount is 1 to 3 mPa · s.
原油に対する芳香族炭化水素の添加量が上記範囲内に制御されることにより、原油中に不活性ガスを好適に拡散して、元素水銀を効果的に除去することができる。 By controlling the amount of the aromatic hydrocarbon added to the crude oil within the above range, the inert gas can be suitably diffused into the crude oil, and the elemental mercury can be effectively removed.
なお、本出願書類において、原油に芳香族炭化水素化合物を添加して得られる測定試料の粘度は、ＪＩＳ Ｋ２２８３ 原油及び石油製品－動粘度試験方法及び粘度指数算出方法、ＪＩＳ Ｚ８８０３ 液体の粘度－測定方法の規定により測定される３０℃の温度条件下における粘度を意味する。 In this application document, the viscosity of the measurement sample obtained by adding an aromatic hydrocarbon compound to crude oil is JIS K2283 crude oil and petroleum products-kinematic viscosity test method and viscosity index calculation method, JIS Z8803 liquid viscosity-measurement. It means the viscosity under the temperature condition of 30 ° C. measured by the specification of the method.
本発明に係る原油中の元素水銀の定量方法においては、原油に芳香族炭化水素化合物を添加して得られた測定試料に対し、不活性ガスの吹き込み前にさらにろ過処理を施すことが好ましい。
上記ろ過処理を施すことにより、測定試料中に微粒子等の夾雑物が含まれる場合であっても、好適に除去することができる。測定試料中に微粒子等の夾雑物が含まれない場合は、本工程は省略して次工程における不活性ガスの吹き込み処理を施してもよい。
In the method for quantifying elemental mercury in crude oil according to the present invention, it is preferable that the measurement sample obtained by adding an aromatic hydrocarbon compound to crude oil is further filtered before blowing in an inert gas.
By performing the above filtration treatment, even if the measurement sample contains impurities such as fine particles, it can be suitably removed. If the measurement sample does not contain impurities such as fine particles, this step may be omitted and the treatment of blowing the inert gas in the next step may be performed.
上記ろ過処理としては、加圧ろ過処理や遠心分離処理を挙げることができ、ろ過処理として加圧ろ過処理や遠心分離処理を行うことにより、ろ過処理時における元素水銀や軽質な有機水銀化合物の揮発を抑制しつつ、測定試料中の微粒子等の夾雑物を好適に除去することができる。 Examples of the filtration treatment include pressure filtration treatment and centrifugation, and by performing pressure filtration treatment and centrifugation as the filtration treatment, volatilization of elemental mercury and light organic mercury compounds during the filtration treatment It is possible to suitably remove impurities such as fine particles in the measurement sample while suppressing the above.
本発明に係る原油中の元素水銀の定量方法においては、得られた測定試料に対し不活性ガスを吹き込む。 In the method for quantifying elemental mercury in crude oil according to the present invention, an inert gas is blown into the obtained measurement sample.
上記不活性ガスとしては、窒素ガスや希ガスが好ましく、希ガスとしては、ヘリウムガスやアルゴンガス等から選ばれる一種以上を挙げることができる。 The inert gas is preferably nitrogen gas or a rare gas, and examples of the rare gas include one or more selected from helium gas, argon gas and the like.
本発明に係る原油中の元素水銀の定量方法においては、得られた測定試料１ｍＬあたり
１～２０ｍＬ／分間の割合で不活性ガスを吹き込み、２～１５ｍＬ／分間の割合で不活性ガスを吹き込むことが好ましく、４～１０ｍＬ／分間の割合で不活性ガスを吹き込むことがより好ましい。
In the method for quantifying elemental mercury in crude oil according to the present invention, the inert gas is blown at a rate of 1 to 20 mL / min per 1 mL of the obtained measurement sample, and the inert gas is blown at a rate of 2 to 15 mL / min. Is preferable, and it is more preferable to blow the inert gas at a rate of 4 to 10 mL / min.
本発明に係る原油中の元素水銀の定量方法においては、測定試料に対して不活性ガスを
１５～２４０分間吹き込み、３０～２００分間吹き込むことが好ましく、６０～１８０分間吹き込むことがより好ましい。
In the method for quantifying elemental mercury in crude oil according to the present invention, it is preferable to blow the inert gas into the measurement sample for 15 to 240 minutes, preferably for 30 to 200 minutes, and more preferably for 60 to 180 minutes.
本発明に係る原油中の元素水銀の定量方法においては、測定試料に対して上記量の不活性ガスを上記時間吹き込むことにより、元素水銀を好適に揮発させることができる。
原油中には、元素水銀の他、イオン性水銀化合物や非イオン性水銀化合物が含まれているが、上記処理により元素水銀を揮発させることにより、イオン性水銀化合物や非イオン性水銀化合物が残存することになる。
In the method for quantifying elemental mercury in crude oil according to the present invention, elemental mercury can be suitably volatilized by blowing the above amount of inert gas into the measurement sample for the above time.
In addition to elemental mercury, crude oil contains ionic mercury compounds and non-ionic mercury compounds. However, by volatilizing elemental mercury by the above treatment, ionic mercury compounds and non-ionic mercury compounds remain. Will be done.
本発明に係る原油中の元素水銀の定量方法においては、上記不活性ガスの吹き込み前後における上記測定試料中の全水銀量の差から上記原油中に元々含まれていた元素水銀量を算出する。 In the method for quantifying elemental mercury in crude oil according to the present invention, the amount of elemental mercury originally contained in the crude oil is calculated from the difference in the total amount of mercury in the measurement sample before and after the injection of the inert gas.
本発明に係る原油中の元素水銀の定量方法において、測定試料中の全水銀量は、日本インスツルメンツ（株）製マーキュリーアナライザーを用い、原子蛍光法により測定した値を意味する。 In the method for quantifying elemental mercury in crude oil according to the present invention, the total amount of mercury in the measurement sample means a value measured by an atomic fluorescence method using a Mercury Analyzer manufactured by Nippon Instruments Co., Ltd.
本発明に係る原油中の元素水銀の定量方法においては、測定試料中に不活性ガスを均一に吹き込み、拡散して元素水銀を効果的に揮発させることができることから、原油中の元素水銀を高精度に定量することができる。 In the method for quantifying elemental mercury in crude oil according to the present invention, since the inert gas can be uniformly blown into the measurement sample and diffused to effectively volatilize the elemental mercury, the elemental mercury in the crude oil is high. It can be quantified with accuracy.
なお、本出願書類において、測定試料に対する不活性ガスの吹き込み処理および原油中の元素水銀の定量は、具体的には、特に断らない限り下記条件下にて行うものとする。 In the documents of this application, the treatment of blowing the inert gas into the measurement sample and the quantification of elemental mercury in the crude oil shall be carried out under the following conditions, unless otherwise specified.
（不活性ガスの吹き込みおよび元素水銀の定量法）
１．上述した測定試料５０ｍＬを２５０ｍＬの洗気ビンに装入する。
２．洗気ビンの側面に５０ｍＬの標線をマーキングする。
３．不活性ガス管を洗気ビン入口につなぎ、出口にデジタルガスフローメーターをつける。洗気ビンをアイスバスに浸漬しつつ、クランプで固定する。
４．洗気ビンをアイスバスに約３０分間浸漬した後、不活性ガスの吹き込みを行う。
５．一定時間不活性ガスを吹き込んだ後、不活性ガスの吹き込みを停止し、デジタルガスフローメーターを外した上で洗気ビンをアイスバスから取り出す。
６．洗気ビンの入口からイソオクタンを加え、トータル容積を不活性ガスの吹き込み前の容積と等しくする。
７．上記「６」で得られた試料５０ｍＬについて、日本インスツルメンツ（株）製マーキュリーアナライザーを用い、原子蛍光法により測定試料中の全水銀量を測定する。
８．上記不活性ガスを吹き込む前の測定試料中の全水銀量と上記「７」で得られた全水銀量の差から原油中に元々含まれていた元素水銀量を算出する。
(Blowing of inert gas and quantification method of elemental mercury)
1. 1. Place 50 mL of the above-mentioned measurement sample in a 250 mL wash bottle.
2. 2. Mark the side of the wash bottle with a 50 mL marking.
3. 3. Connect the inert gas pipe to the inlet of the wash bottle and attach a digital gas flow meter to the outlet. Immerse the wash bottle in an ice bath and clamp it.
4. After immersing the wash bottle in an ice bath for about 30 minutes, the inert gas is blown into the bottle.
5. After blowing the inert gas for a certain period of time, the blowing of the inert gas is stopped, the digital gas flow meter is removed, and the washing air bottle is taken out from the ice bath.
6. Add isooctane from the inlet of the wash bottle to make the total volume equal to the volume before the Blow of the inert gas.
7. With respect to 50 mL of the sample obtained in the above "6", the total amount of mercury in the measurement sample is measured by the atomic fluorescence method using a Mercury analyzer manufactured by Nippon Instruments Co., Ltd.
8. The amount of elemental mercury originally contained in the crude oil is calculated from the difference between the total amount of mercury in the measurement sample before blowing the inert gas and the total amount of mercury obtained in "7".
本発明によれば、原油中の元素水銀を高精度に定量する方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for quantifying elemental mercury in crude oil with high accuracy.
次に、本発明に係る原油の選別方法について説明する。
本発明に係る原油の選別方法は、原油を選別する方法であって、
原油に対して炭素数６～１０の芳香族炭化水素化合物を添加して、粘度を０．５～７．５ｍＰａ・ｓに制御した測定試料を調製し、
得られた測定試料１ｍＬあたり１～２０ｍＬ／分間の割合で１５～２４０分間不活性ガスを吹き込み、
前記不活性ガスの吹き込み前後における前記測定試料中の全水銀量の差から前記原油中に元々含まれていた元素水銀量を算出し、
前記元素水銀量の多少に基づいて原油を選別する
ことを特徴とするものである。
Next, a method for selecting crude oil according to the present invention will be described.
The method for sorting crude oil according to the present invention is a method for sorting crude oil.
An aromatic hydrocarbon compound having 6 to 10 carbon atoms was added to the crude oil to prepare a measurement sample having a viscosity controlled to 0.5 to 7.5 mPa · s.
The inert gas was blown into the obtained measurement sample at a rate of 1 to 20 mL / min for 15 to 240 minutes per 1 mL.
The amount of elemental mercury originally contained in the crude oil was calculated from the difference in the total amount of mercury in the measurement sample before and after the injection of the inert gas.
It is characterized in that crude oil is sorted based on the amount of the elemental mercury.
本発明に係る原油の選別方法は、原油に対して芳香族炭化水素化合物を添加した後、原油中に元々含まれていた元素水銀量を算出する工程までは、本発明の元素水銀の定量方法と共通しており、その詳細についても、上述した内容と共通する。 The crude oil sorting method according to the present invention is the method for quantifying elemental mercury of the present invention up to the step of calculating the amount of elemental mercury originally contained in the crude oil after adding an aromatic hydrocarbon compound to the crude oil. The details are also the same as the above-mentioned contents.
本発明に係る原油の選別方法は、原油中に元々含まれていた元素水銀量を算出した後、上記元素水銀量の多少に基づいて原油を選別する。 In the method for selecting crude oil according to the present invention, the amount of elemental mercury originally contained in the crude oil is calculated, and then the crude oil is selected based on the amount of the elemental mercury.
上述したとおり、原油中の水銀量が増加すると、原油を常圧蒸留装置で蒸留処理して得られる、液化石油ガス（ＬＰＧ）、ライトナフサ（Ｌ／Ｎ）、ヘビーナフサ（Ｈ／Ｎ）等の石油留分中の元素水銀濃度も増加し易くなることから、上記液化石油ガス（ＬＰＧ）、ライトナフサ（Ｌ／Ｎ）、ヘビーナフサ（Ｈ／Ｎ）等の石油留分の流通ラインに元素水銀除去装置を設け、活性炭等により元素水銀を除去する必要があり、上記元素水銀除去装置の処理能力の過不足を管理する上で、原油中の元素水銀量を把握することが便宜である。
本発明に係る原油の選別方法においては、原油中の元素水銀の含有量を高精度に分析し得ることから、処理すべき原油を適式に選別した上で、その処理量を制御したり、元素水銀除去装置の処理能力を調整することにより、原油由来の元素水銀を好適に除去して、二次処理装置の腐食を効果的に抑制することができる。
As described above, when the amount of mercury in crude oil increases, liquefied petroleum gas (LPG), light naphtha (L / N), heavy naphtha (H / N), etc. obtained by distilling the crude oil with an atmospheric distillation apparatus, etc. Since the concentration of elemental mercury in petroleum distillates tends to increase, elemental mercury is removed from the distribution lines of petroleum distillates such as liquefied petroleum gas (LPG), light naphtha (L / N), and heavy naphtha (H / N). It is necessary to install an apparatus and remove elemental mercury with activated charcoal or the like, and it is convenient to grasp the amount of elemental mercury in crude oil in order to control the excess or deficiency of the processing capacity of the elemental mercury removing apparatus.
In the crude oil sorting method according to the present invention, since the content of elemental mercury in the crude oil can be analyzed with high accuracy, the crude oil to be treated can be appropriately sorted and then the treated amount can be controlled. By adjusting the processing capacity of the elemental mercury removing device, elemental mercury derived from crude oil can be suitably removed, and corrosion of the secondary processing device can be effectively suppressed.
本発明によれば、原油中の元素水銀の含有量を高精度に分析して原油を選別する方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for selecting crude oil by analyzing the content of elemental mercury in crude oil with high accuracy.
以下に実施例を示して本発明をさらに具体的に説明するが、本発明はこれに制限されるものではない。
なお、以下の実施例および比較例において、原油中の全水銀量や測定試料中の全水銀量は、日本インスツルメンツ（株）製マーキュリーアナライザーを用い、原子蛍光法により測定した値を意味する。
また、以下の実施例および比較例において、原油の粘度および原油に芳香族炭化水素化合物を添加して得られる測定試料の粘度は、ＪＩＳ Ｋ２２８３ 原油及び石油製品－動粘度試験方法及び粘度指数算出方法およびＪＩＳ Ｚ８８０３ 液体の粘度－測定方法の規定により測定される３０℃の温度条件下における粘度を意味する。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
In the following Examples and Comparative Examples, the total amount of mercury in the crude oil and the total amount of mercury in the measurement sample mean the values measured by the atomic fluorescence method using the Mercury Analyzer manufactured by Nippon Instruments Co., Ltd.
Further, in the following Examples and Comparative Examples, the viscosity of the crude oil and the viscosity of the measurement sample obtained by adding the aromatic hydrocarbon compound to the crude oil are determined by JIS K2283 crude oil and petroleum products-kinematic viscosity test method and viscosity index calculation method. And JIS Z8803 Liquid Viscosity-means the viscosity under 30 ° C. temperature conditions as measured by the rules of the measuring method.
（実施例１）
全水銀量が０ｎｇ／ｍＬ、粘度が２０３ｍＰａ・ｓである原油１中に、イオン性水銀化合物である塩化第二水銀を５ｎｇ／ｍＬ、元素水銀を１０ｎｇ／ｍＬ加え、全水銀量を１５ｎｇ／ｍＬに調整した調整原油２５ｍＬに対し、トルエン２５ｍＬを加えて粘度を２ｍＰａ・ｓに制御した測定試料５０ｍＬを調製した。
上記測定試料５０ｍＬを２５０ｍＬの洗気ビンに装入し、洗気ビンの側面に５０ｍＬの標線をマーキングした。不活性ガス管を洗気ビン入口につなぎ、出口にデジタルガスフローメーターを取り付け、洗気ビンをアイスバスに浸漬しつつ、クランプで固定した。上記洗気ビンをアイスバスに約３０分間浸漬し、次いでヘリウムガスを３５０ｍＬ／分間の流速で（測定試料１ｍＬあたり７ｍＬ／分間の割合で）１２０分間吹き込んだ後、ヘリウムガスの吹き込みを停止し、デジタルガスフローメーターを外した上で洗気ビンをアイスバスから取り出し、取り出した洗気ビンの入口からイソオクタンを加え、トータル容積を５０ｍＬに調整した。得られた試料５０ｍＬについて、日本インスツルメンツ（株）製マーキュリーアナライザーを用いて原子蛍光法により測定試料中の全水銀量を測定し、上記不活性ガスを吹き込む前の測定試料中の全水銀量との差に基づいて、調整原油中に元々含まれていた元素水銀量は１０ｎｇ／ｍＬであることが算出できた。
(Example 1)
In crude oil 1 having a total mercury amount of 0 ng / mL and a viscosity of 203 mPa · s, 5 ng / mL of mercuric chloride, which is an ionic mercury compound, and 10 ng / mL of elemental mercury are added, and the total amount of mercury is 15 ng / mL. To 25 mL of the adjusted crude oil adjusted to the above, 25 mL of mercury was added to prepare 50 mL of a measurement sample whose viscosity was controlled to 2 mPa · s.
50 mL of the above measurement sample was placed in a 250 mL air wash bottle, and a 50 mL mark was marked on the side surface of the air wash bottle. The inert gas pipe was connected to the inlet of the washing air bottle, a digital gas flow meter was attached to the outlet, and the washing air bottle was immersed in an ice bath and fixed with a clamp. The above wash bottle was immersed in an ice bath for about 30 minutes, then helium gas was blown at a flow rate of 350 mL / min (at a rate of 7 mL / min per 1 mL of the measurement sample) for 120 minutes, and then the blowing of helium gas was stopped. After removing the digital gas flow meter, the wash air bottle was taken out from the ice bath, and isooctane was added from the inlet of the taken out air wash bottle to adjust the total volume to 50 mL. For 50 mL of the obtained sample, the total amount of mercury in the measurement sample was measured by the atomic fluorescence method using a Mercury analyzer manufactured by Nippon Instruments Co., Ltd., and the total amount of mercury in the measurement sample before blowing the inert gas was the same. Based on the difference, it was possible to calculate that the amount of elemental mercury originally contained in the adjusted crude oil was 10 ng / mL.
（実施例２）
全水銀量が１０ｎｇ／ｍＬ、粘度が２０３ｍＰａ・ｓである原油２中に、元素水銀を１０ｎｇ／ｍＬ加え、全水銀量を２０ｎｇ／ｍＬに調整した調整原油２５ｍＬに対し、トルエン２５ｍＬを加えて粘度を２ｍＰａ・ｓに制御した測定試料５０ｍＬを調製した。
上記測定試料５０ｍＬを２５０ｍＬの洗気ビンに装入し、洗気ビンの側面に５０ｍＬの標線をマーキングした。不活性ガス管を洗気ビン入口につなぎ、出口にデジタルガスフローメーターを取り付け、洗気ビンをアイスバスに浸漬しつつ、クランプで固定した。上記洗気ビンをアイスバスに約３０分間浸漬し、次いでヘリウムガスを３５０ｍＬ／分間の流速で（測定試料１ｍＬあたり７ｍＬ／分間の割合で）１２０分間吹き込んだ後、ヘリウムガスの吹き込みを停止し、デジタルガスフローメーターを外した上で洗気ビンをアイスバスから取り出し、取り出した洗気ビンの入口からイソオクタンを加え、トータル容積を５０ｍＬに調整した。得られた試料５０ｍＬについて、日本インスツルメンツ（株）製マーキュリーアナライザーを用い、原子蛍光法により測定試料中の全水銀量を測定し、上記不活性ガスを吹き込む前の測定試料中の全水銀量との差に基づいて、調整原油中に元々含まれていた元素水銀量が１５ｎｇ／ｍＬであることが算出できた。
(Example 2)
Add 10 ng / mL of elemental mercury to crude oil 2 having a total mercury content of 10 ng / mL and a viscosity of 203 mPa · s, and add 25 mL of toluene to 25 mL of adjusted crude oil adjusted to a total mercury content of 20 ng / mL. To 2 mPa · s, 50 mL of the measurement sample was prepared.
50 mL of the above measurement sample was placed in a 250 mL air wash bottle, and a 50 mL mark was marked on the side surface of the air wash bottle. The inert gas pipe was connected to the inlet of the washing air bottle, a digital gas flow meter was attached to the outlet, and the washing air bottle was immersed in an ice bath and fixed with a clamp. The above wash bottle was immersed in an ice bath for about 30 minutes, then helium gas was blown at a flow rate of 350 mL / min (at a rate of 7 mL / min per 1 mL of the measurement sample) for 120 minutes, and then the blowing of helium gas was stopped. After removing the digital gas flow meter, the wash air bottle was taken out from the ice bath, and isooctane was added from the inlet of the taken out air wash bottle to adjust the total volume to 50 mL. About 50 mL of the obtained sample, the total amount of mercury in the measurement sample was measured by the atomic fluorescence method using a Mercury analyzer manufactured by Nippon Instruments Co., Ltd., and the total amount of mercury in the measurement sample before blowing the inert gas was used. Based on the difference, it was possible to calculate that the amount of elemental mercury originally contained in the adjusted crude oil was 15 ng / mL.
（実施例３）
全水銀量が１０ｎｇ／ｍＬ、粘度が２０３ｍＰａ・ｓである原油２を２５ｍＬ採取し、さらにトルエン２５ｍＬを加えて粘度を２ｍＰａ・ｓに制御した測定試料５０ｍＬを調製した。
上記測定試料５０ｍＬを２５０ｍＬの洗気ビンに装入し、洗気ビンの側面に５０ｍＬの標線をマーキングした。不活性ガス管を洗気ビン入口につなぎ、出口にデジタルガスフローメーターを取り付け、洗気ビンをアイスバスに浸漬しつつ、クランプで固定した。上記洗気ビンをアイスバスに約３０分間浸漬し、次いでヘリウムガスを３５０ｍＬ／分間の流速で（測定試料１ｍＬあたり７ｍＬ／分間の割合で）１２０分間吹き込んだ後、ヘリウムガスの吹き込みを停止し、デジタルガスフローメーターを外した上で洗気ビンをアイスバスから取り出し、取り出した洗気ビンの入口からイソオクタンを加え、トータル容積を５０ｍＬに調整した。得られた試料５０ｍＬについて、日本インスツルメンツ（株）製マーキュリーアナライザーを用い、原子蛍光法により測定試料中の全水銀量を測定し、上記不活性ガスを吹き込む前の測定試料中の全水銀量との差に基づいて、原油２中に元々含まれていた元素水銀量が５ｎｇ／ｍＬであることが算出できた。
(Example 3)
25 mL of crude oil 2 having a total mercury amount of 10 ng / mL and a viscosity of 203 mPa · s was collected, and 25 mL of toluene was further added to prepare 50 mL of a measurement sample whose viscosity was controlled to 2 mPa · s.
50 mL of the above measurement sample was placed in a 250 mL air wash bottle, and a 50 mL mark was marked on the side surface of the air wash bottle. The inert gas pipe was connected to the inlet of the washing air bottle, a digital gas flow meter was attached to the outlet, and the washing air bottle was immersed in an ice bath and fixed with a clamp. The above wash bottle was immersed in an ice bath for about 30 minutes, then helium gas was blown at a flow rate of 350 mL / min (at a rate of 7 mL / min per 1 mL of the measurement sample) for 120 minutes, and then the blowing of helium gas was stopped. After removing the digital gas flow meter, the wash air bottle was taken out from the ice bath, and isooctane was added from the inlet of the taken out air wash bottle to adjust the total volume to 50 mL. About 50 mL of the obtained sample, the total amount of mercury in the measurement sample was measured by the atomic fluorescence method using a Mercury analyzer manufactured by Nippon Instruments Co., Ltd., and the total amount of mercury in the measurement sample before blowing the inert gas was used. Based on the difference, it was possible to calculate that the amount of elemental mercury originally contained in the crude oil 2 was 5 ng / mL.
（実施例４）
実施例３において、全水銀量が１０ｎｇ／ｍＬ、粘度が２０３ｍＰａ・ｓである２５ｍＬの原油２に対し、トルエン２５ｍＬを加えることに代えてキシレン２５ｍＬを加え粘度を２ｍＰａ・ｓに制御した測定試料５０ｍＬを調製した以外は、実施例３と同様の条件でヘリウムガスの吹き込みを行い、ヘリウムガスを吹き込む前の測定試料中の全水銀量との差に基づいて、原油２中に元々含まれていた元素水銀量を算出したところ、元素水銀量が５ｎｇ／ｍＬであることが算出できた。
(Example 4)
In Example 3, 50 mL of a measurement sample whose viscosity was controlled to 2 mPa · s by adding 25 mL of xylene instead of 25 mL of toluene to 25 mL of crude oil 2 having a total mercury amount of 10 ng / mL and a viscosity of 203 mPa · s. The helium gas was blown under the same conditions as in Example 3 except that the amount of mercury was originally contained in the crude oil 2 based on the difference from the total amount of mercury in the measurement sample before the helium gas was blown. When the amount of elemental mercury was calculated, it was possible to calculate that the amount of elemental mercury was 5 ng / mL.
実施例１～実施例４の実験条件および結果を以下表１および表２に記載する。 The experimental conditions and results of Examples 1 to 4 are shown in Tables 1 and 2 below.
表１および表２より、実施例１においては、原油に対して特定の芳香族炭化水素化合物を添加して、粘度を所定範囲に制御した測定試料を調製し、得られた測定試料１ｍＬあたり所定の流量で所定時間不活性ガスを吹き込み、不活性ガスの吹き込み前後における測定試料中の全水銀量の差から原油中に元々含まれていた元素水銀量を算出していることから、元素水銀量を１０ｎｇ／ｍＬに調整した調整原油中の元素水銀量が１０ｎｇ／ｍＬと高い精度で測定できていることが分かる。
また、表１および表２より、実施例２～実施例４においても、原油に対して特定の芳香族炭化水素化合物を添加して、粘度を所定範囲に制御した測定試料を調製し、得られた測定試料１ｍＬあたり所定の流量で所定時間不活性ガスを吹き込み、不活性ガスの吹き込み前後における測定試料中の全水銀量の差から原油中に元々含まれていた元素水銀量を算出していることから、原油２中に元々含まれていた元素水銀量が５ｎｇ／ｍＬであることが高い精度で測定できていることが分かる。
From Tables 1 and 2, in Example 1, a specific aromatic hydrocarbon compound was added to the crude oil to prepare a measurement sample whose viscosity was controlled within a predetermined range, and a predetermined measurement sample was prepared per 1 mL of the obtained measurement sample. Since the amount of elemental mercury originally contained in the crude oil is calculated from the difference in the total amount of mercury in the measurement sample before and after the injection of the inert gas at the flow rate of It can be seen that the amount of elemental mercury in the adjusted crude oil adjusted to 10 ng / mL can be measured with high accuracy of 10 ng / mL.
Further, from Tables 1 and 2, also in Examples 2 to 4, a specific aromatic hydrocarbon compound was added to the crude oil to prepare a measurement sample whose viscosity was controlled within a predetermined range, and obtained. The inert gas is blown at a predetermined flow rate per 1 mL of the measured sample, and the amount of elemental hydrocarbon originally contained in the crude oil is calculated from the difference in the total amount of hydrocarbon in the measured sample before and after the blowing of the inert gas. From this, it can be seen that the amount of elemental hydrocarbon originally contained in the crude oil 2 is 5 ng / mL, which can be measured with high accuracy.
（比較例１）
実施例３において、全水銀量が１０ｎｇ／ｍＬ、粘度が２０３ｍＰａ・ｓである２５ｍＬの原油２に対し、トルエン２５ｍＬを加えることに代えてヘプタン２５ｍＬを加えて粘度を制御した測定試料５０ｍＬを調製した以外は、実施例３と同様の条件でヘリウムガスの吹き込みを行おうとしたところ、原油２に対しヘプタンを添加した時点でスラッジが大量に析出して容器の内壁に大量に吸着してしまい、得られた測定試料の粘度を測定することができなかった。
また、得られた測定試料に対してヘリウムガスを吹き込もうとしても、バブリングさせることができなかった。
(Comparative Example 1)
In Example 3, 50 mL of a measurement sample whose viscosity was controlled was prepared by adding 25 mL of heptane instead of 25 mL of toluene to 25 mL of crude oil 2 having a total mercury amount of 10 ng / mL and a viscosity of 203 mPa · s. Except for the above, when an attempt was made to blow helium gas under the same conditions as in Example 3, a large amount of sludge was deposited when heptane was added to the crude oil 2, and a large amount was adsorbed on the inner wall of the container. It was not possible to measure the viscosity of the measured sample.
Further, even if an attempt was made to blow helium gas into the obtained measurement sample, bubbling could not be performed.
（比較例２）
実施例３において、全水銀量が１０ｎｇ／ｍＬ、粘度が２０３ｍＰａ・ｓである２５ｍＬの原油２に対し、トルエン２５ｍＬを加えることに代えてイソオクタン２５ｍＬを加えて粘度を制御した測定試料５０ｍＬを調製した以外は、実施例３と同様の条件でヘリウムガスの吹き込みを行おうとしたところ、原油２に対しイソオクタンを添加した時点でスラッジが大量に析出して容器の内壁に大量に吸着してしまい、得られた測定試料の粘度を測定することができなかった。
また、得られた測定試料に対してヘリウムガスを吹き込もうとしても、バブリングさせることができなかった。
(Comparative Example 2)
In Example 3, 50 mL of a measurement sample whose viscosity was controlled was prepared by adding 25 mL of isooctane instead of 25 mL of toluene to 25 mL of crude oil 2 having a total mercury amount of 10 ng / mL and a viscosity of 203 mPa · s. Except for the above, when an attempt was made to blow helium gas under the same conditions as in Example 3, a large amount of sludge was deposited when isooctane was added to the crude oil 2, and a large amount was adsorbed on the inner wall of the container. It was not possible to measure the viscosity of the measured sample.
Further, even if an attempt was made to blow helium gas into the obtained measurement sample, bubbling could not be performed.
（比較例３）
実施例３において、全水銀量が１０ｎｇ／ｍＬ、粘度が２０３ｍＰａ・ｓである２５ｍＬの原油２に対し、トルエン２５ｍＬを加えることに代えてトルエン０．５ｍＬを加えて粘度４３ｍＰａ・ｓの測定試料２５．５ｍＬを調製した。
上記測定試料２５．５ｍＬを２５０ｍＬの洗気ビンに装入し、洗気ビンの側面に２５．５ｍＬの標線をマーキングした。不活性ガス管を洗気ビン入口につなぎ、出口にデジタルガスフローメーターを取り付け、洗気ビンをアイスバスに浸漬しつつ、クランプで固定した。上記洗気ビンをアイスバスに約３０分間浸漬し、次いでヘリウムガスを３５０ｍＬ／分間の流速で（測定試料１ｍＬあたり１３．７ｍＬ／分間の割合で）１２０分間吹き込んだ後、ヘリウムガスの吹き込みを停止し、デジタルガスフローメーターを外した上で洗気ビンをアイスバスから取り出し、取り出した洗気ビンの入口からイソオクタンを加え、トータル容積を２５．５ｍＬに調整した。得られた試料２５．５ｍＬについて、日本インスツルメンツ（株）製マーキュリーアナライザーを用い、原子蛍光法により測定試料中の全水銀量を測定し、上記不活性ガスを吹き込む前の測定試料中の全水銀量との差に基づいて、原油２中に元々含まれていた元素水銀量を算出したところ、元素水銀量が１ｎｇ／ｍＬであることが算出できた。
(Comparative Example 3)
In Example 3, a measurement sample 25 having a viscosity of 43 mPa · s was obtained by adding 0.5 mL of toluene instead of adding 25 mL of toluene to 25 mL of crude oil 2 having a total mercury amount of 10 ng / mL and a viscosity of 203 mPa · s. .5 mL was prepared.
25.5 mL of the above measurement sample was placed in a 250 mL air wash bottle, and a 25.5 mL marked line was marked on the side surface of the air wash bottle. The inert gas pipe was connected to the inlet of the washing air bottle, a digital gas flow meter was attached to the outlet, and the washing air bottle was immersed in an ice bath and fixed with a clamp. Immerse the above wash bottle in an ice bath for about 30 minutes, then blow helium gas at a flow rate of 350 mL / min (at a rate of 13.7 mL / min per 1 mL of measurement sample) for 120 minutes, and then stop blowing helium gas. Then, after removing the digital gas flow meter, the wash air bottle was taken out from the ice bath, and isooctane was added from the inlet of the taken out air wash bottle to adjust the total volume to 25.5 mL. About 25.5 mL of the obtained sample, the total amount of mercury in the measurement sample was measured by the atomic fluorescence method using a Mercury analyzer manufactured by Nippon Instruments Co., Ltd., and the total amount of mercury in the measurement sample before blowing the inert gas. When the amount of elemental mercury originally contained in the crude oil 2 was calculated based on the difference from the above, it was possible to calculate that the amount of elemental mercury was 1 ng / mL.
（比較例４）
実施例３において、ヘリウムガスの吹き込み流量を３５０ｍＬ／分間から４０ｍＬ／分間に変更した（測定試料１ｍＬあたり０．８ｍＬ／分間の吹き込み流量に変更した）以外は実施例３と同様にして試験を行い、上記不活性ガスを吹き込む前の測定試料中の全水銀量との差に基づいて、原油２中に元々含まれていた元素水銀量を算出したところ、元素水銀量が１ｎｇ／ｍＬであることが算出できた。
(Comparative Example 4)
In Example 3, the test was carried out in the same manner as in Example 3 except that the blowing flow rate of helium gas was changed from 350 mL / min to 40 mL / min (changed to a blowing flow rate of 0.8 mL / min per 1 mL of the measurement sample). The amount of elemental mercury originally contained in the crude oil 2 was calculated based on the difference from the total amount of mercury in the measurement sample before blowing the inert gas. As a result, the amount of elemental mercury was 1 ng / mL. Was calculated.
（比較例５）
実施例３において、ヘリウムガスの吹き込み流量を３５０ｍＬ／分間から１０５０ｍＬ／分間に変更した（測定試料１ｍＬあたり２１ｍＬ／分間の吹き込み流量に変更した）以外は実施例３と同様にして試験を行い、上記不活性ガスを吹き込む前の測定試料中の全水銀量との差に基づいて、原油２中に元々含まれていた元素水銀量を算出したところ、元素水銀量が２ｎｇ／ｍＬであることが算出できた。
(Comparative Example 5)
In Example 3, the test was carried out in the same manner as in Example 3 except that the blowing flow rate of helium gas was changed from 350 mL / min to 1050 mL / min (changed to the blowing flow rate of 21 mL / min per 1 mL of the measurement sample). When the amount of elemental mercury originally contained in the crude oil 2 was calculated based on the difference from the total amount of mercury in the measurement sample before blowing the inert gas, it was calculated that the amount of elemental mercury was 2 ng / mL. did it.
（比較例６）
実施例３において、ヘリウムガスの吹き込み時間を１２０分間から１０分間に変更した以外は実施例３と同様にして試験を行い、上記不活性ガスを吹き込む前の測定試料中の全水銀量との差に基づいて、原油２中に元々含まれていた元素水銀量を算出したところ、元素水銀量が１ｎｇ／ｍＬであることが算出できた。
(Comparative Example 6)
In Example 3, the test was carried out in the same manner as in Example 3 except that the blowing time of helium gas was changed from 120 minutes to 10 minutes, and the difference from the total amount of mercury in the measurement sample before blowing the inert gas. When the amount of elemental mercury originally contained in the crude oil 2 was calculated based on the above, it was possible to calculate that the amount of elemental mercury was 1 ng / mL.
（比較例７）
実施例３において、全水銀量が１０ｎｇ／ｍＬ、粘度が２０３ｍＰａ・ｓである２５ｍＬの原油２に対し、トルエン２５ｍＬを加えることに代えてトルエン５００ｍＬを加えて粘度２ｍＰａ・ｓ未満の測定試料５２５ｍＬを調製した。
上記測定試料５０ｍＬを２５０ｍＬの洗気ビンに装入し、洗気ビンの側面に５０ｍＬの標線をマーキングした。不活性ガス管を洗気ビン入口につなぎ、出口にデジタルガスフローメーターを取り付け、洗気ビンをアイスバスに浸漬しつつ、クランプで固定した。上記洗気ビンをアイスバスに約３０分間浸漬し、次いでヘリウムガスを３５０ｍＬ／分間の流速で（測定試料１ｍＬあたり７ｍＬ／分間の割合で）１２０分間吹き込んだ後、ヘリウムガスの吹き込みを停止し、デジタルガスフローメーターを外した上で洗気ビンをアイスバスから取り出し、取り出した洗気ビンの入口からイソオクタンを加え、トータル容積を５０ｍＬに調整した。得られた試料５０ｍＬについて、日本インスツルメンツ（株）製マーキュリーアナライザーを用い、原子蛍光法により測定試料中の全水銀量を測定しようとしたところ、残存する水銀の濃度が低過ぎて定量下限未満となり、原油２中に元々含まれていた元素水銀量を算出することができなかった。
(Comparative Example 7)
In Example 3, to 25 mL of crude oil 2 having a total mercury amount of 10 ng / mL and a viscosity of 203 mPa · s, 500 mL of toluene was added instead of 25 mL of toluene to obtain 525 mL of a measurement sample having a viscosity of less than 2 mPa · s. Prepared.
50 mL of the above measurement sample was placed in a 250 mL air wash bottle, and a 50 mL mark was marked on the side surface of the air wash bottle. The inert gas pipe was connected to the inlet of the washing air bottle, a digital gas flow meter was attached to the outlet, and the washing air bottle was immersed in an ice bath and fixed with a clamp. The above wash bottle was immersed in an ice bath for about 30 minutes, then helium gas was blown at a flow rate of 350 mL / min (at a rate of 7 mL / min per 1 mL of the measurement sample) for 120 minutes, and then the blowing of helium gas was stopped. After removing the digital gas flow meter, the wash air bottle was taken out from the ice bath, and isooctane was added from the inlet of the taken out air wash bottle to adjust the total volume to 50 mL. When we tried to measure the total amount of mercury in the measured sample by the atomic fluorescence method using a Mercury Analyzer manufactured by Nippon Instruments Co., Ltd. for 50 mL of the obtained sample, the concentration of residual mercury was too low and was below the lower limit of quantification. It was not possible to calculate the amount of elemental mercury originally contained in the crude oil 2.
比較例１～比較例７の実験条件および結果を以下表３および表４に記載する。 The experimental conditions and results of Comparative Examples 1 to 7 are shown in Tables 3 and 4 below.
表３および表４より、比較例１～比較例７においては、原油に対して特定の芳香族炭化水素化合物を添加していなかったり（比較例１および比較例２）、測定試料の粘度が所定範囲に制御されていなかったり（比較例３および比較例７）、得られた測定試料１ｍＬあたりの不活性ガスの流量または吹き込み時間が所定範囲外であることから（比較例４～比較例６）、原油２中の元素水銀量を高い精度で測定できなかったり、測定自体が困難であることが分かる。 From Tables 3 and 4, in Comparative Examples 1 to 7, a specific aromatic hydrocarbon compound was not added to the crude oil (Comparative Example 1 and Comparative Example 2), and the viscosity of the measurement sample was predetermined. The range is not controlled (Comparative Example 3 and Comparative Example 7), or the flow rate or blowing time of the inert gas per 1 mL of the obtained measurement sample is out of the predetermined range (Comparative Example 4 to Comparative Example 6). It can be seen that the amount of elemental mercury in the crude oil 2 cannot be measured with high accuracy, or the measurement itself is difficult.
本発明によれば、原油中の元素水銀を高精度に定量する方法および原油中の元素水銀の含有量を高精度に分析して原油を選別する方法を提供することができる。
INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for quantifying elemental mercury in crude oil with high accuracy and a method for selecting crude oil by analyzing the content of elemental mercury in crude oil with high accuracy.
Claims (4)
原油に対して炭素数６～１０の芳香族炭化水素化合物を添加して、粘度を０．５～７．５ｍＰａ・ｓに制御した測定試料を調製し、
得られた測定試料１ｍＬあたり１～２０ｍＬ／分間の割合で１５～２４０分間不活性ガスを吹き込み、
前記不活性ガスの吹き込み前後における前記測定試料中の全水銀量の差から前記原油中に元々含まれていた元素水銀量を算出する
ことを特徴とする原油中の元素水銀の定量方法。 A method for quantifying elemental mercury in crude oil.
An aromatic hydrocarbon compound having 6 to 10 carbon atoms was added to the crude oil to prepare a measurement sample having a viscosity controlled to 0.5 to 7.5 mPa · s.
The inert gas was blown into the obtained measurement sample at a rate of 1 to 20 mL / min for 15 to 240 minutes per 1 mL.
A method for quantifying elemental mercury in crude oil, which comprises calculating the amount of elemental mercury originally contained in the crude oil from the difference in the total amount of mercury in the measurement sample before and after blowing the inert gas.
原油に対して炭素数６～１０の芳香族炭化水素化合物を添加して、粘度を０．５～７．５ｍＰａ・ｓに制御した測定試料を調製し、
得られた測定試料１ｍＬあたり１～２０ｍＬ／分間の割合で１５～２４０分間不活性ガスを吹き込み、
前記不活性ガスの吹き込み前後における前記測定試料中の全水銀量の差から前記原油中に元々含まれていた元素水銀量を算出し、
前記元素水銀量の多少に基づいて原油を選別する
ことを特徴とする原油の選別方法。 It ’s a method of sorting crude oil.
An aromatic hydrocarbon compound having 6 to 10 carbon atoms was added to the crude oil to prepare a measurement sample having a viscosity controlled to 0.5 to 7.5 mPa · s.
The inert gas was blown into the obtained measurement sample at a rate of 1 to 20 mL / min for 15 to 240 minutes per 1 mL.
The amount of elemental mercury originally contained in the crude oil was calculated from the difference in the total amount of mercury in the measurement sample before and after the injection of the inert gas.
A method for selecting crude oil, which comprises selecting crude oil based on the amount of elemental mercury.
The method for selecting crude oil according to claim 3, wherein the measurement sample is further filtered after the measurement sample is prepared and before the inert gas is blown into the measurement sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018054046A JP7000217B2 (en) | 2018-03-22 | 2018-03-22 | Quantitative method of elemental mercury in crude oil and selection method of crude oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018054046A JP7000217B2 (en) | 2018-03-22 | 2018-03-22 | Quantitative method of elemental mercury in crude oil and selection method of crude oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019168237A JP2019168237A (en) | 2019-10-03 |
| JP7000217B2 true JP7000217B2 (en) | 2022-01-19 |
Family
ID=68108166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018054046A Active JP7000217B2 (en) | 2018-03-22 | 2018-03-22 | Quantitative method of elemental mercury in crude oil and selection method of crude oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7000217B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005233756A (en) | 2004-02-19 | 2005-09-02 | Japan Petroleum Exploration Co Ltd | Method for measuring concentration of mercury in hydrocarbon |
| WO2009028149A1 (en) | 2007-08-27 | 2009-03-05 | Nippon Instruments Corporation | Mercury measuring apparatus for measuring mercury contained in sample composed mainly of hydrocarbon |
| JP2011116700A (en) | 2009-12-03 | 2011-06-16 | Kakei Gakuen | Mercury scavenger and method for excreting mercury in body |
| JP5026592B2 (en) | 2007-07-06 | 2012-09-12 | エルジー エレクトロニクス インコーポレイティド | Method for performing cell search in a wireless communication system |
| US20140371105A1 (en) | 2013-06-12 | 2014-12-18 | Chevron U.S.A. Inc. | Mercury sensor for detecting, differentiating, and measuring organic and inorganic mercury compounds |
-
2018
- 2018-03-22 JP JP2018054046A patent/JP7000217B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005233756A (en) | 2004-02-19 | 2005-09-02 | Japan Petroleum Exploration Co Ltd | Method for measuring concentration of mercury in hydrocarbon |
| JP5026592B2 (en) | 2007-07-06 | 2012-09-12 | エルジー エレクトロニクス インコーポレイティド | Method for performing cell search in a wireless communication system |
| WO2009028149A1 (en) | 2007-08-27 | 2009-03-05 | Nippon Instruments Corporation | Mercury measuring apparatus for measuring mercury contained in sample composed mainly of hydrocarbon |
| JP2011116700A (en) | 2009-12-03 | 2011-06-16 | Kakei Gakuen | Mercury scavenger and method for excreting mercury in body |
| US20140371105A1 (en) | 2013-06-12 | 2014-12-18 | Chevron U.S.A. Inc. | Mercury sensor for detecting, differentiating, and measuring organic and inorganic mercury compounds |
Non-Patent Citations (1)
| Title |
|---|
| SHAFAWI Azman et al.，Determination of total mercury in hydrocarbons and natural gas condensate by atomic fluorescence spectrometry，Analyst，1999年，Vol.124，pp.185-189 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019168237A (en) | 2019-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2577781A1 (en) | Refinery crude unit performance monitoring using advanced analytic techniques for raw material quality prediction | |
| TW554039B (en) | Method and apparatus for refining heavy oil | |
| US9029160B2 (en) | Method for determining the content of hydrogen sulfide in crude and residual oils | |
| JP7000217B2 (en) | Quantitative method of elemental mercury in crude oil and selection method of crude oil | |
| EP1571447A1 (en) | Process for measuring mercury concentration within hydrocarbons | |
| JP5373695B2 (en) | Sulfur online analyzer | |
| ATE462642T1 (en) | METHOD AND APPARATUS FOR LOADING PETROLEUM | |
| US9523043B2 (en) | Process, method, and system for removing heavy metals from fluids | |
| NO163906B (en) | PROCEDURES FOR REFINING USED OILS. | |
| US10746659B2 (en) | Determination of organic silicon in hydrocarbonaceous streams | |
| US2761815A (en) | Preparation of specialty naphthas from high sulfur crudes | |
| JP6832953B2 (en) | How to disperse the by-products formed in the dilution steam system | |
| US7402192B2 (en) | Method and device for continuously treating waste water of industrial origin by water vapour stripping | |
| Adetoro et al. | Characterization of Nigerian crude oil using ASTM86 test method for design of mini refinery | |
| CN111830166A (en) | Detection method and application of normal alkane in microcrystalline wax | |
| US3562151A (en) | Demetalation with cyanide ion | |
| JPH06166640A (en) | Distillation of benzene | |
| RU2777703C1 (en) | Method for preparing samples of oilfield chemicals for the determination of organochlorine compounds | |
| US10633600B2 (en) | Process for removing mercury from crude oil | |
| US20200191762A1 (en) | Procedure for measuring total reactive sulfur | |
| Jadoon et al. | Determination of the total sulphur content in Khurmala and Guwayar oil fields of Kurdistan region, Iraq | |
| Guo et al. | Characterization of chemical and carbon isotopic compositions of gases during thermochemical sulfate reduction and implications for gas origin and content | |
| US2971368A (en) | Determination of concentration of components of a gaseous mixture | |
| Bieber et al. | Volatility of Metal-Porphyrin Complexes in Petroleum. | |
| JP2022057001A (en) | Pretreatment method for measuring concentration of mercury contained in hydrocarbon mixture, and method of measuring concentration of mercury contained in hydrocarbon mixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210204 |
|
| TRDD | Decision of grant or rejection written | ||
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20211215 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20211221 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20211223 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7000217 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |