JPH0249655B2 - - Google Patents
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- Publication number
- JPH0249655B2 JPH0249655B2 JP58086700A JP8670083A JPH0249655B2 JP H0249655 B2 JPH0249655 B2 JP H0249655B2 JP 58086700 A JP58086700 A JP 58086700A JP 8670083 A JP8670083 A JP 8670083A JP H0249655 B2 JPH0249655 B2 JP H0249655B2
- Authority
- JP
- Japan
- Prior art keywords
- measurement sample
- salt
- crude oil
- salinity
- standard measurement
- 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.)
- Expired - Lifetime
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2823—Raw oil, drilling fluid or polyphasic mixtures
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pathology (AREA)
- Immunology (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Medicinal Chemistry (AREA)
- Food Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Description
本発明は原油中に含まれる高濃度塩分の測定方
法に関する。
従来、原油中の塩分測定方法としては
ASTMD−3230「スタンダード・テスト・メソツ
ド・フオー・ソルト・イン・クルード・オイル
（Standard Test Method for Salt in Crude
Oil）」がある。この測定方法（以下ASTM法と
する）は、中性油、キシレン、混合アルコール溶
液（ブタノール、メタノール、蒸留水を体積比
630：370：３で混合したもの）及び塩（CaCl2，
MgCl2，NaClを混合比10：20：70で混合したも
の）を適量ずつ混合した標準測定試料の導電率と
塩分濃度との関係を表わした検量線を用いて、被
測定原油にキシレン、混合アルコール溶液を適量
ずつ混合した測定試料の導電率から被測定原油の
塩分濃度を上記塩類の等価濃度として定量する。
しかし、このASTM法では428mg／の塩分濃度
までしか規定がなく、それ以上の原油中の塩分濃
度は定量できなかつた。そこで、このASTM法
による標準測定試料を用いて429mg／以上の高
塩分濃度における塩分濃度と導電率との関係を求
めたところ傾きが小さく精度が悪いため429mg／
以上の塩分濃度の測定は実質上不可能であるこ
とが判明した。そこで標準測定試料の組成を種々
変更して測定を重ね、水分量を0.3％，0.5％，1.0
％，1.5％に増加して導電率を測定したところ、
末だこれらの水分量では第１図に示すように、あ
る塩分濃度の値から導電率が変化しなくなる。従
つて、塩分濃度変化に応ずる導電率の変化がない
ので塩分濃度の測定が不可能であつた。ところ
が、さらに水分量を増加して2.0％，2.5％，3.0％
としたところ、塩分濃度と導電率との関係は意外
にも同一の勾配の直線となり、しかも水分量に依
存しないことを見出した。すなわち、混合アルコ
ール溶液成分中の蒸留水添加量を調節して標準測
定試料の水分量が2.0〜3.0％の範囲となるような
組成とすることによつて、直線のしかも同一の検
量線を用いて原油中に微少量（約0.1％程度）の
水分が存在してもその水分に無関係に塩分濃度の
定量が可能であることが判明した。こうしてこれ
まで定量できなかつた原油中の429mg／〜5000
mg／の高濃度塩分の測定が可能となる。
なお、この高塩分濃度では水分量が2.0％以下
の場合、例えば顕著には1.0％の場合第１図にお
いて塩分濃度3000mg／以上においては、塩分濃
度が増加しても導電率に変化がみられない。すな
わち、導電率を測定して塩分濃度を知るというこ
とが不可能である。また、水分量を3.0％を越え
て増加したところ、標準測定試料の調製過程で水
の油に対する溶解度の限界のため試薬類が２相に
分離するという現象を起し、水分量を3.0％以上
とすることは好ましくないことが判つた。次に、
水分量が2.0〜3.0％の標準測定試料を用いて塩分
濃度428mg／以下の試料について測定したが、
データはばらつきASTM法に比べて再現性がや
や乏しかつた。
本発明は上記の事実に基づき、前記した
ASTM法では測定できない原油中の429mg／〜
5000mg／という高濃度域塩分を測定する方法を
提供することを目的とする。
本発明は、中性油、キシレン、混合アルコール
溶液及び塩を含む水性液を所定量ずつ混合した標
準測定試料の導電率を測定して検量線を作成し、
上記標準測定試料中の中性油の代りに被測定原油
を使用し塩を含まない水性液及び混合アルコール
の代りにそれらの合計量と同量の混合アルコール
を使用して調製した測定試料の導電率を求め、求
めた導電率を上記検量線に適用して被測定原油の
塩分濃度を定量する塩分測定方法において、上記
標準測定試料中の水分量を2.0〜3.0体積％とする
ことを特徴とする、原油中の429mg／以上の高
濃度塩分測定方法に存する。
以下、実施例に基づき本発明をさらに具体的に
説明する。
実施例
(1) 本発明の測定方法に用いる各種試薬の調製を
下記のように行なつた。
イ 混合アルコール溶液
特級１−ブタノール610ml、特級メタノール
360ml、及び蒸留水40mlを混合する。
ロ キシレン
JIS1級品を使用する。
ハ 中性油
潤滑油を使用する。
ニ 塩化カルシウム溶液（2.5ｇ／100ml）
塩化カルシウム（CaCl2）2.5ｇを蒸留水25ml
に溶かし、メスフラスコ100mlに混合アルコ
ール溶液で標線まで希釈する。
ホ 塩化マグネシウム溶液（2.5ｇ／100ml）
塩化マグネシウム（MgCl2）2.5ｇを蒸留水
25mlに溶かし、メスフラスコ100mlに混合ア
ルコール溶液で標線まで希釈する。
ヘ 塩化ナトリウム溶液（2.5ｇ／100ml）
塩化ナトリウム（NaCl）2.5ｇを蒸留水25ml
に溶かし、メスフラスコ100mlに混合アルコ
ール溶液で標線まで希釈する。
ト 塩分溶液（塩分1.0mg／ml）
塩化カルシウム溶液10ml、塩化マグネシウム
溶液20ml、及び塩化ナトリウム溶液70mlをメ
スフラスコ100mlに採り混合する。さらに、
この混合溶液40mlをメスフラスコ1000mlに分
取し、混合アルコール溶液で標線まで希釈し
て濃度1.0mg／mlの塩分溶液とする。この塩
分溶液１mlがすなわち塩分１mgに相当する。
(2) 検量線作成のための標準測定試料は前述のキ
シレン、中性油、塩分溶液、及び混合アルコー
ル溶液を次の第１表に示す量で混合することに
よつて調製した。得られた標準測定試料の塩分
濃度は第１表に示す通りである。なお、塩分濃
度（mg／）は中性油（又は原油）の単位体積
（）に対する塩分の重量（mg）である。
The present invention relates to a method for measuring high concentration salts contained in crude oil. Conventionally, the method for measuring salt content in crude oil is
ASTMD-3230 “Standard Test Method for Salt in Crude Oil”
Oil)" is available. This measurement method (hereinafter referred to as ASTM method) uses neutral oil, xylene, and a mixed alcohol solution (butanol, methanol, and distilled water in volume ratios).
630:370:3 mixture) and salt (CaCl 2 ,
Using a calibration curve representing the relationship between conductivity and salinity of a standard measurement sample in which appropriate amounts of MgCl 2 and NaCl (MgCl 2 , NaCl mixed at a mixing ratio of 10:20:70) were mixed, xylene and The salt concentration of the crude oil to be measured is determined as the equivalent concentration of the above salts from the conductivity of the measurement sample mixed with an appropriate amount of alcohol solution.
However, this ASTM method only specifies a salt concentration of 428 mg/ml, and it was not possible to quantify the salt concentration in crude oil beyond that level. Therefore, when we calculated the relationship between salt concentration and conductivity at high salinity concentrations of 429 mg/ or more using the standard measurement sample by this ASTM method, the slope was small and the accuracy was low.
It turned out that it is virtually impossible to measure the above salinity concentration. Therefore, we repeated measurements by changing the composition of the standard measurement sample, and the moisture content was determined to be 0.3%, 0.5%, and 1.0%.
%, when the conductivity was measured by increasing to 1.5%,
At these water contents, as shown in Figure 1, the conductivity stops changing after a certain salinity value. Therefore, since there is no change in electrical conductivity in response to changes in salinity, it has been impossible to measure salinity. However, when the moisture content is further increased to 2.0%, 2.5%, and 3.0%
As a result, they surprisingly found that the relationship between salt concentration and electrical conductivity is a straight line with the same slope, and that it does not depend on water content. In other words, by adjusting the amount of distilled water added to the mixed alcohol solution components to obtain a composition such that the water content of the standard measurement sample is in the range of 2.0 to 3.0%, it is possible to use a linear and identical calibration curve. It was found that even if a small amount (approximately 0.1%) of water is present in crude oil, it is possible to quantify the salinity concentration regardless of the water content. In this way, 429 mg/~5000 in crude oil, which could not be quantified until now.
It becomes possible to measure high concentrations of salt in mg/ml. In addition, at this high salinity concentration, when the water content is 2.0% or less, for example, when it is significantly 1.0%, in Figure 1, at a salinity concentration of 3000 mg/ or more, there is no change in conductivity even if the salinity concentration increases. do not have. That is, it is impossible to know the salt concentration by measuring the conductivity. In addition, when the water content was increased beyond 3.0%, a phenomenon occurred in which the reagents separated into two phases due to the limit of solubility of water in oil during the preparation process of the standard measurement sample. It was found that it is not desirable to do so. next,
A sample with a salt concentration of 428 mg/or less was measured using a standard measurement sample with a moisture content of 2.0 to 3.0%.
The data varied and had slightly poor reproducibility compared to the ASTM method. The present invention is based on the above facts.
429 mg/~ in crude oil that cannot be measured by ASTM method
The purpose is to provide a method for measuring salinity in a high concentration range of 5000mg/. The present invention measures the conductivity of a standard measurement sample prepared by mixing a predetermined amount of an aqueous liquid containing neutral oil, xylene, a mixed alcohol solution, and a salt, and creates a calibration curve.
Conductivity of a measurement sample prepared by using the crude oil to be measured in place of the neutral oil in the above standard measurement sample, and using a salt-free aqueous liquid and a mixed alcohol in the same amount as the total amount of mixed alcohol in place of the above standard measurement sample. A salinity measurement method in which the salinity concentration of the crude oil to be measured is determined by determining the conductivity and applying the determined conductivity to the calibration curve, characterized in that the water content in the standard measurement sample is 2.0 to 3.0% by volume. It consists in a method for measuring high concentration of salt of 429mg/or more in crude oil. Hereinafter, the present invention will be explained in more detail based on Examples. Example (1) Various reagents used in the measurement method of the present invention were prepared as follows. B Mixed alcohol solution Special grade 1-butanol 610ml, Special grade methanol
Mix 360 ml and 40 ml of distilled water. Use Roxylene JIS grade 1 product. C. Use neutral oil lubricating oil. D. Calcium chloride solution (2.5g/100ml) Add 2.5g of calcium chloride (CaCl 2 ) to 25ml of distilled water.
and dilute to the marked line with mixed alcohol solution in a 100 ml volumetric flask. E Magnesium chloride solution (2.5g/100ml) 2.5g of magnesium chloride (MgCl 2 ) in distilled water
Dissolve in 25 ml and dilute to the mark with mixed alcohol solution in a 100 ml volumetric flask. f Sodium chloride solution (2.5g/100ml) 2.5g of sodium chloride (NaCl) in 25ml of distilled water
and dilute to the marked line with mixed alcohol solution in a 100 ml volumetric flask. G. Salt solution (salt 1.0 mg/ml) Add 10 ml of calcium chloride solution, 20 ml of magnesium chloride solution, and 70 ml of sodium chloride solution to a 100 ml volumetric flask and mix. moreover,
Transfer 40 ml of this mixed solution into a 1000 ml volumetric flask and dilute to the marked line with the mixed alcohol solution to obtain a salt solution with a concentration of 1.0 mg/ml. 1 ml of this salt solution corresponds to 1 mg of salt. (2) Standard measurement samples for creating a calibration curve were prepared by mixing the aforementioned xylene, neutral oil, salt solution, and mixed alcohol solution in the amounts shown in Table 1 below. The salt concentration of the obtained standard measurement sample is as shown in Table 1. Note that the salt concentration (mg/) is the weight (mg) of salt per unit volume () of neutral oil (or crude oil).
【表】
調製した標準測定試料中に含まれる水分量は試
料中に含まれる蒸留水の容積比であり、以下の通
りであつた。
塩分濃度500mg／の試料 ……約2.03％
塩分濃度1000mg／の試料 ……約2.08％
塩分濃度2000mg／の試料 ……約2.18％
塩分濃度3000mg／の試料 ……約2.28％
塩分濃度5000mg／の試料 ……約2.48％
この様に水分量を2.0〜3.0％の範囲とした標準
測定試料の導電率を測定したところ第２表に示す
結果となり、これに基づき第２図の検量線を作成
した。[Table] The amount of water contained in the prepared standard measurement sample was the volume ratio of distilled water contained in the sample, and was as follows. Sample with a salinity of 500mg/...Approx. 2.03% Sample with a salinity of 1000mg/...Approx. 2.08% Sample with a salinity of 2000mg/...Approx. 2.18% Sample with a salinity of 3000mg/...Approx. 2.28% Sample with a salinity of 5000mg/ ...About 2.48% When the conductivity of the standard measurement sample with the moisture content in the range of 2.0 to 3.0% was measured, the results are shown in Table 2. Based on this, the calibration curve shown in FIG. 2 was created.
【表】
なお、塩分濃度429〜500mg／の範囲について
は、確認実験の結果第１図及び第２図の延長線上
にあることが確認できた。
(3) 次に標準測定試料中の中性油の代りに被測定
原油を使用し、塩分溶液及び混合アルコール溶
液の代りにそれらの合計量と同量の混合アルコ
ール溶液を使用して水分量を2.0〜3.0％の範囲
とした測定試料を調製する。例えば第１表に示
すような割合で原油10ml、キシレン40ml、及び
混合アルコール溶液50mlを混合して調製でき
る。次いで調製した測定試料の導電率を測定
し、第２図のように求めた検量線を用いて原油
中の塩分量を定量する。
本発明によつて、従来測定できなかつた原油の
高濃度塩分が簡便に定量することができる。[Table] Regarding the range of salt concentration from 429 to 500 mg/, it was confirmed as a result of the confirmation experiment that it was on the extension line of Figures 1 and 2. (3) Next, use the crude oil to be measured in place of the neutral oil in the standard measurement sample, and use the same amount of mixed alcohol solution as the total amount of salt solution and mixed alcohol solution in place of the salt solution and mixed alcohol solution to calculate the water content. Prepare a measurement sample in the range of 2.0 to 3.0%. For example, it can be prepared by mixing 10 ml of crude oil, 40 ml of xylene, and 50 ml of mixed alcohol solution in the proportions shown in Table 1. Next, the electrical conductivity of the prepared measurement sample is measured, and the amount of salt in the crude oil is determined using a calibration curve obtained as shown in FIG. According to the present invention, high concentration salts in crude oil, which could not be measured conventionally, can be easily quantified.
第１図は水分量を種々に変えた標準測定試料の
塩分濃度と導電率との関係を示す図、第２図は本
発明に基いて調製した標準測定試料の検量線を示
す図である。
FIG. 1 is a diagram showing the relationship between salt concentration and conductivity of standard measurement samples with various water contents, and FIG. 2 is a diagram showing a calibration curve of standard measurement samples prepared based on the present invention.
Claims (1)
塩を含む水性液を所定量ずつ混合した標準測定試
料の導電率を測定して検量線を作成し、上記標準
測定試料中の中性油の代りに被測定原油を使用し
塩を含まない水性液及び混合アルコールの代りに
それらの合計量と同量の混合アルコールを使用し
て調製した測定試料の導電率を求め、求めた導電
率を上記検量線に適用して被測定原油の塩分濃度
を定量する塩分測定方法において、標準測定試料
中の水分量を2.0〜3.0体積％とすることを特徴と
する、原油中の429mg／以上の高濃度塩分測定
方法。1 Create a calibration curve by measuring the conductivity of a standard measurement sample in which a predetermined amount of an aqueous liquid containing neutral oil, xylene, mixed alcohol solution, and salt was mixed, and use the standard measurement sample instead of the neutral oil in the above standard measurement sample. The electrical conductivity of a measurement sample prepared using the crude oil to be measured using a salt-free aqueous liquid and the same amount of mixed alcohol as the total amount of these in place of the mixed alcohol was determined, and the obtained electrical conductivity was calculated using the above calibration curve. In the salinity measurement method that is applied to quantify the salinity concentration of the crude oil to be measured, the water content in the standard measurement sample is set to 2.0 to 3.0% by volume, and the high concentration salt concentration of 429 mg / more in crude oil is measured. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8670083A JPS59212748A (en) | 1983-05-19 | 1983-05-19 | Measuring method of high-concentration salinity in crude oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8670083A JPS59212748A (en) | 1983-05-19 | 1983-05-19 | Measuring method of high-concentration salinity in crude oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59212748A JPS59212748A (en) | 1984-12-01 |
| JPH0249655B2 true JPH0249655B2 (en) | 1990-10-30 |
Family
ID=13894215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8670083A Granted JPS59212748A (en) | 1983-05-19 | 1983-05-19 | Measuring method of high-concentration salinity in crude oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59212748A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0489451U (en) * | 1990-09-18 | 1992-08-05 | ||
| JP2012026912A (en) * | 2010-07-26 | 2012-02-09 | Atago:Kk | Salinity concentration measuring instrument and salinity concentration measuring method |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1011499C2 (en) * | 1999-03-09 | 2000-09-14 | Nmi Van Swinden Lab B V | Fluid reference standard for measuring conductivity of liquids. |
| US9448221B2 (en) * | 2011-05-18 | 2016-09-20 | Saudi Arabian Oil Company | Method, solvent formulation and apparatus for the measurement of the salt content in petroleum fluids |
| CN105548320A (en) * | 2015-12-16 | 2016-05-04 | 广东石油化工学院 | Method for researching cracking of organic chlorine in crude oil |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1048235B (en) * | 1975-10-13 | 1980-11-20 | Dasco Spa | Conductivity meter for concentration determination - incorporating circuit with thermistor temperature compensation |
-
1983
- 1983-05-19 JP JP8670083A patent/JPS59212748A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0489451U (en) * | 1990-09-18 | 1992-08-05 | ||
| JP2012026912A (en) * | 2010-07-26 | 2012-02-09 | Atago:Kk | Salinity concentration measuring instrument and salinity concentration measuring method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59212748A (en) | 1984-12-01 |
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