WO2009123496A1 - Method and device for measuring impurities in oil and petroleum products - Google Patents
Method and device for measuring impurities in oil and petroleum products Download PDFInfo
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- WO2009123496A1 WO2009123496A1 PCT/RU2008/000209 RU2008000209W WO2009123496A1 WO 2009123496 A1 WO2009123496 A1 WO 2009123496A1 RU 2008000209 W RU2008000209 W RU 2008000209W WO 2009123496 A1 WO2009123496 A1 WO 2009123496A1
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- silver
- electrode
- measuring
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- oil
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000012535 impurity Substances 0.000 title claims abstract description 11
- 239000003209 petroleum derivative Substances 0.000 title abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- -1 sulphide ions Chemical class 0.000 claims abstract description 8
- 238000005443 coulometric titration Methods 0.000 claims abstract description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- 239000011707 mineral Substances 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 238000004313 potentiometry Methods 0.000 claims abstract description 3
- 238000005070 sampling Methods 0.000 claims abstract description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 3
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012457 nonaqueous media Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229940031993 lithium benzoate Drugs 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/42—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
- G01N27/44—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte using electrolysis to generate a reagent, e.g. for titration
-
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/42—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
- G01N27/423—Coulometry
-
- 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
- G01N33/2835—Specific substances contained in the oils or fuels
Definitions
- the invention relates to the field of determining the content of mercaptans, chloride and sulfide ions in oil and oil products and can be used for coulometric titration in non-aqueous solutions with potentiometric indication of equivalence points.
- a known method of measuring individual components in non-aqueous media comprising burning a sample, absorbing gases, followed by coulometric titration of the components.
- the disadvantage of this method is that in this method the total content of chlorine and sulfide is determined.
- the voltage applied to the generator and auxiliary electrodes due to the voltage drop in the solution significantly affects the emf of the galvanic cell and does not allow fixing the equivalence points, and thus measure (patent RU 2243552 , 2004).
- the technical result from the use of the present invention is the ability to determine in oil impurities of sulfides, chlorides and mercaptans (as well as bromides and iodides, if present) without the use of titrants, giving a systematic error in the determination, as well as the possibility of automation of the method.
- a method for determining impurities in oil and oil products includes automatic sampling, transferring it to a measuring electrochemical cell, mixing with a mineral or organic electrolyte, homogenizing the resulting mixture, electrochemical generation of silver by anodic oxidation of a silver generator electrode, and sequential coulometric titration of the mixture with generated silver ions with fixing points of equivalence by potentiometric method using indicator sulfur ro-selective electrode.
- Anodic oxidation of silver is mainly carried out in an environment containing an electrolyte with concentrations from 0.001 to O, IM at electrolysis currents from 3 to 0.01 mA.
- an organic electrolyte a solution of lithium salt with an anion of an organic acid is predominantly used.
- a solution of lithium salts with inorganic anions is mainly used as a mineral electrolyte.
- Lithium salts such as hexafluorophosphate, pechlorate, etc., are good electrolytes and have high solubility in organic solvents.
- a pH sensitive glass electrode is usually used as a reference electrode.
- the proposed device for implementing this method includes a chamber with a mixing device and fittings for supplying and removing liquids.
- the chamber consists of two interconnected electrochemical cells located one below the other.
- a generating cell with two horizontally mounted plate electrodes, of which the lower is a cathode and made of platinum, and the upper is made of silver and has openings for communication with the measuring electrochemical cell located above.
- This cell includes a measuring ion-selective electrode and a reference electrode.
- the most suitable mixing device is a magnetic stirrer, which is located between the electrodes of the generating cell.
- the cathode of the generating cell can be mounted in the bottom of the chamber. It is desirable that the area of the holes in the anode of the generating cell be at least 30% of the total surface of the plate of the anode, which will provide more complete and reliable homogenization of the mixture in the chamber.
- the measuring device is shown in Fig. L and is a cylindrical chamber 1 with a nozzle 9 for supplying liquids and a nozzle 10 for withdrawing the mixture. Preferred dimensions of the chamber 1: inner diameter - 40-50 mm; height - 60 mm.
- the generating electrochemical cell includes two horizontal plate electrodes 6 and 7.
- the lower electrode, cathode 7, can be mounted in the bottom of chamber 1, and the second electrode, anode 6, is located at a distance not exceeding 20 mm from cathode 7.
- the device is a magnetic stirrer 5, which functions from external influences — a source 8 of an alternating magnetic field.
- the plate of the upper electrode - anode 6 has holes, which allows homogenization of the measured solution in the entire volume of both cells of chamber 1.
- the area of the holes in the anode 6 of the generating cell is at least 30% of the total surface area of the anode plate.
- Measuring silver-selective electrode 2 is a modification of the ion-selective electrode IONIKS 122 (LLC IOHIKC alpha). Which is made in the form of a tube, at the end of which an element sensitive to silver ions is fixed.
- the reference electrode 3 can be selected, for example, pH is a sensitive sensor.
- a device in which the proposed method is implemented operates as follows.
- a sample of a fixed volume for example, taken from an oil pipeline using an automatic peristaltic pump, is supplied into the chamber 1 through the nozzle 9. Then, a fixed volume of electrolyte is supplied to chamber 1 in the same way.
- the mixture of liquids is homogenized - mixed with a magnetic stirrer 5 for 2-3 minutes.
- the EMF of the measuring cell 4 composed of a glass electrode 3 used as a reference electrode, and a silver-selective measuring electrode 2 (indicator electrode of the IONIKS 122 type) is recorded.
- a constant voltage is applied to the electrodes 6 and 7 of the generating electrochemical cell and the change in the EMF of the measuring cell 4 in time is recorded.
- the equivalence points are successively reached, the amount of electricity spent on electrolysis is measured, and based on the combined Faraday law, the amount of this or that impurity contained in the sample is calculated.
- the mixture of liquids is removed from the chamber 1 through the nozzle 10 using a pump.
- the chamber 1 is washed with a washing reagent with a working magnetic stirrer 5.
- mineral and organic salts for example, lithium perchlorate or lithium benzoate
- the horizontally located indicator and generator electrodes with a mixing device between them and a galvanic measuring cell located above them allow measurements in organic media, while eliminating the influence of voltage in the generator part on the potential of the measuring measuring cell.
- the device of the claimed design allows to increase the accuracy of determination of chlorides, mercaptans and sulfides in oil by eliminating errors associated with the standardization of titrant, simplify the design of the analyzer and, as a result, increase the accuracy of the determination.
- FIG. 2 A typical sequential coulometric titration curve of sulfides, mercaptans and chlorides is shown in FIG. 2. The curve was obtained at a concentration of sulfides, mercaptans and chlorides equal to 10 "4 mEq / L. The current strength was 0.98 mA. A 0.0 IM solution of lithium perchlorate in a mixed solvent of equal volumes of toluene and decyl alcohol was used as an electrolyte. Prior to titration of the admixture mixture, equivalence points on the control samples were determined, each of which contained only one of these impurities.
- Determination of the content of mercaptans is possible in the concentration range from 10 to 200 mg / l. In the concentration range of less than 1 mg / L, a relatively small jump in the potentiometric detector does not allow us to fix the equivalence point; when the concentration of mercaptans is above 200 mr / L, the determination error associated with a decrease in current efficiency increases.
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
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- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Immunology (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to measuring the mercaptan, chloride- and sulphide ions in oil and petroleum products. The inventive method for measuring impurities in oil and petroleum products involves automatically sampling, transferring a sample into a measuring electrochemical cell, mixing with a mineral or organic electrolyte, homogenising the thus produced mixture, electrochemically generating silver by means of the anodic oxidation of a generator silver electrode and subsequently carrying out the coulometric titration of the mixture and generating silver ions with fixing equivalence points by a potentiometric method using a test silver-selective electrode. The silver is anode-oxidized in an electrolyte-containing medium with concentrations ranging from 0.001 to 0.1 M and an electrolysis current ranging from 3 to 0.01 mA. The impurity measuring device comprises a chamber with a mixing unit and fittings for feeding and evacuating liquids, which chamber consists of two interconnected electrochemical cells arranged one under the other. A generating cell is placed in the lower part of the chamber and comprises two horizontally positioned plate-type electrodes, wherein the lower electrode is used as a cathode and is made of platinum, the upper electrode is made of silver and provided with holes for communicating with a measuring electrochemical cell which is situated above it and contains a measuring ion-selective electrode and a comparison electrode.
Description
СПОСОБ И УСТРОЙСТВО ДЛЯ ОПРЕДЕЛЕНИЯ ПРИМЕСЕЙ В НЕФТИ И НЕФТЕПРОДУКТАХ METHOD AND DEVICE FOR DETERMINING IMPURITIES IN OIL AND OIL PRODUCTS
Изобретение относится к области определения содержания меркаптанов, хлорид- и сульфид- ионов в нефти и нефтепродуктах и может использоваться при кулонометриче- ском титровании в неводных растворах с потенциометрической индикацией точек эквивалентности. Известен способ измерения отдельных компонентов в неводных средах включающий сжигание пробы поглощение газов с последующим кулонометрическим титрованием компонентов. Недостатком известного способа является то, что в данном методе определяется общее содержание хлора и сульфида. При использовании известной конструкции ячеек для определения ионов в неводных средах напряжение накладываемое на rенера- торный и вспомогательный электроды за счет падения напряжения в растворе существенным образом влияет на ЭДС гальванической ячейки и не позволяет фиксировать точки эквивалентности, и таким образом, проводить измерения (патент RU 2243552, 2004 г.).The invention relates to the field of determining the content of mercaptans, chloride and sulfide ions in oil and oil products and can be used for coulometric titration in non-aqueous solutions with potentiometric indication of equivalence points. A known method of measuring individual components in non-aqueous media comprising burning a sample, absorbing gases, followed by coulometric titration of the components. The disadvantage of this method is that in this method the total content of chlorine and sulfide is determined. When using the well-known cell design for determining ions in non-aqueous media, the voltage applied to the generator and auxiliary electrodes due to the voltage drop in the solution significantly affects the emf of the galvanic cell and does not allow fixing the equivalence points, and thus measure (patent RU 2243552 , 2004).
Известен также способ определения компонентов в нефти потенциометрическим титрованием нитратом серебра с потенциометрической фиксацией точек эквивалентности [UOP LАВОRАТОRY TEST METHODS: 163-89 Нуdrоgеп Sulfidе апd Меrсарtап Sulfur iп Liquid Нуdrосаrbопs]. К недостаткам данного способа следует отнести наличие систематической погрешности, связанной с установлением характеристик титранта, а также необходимость достаточно частого переустановления характеристик титранта, что затрудняет возможность его использования в автоматических анализаторах. Техническим результатом от использования предлагаемого изобретения является возможность определения в нефти примесей сульфидов, хлоридов и меркаптанов (а также бромидов и иодидов, в случае их присутствия) без применения титрантов, дающих систематическую погрешность определений, а также возможность автоматизации метода.There is also a known method for determining components in oil by potentiometric titration with silver nitrate with potentiometric fixation of equivalence points [UOP LAVORATORY TEST METHODS: 163-89 Sound Hydrogen Sulfide Ap Sulfur Liquid Sulfur Liquid]. The disadvantages of this method include the presence of a systematic error associated with the establishment of the characteristics of the titrant, as well as the need for a fairly frequent reinstallation of the characteristics of the titrant, which complicates the possibility of its use in automatic analyzers. The technical result from the use of the present invention is the ability to determine in oil impurities of sulfides, chlorides and mercaptans (as well as bromides and iodides, if present) without the use of titrants, giving a systematic error in the determination, as well as the possibility of automation of the method.
Согласно изобретению, способ определения примесей в нефти и нефтепродуктах, включает автоматический отбор пробы, перенос ее в измерительную электрохимическую ячейку, смешивание с минеральным или органическим электролитом, гомогенизацию полученной смеси, электрохимическую генерацию серебра анодным окислением генераторного серебряного электрода и последовательное кулонометрическое титрование смеси генерированными ионами серебра с фиксацией точек эквивалентности потенциометриче- ским способом с использованием индикаторного серебро-селективного электрода.
Анодное окисление серебра преимущественно проводят в среде содержащей электролит с концентрациями от 0,001 до О, IM при значениях тока электролиза от 3 до 0,01мA.According to the invention, a method for determining impurities in oil and oil products includes automatic sampling, transferring it to a measuring electrochemical cell, mixing with a mineral or organic electrolyte, homogenizing the resulting mixture, electrochemical generation of silver by anodic oxidation of a silver generator electrode, and sequential coulometric titration of the mixture with generated silver ions with fixing points of equivalence by potentiometric method using indicator sulfur ro-selective electrode. Anodic oxidation of silver is mainly carried out in an environment containing an electrolyte with concentrations from 0.001 to O, IM at electrolysis currents from 3 to 0.01 mA.
В качестве органического электролита преимущественно используют раствор соли лития с анионом органической кислоты. В качестве минерального электролита преимущественно используют раствор солей лития с неорганическими анионами. Соли лития, такие как гексафторфосфат, пехлорат и т.д., являются хорошими электролитами и обладают высокой растворимостью в органических растворителях.As an organic electrolyte, a solution of lithium salt with an anion of an organic acid is predominantly used. A solution of lithium salts with inorganic anions is mainly used as a mineral electrolyte. Lithium salts, such as hexafluorophosphate, pechlorate, etc., are good electrolytes and have high solubility in organic solvents.
При потенциометрической индикации точек эквивалентности в качестве электрода сравнения обычно используют рН - чувствительный стеклянный электрод.For potentiometric indications of equivalence points, a pH sensitive glass electrode is usually used as a reference electrode.
Предлагаемое устройство для реализации такого способа включает камеру с перемешивающим устройством и штуцерами для подачи и удаления жидкостей. Камера состоит из двух сообщающихся между собой электрохимических ячеек, расположенных одна под другой. В нижней части камеры расположена генерирующая ячейка с двумя гори- зонтально установленными пластинчатыми электродами, из которых нижний является катодом и выполнен из платины, а верхний выполнен из серебра и имеет отверстия для сообщения с расположенной выше измерительной электрохимической ячейкой. В состав этой ячейки входят измерительный ионоселективный электрод и электрод сравнения.The proposed device for implementing this method includes a chamber with a mixing device and fittings for supplying and removing liquids. The chamber consists of two interconnected electrochemical cells located one below the other. In the lower part of the chamber there is a generating cell with two horizontally mounted plate electrodes, of which the lower is a cathode and made of platinum, and the upper is made of silver and has openings for communication with the measuring electrochemical cell located above. This cell includes a measuring ion-selective electrode and a reference electrode.
Наиболее подходящим перемешивающим устройством служит магнитная мешалка, которую располагают между электродами генерирующей ячейки.The most suitable mixing device is a magnetic stirrer, which is located between the electrodes of the generating cell.
Катод генерирующей ячейки может быть вмонтирован в дно камеры. Желательно, чтобы площадь отверстий в аноде генерирующей ячейки составляла не менее 30% от общей поверхности пластины анода, что обеспечит более полную и надежную гомогенизацию смеси в камере. Схематически измерительное устройство показано на Фиг.l и представляет собой цилиндрическую камеру 1 со штуцером 9 подачи жидкостей и штуцером 10 отвода смеси. Предпочтительные размеры камеры 1: внутренний диаметр - 40-50 мм; высота - 60 мм. В камере 1 находятся две электрохимические ячейки, расположенные соосно, одна над другой, при этом генерирующая ячейка, ограниченная электродами 6 и 7, находится в нижней части камеры 1. Над ней располагается измерительная ячейка 4, в которой находятся измерительный ионоселективный электрод 2 и электрод 3 сравнения.The cathode of the generating cell can be mounted in the bottom of the chamber. It is desirable that the area of the holes in the anode of the generating cell be at least 30% of the total surface of the plate of the anode, which will provide more complete and reliable homogenization of the mixture in the chamber. Schematically, the measuring device is shown in Fig. L and is a cylindrical chamber 1 with a nozzle 9 for supplying liquids and a nozzle 10 for withdrawing the mixture. Preferred dimensions of the chamber 1: inner diameter - 40-50 mm; height - 60 mm. In chamber 1 there are two electrochemical cells located coaxially, one above the other, while the generating cell bounded by electrodes 6 and 7 is located in the lower part of chamber 1. Above it is located measuring cell 4, in which there is an ion-selective measuring electrode 2 and electrode 3 comparisons.
Генерирующая электрохимическая ячейка включает два пластинчатых горизонтально расположенных электрода 6 и 7. При этом нижний электрод - катод 7 может быть вмонтирован в дно камеры 1, а второй электрод - анод 6 находится на расстоянии, не пре- вышающем 20 мм от катода 7. Между электродами располагается перемешивающее уст-
ройство - магнитная мешалка 5, функционирующая от внешнего воздействия - источника 8 переменного магнитного поля. Пластина верхнего электрода - анода 6 имеет отверстия, что позволяет осуществлять гомогенизацию измеряемого раствора во всем объеме обеих ячеек камеры 1. Площадь отверстий в аноде 6 генерирующей ячейки составляет не менее 30% от общей площади поверхности пластины анода.The generating electrochemical cell includes two horizontal plate electrodes 6 and 7. In this case, the lower electrode, cathode 7, can be mounted in the bottom of chamber 1, and the second electrode, anode 6, is located at a distance not exceeding 20 mm from cathode 7. Between the electrodes the mixing device is located The device is a magnetic stirrer 5, which functions from external influences — a source 8 of an alternating magnetic field. The plate of the upper electrode - anode 6 has holes, which allows homogenization of the measured solution in the entire volume of both cells of chamber 1. The area of the holes in the anode 6 of the generating cell is at least 30% of the total surface area of the anode plate.
Измерительный серебро-селективный электрод 2 представляет собой модификацию ионоселективного электрода ИОНИКС 122 (ООО «ИOHИKC aльфa»). Который выполнен в виде трубки, на конце которой закреплен элемент, чувствительный к ионам серебра. Электродом 3 сравнения может быть выбран, например, рН - чувствительный дат- чик.Measuring silver-selective electrode 2 is a modification of the ion-selective electrode IONIKS 122 (LLC IOHIKC alpha). Which is made in the form of a tube, at the end of which an element sensitive to silver ions is fixed. The reference electrode 3 can be selected, for example, pH is a sensitive sensor.
Устройство, в котором реализуется предложенный способ, работает следующим образом.A device in which the proposed method is implemented operates as follows.
В камеру 1 через штуцер 9 подается проба фиксированного объема, отобранная, например, из нефтепровода с помощью автоматического перистальтического насоса. За- тем в камеру 1 тем же путем подается фиксированный объем электролита. Смесь жидкостей гомогенизируется - перемешивается с помощью магнитной мешалки 5 в течение 2-3 минут.A sample of a fixed volume, for example, taken from an oil pipeline using an automatic peristaltic pump, is supplied into the chamber 1 through the nozzle 9. Then, a fixed volume of electrolyte is supplied to chamber 1 in the same way. The mixture of liquids is homogenized - mixed with a magnetic stirrer 5 for 2-3 minutes.
Одновременно фиксируется ЭДС измерительной ячейки 4, составленной из стеклянного электрода 3, используемого в качестве электрода сравнения, и измерительного серебро-селективного электрода 2 (индикаторного электрода типа ИОНИКС 122).At the same time, the EMF of the measuring cell 4, composed of a glass electrode 3 used as a reference electrode, and a silver-selective measuring electrode 2 (indicator electrode of the IONIKS 122 type) is recorded.
Подается постоянное напряжение на электроды 6 и 7 генерирующей электрохимической ячейки и фиксируется изменение ЭДС измерительной ячейки 4 во времени. При последовательном достижении точек эквивалентности, измеряется количество электричества, затраченное на электролиз, и на основе объединенного закона Фарадея, рассчитыва- ется количество той или иной примеси, содержащейся в пробе.A constant voltage is applied to the electrodes 6 and 7 of the generating electrochemical cell and the change in the EMF of the measuring cell 4 in time is recorded. When the equivalence points are successively reached, the amount of electricity spent on electrolysis is measured, and based on the combined Faraday law, the amount of this or that impurity contained in the sample is calculated.
После окончания измерений смесь жидкостей удаляют из камеры 1 по штуцеру 10 с помощью насоса. Перед измерением следующей пробы камера 1 промывается реагентом для промывки при работающей магнитной мешалке 5.After the measurement, the mixture of liquids is removed from the chamber 1 through the nozzle 10 using a pump. Before measuring the next sample, the chamber 1 is washed with a washing reagent with a working magnetic stirrer 5.
Для обеспечения 100% выхода по току и требуемой электропроводности растворов в качестве электролита (буферного раствора) используются минеральные и органические соли, например, перхлорат или бензоат лития. Горизонтально расположенные индикаторный и генераторный электроды с расположенным между ними перемешивающим устройством и расположенной над ними гальванической измерительной ячейкой позволяют проводить измерения в органических средах, при этом устраняется влияние напряжения в ге- нераторной части на потенциал измерительного измерительной ячейки.
Устройство заявленной конструкции позволяет повысить точность определения хлоридов, меркаптанов и сульфидов в нефти за счет исключения ошибок, связанных со стандартизацией титранта, упростить конструкцию анализатора и как следствие повысить точность определений. Типичная кривая последовательного кулонометрического титрования сульфидов, меркаптанов и хлоридов приведена на Фиг. 2. Кривая получена при концентрации сульфидов, меркаптанов и хлоридов равной 10"4м-эквл/л. Сила тока составляла 0,98 мА. В качестве электролита использовался 0,0 IM раствор перхлората лития в смешанном растворителе из равных объемов толуола и децилового спирта. Перед титрованием смеси приме- сей были определены точки эквивалентности на контрольных образцах, каждый из которых содержал только одну из названных примесей.To ensure 100% current efficiency and the required conductivity of the solutions, mineral and organic salts, for example, lithium perchlorate or lithium benzoate, are used as the electrolyte (buffer solution). The horizontally located indicator and generator electrodes with a mixing device between them and a galvanic measuring cell located above them allow measurements in organic media, while eliminating the influence of voltage in the generator part on the potential of the measuring measuring cell. The device of the claimed design allows to increase the accuracy of determination of chlorides, mercaptans and sulfides in oil by eliminating errors associated with the standardization of titrant, simplify the design of the analyzer and, as a result, increase the accuracy of the determination. A typical sequential coulometric titration curve of sulfides, mercaptans and chlorides is shown in FIG. 2. The curve was obtained at a concentration of sulfides, mercaptans and chlorides equal to 10 "4 mEq / L. The current strength was 0.98 mA. A 0.0 IM solution of lithium perchlorate in a mixed solvent of equal volumes of toluene and decyl alcohol was used as an electrolyte. Prior to titration of the admixture mixture, equivalence points on the control samples were determined, each of which contained only one of these impurities.
Определение концентрации хлорид ионов (Табл.l) возможно в диапазоне концентраций от 10 до 2000 мг/л. При концентрации хлорид ионов менее 10 мг/л фиксация точки эквивалентности затруднена т.к. скачок титрования достаточно сильно размыт. При концентрации выше 2000мг/л для сохранения временных характеристик анализа необходимо поддержание достаточно высокого тока электролиза выше 7 мА, что уменьшает выход по току и приводит к значительным погрешностям определений (выше 10% отн).Determination of chloride ion concentration (Table l) is possible in the concentration range from 10 to 2000 mg / l. At a chloride ion concentration of less than 10 mg / l, fixing the equivalence point is difficult because the titration jump is quite blurry. At a concentration above 2000 mg / l, in order to preserve the temporal characteristics of the analysis, it is necessary to maintain a sufficiently high electrolysis current above 7 mA, which reduces the current efficiency and leads to significant measurement errors (above 10% rel.).
Табл.l Определение содержания хлоридов в нефти.Table.l Determination of chloride content in oil.
Определение содержания меркаптанов (Taбл.2) возможно в диапазоне концентраций от 10 до 200 мг/л. В области концентраций меньше 1 мг/л сравнительно небольшая величина скачка потенциометрического детектора не позволяет зафиксировать точку эк- вивалентности, при концентрации меркаптанов выше 200 мr/л увеличивается ошибка определения, связанная с уменьшением выхода по току.Determination of the content of mercaptans (Table 2) is possible in the concentration range from 10 to 200 mg / l. In the concentration range of less than 1 mg / L, a relatively small jump in the potentiometric detector does not allow us to fix the equivalence point; when the concentration of mercaptans is above 200 mr / L, the determination error associated with a decrease in current efficiency increases.
Определение содержания сульфидов в нефти (Табл.З) возможно в диапазоне концентраций от 5 до 200 мг/л. При содержании сульфидов меньше 5 мг/л фиксация точки эквивалентности затруднена, что приводит к увеличению погрешности определения, уве- личение концентрации выше 200 мг/л увеличение погрешности определения связано с уменьшением выхода по току.
Табл.2 Определение содержания меркаптанов в нефтиDetermination of sulfide content in oil (Table.Z) is possible in the concentration range from 5 to 200 mg / l. When the sulfide content is less than 5 mg / L, the fixation of the equivalence point is difficult, which leads to an increase in the determination error, an increase in concentration above 200 mg / L, an increase in the determination error is associated with a decrease in current efficiency. Table 2 Determination of mercaptan content in oil
Табл.З Определение содержания сульфидов в нефтиTable 3 Determination of sulphide content in oil
Taбл.4 Одновременное определение сульфидов, меркаптанов и хлоридов в нефти.Table 4 Simultaneous determination of sulfides, mercaptans and chlorides in oil.
Пример 1Example 1
Пример 2Example 2
Пример 3Example 3
Пример 4
Пример 5Example 4 Example 5
Пример 6Example 6
Пример 7Example 7
Пример 8Example 8
Как видно из приведенных таблиц, существуют нефти и нефтепродукты с содержанием примесей в концентрациях меньше нижнего предела обнаружения, которые не детектируются данным способом.
As can be seen from the tables, there are petroleum and petroleum products with impurities in concentrations below the lower detection limit, which are not detected by this method.
Claims
1. Способ определения примесей в нефти и нефтепродуктах, включающий автоматический отбор пробы, перенос ее в измерительную электрохимическую ячейку, смешивание с минеральным или органическим электролитом, гомогенизацию полученной смеси, электрохимическую генерацию серебра анодным окислением генераторного серебряного электрода и последовательное кулонометрическое титрование смеси генерированными ионами серебра с фиксацией точек эквивалентности потенциометрическим способом с использованием индикаторного серебро-селективного электрода. 1. A method for determining impurities in oil and oil products, including automatic sampling, transferring it to a measuring electrochemical cell, mixing with a mineral or organic electrolyte, homogenization of the resulting mixture, electrochemical generation of silver by anodic oxidation of a silver generator electrode, and sequential coulometric titration of the mixture with generated silver ions with fixation of equivalence points by potentiometric method using silver-selective electronic indicator ktroda.
2. Способ по п.l отличающееся тем, что анодное окисление серебра проводят в среде содержащий электролит с концентрациями от 0,001 до 0,1 M при значениях тока электролиза от 3 до 0,01м А.2. The method according to claim 1, characterized in that the anodic oxidation of silver is carried out in a medium containing an electrolyte with concentrations from 0.001 to 0.1 M at an electrolysis current of 3 to 0.01 m A.
3. Способ по п.l, отличающийся тем, что в качестве органического электролита используют раствор литиевой соли органической кислоты. 3. The method according to claim 1, characterized in that a solution of a lithium salt of an organic acid is used as an organic electrolyte.
4. Способ по п.l, отличающийся тем, что в качестве минерального электролита используют раствор солей лития с неорганическими анионами с концентрацией 0,001 - 0,1 M.4. The method according to claim 1, characterized in that a solution of lithium salts with inorganic anions with a concentration of 0.001-0.1 M is used as a mineral electrolyte.
5. Способ по п.l отличающееся тем, что при потенциометрической индикации точек эквивалентности в качестве электрода сравнения используются рН - чувствитель- ный стеклянный электрод.5. The method according to claim 1, characterized in that for potentiometric indication of the equivalence points, a pH sensitive glass electrode is used as a reference electrode.
6. Устройство для определения примесей в нефти и нефтепродуктах включающее камеру с перемешивающим устройством и штуцерами для подачи и удаления жидкостей, причем камера состоит из двух сообщающихся между собой электрохимических ячеек, расположенных одна под другой, при этом в нижней части камеры располо- жена генерирующая ячейка с двумя горизонтально установленными пластинчатыми электродами, из которых нижний является катодом и выполнен из платины, а верхний выполнен из серебра и имеет отверстия для сообщения с расположенной выше измерительной электрохимической ячейкой, в состав которой входят измерительный ионоселективный электрод и электрод сравнения. 6. A device for determining impurities in oil and oil products comprising a chamber with a mixing device and fittings for supplying and removing liquids, the chamber consisting of two interconnected electrochemical cells located one below the other, while a generating cell is located in the lower part of the chamber with two horizontally mounted plate electrodes, of which the lower is the cathode and is made of platinum, and the upper is made of silver and has openings for communication with the higher ritelnoy electrochemical cell which comprises an ion-selective measuring electrode and a reference electrode.
7. Устройство по п.6, отличающееся тем, что перемешивающее устройство представляет собой магнитную мешалку, расположенную между электродами генерирующей ячейки.7. The device according to claim 6, characterized in that the mixing device is a magnetic stirrer located between the electrodes of the generating cell.
8. Устройство по п.6, отличающееся тем, что катод генерирующей ячейки вмонтирован в дно камеры. 8. The device according to claim 6, characterized in that the cathode of the generating cell is mounted in the bottom of the chamber.
9. Устройство по п.6, отличающееся тем, что площадь отверстий в аноде генерирующей ячейки составляет не менее 30% от общей поверхности пластины анода. 9. The device according to claim 6, characterized in that the area of the holes in the anode of the generating cell is at least 30% of the total surface of the plate of the anode.
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| CN110108836A (en) * | 2019-05-30 | 2019-08-09 | 岭东核电有限公司 | The measuring method and its application of chlorine ion concentration in nuclear power plant's liquid waste treatment system |
| RU2735372C1 (en) * | 2020-05-29 | 2020-10-30 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method of determining content of sulphides in deposits in oil-field equipment |
| RU2743783C1 (en) * | 2020-06-30 | 2021-02-25 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for determining sediment composition in oil preparation equipment |
| CN112964826A (en) * | 2021-03-17 | 2021-06-15 | 中国大唐集团科学技术研究院有限公司华中电力试验研究院 | Trapping device and method for measuring chloride ions in oil through high-temperature combustion hydrolysis-potentiometric titration |
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| CN110108836A (en) * | 2019-05-30 | 2019-08-09 | 岭东核电有限公司 | The measuring method and its application of chlorine ion concentration in nuclear power plant's liquid waste treatment system |
| RU2735372C1 (en) * | 2020-05-29 | 2020-10-30 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method of determining content of sulphides in deposits in oil-field equipment |
| RU2743783C1 (en) * | 2020-06-30 | 2021-02-25 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for determining sediment composition in oil preparation equipment |
| CN112964826A (en) * | 2021-03-17 | 2021-06-15 | 中国大唐集团科学技术研究院有限公司华中电力试验研究院 | Trapping device and method for measuring chloride ions in oil through high-temperature combustion hydrolysis-potentiometric titration |
| CN112964826B (en) * | 2021-03-17 | 2023-10-17 | 中国大唐集团科学技术研究院有限公司华中电力试验研究院 | Device and method for capturing chloride ions in high-temperature combustion hydrolysis-potentiometric titration measurement oil |
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