CN103389233A - Method for measuring metal contents in oil product and sample pretreatment method thereof - Google Patents

Method for measuring metal contents in oil product and sample pretreatment method thereof Download PDF

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CN103389233A
CN103389233A CN2013103006908A CN201310300690A CN103389233A CN 103389233 A CN103389233 A CN 103389233A CN 2013103006908 A CN2013103006908 A CN 2013103006908A CN 201310300690 A CN201310300690 A CN 201310300690A CN 103389233 A CN103389233 A CN 103389233A
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oil
sample
content
metal
samples
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CN2013103006908A
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CN103389233B (en
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成勇
袁金红
李军
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攀钢集团攀枝花钢铁研究院有限公司
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Abstract

The invention discloses a sample pretreatment method for measurement of metal contents in an oil product. The method comprises the following steps: a) dilute aqueous solution of hydrochloric acid is added into an oil sample, and is put in a hot water bath for ultrasonic oscillation to obtain an oil mixture; and b) the oil mixture stands to stratify and then is separated, and water-phase solution in the lower layer is collected to obtain a pretreated sample of the oil sample. The invention also discloses a method for measuring metal contents in the oil product. The method uses the above sample pretreatment method to treat an oil sample to obtain a pretreated sample of the oil sample; directly measures metal contents of the pretreated sample using one or a plurality of methods among graphite furnace atomic absorption spectrometry, flame atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry; and finally calculates metal contents of the oil product.

Description

Measure method and the sample pretreating method thereof of metal element content in oil product
Technical field
The invention belongs to the trace element detection analysis field, relate to a kind of method and sample pretreating method thereof of measuring metal element content in oil product, more particularly, the present invention relates to a kind of by adding diluted hydrochloric acid aqueous solution and taking the sample pretreating method of mechanical shaking extraction mode, and the detection method of measuring its contained metal element content.
Background technology
Usually, need to add adjuvant in order to improve the performance of oil product in petroleum refining process, thereby but may causing introducing metallic element, this technique affects oil quality and secondary deep processing thereof, contain the elements such as iron, copper, nickel as fuel oil, lubricating oil, light diesel fuel etc. and will cause catalyst poisoning, in transformer insulation oil, the pollution elements such as iron, copper, lead, tin affect insulation effect, and therefore detecting metallic impurity elements in oil product can instruct the improvement of Oil Production technique and the raising of product quality; And, by detecting and monitor the variation tendency of existing metallic element in transformer insulated wet goods oil product and content thereof, can effectively help to pass judgment on the replacing opportunity of oil product and search the transformer potential risk or the accident failure cause, as, in transformer insulation oil, iron content raises and to need to detect the metal baffle of stainless steel etc. and have zero defect, copper content to raise to need to detect the copper parts such as wire zero defect is arranged; In addition,, for probing into equipment attrition mechanism and prediction wear trend, need to detect composition and the content such as wear metal, pollution element in oil product, according to composition and the content trend thereof of Wear metal, the abrasion condition of the relevant parts of judgment device.
The sample pretreatment mode of analysis of oil method mainly contains ashing method, Wet method, high pressure-volume bullet method, Microwave Digestion and organism direct injected method, there are atomic emission spectrometry, atomic absorption spectrography (AAS) and x ray fluorescence spectrometry three major types in the mensuration mode past, along with the development of plasma mass technology is universal, its application in oil product detects increases day by day in recent years.At present, mostly main stream approach is to adopt the modes such as evaporation, ashing, reagent oxidation decomposition the organism in oil product is separated or destroy, thereby eliminate the disturbing effect of organism to measuring, adopt inductively coupled plasma mass spectrometry (ICP-MS) or ICP-AES (ICP-OES) to measure the metallic elements such as iron, copper, lead, tin, arsenic, silver, chromium, nickel, vanadium in oil product after then residue being dissolved with acid.
Particularly, now with the method for metallic element in the detection oil product, directly by the instruments such as oil product sample introduction transmission system importing inductively coupled plasma atomic emission spectrum (ICP-OES) of special use, being measured after adopting organic reagent with the oil product dilution, the oil product pre-service preparation methods such as other ashing method, Wet method, high pressure-volume bullet method, Microwave Digestion, be mostly at first by oxidative decomposition in order to destroy the organic substance in oil product, then residual inorganic metal element is cleared up and is entered aqueous solution and measure.For example, at first low-temperature evaporation is removed contained organic substance in oil product in platinum crucible, follow the carbonization residue, then the high temperature sintering ashing is until only remain the inorganics residuals, add finally hydrochloric acid or the heating leachings such as nitric acid, hydrogen peroxide to clear up reaction to the elimination preparation of carrying out organic oils sample fully, adopt the instrument analytical methods such as ICP-OES, ICP-MS to measure constituent content in oil product.Although these class methods can be decomposed the organic substance that destroys in oil product effectively, eliminate its impact on measuring, but shortcoming is also apparent, as analysis process is long, operation steps is many, labour intensity is large, particularly for the poor insulating oil of volatility, lubricated wet goods oil product, because impurity content is low, it is larger to take sample size, only completing evaporation step just may need the time of 2-3 days.
Also have by adopting nitric acid-hydrogen peroxide-sherwood oil system oil sample to be carried out the pre-service of extract and separate, then with ICP-OES, measure the method for the impurity metallic elements content in the nitric acid cut.The shortcoming that causes emulsion but also there is the easy oxygenolysis organism of oxidisability extractive reaction medium in these class methods, and the toxic gases such as reaction or the brown flue gas of the decomposition meeting a large amount of nitrogen dioxide of generation, thereby carry out in can only and being positioned over the sterilization cupboard at open container; Need a large amount of sherwood oil reagent that use to increase the analytical control cost, and be difficult to overcome the secondary pollution of discarded test solution to environment; The complex operations such as repeated multiple times extraction, cleaning are complicated, and inspection process is long; And to the metallic impurity elements in oil product without enrichment method function or effect, be unfavorable in oil product the shortcomings such as mensuration of trace, trace metal element.
Therefore, need to provide a kind of method and sample pretreating method thereof that operates metal element content in the mensuration oil product simple and easy, that the cycle is short and precision is higher.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention is to solve in above-mentioned prior art the one or more problems that exist.
The object of the present invention is to provide and a kind ofly can obtain simply, quickly and accurately the pretreatment sample of oil product and the method for contained concentration of metallic impurities wherein.
An aspect of of the present present invention provides a kind of sample pretreating method for measuring the oil product metal element content, said method comprising the steps of: a) add diluted hydrochloric acid aqueous solution in petroleum product samples, be placed in hot bath and carry out supersonic oscillations and obtain oil mixture; B) after the oil mixture standing and demixing, separate and collect the aqueous phase solution of lower floor, obtain the pretreatment sample of petroleum product samples.
According to an embodiment of the sample pretreating method for measuring the oil product metal element content of the present invention, described diluted hydrochloric acid aqueous solution is, and to be 36~38% concentrated hydrochloric acid and water by mass percent concentration form according to the volume ratio mixed preparing of 1:1 to 2:1.
According to an embodiment of the sample pretreating method for measuring the oil product metal element content of the present invention, the temperature of described diluted hydrochloric acid aqueous solution is 50~80 ℃, and the temperature of described hot bath is 80~90 ℃.
According to an embodiment of the sample pretreating method for measuring the oil product metal element content of the present invention, the addition of described diluted hydrochloric acid aqueous solution is 1/10 to 1/5 of petroleum product samples quality.
According to an embodiment of the sample pretreating method for measuring the oil product metal element content of the present invention, the time of supersonic oscillations is 1~3 hour, and in 30 minutes of starting oscillation, discharging reacting gas 3~5 times.
An embodiment according to the sample pretreating method for measuring the oil product metal element content of the present invention, after the oil mixture standing and demixing, separate and collect the aqueous phase solution of part lower floor.
According to an embodiment of the sample pretreating method for measuring the oil product metal element content of the present invention, described petroleum product samples is insulating oil, lubricating oil, gasoline, diesel oil.
Another aspect of the present invention provides a kind of method of measuring metal element content in oil product, said method comprising the steps of: a) adopt above-mentioned sample pretreating method for measuring the oil product metal element content to process petroleum product samples, obtain the pretreatment sample of petroleum product samples; B) directly adopt one or more methods in GFAAS (graphite furnace atomic absorption spectrometry), flame atomic absorption spectrometry, ICP-AES or inductively coupled plasma mass spectrometry to measure metallic element in the pretreatment sample of described petroleum product samples, and finally calculate the metal element content in oil product.
An embodiment according to the method for metal element content in mensuration oil product of the present invention, calculate the metal element content in oil product according to the following formula, with mass percent, represents:
W M = V × ( c - c 0 ) × 10 - 6 m × 100
Wherein, W M---the content of the metallic element to be measured in petroleum product samples, %;
C---the concentration determination value of the metallic element to be measured in pretreatment sample, ug/mL;
c 0---the concentration determination value of the metallic element to be measured in blank diluted hydrochloric acid aqueous solution, ug/mL;
The volume of V---the diluted hydrochloric acid aqueous solution that adds during sample pretreatment, mL;
M---petroleum product samples take quality, g.
the present invention can effectively eliminate the impact of organic substance on measuring in oil product, has made up simultaneously existing methodical technological deficiency, does not need through numerous and diverse and very long evaporation, carbonization, the course of reaction such as ashing and leaching, therefore not only avoided in evaporation, in the processes such as ashing, metallic element to be measured is taken away loss and causes testing result on the low side by flue gas, and only need add extraction reagent and carry out oscillating operation, and the aqueous phase solution of separated and collected also need not to carry out oxidation again, clear up, dilution, impurity content can be directly measured in any processing such as constant volume, has greatly simplified operation steps and formality, and the whole process round of visits of sample pretreatment preparation and element determination can foreshorten to 2-4 hour, and easy grasp simple to operate, analysis precision is higher, the detection solution-based body medium of preparation is simpler, the disturbing effect factor still less, meets accurately to detect fully and analyzes insulating oil, lubricating oil, gasoline, iron in all kinds of oil product samples such as diesel oil, copper, aluminium, zinc, chromium, nickel, vanadium, manganese, magnesium, the needs of the metal element contents such as cobalt.
The present invention can be used in the metallic impurity elements of wearing and tearing or pollution in insulating oil, lubricated wet goods oil product is carried out regular tracking and monitoring, in time understand the insulation of grasp equipment, lubricated and state of wear information, type, position and the reason of diagnostic device wearing and tearing or generation fault, for maintenance of equipment provides scientific basis, instruct enterprise to carry out State Maintenance and the lubricating management of equipment, thereby prevention substantial equipment accident occurs, and reduces equipment maintenance cost.
Embodiment
Hereinafter, specifically describe method and the sample pretreating method thereof of metal element content in mensuration oil product of the present invention in connection with embodiment.
technical essential of the present invention is by adding diluted hydrochloric acid aqueous solution that a kind of and organic oil phase do not dissolve each other mutually as dissolving extraction agent in petroleum product samples, mode with supersonic oscillations is efficient, rapidly the metallic impurity elements to be measured in oil product being dissolved and extracted makes it enter inorganic aqueous phase solution, standing and demixing by inorganic water and organic oil phase, thereby simply and easily prepared metallic element being detected aqueous solution is not separated by the complete organic oil phase that remains fully with going to pot, lower floor's aqueous phase solution of institute's separated and collected is namely as the pretreatment sample of petroleum product samples.Because the substrate medium of lower floor's aqueous phase solution forms very simply, thereby need not to carry out again any processing, can directly adopt the metallic element that contains in the instrument such as ICP-OES, ICP-MS, AAS or other chemical gauging aqueous phase solution.
Be used for measuring according to an exemplary embodiment of the present invention the sample pretreating method of oil product metal element content, its concrete steps comprise:
At first, add diluted hydrochloric acid aqueous solution in petroleum product samples, be placed in hot bath and carry out supersonic oscillations and obtain oil mixture; Secondly, after the oil mixture standing and demixing, separate and collect the aqueous phase solution of lower floor, obtain the pretreatment sample of petroleum product samples.
Preferably, after the oil mixture standing and demixing, the water that only need separate and collect part lower floor is molten as pretreatment sample, do not need the whole aqueous phase solution of complete separated and collected, this makes lock out operation greatly simplify, reliability improves, in oil mixture residual have do not separate aqueous phase solution completely and measurement result had no effect yet.
Preferably, described diluted hydrochloric acid aqueous solution is that to be 36~38% concentrated hydrochloric acid and water by mass percent concentration form according to the volume ratio mixed preparing of 1:1 to 2:1.The present invention adopts single diluted hydrochloric acid aqueous solution to extract reagent as metallic impurity elements, disposable joining in oil product, then omnidistance disposable continuous ultrasonic oscillating reactions in the hot bath of 80~90 ℃ in airtight separating funnel, only need to collect lower floor's hydrochloric acid aqueous phase solution and can directly for methods such as ICP-OES or ICP-MS, measure the content of metallic impurity elements as pretreatment sample after standing dividing potential drop.
An embodiment according to the sample pretreating method for measuring the oil product metal element content of the present invention, the addition of diluted hydrochloric acid aqueous solution is 1/10 to 1/5 of petroleum product samples quality, and the addition that is equivalent to diluted hydrochloric acid aqueous solution is the diluted hydrochloric acid aqueous solution that every gram petroleum product samples adds 0.1~0.2ml.Usually, the approval of the density of diluted hydrochloric acid aqueous solution is the consistent in density with water, milliliter is equal to the numerical value of gram, also namely for diluted hydrochloric acid aqueous solution, 1ml is 1g, in the present invention, takes petroleum product samples 50~100g, can add diluted hydrochloric acid aqueous solution 5~20g, be equivalent to 5~20mL.Also being about in petroleum product samples contained metallic element dissolves to extract with the concentrated proportionate relationship of 5~10 times and enters among aqueous phase solution, thereby realize dissolving once the purpose of extraction and concentration enrichment metallic ion to be measured, having solved usually requires follow-up element determination method to have the technical barrier of stronger detectability because metallic impurity elements content in oil product is low, reduced the detection method requirement, improved accuracy and the precision of determination of trace element.
Preferably, to be heated to 50~80 ℃ as the diluted hydrochloric acid aqueous solution that dissolves extraction agent, and, the temperature of hot bath is 80~90 ℃, can greatly accelerate like this to dissolve the reaction velocity of extracting metallic element, reduce the consumption of diluted hydrochloric acid aqueous solution, shorten sample detection solution preparation process required time the most consuming time in the inspection process of measuring metallic element in oil product, greatly improved the speed of analyzing that detects.
In oscillatory process, preferably, the time of supersonic oscillations is 1~3 hour, and in 30 minutes of starting oscillation, the closed reaction vessels such as separating funnel is opened the discharging reacting gas such as piston 3~5 times.
Those skilled in the art will be appreciated that oil product is petroleum products, are specifically as follows insulating oil, lubricating oil, gasoline, diesel oil etc.
particularly, an embodiment according to the sample pretreating method for measuring the oil product metal element content of the present invention, taking 50~100g petroleum product samples is placed among separating funnel or other chemical reaction container, a temperature of/5th to 1/10th that adds taking oil quality is that the above-mentioned diluted hydrochloric acid aqueous solution of 50~80 ℃ is as dissolving extraction agent, be placed in again ultrasonic oscillator the hot bath continuous oscillation of 80~90 ℃, then after waiting for inorganic water and organic oil phase layering in standing 5~15 minutes, only need separate and to collect a part of solution of the aqueous phase solution that is arranged in lower floor to be measured as the pretreatment sample aqueous solution of petroleum product samples.Wherein, the running parameter of ultrasonic oscillator can be set is frequency 53KHz and power 100% to the condition of supersonic oscillations.
Measure according to an exemplary embodiment of the present invention the method for metal element content in oil product, it comprises the following steps: a) adopt above-mentioned sample pretreating method for measuring the oil product metal element content to process petroleum product samples, obtain the pretreatment sample of petroleum product samples; B) directly adopt one or more methods in GFAAS (graphite furnace atomic absorption spectrometry), flame atomic absorption spectrometry, ICP-AES or inductively coupled plasma mass spectrometry to measure metallic element in the pretreatment sample of described petroleum product samples, and finally calculate the metal element content in petroleum product samples.adopt the sample pretreating method for measuring the oil product metal element content of the present invention to process the petroleum product samples pretreatment sample that obtains and need not to carry out oxygenolysis, any processing again such as concentration and evaporation or dilution constant volume operate, directly adopt GFAAS (graphite furnace atomic absorption spectrometry), flame atomic absorption spectrometry, ICP-AES, one or more methods in inductively coupled plasma mass spectrometry or other chemical analysis method are measured iron in aqueous phase solution, copper, aluminium, zinc, chromium, nickel, vanadium, manganese, magnesium, the metallic elements such as cobalt, finally calculate insulating oil, lubricating oil, gasoline, in the original oil product such as diesel oil, the content of metallic element gets final product.
Measure each concentration of element value that obtains according to methods such as ICP-OES, ICP-MS, by formula calculate the content W of metallic element M in the oil product mother liquor M, represent with mass percent:
W M = V × ( c - c 0 ) × 10 - 6 m × 100
In formula:
W M---metal element content to be measured in petroleum product samples, %;
C---the concentration determination value of the metallic element to be measured in pretreatment sample, ug/mL;
c 0---the concentration determination value of the metallic element to be measured in blank diluted hydrochloric acid aqueous solution, ug/mL;
The volume of V---the diluted hydrochloric acid aqueous solution that adds during sample pretreatment, mL;
M---petroleum product samples take quality, g.
Thus, according to technical characterstic of the present invention and with the difference of existing Wet method, compare, invention has following advantage:
⑴ extract in reagent and only contain reductibility hydrochloric acid, be different from existing method and use perchloric acid, nitric acid, the oxidisability such as hydrogen peroxide or sulfuric acid reagent, therefore only with metallic element, react and can not react with the oil product organism, gas that chemical reaction produces seldom, thereby can directly carry out extractive reaction in airtight separating funnel, avoided the excessive hidden danger that causes of closed container internal pressure, do not need frequently to the reaction units such as separating funnel venting pressure release yet, intermediary operation link and labour intensity have been reduced, the dissolving that more is conducive to adopt the automation equipment such as ultrasonic fluctuation oscillator to carry out metallic element is extracted.
⑵ because the reductibility diluted hydrochloric acid aqueous solution does not produce destruction to organic substance in oil product, avoided oil product solution in extraction oscillating reactions process to produce phenomenons such as " emulsifications " fully, and because the organic phase of oil product still keeps its original character, the organic phase of collecting after standing and demixing owing to effectively having removed wearing and tearing or the metallic element of pollution, its physical performance index of detection that is mingled with can be used for noiseless impact.
⑶ whole extracting operation adopts disposable diluted hydrochloric acid aqueous solution and the whole process of adding to complete at the hot bath vibration one-time reaction of 80~90 ℃, need not repeatedly repeatedly to carry out extractive reaction, greatly simplify operation steps, shortened analysis process, omnidistance high-temperature extraction efficiency is high, and metallic impurity elements is dissolved and extracted fully.
⑷ extractive reaction whole process is carried out in airtight container, to add the volume of diluted hydrochloric acid aqueous solution be namely the volume of the pretreatment sample of the petroleum product samples for preparing, and use the basis of this volume as metal element content.Therefore, only need be after oscillating reactions finishes the oil mixture standing and demixing, separate and collect the aqueous phase solution of lower floor, directly with ICP-OE, ICP-MS etc., measure metallic element, not only need not to dilute the constant volume operation, and the consumption of diluted hydrochloric acid aqueous solution is controlled at 1/5th to 1/10th of oil quality, also namely according to the ratio of 5 to 10 times effectively enrichment method metallic impurity elements to be measured, more be conducive to improve the Accurate Determining of trace, trace element in oil product.
due to water phase separated and organic phase entirely with visual inspection, be difficult to complete noresidue or without being mingled with organic phase ground, lower floor's water separated and collected from blend mixture got off, this method has been defined as the volume of adding of diluted hydrochloric acid aqueous solution due to the volume of pretreatment sample to be measured, therefore do not require the complete separated and collected of lower floor's aqueous phase solution is got off, can only collect the part aqueous phase solution for ICP-OES, ICP-MS etc. measure required getting final product, make thus lock out operation greatly simple, reliability improves, in oil mixture residual have do not separate aqueous phase solution completely and measurement result had no effect yet.
⑹ the prepared aqueous phase solution of separated and collected only consists of metallic ion to be measured, hydrochloric acid and water, substrate medium is very simple, there are not residual organic matter matter or other chemical reagent, more are conducive to following adopted ICP-MS, ICP-OES, AAS or chemical analysis method and carry out Determination of Metals.
⑺ do not use other organic extraction reagent, and not only the analytical control cost is low, and the discard solution after detecting neutralizes after neutrality and effluxes the secondary pollution that can avoid environment with alkali.
Below in conjunction with concrete example, the present invention is described.
What the sample in concrete example of the present invention was selected is high-tension transformer insulating oil, equipment lubrication oil, gasoline and diesel oil, but is not limited to this.The abstraction reaction of adopting and multi_layer extraction container are separating funnel, but are not limited to this.Hydrochloric acid is that to be 36~38% concentrated hydrochloric acid and water form according to the volume ratio mixed preparing of 1:1 to 2:1 other mass percent concentration of the pure level of top grade, be also 1 part of diluted hydrochloric acid aqueous solution that concentrated hydrochloric acid adds 1 part of water to 2 part concentrated hydrochloric acid to add the dilution proportion of 1 part to form, and be heated to before use 50~80 ℃.Water is the distilled water that meets laboratory secondary water requirement.Use in example to be that the match of SK7200LHC type ultrasonic oscillator and the U.S. is silent fly your the X Series2 of company type icp ms of generation, but be not limited to this.
Particularly, what add in the vibration groove of ultrasonic oscillator is to be warmed in advance the hot water of 80~90 ℃, it is frequency 53KHz and power 100% that the ultrasonic oscillator running parameter is set, according to the oil quality that takes and metals content impurity thereof, carried out continuously sonic oscillation reaction 1~3 hour, the reacting gas that produces in the discharging reaction vessel 3~5 times in starting of oscillation 30 minutes.Oscillating reactions finishes rear standing 5~15 minutes after inorganic aqueous phase solution and organic oil phase layering, separates and collects the aqueous phase solution that is positioned at lower floor, and the last ICP-MS that directly adopts measures the content of metallic element.
Example 1:
The preparation of insulating oil pretreatment sample
Take 100g high-tension transformer insulating oil sample (hereinafter being called sample No. 1) among separating funnel, adding the 20mL temperature is the concentrated hydrochloric acid of 80 ℃ and the water diluted hydrochloric acid aqueous solution according to the volume ratio mixed preparing of 2:1, be placed in ultrasonic oscillator the hot bath continuous oscillation of 90 ℃ 3 hours, in firm starting oscillation 30 minutes, every 6 minutes unlatching separating funnel piston discharging reacting gas, after vibration finishes standing 15 minutes after inorganic aqueous phase solution and the complete layering of organic oil phase, separate and collect the about 10mL of aqueous phase solution that is positioned at lower floor.
Detect metal element content in oil product with icp ms (ICP-MS)
Collected lower floor's aqueous phase solution directly adopts ICP-MS as detection means, need not to take Internal standard correction methods and Matrix Match etc. to clear up jamming countermeasure, sensing range according to element to be measured, preparation and the aqueous phase solution of separated and collected contain the mixed standard solution of each element debita spissitudo to be measured of same concentrations hydrochloric acid as the working curve standard solution, and the metallic elements such as iron, copper, aluminium, zinc, chromium, nickel, vanadium, manganese, magnesium, cobalt are analyzed mensuration simultaneously.
The ICP-MS determination step carries out in the usual way, and for example, the running parameter that icp ms is set is: ICP power 1184W, cooling gas flow 13L/min, assisted gas flow 0.7L/min, atomization gas flow 0.90L/min, sample introduction speed 0.85mL/min.The Xt interface system, intercepting cone mouth aperture 0.75mm.Condenser lens voltage (Focus) 8.0v, level Four bar bias voltage (Pole Bias)-3.3v, six grades of bar bias voltages (Hex Bias)-4.0v, sampling depth (Samp ling Depth) 140 mm.Standard resolution 0.7amu, residence time 100ms, pulse detector (PC Detector) 2800v, analog detector (Analogue Detector) 1450v.
Test findings is in Table each element determination result of No. 1 sample in 1.
Example 2
Take 50g high-tension transformer insulating oil sample (hereinafter being called sample No. 2) among separating funnel, adding the 10mL temperature is the concentrated hydrochloric acid of 50 ℃ and the water diluted hydrochloric acid aqueous solution according to the volume ratio mixed preparing of 1:1, be placed in ultrasonic oscillator the hot bath continuous oscillation of 80 ℃ 1 hour, in firm starting oscillation 30 minutes, every 10 minutes unlatching separating funnel piston emission gases, after vibration finishes standing 5 minutes, separate and collect the about 8mL of aqueous phase solution that is positioned at lower floor.
In addition, dissolve according to the step identical with example 1 aqueous phase solution that extracts metallic element in oil product and detect separated and collected with ICP-MS.
Test findings is in Table each element determination result of No. 2 samples in 2.
Example 3
Take 80g lubricating oil sample (hereinafter being called sample No. 3) among separating funnel, adding the 10mL temperature is the concentrated hydrochloric acid of 65 ℃ and the water diluted hydrochloric acid aqueous solution according to the volume ratio mixed preparing of 1.5:1, be placed in ultrasonic oscillator the hot bath continuous oscillation of 85 ℃ 2 hours, in firm starting oscillation 30 minutes, every 7 minutes unlatching separating funnel piston emission gases, after vibration finishes standing 12 minutes, separate and collect the about 8mL of aqueous phase solution that is positioned at lower floor.
In addition, dissolve according to the step identical with embodiment 1 aqueous phase solution that extracts metallic element in oil product and detect separated and collected with ICP-MS.
Test findings is in Table each element determination result of No. 3 samples in 1.
Example 4
Take 60g lubricating oil sample (hereinafter being called sample No. 4) among separating funnel, adding the 10mL temperature is the concentrated hydrochloric acid of 70 ℃ and the water diluted hydrochloric acid aqueous solution according to the volume ratio mixed preparing of 1:1, be placed in ultrasonic oscillator the hot bath continuous oscillation of 85 ℃ 2 hours, in firm starting oscillation 30 minutes, every 6 minutes unlatching separating funnel piston emission gases, after vibration finishes standing 15 minutes, separate and collect the about 8mL of aqueous phase solution that is positioned at lower floor.
In addition, dissolve according to the step identical with embodiment 1 aqueous phase solution that extracts metallic element in oil product and detect separated and collected with ICP-MS.
Test findings is in Table each element determination result of No. 4 samples in 2.
Example 5
Take 70g gasoline sample (hereinafter being called sample No. 5) among separating funnel, adding the 10mL temperature is the concentrated hydrochloric acid of 80 ℃ and the water diluted hydrochloric acid aqueous solution according to the volume ratio mixed preparing of 1:1, be placed in ultrasonic oscillator the hot bath continuous oscillation of 90 ℃ 2 hours, in firm starting oscillation 30 minutes, every 6 minutes unlatching separating funnel piston emission gases, after vibration finishes standing 15 minutes, separate and collect the about 8mL of aqueous phase solution that is positioned at lower floor.
In addition, dissolve according to the step identical with embodiment 1 aqueous phase solution that extracts metallic element in oil product and detect separated and collected with ICP-MS.
Test findings is in Table each element determination result of No. 5 samples in 1.
Example 6
Take 90g diesel samples (hereinafter being called sample No. 6) among separating funnel, adding the 15mL temperature is the concentrated hydrochloric acid of 80 ℃ and the water diluted hydrochloric acid aqueous solution according to the volume ratio mixed preparing of 1:1, be placed in ultrasonic oscillator the hot bath continuous oscillation of 90 ℃ 2 hours, in firm starting oscillation 30 minutes, every 6 minutes unlatching separating funnel piston emission gases, after vibration finishes standing 15 minutes, separate and collect the aqueous phase solution that is positioned at lower floor.
In addition, dissolve approximately 10mL of the aqueous phase solution that extracts metallic element in oil product and detect separated and collected with ICP-MS according to the step identical with embodiment 1.
Test findings is in Table each element determination result of No. 6 samples in 2.
Example 7
No. 1, No. 3, No. 5 oil product samples are carried out respectively independently preparation and the analysis mensuration of petroleum product samples pretreatment sample 8 times, 8 measurement results are carried out statistical treatment, (RSD) assesses precision of the present invention according to relative standard deviation.Measurement result is in Table 1.
Table 1 measurement result precision of the present invention (n=8) (%)
As seen from Table 1, RSD<10%.As seen the precision of the petroleum product samples pre-service preparation of example and element determination method is good according to the present invention, easy grasp simple to operation, except artificial title sample, acid adding, all the other preparation process are automatically performed according to setting program by ultrasonic oscillator, repeatedly measurement result is consistent, and repeatability, repeatability is good.
Example 8
By ICP-MS, No. 2, No. 4 of 6 pre-service preparations of embodiment 2, embodiment 4, embodiment and No. 6 pretreatment sample are carried out the mensuration of metal element content.
then, adopt respectively more existing analytical approach to No. 2, No. 4 and No. 6 petroleum product samples are carried out the mensuration of metal element content to carry out the contrast of result, its concrete steps are: take the 50g petroleum product samples in the platinum crucible of 50mL, temperature is controlled at slightly lower than carrying out the Asia heating evaporation that boils below the oil product boiling point and removes organic substance in oil product until only remain the inorganics residue, then in muffle furnace at 600 ℃ of temperature the about 1h of calcination ash residue, be placed in platinum crucible on electric hot plate and add 5mL nitric acid heating leaching to clear up, drip approximately 2~3mL hydrogen peroxide therebetween, until being cleared up fully, residue enters solution, boil the reagent such as decomposing excessive hydrogen peroxide, with the water constant volume in the color comparison tube of 10mL, measure metal element content with ICP-MS finally.The measurement result contrast of the present invention and existing analytical approach is in Table 2.
Table 2 analysis result control test (10 -9G/g)
By as seen from Table 2, detection analysis result of the present invention is consistent with traditional assay method, shows that this method has higher accuracy and reliability.
Oil product sample pretreatment preparation method of the present invention is simple to operate, efficient quick, labour intensity are little, artifical influence factor is few, easily accurately control and repetition, the technical indicator such as analysis result accuracy, precision is good, few cycle of inspection process is short, analysis speed is fast, in conjunction with using the Instrument measuring methods such as ICP-MS, ICP-OES, easily completed sample preparation and element determination with interior in 2-4 hour, and more can meet the on-the-spot oil quality of modern industry fast pace production application and detect the needs of analysis and Control.
Although in conjunction with exemplary embodiment, illustrated and described the present invention, the invention is not restricted to this., in the situation that do not break away from spirit of the present invention and instruction, can make and revising and distortion embodiment.Scope of the present invention is limited by claim and equivalent thereof.

Claims (9)

1. a sample pretreating method that is used for measuring the oil product metal element content, is characterized in that, said method comprising the steps of:
A) add diluted hydrochloric acid aqueous solution in petroleum product samples, be placed in hot bath and carry out supersonic oscillations and obtain oil mixture;
B) after the oil mixture standing and demixing, separate and collect the aqueous phase solution of lower floor, obtain the pretreatment sample of petroleum product samples.
2. the sample pretreating method for measuring the oil product metal element content according to claim 1, it is characterized in that, described diluted hydrochloric acid aqueous solution is, and to be 36~38% concentrated hydrochloric acid and water by mass percent concentration form according to the volume ratio mixed preparing of 1:1 to 2:1.
3. the sample pretreating method for measuring the oil product metal element content according to claim 1, is characterized in that, the temperature of described diluted hydrochloric acid aqueous solution is 50~80 ℃, and the temperature of described hot bath is 80~90 ℃.
4. the sample pretreating method for measuring the oil product metal element content according to claim 2, is characterized in that, the addition of described diluted hydrochloric acid aqueous solution is 1/10 to 1/5 of petroleum product samples quality.
5. the sample pretreating method for measuring the oil product metal element content according to claim 1, is characterized in that, the time of supersonic oscillations is 1~3 hour, and in 30 minutes of starting oscillation, discharging reacting gas 3~5 times.
6. the sample pretreating method for measuring the oil product metal element content according to claim 1, is characterized in that, after the oil mixture standing and demixing, separates and collect the aqueous phase solution of part lower floor.
7. the sample pretreating method for measuring the oil product metal element content according to claim 1, is characterized in that, described petroleum product samples is insulating oil, lubricating oil, gasoline, diesel oil.
8. a method of measuring metal element content in oil product, is characterized in that, said method comprising the steps of:
A) adopt the described sample pretreating method for measuring the oil product metal element content of any one in claim 1 to 7 to process petroleum product samples, obtain the pretreatment sample of petroleum product samples;
B) directly adopt one or more methods in GFAAS (graphite furnace atomic absorption spectrometry), flame atomic absorption spectrometry, ICP-AES or inductively coupled plasma mass spectrometry to measure metallic element in the pretreatment sample of described petroleum product samples, and finally calculate the metal element content W in oil product M.
9. the method for metal element content in mensuration oil product according to claim 8, is characterized in that, calculates according to the following formula the metal element content in oil product, with mass percent, represents:
W M = V × ( c - c 0 ) × 10 - 6 m × 100
Wherein, W M---the content of the metallic element to be measured in petroleum product samples, %;
C---the concentration determination value of the metallic element to be measured in pretreatment sample, ug/mL;
c 0---the concentration determination value of the metallic element to be measured in blank diluted hydrochloric acid aqueous solution, ug/mL;
The volume of V---the diluted hydrochloric acid aqueous solution that adds during sample pretreatment, mL;
M---petroleum product samples take quality, g.
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CN105319201A (en) * 2014-07-29 2016-02-10 上海宝钢工业技术服务有限公司 Simultaneous determination method of contents of nickel, iron, and zinc in pre-plating nickel solution
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CN105572053B (en) * 2015-12-30 2018-07-10 中国神华能源股份有限公司 Lubricating oil sample impurity minimizing technology and analysis method in mining equipment oil liquid monitoring spectrum analysis
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CN111965227B (en) * 2020-08-24 2021-04-20 江苏新智合电力技术有限公司 Safety monitoring management platform of transformer substation

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