CN103389233B - 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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CN103389233B
CN103389233B CN201310300690.8A CN201310300690A CN103389233B CN 103389233 B CN103389233 B CN 103389233B CN 201310300690 A CN201310300690 A CN 201310300690A CN 103389233 B CN103389233 B CN 103389233B
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oil
sample
samples
petroleum
content
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CN201310300690.8A
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CN103389233A (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 trace element detection analysis field, relate to a kind of method and the sample pretreating method thereof that measure 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 measure the detection method of metal element content contained by it.
Background technology
Usually, need to add adjuvant in order to improve the performance of oil product in petroleum refining process, but this technique may cause introducing metallic element thus affecting oil quality and secondary deep processing thereof, as fuel oil, lubricating oil, light diesel fuel etc. will cause catalyst poisoning containing elements such as iron, copper, nickel, in transformer insulation oil, the pollution element such as iron, copper, lead, tin affects insulation effect, therefore detects metallic impurity elements in oil product and can instruct the improvement of Oil Production technique and the raising of product quality; And, by detecting and monitoring metallic element existing in transformer insulated wet goods oil product and the variation tendency of content thereof, effectively can help the replacing opportunity of judge oil product and search transformer potential risk or accident classification reason, as, in transformer insulation oil, iron content raises the metal baffle etc. then needing to detect stainless steel zero defect, and copper content raises parts such as then needing the copper wire of detection zero defect; In addition, for probing into equipment attrition mechanism and prediction wear trend, need to detect the composition such as wear metal, pollution element and content in oil product, according to composition and the content trend thereof of Wear metal, the abrasion condition of judgment device associate components.
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-injection technique, there are atomic emission spectrometry, atomic absorption spectrography (AAS) and x ray fluorescence spectrometry three major types in the mensuration mode past, in recent years along with the development of plasma mass technology is popularized, its oil product detect in application day by day increase.At present, mostly main stream approach is to adopt the modes such as evaporation, ashing, reagent oxidation decomposition be separated by the organism in oil product or destroy, thus eliminate organism to the disturbing effect measured, then residue is measured the metallic elements such as iron in oil product, copper, lead, tin, arsenic, silver, chromium, nickel, vanadium to adopt inductively coupled plasma mass spectrometry (ICP-MS) or ICP-AES (ICP-OES) after acid dissolve.
Specifically, now by special oil product sample introduction transmission system imported the instruments such as inductively coupled plasma atomic emission spectrum (ICP-OES) measure except except adopting organic reagent by direct after oil product dilution by the method detecting metallic element in oil product, other the oil product pre-service preparation method such as ashing method, Wet method, high pressure-volume bullet method, Microwave Digestion, be mostly first by oxidative decomposition in order to destroy the organic substance in oil product, then residual inorganic metal element is cleared up and enters aqueous solution and measure.Such as, first in platinum crucible, low-temperature evaporation removes contained organic substance in oil product, then carbonized residue, then high temperature sintering ashing is until only remain inorganic residue material, finally add hydrochloric acid or the heating leaching such as nitric acid, hydrogen peroxide and clear up reaction to the elimination preparation carrying out organic oils sample completely, adopt the instrument analytical methods such as ICP-OES, ICP-MS to measure constituent content in oil product.Although these class methods can decompose the organic substance destroyed in oil product effectively, eliminate it to the impact measured, but shortcoming is also apparent, as long in analysis process, operation steps is many, labour intensity is large, particularly for insulating oil, the lubrication wet goods oil product of volatility difference, because impurity content is low, it is comparatively large to take sample size, only complete the time that evaporation step just may need 2-3 days.
Also there is the pre-service by employing nitric acid-hydrogen peroxide-petroleum ether system, oil sample being carried out to extract and separate, then measure the method for the impurity metallic elements content in nitric acid cut with ICP-OES.But also there is the oxidizable decomposing organic matter of oxidisability extractive reaction medium and cause the shortcoming of emulsion in these class methods, and reaction or decomposition can produce the toxic gases such as the brown flue gas of a large amount of nitrogen dioxide, thus can only at open container and be positioned over sterilization cupboard in carry out; Need a large amount of sherwood oil reagent that uses to add 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 for the shortcomings such as the mensuration of trace, trace metal element in oil product.
Therefore, need to provide a kind of operate simple and easy, the cycle is short and the method for metal element content and sample pretreating method thereof in the mensuration oil product that precision is higher.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to solve in above-mentioned prior art the one or more problems existed.
The object of the present invention is to provide a kind of can obtain oil product simply, quickly and accurately pretreatment sample and the method for wherein contained concentration of metallic impurities.
An aspect of of the present present invention provides a kind of sample pretreating method for measuring metal element content in oil product, said method comprising the steps of: a) in petroleum product samples, add diluted hydrochloric acid aqueous solution, be placed in hot bath and carry out supersonic oscillations and obtain oil mixture; B) after oil mixture stratification, be separated and collect the aqueous phase solution of lower floor, obtaining the pretreatment sample of petroleum product samples.
According to an embodiment of the sample pretreating method for measuring metal element content in oil product of the present invention, described diluted hydrochloric acid aqueous solution be by mass percent concentration be 36 ~ 38% concentrated hydrochloric acid and water 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 metal element content in oil product of the present invention, the temperature of described diluted hydrochloric acid aqueous solution is 50 ~ 80 DEG C, and the temperature of described hot bath is 80 ~ 90 DEG C.
According to an embodiment of the sample pretreating method for measuring metal element content in oil product 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 metal element content in oil product of the present invention, the time of supersonic oscillations is 1 ~ 3 hour, and in 30 minutes that start to vibrate, discharge reacting gas 3 ~ 5 times.
According to an embodiment of the sample pretreating method for measuring metal element content in oil product of the present invention, after oil mixture stratification, being separated and collecting the aqueous phase solution of section bottom.
According to an embodiment of the sample pretreating method for measuring metal element content in oil product of the present invention, described petroleum product samples is insulating oil, lubricating oil, gasoline, diesel oil.
Another aspect provides a kind of method measuring metal element content in oil product, said method comprising the steps of: a) adopting the above-mentioned sample pretreating method process petroleum product samples for measuring metal element content in oil product, obtaining the pretreatment sample of petroleum product samples; B) one or more methods in GFAAS (graphite furnace atomic absorption spectrometry), flame atomic absorption spectrometry, ICP-AES or inductively coupled plasma mass spectrometry are directly adopted to measure metallic element in the pretreatment sample of described petroleum product samples, and the final metal element content calculated in oil product.
According to an embodiment of 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, represent with mass percent:
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 measurement of the metallic element to be measured in pretreatment sample, ug/mL;
C 0---the concentration measurement of the metallic element to be measured in blank diluted hydrochloric acid aqueous solution, ug/mL;
V---the volume of the diluted hydrochloric acid aqueous solution added during sample pretreatment, mL;
M---petroleum product samples take quality, g.
The present invention effectively can eliminate organic substance in oil product and, on the impact measured, compensate for now methodical technological deficiency simultaneously, do not need through numerous and diverse and very long evaporation, carbonization, the course of reaction such as ashing and leaching, therefore not only avoid in evaporation, in the processes such as ashing, metallic element to be measured is taken away loss by flue gas and causes testing result on the low side, and only needs add extraction reagent and carry out oscillating operation, and the aqueous phase solution of separated and collected is also without the need to being oxidized again, clear up, dilution, any process such as constant volume directly can measure impurity content, enormously simplify 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 matrix medium of preparation is simpler, disturbing effect factor is less, meets accurately to detect completely to analyze insulating oil, lubricating oil, gasoline, iron in all kinds of oil product sample 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 carrying out regular tracking and monitoring to the metallic impurity elements of wearing and tearing or pollution in insulating oil, lubrication wet goods oil product, the insulation of timely understanding grasp equipment, lubrication and state of wear information, diagnostic device weares and teares or produces the type of fault, position and reason, for maintenance of equipment provides scientific basis, enterprise is instructed to carry out State Maintenance and the lubricating management of equipment, thus prevention substantial equipment accident occurs, and reduces equipment maintenance cost.
Embodiment
Hereinafter, method and the sample pretreating method thereof of metal element content in mensuration oil product of the present invention will be specifically described in conjunction with the embodiments.
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, efficient in the mode of supersonic oscillations, rapidly the metallic impurity elements to be measured in oil product being dissolved and extracted makes it enter inorganic aqueous phase solution, by the stratification of inorganic aqueous phase and organic oil phase, thus simply and easily prepared metallic element detected aqueous solution and do not go to pot and separated completely by the complete organic oil phase remained, lower floor's aqueous phase solution of institute's separated and collected is namely as the pretreatment sample of petroleum product samples.Substrate medium due to lower floor's aqueous phase solution forms very simple, thus without the need to carrying out any process again, directly can adopt the metallic element contained in the instruments such as ICP-OES, ICP-MS, AAS or other chemical gauging aqueous phase solution.
According to an exemplary embodiment of the present invention for measuring the sample pretreating method of metal element content in oil product, its concrete steps comprise:
First, in petroleum product samples, add diluted hydrochloric acid aqueous solution, be placed in hot bath and carry out supersonic oscillations and obtain oil mixture; Secondly, after oil mixture stratification, be separated and collect the aqueous phase solution of lower floor, obtaining the pretreatment sample of petroleum product samples.
Preferably, after oil mixture stratification, only need to be separated and to collect the aqueous phase of section bottom molten as pretreatment sample, do not need the aqueous phase solution that complete separated and collected is whole, this makes lock out operation greatly simplify, reliability improves, and remains and be not separated aqueous phase solution completely and also have no effect to measurement result in oil mixture.
Preferably, described diluted hydrochloric acid aqueous solution be by mass percent concentration be 36 ~ 38% concentrated hydrochloric acid and water 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, disposablely join in oil product, then omnidistance disposable continuous ultrasonic oscillating reactions in the hot bath of 80 ~ 90 DEG C in airtight separating funnel, only needs after leaving standstill dividing potential drop to collect lower floor's hydrochloric acid aqueous phase solution directly can measure metallic impurity elements for methods such as ICP-OES or ICP-MS content as pretreatment sample.
According to an embodiment of the sample pretreating method for measuring metal element content in oil product 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 being equivalent to diluted hydrochloric acid aqueous solution is the diluted hydrochloric acid aqueous solution that every gram of petroleum product samples adds 0.1 ~ 0.2ml.Usually, the density of diluted hydrochloric acid aqueous solution is admitted for the consistent in density with water, then milliliter with gram numerical value be equal to, also namely for diluted hydrochloric acid aqueous solution, 1ml is 1g, in the present invention, takes petroleum product samples 50 ~ 100g, diluted hydrochloric acid aqueous solution 5 ~ 20g can be added, be equivalent to 5 ~ 20mL.Also dissolving extraction by metallic element contained in petroleum product samples with the concentration ratio relation of 5 ~ 10 times enters among aqueous phase solution, thus realize the object of dissolving extraction and concentration enrichment metallic ion to be measured once, solve and usually require that further element assay method has the technical barrier of stronger detectability because metallic impurity elements content in oil product is low, reduce detection method requirement, improve accuracy and the precision of determination of trace element.
Preferably, 50 ~ 80 DEG C are heated to using as the diluted hydrochloric acid aqueous solution dissolving extraction agent, and, the temperature of hot bath is 80 ~ 90 DEG C, can greatly accelerate like this to dissolve the reaction velocity extracting metallic element, reduce the consumption of diluted hydrochloric acid aqueous solution, shorten and measure sample detection solution preparation step required time the most consuming time in the inspection process of metallic element in oil product, substantially increase the speed detecting and analyze.
In oscillatory process, preferably, the time of supersonic oscillations is 1 ~ 3 hour, and in 30 minutes that start to vibrate, the closed reaction vessels such as separating funnel is opened to the discharge 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, according to an embodiment of the sample pretreating method for measuring metal element content in oil product of the present invention, taking 50 ~ 100g petroleum product samples is placed among separating funnel or other chemical reaction container, the temperature adding 1/to ten/5th of taken oil quality is that the above-mentioned diluted hydrochloric acid aqueous solution of 50 ~ 80 DEG C is as dissolving extraction agent, be placed in ultrasonic oscillator again the hot bath continuous oscillation of 80 ~ 90 DEG C, then leave standstill after within 5 ~ 15 minutes, waiting for inorganic aqueous phase and organic oil phase layering, only need to be separated and to collect a part of solution of the aqueous phase solution being arranged in lower floor to be measured as the pretreatment sample aqueous solution of petroleum product samples.Wherein, the condition of supersonic oscillations can arrange the running parameter of ultrasonic oscillator is frequency 53KHz and power 100%.
Measure the method for metal element content in oil product according to an exemplary embodiment of the present invention, it comprises the following steps: a) adopting the above-mentioned sample pretreating method process petroleum product samples for measuring metal element content in oil product, obtaining 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 petroleum product samples pretreatment sample obtained for the sample pretreating method process measuring metal element content in oil product of the present invention without the need to carrying out oxygenolysis, any reprocessing operations such as concentration and evaporation or dilution constant volume, direct employing 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 measure 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, the content of metallic element in the original oil product such as diesel oil.
The each concentration of element value obtained is measured, by the content W of metallic element M in formulae discovery oil product mother liquor according to methods such as ICP-OES, ICP-MS 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 measurement of the metallic element to be measured in pretreatment sample, ug/mL;
C 0---the concentration measurement of the metallic element to be measured in blank diluted hydrochloric acid aqueous solution, ug/mL;
V---the volume of the diluted hydrochloric acid aqueous solution added during sample pretreatment, mL;
M---petroleum product samples take quality, g.
Thus, compare according to technical characterstic of the present invention and with the difference of existing Wet method, invention tool has the following advantages:
(1) extract in reagent only containing reductibility hydrochloric acid, be different from existing method and use perchloric acid, nitric acid, the oxidative reagent such as hydrogen peroxide or sulfuric acid, therefore only react with metallic element and can not react with oil product organism, gas that chemical reaction produces is little, thus in airtight separating funnel, directly can carry out extractive reaction, avoid the hidden danger that pressure in closed container is excessive caused, do not need frequently to reaction unit venting pressure releases such as separating funnels yet, decrease intermediary operation link and labour intensity, the dissolving being more conducive to adopting the automation equipments such as ultrasonic fluctuation oscillator to carry out metallic element is extracted.
(2) because reductibility diluted hydrochloric acid aqueous solution does not produce destruction to organic substance in oil product, completely avoid oil product solution in extraction oscillating reactions process and produce phenomenons such as " emulsifications ", and still keep its original character due to the organic phase of oil product, the organic phase of collecting after stratification, owing to effectively removing the metallic element of wearing and tearing or the pollution be mingled with, detects its physical performance index with can be used for noiseless impact.
(3) whole extracting operation adopts and disposablely adds diluted hydrochloric acid aqueous solution and whole process completes at the hot bath vibration one-time reaction of 80 ~ 90 DEG C, without the need to repeatedly repeatedly carrying out extractive reaction, enormously simplify operation steps, shorten analysis process, omnidistance high-temperature extraction efficiency is high, and metallic impurity elements is dissolved and extracted completely.
(4) extractive reaction whole process is carried out in airtight container, add diluted hydrochloric acid aqueous solution volume be namely the volume of the pretreatment sample of the petroleum product samples prepared, and using this volume as the basis of metal element content.Therefore, only need after oscillating reactions terminates oil mixture stratification, be separated and collect the aqueous phase solution of lower floor, directly measure metallic element with ICP-OE, ICP-MS etc., not only without the need to diluting constant volume operation, and the consumption of diluted hydrochloric acid aqueous solution controls at 1/10 to ten/5th of oil quality, also namely according to the ratio enrichment method metallic impurity elements to be measured effectively of 5 to 10 times, be more conducive to the Accurate Determining improving trace, trace element in oil product.
(5) because water phase separated and organic phase are entirely with visual inspection, lower floor's aqueous phase separated and collected from blend mixture is got off by very difficult complete noresidue or nothing with being mingled with organic phase, this method has been defined as the volume of added diluted hydrochloric acid aqueous solution due to the volume of pretreatment sample to be measured, therefore complete for lower floor's aqueous phase solution separated and collected is not required to get off, only can collect part aqueous phase solution for ICP-OES, ICP-MS etc. measure required, make lock out operation greatly simple thus, reliability improves, remain in oil mixture and be not separated aqueous phase solution completely and also measurement result had no effect.
(6) the prepared aqueous phase solution of separated and collected is only made up of metallic ion to be measured, hydrochloric acid and water, substrate medium is very simple, there is not residual organic matter matter or other chemical reagent, advantageously carry out Determination of Metals in follow-up employing ICP-MS, ICP-OES, AAS or chemical analysis method.
(7) do not use other organic extraction reagent, not only analytical control cost is low, and the discard solution after detecting neutralizes with alkali, and neutrality is outer afterwards arranges the secondary pollution can avoided environment.
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 adopted and multi_layer extraction container are separating funnel, but are not limited to this.Hydrochloric acid to be the mass percent concentration of the pure rank of top grade be 36 ~ 38% concentrated hydrochloric acid and water form according to the volume ratio mixed preparing of 1:1 to 2:1, namely also 1 part of concentrated hydrochloric acid adds the diluted hydrochloric acid aqueous solution that 1 part of water to 2 part concentrated hydrochloric acid adds the dilution proportion of 1 part, and is heated to 50 ~ 80 DEG C before use.Water is the distilled water meeting laboratory secondary water requirement.Use SK7200LHC type ultrasonic oscillator and U.S. match Mo Feishier company X Series2 type icp ms in example, but be not limited to this.
Particularly, what add in the vibration groove of ultrasonic oscillator is be warmed to the hot water of 80 ~ 90 DEG C in advance, arranging ultrasonic oscillator running parameter is frequency 53KHz and power 100%, according to taken oil quality and metals content impurity thereof, carry out sonic oscillation reaction 1 ~ 3 hour continuously, discharge the reacting gas that produces in reaction vessel in 30 minutes 3 ~ 5 times at starting of oscillation.Oscillating reactions terminates latter standing 5 ~ 15 minutes after inorganic aqueous phase solution and organic oil phase layering, is separated and collects the aqueous phase solution being 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 (being hereafter called No. 1 sample) among separating funnel, adding 20mL temperature is the concentrated hydrochloric acid of 80 DEG C 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 3 hours of 90 DEG C, just starting to vibrate in 30 minutes, separatory funnel stopcock discharge reacting gas is opened every 6 minutes, vibration terminates latter standing 15 minutes after inorganic aqueous phase solution and the complete layering of organic oil phase, is separated and collects the aqueous phase solution being positioned at lower floor to be about 10mL.
metal element content in oil product is detected with icp ms (ICP-MS)
Collected lower floor's aqueous phase solution directly adopts ICP-MS as detection means, jamming countermeasure is cleared up without the need to taking Internal standard correction methods and Matrix Match etc., according to the sensing range of element to be measured, preparation contains the mixed standard solution of the element debita spissitudo each to be measured of same concentrations hydrochloric acid as working curve standard solution with the aqueous phase solution of separated and collected, carries out analysis simultaneously measure metallic elements such as iron, copper, aluminium, zinc, chromium, nickel, vanadium, manganese, magnesium, cobalts.
ICP-MS determination step carries out in the usual way, and such as, the running parameter arranging icp ms 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.Xt interface system, intercepts 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 voltage (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 each element determination result of No. 1 sample in table 1.
example 2
Take 50g high-tension transformer insulating oil sample (being hereafter called No. 2 samples) among separating funnel, adding 10mL temperature is the concentrated hydrochloric acid of 50 DEG C 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 1 hour of 80 DEG C, just starting to vibrate in 30 minutes, separatory funnel stopcock emission gases is opened every 10 minutes, vibration terminates latter standing 5 minutes, is separated and collects the aqueous phase solution being positioned at lower floor to be about 8mL.
In addition, dissolve according to the step identical with example 1 and extract metallic element in oil product and the aqueous phase solution detecting separated and collected with ICP-MS.
Test findings is in each element determination result of No. 2 samples in table 2.
example 3
Take 80g lubricating oil sample (being hereafter called No. 3 samples) among separating funnel, adding 10mL temperature is the concentrated hydrochloric acid of 65 DEG C 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 2 hours of 85 DEG C, just starting to vibrate in 30 minutes, separatory funnel stopcock emission gases is opened every 7 minutes, vibration terminates latter standing 12 minutes, is separated and collects the aqueous phase solution being positioned at lower floor to be about 8mL.
In addition, dissolve according to the step identical with embodiment 1 and extract metallic element in oil product and the aqueous phase solution detecting separated and collected with ICP-MS.
Test findings is in each element determination result of No. 3 samples in table 1.
example 4
Take 60g lubricating oil sample (being hereafter called No. 4 samples) among separating funnel, adding 10mL temperature is the concentrated hydrochloric acid of 70 DEG C 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 2 hours of 85 DEG C, just starting to vibrate in 30 minutes, separatory funnel stopcock emission gases is opened every 6 minutes, vibration terminates latter standing 15 minutes, is separated and collects the aqueous phase solution being positioned at lower floor to be about 8mL.
In addition, dissolve according to the step identical with embodiment 1 and extract metallic element in oil product and the aqueous phase solution detecting separated and collected with ICP-MS.
Test findings is in each element determination result of No. 4 samples in table 2.
example 5
Take 70g gasoline sample (being hereafter called No. 5 samples) among separating funnel, adding 10mL temperature is the concentrated hydrochloric acid of 80 DEG C 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 2 hours of 90 DEG C, just starting to vibrate in 30 minutes, separatory funnel stopcock emission gases is opened every 6 minutes, vibration terminates latter standing 15 minutes, is separated and collects the aqueous phase solution being positioned at lower floor to be about 8mL.
In addition, dissolve according to the step identical with embodiment 1 and extract metallic element in oil product and the aqueous phase solution detecting separated and collected with ICP-MS.
Test findings is in each element determination result of No. 5 samples in table 1.
example 6
Take 90g diesel samples (being hereafter called No. 6 samples) among separating funnel, adding 15mL temperature is the concentrated hydrochloric acid of 80 DEG C 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 2 hours of 90 DEG C, just starting to vibrate in 30 minutes, separatory funnel stopcock emission gases is opened every 6 minutes, vibration terminates latter standing 15 minutes, is separated and collects the aqueous phase solution being positioned at lower floor.
In addition, dissolve according to the step identical with embodiment 1 and extract metallic element in oil product and be about 10mL with the aqueous phase solution that ICP-MS detects separated and collected.
Test findings is in each element determination result of No. 6 samples in table 2.
example 7
To No. 1, No. 3, No. 5 oil product samples carry out respectively 8 times independently petroleum product samples pretreatment sample preparation and analyze measure, statistical treatment is carried out to 8 measurement results, assesses precision of the present invention according to relative standard deviation (RSD).Measurement result is in table 1.
Table 1 measurement result precision (n=8) (%) of the present invention
As seen from Table 1, RSD < 10%.Visible according to the petroleum product samples pre-service preparation of example of the present invention and the precision of element determination method good, easy grasp simple to operation, except manually sampling, except 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 are good.
example 8
No. 2, No. 4 that are prepared embodiment 2, embodiment 4, embodiment 6 pre-service by ICP-MS and No. 6 pretreatment sample carry out the mensuration of metal element content.
Then, adopt existing analytical approach to No. 2 more respectively, No. 4 and No. 6 petroleum product samples carry out the mensuration of metal element content to carry out the contrast of result, its concrete steps are: take 50g petroleum product samples in the platinum crucible of 50mL, temperature control slightly lower than carry out below oil product boiling point Asia boil heating evaporation removing oil product in organic substance until only remain mineral residue, then in muffle furnace, at 600 DEG C of temperature, calcination ash residue is about 1h, platinum crucible to be placed on electric hot plate and to add the leaching of 5mL nitration acid heat and clear up, drip about 2 ~ 3mL hydrogen peroxide therebetween, until residue is cleared up completely enter solution, boil the reagent such as decomposing excessive hydrogen peroxide, with water constant volume in the color comparison tube of 10mL, finally measure metal element content with ICP-MS.The present invention contrasts in table 2 with the measurement result of existing analytical approach.
Table 2 analysis result control test (10 -9g/g)
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, inspection process few cycle is short, analysis speed is fast, the Instrument measuring methods such as R. concomitans ICP-MS, ICP-OES, easily complete sample preparation and element determination within 2-4 hour, more can meet the needs that the on-the-spot oil quality of modern industry fast pace production application detects analysis and Control.
Although illustrate and describe the present invention in conjunction with exemplary embodiment, the present invention is not limited thereto.When not departing from spirit of the present invention and instruction, amendment and distortion can be made to embodiment.Scope of the present invention is by claim and equivalents thereof.

Claims (5)

1. for measuring a sample pretreating method for metal element content in oil product, it is characterized in that, said method comprising the steps of:
A) in petroleum product samples, the diluted hydrochloric acid aqueous solution that temperature is 50 ~ 80 DEG C is added, be placed in temperature and be the hot bath of 80 ~ 90 DEG C and the supersonic oscillations of carrying out 1 ~ 3 hour obtain oil mixture, in 30 minutes that start to vibrate, discharge reacting gas 3 ~ 5 times, described diluted hydrochloric acid aqueous solution is the concentrated hydrochloric acid of 36 ~ 38% and water forms according to the volume ratio mixed preparing of 1:1 to 2:1 and the addition of described diluted hydrochloric acid aqueous solution is 1/10 to 1/5 of petroleum product samples quality by mass percent concentration;
B) after oil mixture stratification, be separated and collect the aqueous phase solution of lower floor, obtaining the pretreatment sample of petroleum product samples,
Wherein, described diluted hydrochloric acid aqueous solution makes it enter in the aqueous phase solution of oil mixture as dissolving extraction agent and the Determination of multiple metal elements in petroleum product samples being dissolved and extracted.
2. the sample pretreating method for measuring metal element content in oil product according to claim 1, is characterized in that, after oil mixture stratification, is separated and collects the aqueous phase solution of section bottom.
3. the sample pretreating method for measuring metal element content in oil product according to claim 1, is characterized in that, described petroleum product samples is insulating oil, lubricating oil, gasoline, diesel oil.
4. measure a method for metal element content in oil product, it is characterized in that, said method comprising the steps of:
A) adopting the sample pretreating method process petroleum product samples for measuring metal element content in oil product according to any one of claims 1 to 3, obtaining the pretreatment sample of petroleum product samples;
B) one or more methods in GFAAS (graphite furnace atomic absorption spectrometry), flame atomic absorption spectrometry, ICP-AES or inductively coupled plasma mass spectrometry are directly adopted to measure metallic element in the pretreatment sample of described petroleum product samples, and the final metal element content W calculated in oil product m.
5. the method for metal element content in mensuration oil product according to claim 4, is characterized in that, calculates the metal element content in oil product according to the following formula, represents with mass percent:
W M = V &times; ( c - c 0 ) &times; 10 - 6 m &times; 100
Wherein, W m---the content of the metallic element to be measured in petroleum product samples, %;
C---the concentration measurement of the metallic element to be measured in pretreatment sample, ug/mL;
C 0---the concentration measurement of the metallic element to be measured in blank diluted hydrochloric acid aqueous solution, ug/mL;
V---the volume of the diluted hydrochloric acid aqueous solution added during sample pretreatment, mL;
M---petroleum product samples take quality, g.
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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103604767B (en) * 2013-11-26 2016-05-04 中国南方航空工业(集团)有限公司 The assay method of cobalt content in cutting oil
CN104880341A (en) * 2014-02-28 2015-09-02 中国科学院寒区旱区环境与工程研究所 Sample pre-treatment method for determining total concentration of trace elements in polar ice and snow
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
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
CN105699466A (en) * 2016-01-15 2016-06-22 刘文涛 High-concentration organic matter sample pretreatment method and heavy metal content measuring method
CN107101961B (en) * 2017-06-22 2019-10-11 甘肃省交通规划勘察设计院股份有限公司 A kind of method of Trace Metals Contents in aas determination pitch
CN108645810A (en) * 2018-04-03 2018-10-12 成都产品质量检验研究院有限责任公司 The precious good and bad rapid detection method of polyisobutene amine fuel oil
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008203032A (en) * 2007-02-19 2008-09-04 Japan Energy Corp Analysis method of trace of metal
CN102928367A (en) * 2012-10-30 2013-02-13 安徽省电力科学研究院 Method for determining content of metal in transformer oil
CN103115917A (en) * 2011-11-17 2013-05-22 江苏天瑞仪器股份有限公司 Method for measuring impurity metallic elements in oil sample by using ICP-AES (inductively coupled plasma-atomic emission spectrometry)

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008203032A (en) * 2007-02-19 2008-09-04 Japan Energy Corp Analysis method of trace of metal
CN103115917A (en) * 2011-11-17 2013-05-22 江苏天瑞仪器股份有限公司 Method for measuring impurity metallic elements in oil sample by using ICP-AES (inductively coupled plasma-atomic emission spectrometry)
CN102928367A (en) * 2012-10-30 2013-02-13 安徽省电力科学研究院 Method for determining content of metal in transformer oil

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
水浴超声波萃取-原子荧光光谱法快速测定蚝油中无机砷;吴庆晖等;《食品科技》;20101130;第35卷(第11期);295-297,304 *
盐酸萃取火焰原子吸收法测定柴油中钠含量;邬蓓蕾;《光谱实验室》;20000425;第17卷(第04期);483-485 *
食用油中铅快速测定方法研究;李优琴等;《江西农业学报》;20091130;第21卷(第11期);99-101 *

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